Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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SUSTAINABLE CONTAINERS AND DISPENSERS FOR CONSUMER
COMPOSITIONS, SUSTAINABLE CONSUMER PRODUCTS COMPRISING
SUSTAINABLE CONSUMER COMPOSITIONS IN SUSTAINABLE
CONTAINERS, AND METHODS THEREOF
TECHNICAL FIELD
The present specification relates generally to sustainable consumer products
and, more
specifically, to sustainable containers and dispersers for consumer products,
to sustainable
consumer products contained in a sustainable container or dispenser and a
treatment composition,
and to sustainable consumer products including a sustainable composition
contained within a
sustainable container or dispenser.
BACKGROUND
Consumer products for fabric-care and home-care represent a multi-billion
dollar
worldwide industry. Typically, these consumer products include a liquid-based
composition
within a packaging. The packaging may include a storage container, a delivery
device such as a
nozzle, and/or secondary packaging that may include a label. Each of these
components requires
consumable resources and energy. A large portion of the consumable resources
are derived at
least in part from petroleum, which, in view of increased global consciousness
of needs for
sustainable products, is rather concerning.
For example, plastic packaging uses nearly 40% of all polymers, a substantial
share of
which is used for consumer products, such as personal care packages (e.g.,
shampoo, conditioner,
and soap bottles) and household packages (e.g., for laundry detergent and
cleaning
compositions). Most of the materials used to produce polymers for plastic
packaging
applications, such as polyethylene, polyethylene terephthalate, and
polypropylene, are derived
from monomers (e.g., ethylene, propylene, terephthalic acid, ethylene glycol),
which are obtained
from non-renewable, fossil-based resources, such as petroleum, natural gas,
and coal. Thus, the
price and availability of the petroleum, natural gas, and coal feedstock
ultimately have a
significant impact on the price of polymers used for plastic packaging
materials. As the
worldwide price of petroleum, natural gas, and/or coal escalates, so does the
price of plastic
packaging materials. Furthermore, many consumers display an aversion to
purchasing products
that are derived from petrochemicals. In some instances, consumers are
hesitant to purchase
products made from limited non-renewable resources (e.g., petroleum, natural
gas and coal).
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Other consumers may have adverse perceptions about products derived from
petrochemicals as
being "unnatural" or not environmentally friendly.
In response, producers of plastic packages have begun to use polymers derived
from
renewable resources to produce parts of their packages. For example,
polyethylene terephthalate
(PET) that is about 30% renewable (i.e., 30% of the monomers used to form PET,
such as
ethylene glycol, are derived from renewable resources) has been used for the
formation of soft
drink bottles. Further, polylactic acid (PLA) derived from corn has been used
for plastic
packaging purposes. Although containers made from PLA are biodegradable and
environmentally friendly, they are currently unfit for long-term preservation
because of their
sensitivity to heat, shock, and moisture. Packages derived from PLA also tend
to shrivel up,
shrink, and often break down when exposed to household chemicals, such as
bleach and alcohol
ethoxylate (iwhen the PLA is in direct contact with the product. Parts of food
packaging and
containers used to hold personal care products have also been formed from
polyethylene derived
from a renewable resource.
Although the current plastic packaging in the art can be partially composed of
polymers
derived from renewable materials, this current packaging contains at least one
component (e.g.,
container, closure, label) that includes at least some virgin petroleum-based
material, such as
polyethylene, polyethylene terephthalate, or polypropylene. None of the
current plastic
packaging is substantially free of virgin petroleum-based compounds, 100%
sustainable, and
100% recyclable, while having a shelf life of at least two years.
Current plastic packaging also can face difficulties during recycling. In the
first few steps
of a typical recycling procedure, a commonly used flotation process is used to
separate polymers
in a mixture based on density. Polymers that are denser than water, such as
polyethylene
terephthalate, sink to the bottom of a solution, while polymers that are less
dense than water,
such as polyethylene and polypropylene, rise to the top of the solution.
Contamination issues
frequently occur during recycling because current plastic packaging that is
highly filled or that is
composed of some renewable materials often contains dense materials that sink
during the
flotation process and contaminate the polyethylene terephthalate stream (e.g.,
polylactic acid,
highly filled high density polyethylene, or highly filled polypropylene). The
polyethylene
terephthalate stream is very sensitive to contamination, while the
polyethylene stream is typically
more robust.
The packaging materials for consumer products are but one global concern. The
compositions packaged within the packaging Materials represent another. The
consumer
compositions typically comprise a number of organic ingredients such as
plastics, fibers,
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surfactants, builders, polymers, and adjuncts. As used here, "organic
ingredients" refers to
ingredients containing chemical compositions having carbon atoms. In typical
commercial
products such as these, the carbon atoms of these organic ingredients trace
their origin to a
petroleum product. There is a constant need for developing products whose
organic ingredients
are derived from sources other than petroleum. Technology for producing
organic molecules
from natural or so-called bio-derived sources continues to improve with regard
to providing
organic chemicals having carbon atoms, of which a substantial portion, or even
all, of the carbon
atoms in the chemicals are bio-derived.
Accordingly, it would be desirable to provide plastic packaging that is
substantially free
of virgin petroleum-based compounds, 100% sustainable, 100% recyclable, has a
long-lasting
shelf life, and that can minimize or eliminate contamination during recycling.
It would be
desirable also to deliver fabric-care and home-care compositions in such
sustainable packaging.
Ultimately, it would be desirable to provide fabric-care and home-care
compositions that
themselves are derived from bio-based, non-petroleum resources, within the
sustainable
packaging materials.
SUMMARY
Embodiments disclosed herein address the foregoing needs by providing
sustainable
articles, such as packaging materials and containers, for use with consumer
compositions, and
sustainable consumer compositions that are packaged in sustainable packaging
materials to result
in a fully-sustainable, eco-friendly consumer product.
Embodiments directed toward a first aspect disclosed herein relate to
sustainable plastic
containers and delivery devices made from bio-derived polymers. The plastic
containers and
delivery devices include, for example, bottles and dispensers such as spray
applicators and pump
applicators.
Embodiments directed toward a second aspect disclosed herein relate to liquid
treatment
compositions packaged in the plastic containers according to the first aspect.
Embodiments directed toward a third aspect disclosed herein relate to consumer
products
including sustainable liquid treatment compositions packaged within the
plastic containers of the
first aspect. The sustainable liquid treatment compositions may contain bio-
derived ingredients
including, but not limited to, bio-derived surfactants, bio-derived solvents,
bio-derived chelants,
bio-derived polymers, and bio-derived thickeners.
These and other features, aspects; and advantages of the present invention
will become
better understood with reference to the following description and appended
claims.
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DETAILED DESCRIPTION
Features and advantages of the invention will now be described with occasional
reference
to specific embodiments. However, the invention may be embodied in different
forms and
should not be construed as limited to the embodiments set forth herein.
Rather, these
embodiments are provided so that this disclosure will be thorough and complete
and will fully
convey the scope of the invention to those skilled in the art.
Unless otherwise defined, all technical and scientific terms used herein have
the same
meaning as commonly understood by one of ordinary skill in the art to which
the invention
belongs. The terminology used in the description herein is for describing
particular embodiments
only and is not intended to be limiting. As used in the specification and
appended claims, the
singular forms "a," "an," and "the" are intended to include the plural forms
as well, unless the
context clearly indicates otherwise.
DEFINITIONS AND BIO-DERIVED CONTENT ASSESSMENT METHODS
As used herein, the term "bio-derived" means derived from or synthesized by a
renewable
biological feedstock, such as, for example, an agricultural, forestry, plant,
bacterial, or animal
feedstock. The renewable biological feedstocks may include biological
feedstocks used in their
naturaly-occurring state (i.e., as they are found in nature without human
intervention), and also
biological feedstocks that are produced with some degree of human intervention
such as through
genetic engineering, for example. Thus, "bio-derived compounds" typically are
compounds
obtained from a plant, animal, or microbe, and then modified via chemical
reaction.
Modification of the compounds can include esterification of fatty acids (e.g.,
ethoxylation,
methoxylation, propoxylation, etc.), transesterification of an oil (e.g.,
reaction of an alcohol with
a glyceride to form esters of the fatty acid portions of the glycerides), etc.
Hydrogenation or
other steps may also be considered.
As used herein, the term "biobased" means a product that is composed, in whole
or in
significant part, of biological products or renewable agricultural materials
(including plant,
animal and marine materials) or forestry materials. "Bio-based", and "bio-
sourced";
"biologically derived"; "bio-derived"; "naturally-derived" and simply any
compound or
composition having the prefix "bio-" are used synonymously herein.
As used herein, the term "petroleum derived" means a product derived from or
synthesized from petroleum or a petrochemical feedstock.
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"Biologically produced" means organic compounds produced by one or more
species or
strains of living organisms, including particularly strains of bacteria,
yeast, fungus and other
microbes. "Bio-produced" and biologically produced are used synonymously
herein. Such
organic compounds are composed of carbon from atmospheric carbon dioxide
converted to
5 sugars and starches by green plants.
"Fermentation" as used refers to the process of metabolizing simple sugars
into other
organic compounds. As used herein fermentation specifically refers to the
metabolism of plant
derived sugars, such sugar are composed of carbon of atmospheric origin.
"Carbon of atmospheric origin" as used herein refers to carbon atoms from
carbon
dioxide molecules that have recently, in the last few decades, been free in
the earth's atmosphere.
Such carbons in mass are identifiable by the present of particular
radioisotopes as described
herein. "Green carbon", "atmospheric carbon", "environmentally friendly
carbon", "life-cycle
carbon", "non-fossil fuel based carbon", "non-petroleum based carbon", "carbon
of atmospheric
origin", and "biobased carbon" are used synonymously herein.
"Carbon of fossil origin" as used herein refers to carbon of petrochemical
origin. Such
carbon has not been exposed to UV rays as atmospheric carbon has, therefore
masses of carbon
of fossil origin has few radioisotopes in their population. Carbon of fossil
origin is identifiable
by means described herein. "Fossil fuel carbon", "fossil carbon", "polluting
carbon",
"petrochemical carbon", "petro-carbon" and carbon of fossil origin are used
synonymously
herein.
"Naturally occurring" as used herein refers to substances that are derived
from a
renewable source and/or are produced by a biologically-based process.
"Fatty acid" as used herein refers to carboxylic acids that are often have
long aliphatic
tails, however, carboxylic acids of carbon length 1 to 40 are specifically
included in this
definition for the purpose of describing the present invention. "Fatty acid
esters" as used herein
are esters, which are composed of such, defined fatty acids.
As used herein, "sustainable" refers to a material having an improvement of
greater than
10% in some aspect of its Life Cycle Assessment or Life Cycle Inventory, when
compared to the
relevant virgin petroleum-based plastic material that would otherwise have
been used to
manufacture the article.
As used herein, "Life Cycle Assessment" (LCA) or "Life Cycle Inventory" (LCI)
refers
to the investigation and evaluation of the environmental impacts of a given
product or service
caused or necessitated by its 'existence. The LCA or LCI can involve a "cradle-
to-grave"
analysis, which refers to the full Life Cycle Assessment or Life Cycle
Inventory from
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manufacture ("cradle") to use phase and disposal phase ("grave"). For example,
high density
polyethylene (HDPE) containers can be recycled into HDPE resin pellets, and
then used to form
containers, films, or injection molded articles, for example, saving a
significant amount of fossil-
fuel energy. At the end of its life, the polyethylene can be disposed of by
incineration, for
example. All inputs and outputs are considered for all the phases of the life
cycle.
As used herein, "End of Life" (EoL) scenario refers to the disposal phase of
the LCA or
LC1. For example, polyethylene can be recycled, incinerated for energy (e.g.,
1 kilogram of
polyethylene produces as much energy as 1 kilogram of diesel oil), chemically
transformed to
other products, and recovered mechanically. Alternatively, LCA or LCI can
involve a "cradle-to-
gate" analysis, which refers to an assessment of a partial product life cycle
from manufacture
("cradle") to the factory gate (i.e., before it is transported to the
customer) as a pellet. Sometimes
this second type is also termed "cradle-to-cradle".
Various methods have been developed for determining biobased content. These
methods
typically require the measurement of variations in isotopic abundance between
biobased products
and petroleum derived products, for example, by liquid scintillation counting,
accelerator mass
spectrometry, or high precision isotope ratio mass spectrometry. Isotopic
ratios of the isotopes of
carbon, such as the 13C/12C carbon isotopic ratio or the
4C/12C carbon isotopic ratio, can be
determined using analytical methods, such as isotope ratio mass spectrometry,
with a high degree
of precision. Studies have shown that isotopic fractionation due to
physiological processes, such
as, for example, CO2 transport within plants during photosynthesis, leads to
specific isotopic
ratios in natural or bioderived compounds. Petroleum and petroleum derived
products have a
different 13C/12C carbon isotopic ratio due to different chemical processes
and isotopic
fractionation during the generation of petroleum. In addition, radioactive
decay of the unstable
14C carbon radioisotope leads to different isotope ratios in biobased products
compared to
petroleum products. Biobased content of a product may be verified by ASTM
International
Radioisotope Standard Method D 6866. ASTM International Radioisotope Standard
Method D
6866 determines biobased content of a material based on the amount of biobased
carbon in the
material or product as a percent of the weight (mass) of the total organic
carbon in the material or
product. Both bioderived and biobased products will have a carbon isotope
ratio characteristic of
a biologically derived composition.
A small amount of the carbon dioxide in the atmosphere is radioactive. This
14C carbon
dioxide is created when nitrogen is struck by a neutron, causing the nitrogen
to lose a proton and
form carbon of molecular weight 14 that is immediately oxidized to carbon
dioxide. This
radioactive isotope represents a small but measurable fraction of atmospheric
carbon.
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Atmospheric carbon dioxide is cycled by green plants to make organic molecules
during the
process known as photosynthesis. The cycle is completed when the green plants
or other forms
of life metabolize the organic molecules producing carbon dioxide which is
released back to the
atmosphere. Virtually all forms of life on Earth depend on this green-plant
production of organic
molecules to produce the chemical energy that facilitates growth and
reproduction. Therefore,
the "C that exists in the atmosphere becomes part of all life forms, and their
biological products.
Because these renewably based organic molecules that biodegrade to CO2 do not
contribute to
global warming as there is no net increase of carbon emitted to the
atmosphere. In contrast,
fossil fuel based carbon does not have the signature radiocarbon ratio of
atmospheric carbon
dioxide.
Assessment of the renewably based carbon in a material can be performed
through
standard test methods. Using radiocarbon and isotope ratio mass spectrometry
analysis, the
biobased content of materials can be determined. ASTM International, formally
known as the
American Society for Testing and Materials, has established a standard method
for assessing the
biobased content of materials. The ASTM method is designated ASTM-D6866.
The application of ASTM-D6866 to derive a "biobased content" is built on the
same
concepts as radiocarbon dating, but without use of age equations. The analysis
is performed by
deriving a ratio of the amount of radiocarbon ("C) in an unknown sample to
that of a modem
reference standard. The ratio is reported as a percentage with the units "pMC"
(percent modern
carbon, sometimes referred to as "RCI", the Renewable Carbon Index). If the
material being
analyzed is a mixture of present day radiocarbon and fossil carbon (containing
no radiocarbon),
then the pMC value obtained correlates directly to the amount of Biomass
material present in the
sample.
The modern reference standard used in radiocarbon dating is a NIST (National
Institute of
Standards and Technology) standard with a known radiocarbon content equivalent
approximately
to the year AD 1950. The year AD 1950 was chosen because it represented a time
prior to
thermo-nuclear weapons testing that introduced large amounts of excess
radiocarbon into the
atmosphere with each explosion (termed "bomb carbon"). The AD 1950 reference
thus is
defined as 100 pMC.
"Bomb carbon" in the atmosphere reached almost twice normal levels in 1963 at
the peak
of testing and prior to the treaty halting the testing. Distribution of bomb
carbon within the
atmosphere has been approximated since its appearance, showing values that are
greater than 100
pMC for plants and animals living since AD 1950. Bomb carbon has gradually
decreased over
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time, with the value in the year 2011 being near 107.5 pMC. This means that a
fresh biomass
material such as corn could give a radiocarbon signature near 107.5 pMC.
Combining fossil carbon with present day carbon into a material will result in
a dilution
of the present day pMC content. By presuming 107.5 pMC represents present day
biomass
materials and 0 pMC represents petroleum derivatives, the measured pMC value
for that material
will reflect the proportions of the two component types. A material derived
100% from present
day soybeans would give a radiocarbon signature near 107.5 pMC. If that
material was diluted
with 50% petroleum derivatives, it would give a radiocarbon signature near 54
pMC.
A biomass content result is derived by assigning 100% equal to 107.5 pMC and
0% equal
to 0 pMC. In this regard, a sample measuring 99 pMC will give an equivalent
biobased content
result of 93%.
Compositions comprising bio-based materials also may be assessed according to
a
"percent natural" standard, as disclosed in U.S. Pat. Appl. Pub. No.
2010/0311179. In contrast to
pMC (RCI), which is understood to refer to the amount of bio-derived carbon in
active
ingredients, the percent natural standard is a measure of the percentage of
natural (e.g., non-
petroleum) materials in a composition, assuming that water in the composition
is 100% natural.
SUSTAINABLE ARTICLES AND BIO-DERIVED MATERIALS FOR THE SUSTAINABLE ARTICLES
According to some embodiments, sustainable consumer products are provided that
comprise a sustainable article such as, for example, a sustainable container,
a sustainable
dispenser, and/or sustainable packaging materials. The sustainable article
contains one or more
bio-derived materials and, in some embodiments, is formed entirely from one or
more bio-
derived materials.
The sustainable article is advantageous because it has the same look and feel
as similar
articles made from virgin petroleum-based sources, similar performance
characteristics as the
articles made from virgin petroleum-based sources (e.g., similar drop and top
load), and can be
disposed of in the same way (e.g., by recycling the article), yet the
sustainable article has
improved sustainability over articles derived from virgin petroleum-based
sources.
The sustainable article is also advantageous because any virgin polymer used
in the
manufacture of the article is derived from a renewable resource. As used
herein, a "renewable
resource" is one that is produced by a natural process at a rate comparable to
its rate of
consumption (e.g., within a 100 year time frame). The resource can be
replenished naturally, or
via agricultural techniques. Nonlimiting examples of renewable resources
include plants (e.g.,
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sugar cane, beets, corn, potatoes, citrus fruit, woody plants,
lignocellulosics, hemicellulosics,
cellulosic waste), animals, fish, bacteria, fungi, and forestry products.
These resources can be
naturally occurring, hybrids, or genetically engineered organisms. Natural
resources such as
crude oil, coal, natural gas, and peat, which take longer than 100 years to
form, are not
considered renewable resources. Because at least part of the sustainable
article is derived from a
renewable resource, which can sequester carbon dioxide, use of the article can
reduce global
warming potential and fossil fuel consumption. For example, some LCA or LCI
studies on the
resin from which the article is derived have shown that about one ton of
polyethylene made from
virgin petroleum-based sources results in the emission of up to about 2.5 tons
of carbon dioxide
to the environment. Because sugar cane, for example, takes up carbon dioxide
during growth,
one ton of polyethylene made from sugar cane removes up to about 2.5 tons of
carbon dioxide
from the environment. Thus, use of about one ton of polyethylene from a
renewable resource,
such as sugar cane, results in a decrease of up to about 5 tons of
environmental carbon dioxide
versus using one ton of polyethylene derived from petroleum-based resources.
Nonlimiting examples of renewable polymers include polymers produced directly
from
organisms, such as polyhydroxyalkanoates (e.g., poly(beta-hydroxyalkanoate),
poly(3-
hydroxybutyrate-co-3-hydroxyvalerate, NODAXTm), and bacterial cellulose;
polymers extracted
from plants and biomass, such as polysaccharides and derivatives thereof
(e.g., gums, cellulose,
cellulose esters, chitin, chitosan, starch, chemically modified starch),
proteins (e.g., zein, whey,
gluten, collagen), lipids, lignins, and natural rubber; and current polymers
derived from naturally
sourced monomers and derivatives, such as bio-derived polyethylene, bio-
polypropylene, bio-
derived polytrimethylene terephthalate, bio-derived polylactic acid, bio-
derived NYLON 11, bio-
derived alkyd resins, bio-derived succinic acid-based polyesters, and bio-
derived polyethylene
terephthalate.
The sustainable article is further advantageous because its properties can be
tuned by
varying the amount of bio-material, recycled material, and regrind material
used to form the
container, closure, label, or mixture thereof, or by the introduction of
fillers. For example,
increasing the amount of bio-material at the expense of recycled material
(when comparing like
for like, e.g., homopolymer versus copolymer), tends to increase the stress
crack resistance,
increase the impact resistance, decrease opaqueness, and increase surface
gloss. Increasing the
amount of specific types of recycled and/or regrind material can improve some
properties. For
example, recycled material containing an elastomeric content will increase
impact resistance, and
reduce the cost of the article, depending on the exact grade. In contrast,
recycled material that
does not contain elastomeric content will often slightly decrease impact
resistance. Further,
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because recycled material is often already colored, use of recycled materials
over virgin materials
often results in cost savings on colorant masterbatches, particularly if the
color of the recycled
material is similar to the intended color of the article.
The ability to tune the composition of the sustainable article allows the
incorporation of
5 polymers that are either less or more dense than water, to result in an
overall composition that has
a density below that of water, such as when the article is not composed of
polyethylene
terephthalate. Therefore, the sustainable article is easier to recycle in
typical recycling streams
than current plastic packaging materials that appear to be at least partly
sustainable (e.g., those
that include polylactic acid as part of the packaging), because issues
concerning the
10 contamination of polyethylene terephthalate streams during the flotation
separation process can
be avoided.
Even further, the sustainable article is advantageous because it can act as a
one to one
replacement for similar articles containing polymers that are wholly or
partially derived from
virgin petroleum-based materials, and can be produced using existing
manufacturing equipment,
reactor conditions, and qualification parameters. Its use results in a
reduction of the
environmental footprint, and in less consumption of non-renewable resources.
The reduction of
the environmental footprint occurs because the rate of replenishment of the
resources used to
produce article's raw construction material is equal to or greater than its
rate of consumption;
because the use of a renewable derived material often results in a reduction
in greenhouse gases
due to the sequestering of atmospheric carbon dioxide, or because the raw
construction material
is recycled (consumer or industrial) or reground within the plant, to reduce
the amount of virgin
plastic used and the amount of used plastic that is wasted, e.g., in a
landfill. Further, the
sustainable article does not lead to the destruction of critical ecosystems,
or the loss of habitat for
endangered species.
Embodiments disclosed herein relate to a sustainable article that has a shelf
life of at least
two years, is 100% recyclable, and is substantially free of virgin petroleum-
based materials (i.e.,
less than 10 wt.%, preferably less than 5 wt.%, more preferably less than 3
wt.% of virgin
petroleum-based materials, based on the total weight of the article). As used
herein, "virgin
petroleum-based" refers to materials that are derived from a petroleum source,
such as oil, natural
gas, or coal, and that have not been recycled, either industrially or through
the consumer waste
stream.
The sustainable article includes a container, a closure, and a label, with
each of the
= components derived from renewable materials, recycled materials, regrind
materials, or a mixture
thereof. Optionally, the sustainable article may further include a sustainable
dispenser such as a
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trigger sprayer or a pump, for example. The container includes at least 90
wt.%, preferably at
least 95 wt.%, more preferably at least 97 wt.%, for example, about 100 wt.%
of bio-polymer,
recycled polymer, regrind polymer, or a mixture thereof. The closure includes
at least 90 wt.%,
preferably at least 95 wt.%, more preferably at least 97 wt.%, for example,
about 100 wt.% of
bio-polymer, recycled polymer, regrind polymer, or a mixture thereof. The
label includes at least
90 wt.%, preferably at least 95 wt.%, more preferably at least 97 wt.%, for
example, about 100
wt.% of bio-polymer, recycled polymer, regrind polymer, or a mixture thereof.
The optional
dispenser, when present, includes at least 90 wt.%, preferably at least 95
wt.%, more preferably
at least 97 wt.%, for example, about 100 wt.% of bio-polymer, recycled
polymer, regrind
polymer, or a mixture thereof. In some embodiments, the sustainable article
may be a component
of a sustainable consumer product that comprises the sustainable article and
at least one of a
sustainable composition and/or sustainable packaging, both of which are
described in greater
detail below. The sustainable packaging may comprise a secondary packaging
and, optionally, a
tertiary packaging, both described below, and each layer of packaging may
optionally be labeled
with one or more sustainable labels, which sustainable tables may be printed
with indicia using
sustainable or bio-derived inks.
Examples of renewable materials include bio-polyethylene, bio-polyethylene
terephthalate, and bio-polypropylene. As used herein and unless otherwise
noted, "polyethylene"
encompasses high density polyethylene (HDPE), low density polyethylene (LDPE),
linear low
density polyethylene (LLDPE), and ultra low density polyethylene (ULDPE). As
used herein
and unless otherwise noted, "polypropylene" encompasses homopolymer
polypropylene, random
copolymer polypropylene, and block copolymer polypropylene.
As used herein, "recycled" materials encompass post-consumer recycled (PCR)
materials,
post-industrial recycled (PIR) materials, and a mixture thereof. In some
embodiments, the
container and/or closure are composed of recycled high density polyethylene,
recycled
polyethylene terephthalate, recycled polypropylene, recycled LLDPE, or
recycled LDPE,
preferably recycled high density polyethylene, recycled polyethylene
terephthalate, or recycled
polypropylene, more preferably recycled high density polyethylene or recycled
polyethylene
terephthalate. In some embodiments, the labels are composed of recycled high
density
polyethylene, polypropylene, or polyethylene terephthalate from containers.
As used herein, "regrind" material is thermoplastic waste material, such as
sprues,
runners, excess parison material, and reject parts from injection and blow
molding and extrusion
operations, which has been reclaimed by shredding or granulating.
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In some preferred embodiments, the sustainable article may contain one or more
bio-
derived polymers or plastics selected from the group consisting of bio-derived
polyethylene, bio-
derived high-density polyethylene, bio-derived polypropylene, bio-derived
polyethylene
terephthalate, and mixtures thereof. In the following sections, these bio-
derived materials and
exemplary methods for attaining them are described.
Bio-Derived Polyethylene and Bio-Derived High Density Polyethylene
In one aspect, the sustainable article includes bio-polyethylene and/or bio-
high density
polyethylene. Bio-polyethylene may be produced from the polymerization of bio-
ethylene,
which is formed from the dehydration of bio-ethanol. Bio-ethanol can be
derived from, for
example, (i) the fermentation of sugar from sugar cane, sugar beet, or
sorghum; (ii) the
saccharification of starch from maize, wheat, or manioc; and (iii) the
hydrolysis of cellulosic
materials. U.S. Patent Application Publication No. 2005/0272134, incorporated
herein by
reference, describes the fermentation of sugars to form alcohols and acids.
Suitable sugars used to form ethanol include monosaccharides, disaccharides,
trisaccharides, and oligosaccharides. Sugars, such as sucrose, glucose,
fructose, and maltose, are
readily produced from renewable resources, such as sugar cane and sugar beets.
As previously
described, sugars also can be derived (e.g., via enzymatic cleavage) from
other agricultural
products (i.e., renewable resources resulting from the cultivation of land or
the husbandry of
animals). For example, glucose can be prepared on a commercial scale by
enzymatic hydrolysis
of corn starch. Other common agricultural crops that can be used as the base
starch for
conversion into glucose include wheat, buckwheat, arracaha, potato, barley,
kudzu, cassava,
sorghum, sweet potato, yam, arrowroot, sago, and other like starchy fruit,
seeds, or tubers. The
sugars produced by these renewable resources (e.g., corn starch from corn) can
be used to
produce alcohols, such as propanol, ethanol, and methanol. For example, corn
starch can be
enzymatically hydrolyzed to yield glucose and/or other sugars. The resultant
sugars can be
converted into ethanol by fermentation.
Monofunctional alcohols, such as ethanol and propanol can also be produced
from fatty
acids, fats (e.g., animal fat), and oils (e.g., monoglycerides, diglycerides,
triglycerides, and
mixtures thereof). These fatty acids, fats, and oils can be derived from
renewable resources, such
as animals or plants. "Fatty acid" refers to a straight chain monocarboxylic
acid having a chain
length of 12 to 30 carbon atoms. "Monoglycerides," "diglycerides," and
"triglycerides" refer to
containing multiple mono-, di- and tri- esters, respectively, of (i) glycerol
and (ii) the same or
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mixed fatty acids unsaturated double bonds. Nonlimiting examples of fatty
acids include oleic
acid, myristoleic acid, palmitoleic acid, sapienic acid, linoleic acid,
linolenic acid, arachidonic
acid, eicosapentaenoic acid, and docosahexaenoic acid. Nonlimiting examples of
monoglyeerides include monoglycerides of any of the fatty acids described
herein. Nonlimiting
examples of diglycerides include diglycerides of any of the fatty acids
described herein.
Nonlimiting examples of the triglycerides include triglycerides of any of the
fatty acids described
herein, such as, for example, tall oil, corn oil, soybean oil, sunflower oil,
safflower oil, linseed
oil, perilla oil, cotton seed oil, tung oil, peanut oil, oiticica oil,
hempseed oil, marine oil (e.g.
alkali-refined fish oil), dehydrated castor oil, and mixtures thereof.
Alcohols can be produced
from fatty acids through reduction of the fatty acids by any method known in
the art. Alcohols
can be produced from fats and oils by first hydrolyzing the fats and oils to
produce glycerol and
fatty acids, and then subsequently reducing the fatty acids.
In a preferred embodiment, the bio-ethylene is produced from sugar cane. The
life cycle
stages of ethylene production from sugar cane include (i) sugar cane farming,
(ii) fermentation of
sugar cane to form bio-ethanol, and (iii) dehydration of bio-ethanol to form
ethylene.
Specifically, sugar cane is washed and transported to mills where sugar cane
juice is extracted,
leaving filter cake, which is used as fertilizer, and bagasse (residual woody
fiber of the cane
obtained after crushing). The bagasse is burned to generate steam and the
electricity used to
power the sugar cane mills, thereby reducing the use of petroleum-derived
fuels. The sugar cane
juice is fermented using yeast to form a solution of ethanol and water. The
ethanol is distilled
from the water to yield about 95% pure bio-ethanol. The bio-ethanol is
subjected to catalytic
dehydration (e.g., with an alumina catalyst) to produce ethylene, which is
subsequently
polymerized to form polyethylene.
Advantageously, a Life Cycle Assessment & Inventory of ethylene produced from
sugar
cane shows favorable benefits in some aspects over ethylene produced from
petroleum feedstock
for global warming potential, abiotic depletion, and fossil fuel consumption.
For example, some
studies have shown that about one ton of polyethylene made from virgin
petroleum-based
sources results in the emission of up to about 2.5 tons of carbon dioxide to
the environment, as
previously described. Thus, use of up to about one ton of polyethylene from a
renewable
resource, such as sugar cane, results in a decrease of up to about 5 tons of
environmental carbon
dioxide versus using one ton of polyethylene derived from petroleum-based
resources.
BRASKEM has demonstrated the production of high density polyethylene (HDPE)
and
linear, low density polyethylene (LLDPE) from sugar cane using a
Hostalen/Basell technology
for the I IDPE production and a Spherilene/Basell technology for the LLDPE
production. These
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catalysts allow (in some cases), superior processability of the bio-
polyethylene and results in
products with superior consistency to incumbent resins made by other
processes.
Bio-Derived Polypropylene
In yet another aspect, the sustainable article may include bio-polypropylene.
Bio-
polypropylene may be produced from the polymerization of propylene formed from
the
dehydration of propanol. Renewable resources used to derive propanol are as
previously
described. Propanol also can be derived from bio-ethylene. In this pathway,
bio-ethylene is
converted into propionaldehyde by hydroformylation using carbon monoxide and
hydrogen in
the presence of a catalyst, such as cobalt octacarbonyl or a rhodium complex.
Hydrogenation of
the propionaldehyde in the presence of a catalyst, such as sodium borohydride
and lithium
aluminum hydride, yields propan-l-ol, which can be dehydrated in an acid
catalyzed reaction to
yield propylene, as described in U.S. Patent Application Publication No.
2007/0219521,
incorporated herein by reference.
Bio-Derived Polyethylene Terephthalate
In another aspect, the sustainable article may include bio-polyethylene
terephthalate.
Bio-polyethylene terephthalate may be produced from the polymerization of bio-
ethylene glycol
with bio-terephthalic acid. Bio-ethylene glycol can be derived from renewable
resources via a
number of suitable routes, such as, for example, those described in WO
2009/155086 and U.S.
Patent No. 4,536,584, each incorporated herein by reference. Bio-terephthalic
acid can be
derived from renewable alcohols through renewable p-xylene, as described in
International
Patent Application Publication No. WO 2009/079213, which is incorporated
herein by reference.
In some embodiments, a renewable alcohol (e.g,. isobutanol) is dehydrated over
an acidic
catalyst in a reactor to form isobutylene. The isobutylene is recovered and
reacted under the
appropriate high heat and pressure conditions in a second reactor containing a
catalyst known to
aromatize aliphatic hydrocarbons to form renewable p-xylene.
In another embodiment, the renewable alcohol, e.g. isobutanol, is dehydrated
and
dimerized over an acid catalyst. The resulting diisobutylene is recovered and
reacted in a second
reactor to form renewable p-xylene.
In yet another embodiment, a renewable alcohol, e.g. isobutanol, containing up
to 15
wt.% water is dehydrated, or dehydrated and oligomerized, and the resulting
oligomers are
aromatized to form renewable p-xylene.
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In yet another embodiment, the dehydration of the renewable alcohol and the
aromatization of the resulting alkene occurs in a single reactor using a
single catalyst, to form a
mixture of renewable aromatic compounds. The resulting renewable aromatic
compounds are
purified, e.g. by distillation or crystallization, to obtain pure streams of
individual renewable
5 aromatic products. The pure xylenes from these reactions are oxidized to
their corresponding
phthalic acids and phthalate esters.
Renewable phthalic acid or phthalate esters can be produced by oxidizing p-
xylene over a
transition metal catalyst (see, e.g., Ind. Eng. Chem. Res., 39:3958-3997
(2000)), optionally in the
presence of one or more alcohols.
10 SUSTAINABLE CONTAINERS AND DISPENSERS
As described above, the sustainable article may comprise a sustainable
container, a
sustainable dispenser, or both, either of which may function as sustainable
packaging for a
sustainable consumer product. In some embodiments, the sustainable article
comprises a
sustainable container such as a bottle and a sustainable dispenser configured
as a trigger sprayer,
15 a pump sprayer, a dosing cap, or a press tab, for example. However, it
should be understood that
the sustainable article may take a variety of other forms suitable for
storing, shipping, delivering,
and dispensing any of the consumer products described herein.
In some embodiments, the sustainable article may further comprise a closure
and/or a
label, either of which may comprise or be made from one or more bio-derived
materials. In
further embodiments, the sustainable article may further comprise a consumer
composition, as
described in detail below. In still further embodiments, the consumer
composition is a
sustainable composition, as described below.
The consumer composition and/or the sustainable composition may be deliverable
with or
without a sustainable dispenser, if present, by a natural, bio-derived, or
sustainable propellant
packaged with the consumer composition or sustainable composition. In some
embodiments, the
sustainable article may comprise a sustainable container and/or a sustainable
dispenser that is
packaged in a sustainable packaging material. Sustainable packaging materials
are described in
greater detail below and may include, for example, secondary packaging and
tertiary packaging.
The any or all layers of sustainable packaging present in the sustainable
article optionally may be
labelled with one or more sustainable labels as described herein, which
labeled optionally may
contain indicia printed with sustainable or bio-derived inks.
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Sustainable Containers
Composition of Sustainable Containers
In some embodiments, the sustainable article may comprise a container, such as
a bottle,
suitable for containing a consumer composition, in particular a liquid
composition. In further
embodiments, the container may be an aerosol container suitable for containing
a liquid or solid
product and a propellant such as a compressed gas. The container comprises or
is made from one
or more bio-derived materials. Preferably, the bio-derived materials selected
for the container all
are chemically and physically compatible with any composition intended to be
contained therein.
As used here, "chemically and physically compatible" means that the consumer
composition
does not react with, substantially soften or harden, dissolve, or cause
deleterious effects such as
crazing within the container that is the sustainable article. The container
may have any desired
shape or size and may include ornamental features being indicative of a
consumer composition
contained therein or intended only to provide pleasing aesthetic value to a
consumer product.
Several embodiments of the bio-derived materials content of such containers
will now be
described. It should be understood that these embodiments are meant to be
exemplary, not
limiting.
In some embodiments, the container may be composed of at least 10 wt.%,
preferably at
least 25 wt.%, more preferably at least 50 wt.%, even more preferably about 75
wt.%, for
example, at least 90 wt.% or 100 wt.% of high density polyethylene (HDPE),
based on the total
weight of the container, which has a biobased content of at least 95%,
preferably at least 97%,
more preferably at least 99%, for example about 100%. The container may
further include a
polymer selected from the group consisting of post-consumer recycled
polyethylene (PCR-PE),
post-industrial recycled polyethylene (PIR-PE), regrind polyethylene, and a
mixture thereof. The
recycled polyethylene is optionally present in an amount of up to about 90
wt.%, preferably up to
about 50 wt.%, more preferably up to about 25 wt. %, based on the total weight
of the container.
The regrind polyethylene is optionally present in an amount of up to about 75
wt.%, preferably
up to about 50 wt.%, more preferably up to about 40 wt. %, based on the total
weight of the
container.The container may include, for example, about 50 wt.% of bio-HDPE,
about 25 wt.%
of PCR-PE, and about 25 wt.% of regrind PE; or, if recycled PE is not
available, about 65 wt.%
of bio-HDPE and about 35 wt.% of regrind PE. The container has a density of
less than 1 g/mL
to aid separation during the floatation process of recycling, as previously
described.
In further embodiments, the container may be composed of at least 10 wt.%,
preferably at
least 25 wt.%, more preferably at least 50 wt.%, even more preferably at least
75 wt.%, for
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example, at least 90 wt.% or about 100 wt.% of polyethylene terephthalate
(PET). In
embodiments when the container includes PET with a biobased content of at
least 90%, the
container further includes a polymer selected from the group consisting of
post-consumer
recycled polyethylene terephthalate (PCR-PET), post-industrial recycled
polyethylene
terephthalate (PIR-PET), regrind polyethylene terephthalate, and a mixture
thereof. The recycled
PET is optionally present in an amount of up to about 90 wt.%, preferably up
to about 50 wt.%,
more preferably up to about 25 wt. cY0, based on the total weight of the
container. The regrind
PET is optionally present in an amount of up to about 75 wt.%, preferably up
to about 50 wt.%,
more preferably up to about 40 wt. %, based on the total weight of the
container. The container
can include, for example, about 30 wt.% bio-PET and about 70 wt.% of PCR-PET.
The
containers according to these embodiments may have densities of greater than 1
g/mL.
Without intent to be limited by theory, it is believed that poly(ethylene
terephthalate)
(PET) aerosol-type containers or bottles may be less desirable in certain
instances. For example,
it is believed that limonene and other perfume raw materials, as well
hydrocarbon propellants and
other formula ingredients, can diffuse into PET and lower its crazing
initiation stress. As a
result, these chemicals can cause crazing of PET in the neck and shoulder
regions of the aerosol
bottle where the tensile stresses, due to the presence of the pressurized
propellant, exceed the
crazing initiation stress. This crazing of PET can progress into cracking and
cause integrity
problems in the aerosol bottles. In still further embodiments, the container
may be composed of
at least 10 wt.%, preferably at least 25 wt.%, more preferably at least 50
wt.%, even more
preferably at least 75 wt.%, for example, at least 90 wt.% or about 100 wt.%.
of polypropylene
(PP), based on the total weight of the container, which has a biobased content
of at least 90%,
preferably at least 93%, more preferably at least 95%, for example, about
100%. The container
further may include a polymer selected from the group consisting of post-
consumer recycled
polypropylene (PCR-PP), post-industrial recycled polypropylene (PIR-PP),
regrind
polypropylene, and a mixture thereof. The recycled polypropylene is optionally
present in an
amount of up to about 90 wt.%, preferably up to about 50 wt.%, more preferably
up to about 25
wt. %, based on the total weight of the container. The regrind polypropylene
is optionally
present in an amount of up to about 75 wt.%, preferably up to about 50 wt.%,
more preferably up
to about 40 wt. %, based on the total weight of the container. The containers
of these
embodiments may have a density of less than 1 g/mL to aid separation during
the floatation
process of typical recycling systems, as previously described. For example,
the container can
include about 50 wt.% of bio-PP, about 25 wt.% of PCR-PP, and about 25 wt.% of
regrind PP;
or, if recycled PP is not available, about 60 wt.% of bio-PP and about 40 wt.%
of regrind PP.
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The sustainable container useful herein may have a hollow body for holding a
consumer
composition, and is typically a bottle or canister formed of bio-derived
plastic, glass, and/or
metal, preferably a bio-derived polymer or resin such as bio-derived
polyethylene, bio-derived
polypropylene, bio-derived polyethylene terephthalate, bio-derived
polycarbonate, bio-derived
polystyrene, bio-derived ethyl vinyl alcohol, bio-derived polyvinyl alcohol,
bio-derived
thermoplastic elastomer, and combinations thereof, although other materials
known in the art
may also be used. Such containers will typically hold from about 100 mL to
about 2 L of liquid,
preferably from about 150 mL to about 1.2 L of liquid, and more preferably
from about 200 mL
to about 1 L of liquid, and are well known for holding liquid consumer
products.
Characterization of Sustainable Containers
Preferably, each bio-derived component and each non-bio-derived component of
the
sustainable article has a shelf life of at least two years. The density of the
container can be
determined using ASTM D792.
A container with a shelf life of at least two years can be characterized by at
least one the
following expedients: its water vapor transmission rate (WVTR), environmental
stress cracking
(ESC), and column crush.
Water vapor transmission rate is the steady state rate at which water vapor
permeates
through a film at specified conditions of temperature and relative humidity,
and can be
determined using ASTM 1249-06. A container that is composed of HDPE has a WVTR
of less
than 0.3 grams per 100 square inches per 1 day (g/100 in2/day), preferably
less than 0.2 g/100
in2/day, more preferably less than 0.1 g/100 in2/day, at about 38 C and about
90% relative
humidity. A container that is composed of PP has a WVTR of less than 0.6 g/100
in2/day,
preferably less than 0.4 g/100 in2/day, more preferably less than 0.2 g/100
in2/day, at about 38 C
and about 90% relative humidity. A container that is composed of PET has a
WVTR of less than
2.5 g/100 in2/day, preferably less than 1.25 g/100 in2/day, more preferably
less than 0.625 g/100
in2/day, at about 38 C and about 90% relative humidity.
Environmental Stress Cracking (ESC) is the premature initiation of cracking
and
embrittlement of a plastic due to the simultaneous action of stress, strain,
and contact with
specific chemical environments. One method of determining ESC is by using ASTM
D-2561. A
container of the invention can survive a 4.5 kilogram load under 60 C for 15
days, preferably for
30 days, when subjected to ASTM D-2561.
Alternatively, the ESC can be determined according to the following procedure.
A
container to be tested is filled with liquid to a target fill level and,
optionally, a closure is fitted
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on the container. If the closure is a screw type closure, it is tightened to a
specified torque. The
test container is conditioned for four hours under 50 C 1.5 C. The screw-
type container
closures are then re-torqued to the original specified torque level and
leaking samples are
eliminated. At its conditioning temperature, the container is placed in an
upright position and a
4.5 to 5.0 kilogram weight is placed on top of it. The container is inspected
every day for thirty
days for evidence of stress cracking or signs of leakage that may indicate
stress cracking. A
container of the invention can survive a 4.5 to 5.0 kilogram load for about
thirty days, during
which the first fifteen days are the most critical.
The Column Crush test provides information about the mechanical crushing
properties
(e.g., crushing yield load, deflection at crushing yield load, crushing load
at failure, apparent
crushing stiffness) of blown thermoplastic containers. When an empty,
uncapped, air vented
container of the invention is subjected to the ASTM D-2659 Column Crush test
using a velocity
of 50 mm/min, the compression strength peak force (at a deflection of no more
than about 5
mm), is no less than SON, preferably no less than 100 N, more preferably no
less than 230 N.
Also, when the container of the invention is tested filled with water at a
temperature between 28
C and 42 C and subjected to the ASTM D-2659 Column Crush test using a
velocity of 12.5
mm/min, the compression strength peak force (at a deflection of no more than
about 5 mm), is no
less than 150 N, preferably no less than 250 N, more preferably no less than
300 N. The Column
Crush tests are performed in a room held at room temperature.
Additionally or alternatively, the raw construction material comprising HDPE,
PET, or
PP; and polymer, as described above, used to produce the container of the
invention preferably
has a heat distortion temperature or Vicat softening point as specified below,
and/or can survive
an applied stress according to the full notch creep test, as specified below.
Heat distortion temperature (HDT) is the temperature at which a test material
deflects a
specified amount when loaded in 3-point bending at a specified maximum outer
fiber stress. The
heat distortion temperature can be determined using the standard procedure
outlined in ISO 75,
where method A uses an outer fiber stress of 1.80 MPa, and method B uses an
outer fiber stress
of 0.45 MPa. The raw construction material of a HDPE container of the
invention has a HDT of
at least 40 C, preferably at least 45 C, more preferably at least 50 C,
according to method A
and at least 73 C, preferably at least 80 C, more preferably at least 90 C,
according to method
B. The raw construction material of a PET container of the invention has a HDT
of at least 61.1
C, preferably at least 63 C, more preferably at least 65 C according to
method A, and at least
66.2 C, preferably at least 68 C, more preferably at least 70 C, according
to method B. The
raw construction material of a PP container of the invention has a HDT of at
least 57 C,
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preferably at least 65 C, more preferably at least 70 C, according to method
A and at least 75
C, preferably at least 90 C, more preferably at least 100 C, according to
method B.
Vicat softening point is the determination of the softening point for
materials that have no
definite melting point, but can still be measured for those materials that do
have melting point. It
5 is taken as the temperature at which the material is penetrated to a
depth of 1 millimeter by a flat-
ended needle with a one square millimeter circular or square cross-section.
The Vicat softening
point can be determined using the standard procedure outlined in ISO 306,
where a load of 10 N
and a heating rate of 50 C per hour is used for test method A50, and a load
of 50 N and a heating
rate of 50 C per hour is used for test method B50. The raw construction
material of a HDPE
10 container of the invention has a Vicat softening temperature of at least
112 C, preferably at least
125 C, more preferably at least 130 C, according to test method A50 and at
least 75 C,
preferably at least 77 C, more preferably at least 80 C, according to test
method B50. The raw
construction material of a PET container of the invention has a Vicat
softening temperature of at
least 79 C, preferably at least 85 C, more preferably at least 90 C,
according to test method
15 A50 and at least 75 C, preferably at least 77 C, more preferably at
least 80 C, according to test
method B50. The raw construction material of a PP container of the invention
has a Vicat
softening temperature of at least 125 C, preferably at least 154 C, more
preferably at least 175
C, according to test method A50 and at least 75 C, preferably at least 85 C,
more preferably at
least 95 C, according to test method B50.
20 The Full Notch Creep Test (FNCT) is an accelerated test used to assess
the resistance of a
polymer to slow crack growth in a chosen environment. When subjected to the
FNCT described
in ISO 16770, the raw construction material of a HDPE or a PP container of the
invention can
survive at least 4 hours, preferably at least 18 hours, more preferably at
least 50 hours, even more
preferably about 100 hours at an applied stress of about 4A MPa, at room
temperature.
Methods for Forming Sustainable Containers
The containers can be produced using blow molding, for example. Blow molding
is a
manufacturing process by which hollow plastic parts are formed from
thermoplastic materials.
The blow molding process begins with melting down thermoplastic and forming it
into a parison
or preform. The parison is a tube-like piece of plastic with a hole in one end
through which
compressed air can pass. Pressurized gas, usually air, is used to expand the
parison or the hot
preform and press it against a mold cavity. The pressure is held until the
plastic cools. After the
plastic has cooled and hardened the mold opens up and the part is ejected.
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There are three main types of blow molding: extrusion blow molding, injection
blow
molding, and injection stretch blow molding. In extrusion blow molding, a
molten tube of plastic
is extruded into a mold cavity and inflated with compressed air. One end of
the cylinder is
pinched closed. After the plastic part has cooled, it is removed from the
mold. Extrusion blow
molding can be used to produce the HDPE and PP containers of the invention.
These containers
can be single layer or multilayer.
Injection blow molding (IBM) involves three steps: injection, blowing and
ejection.
First, molten polymer is fed into a manifold where it is injected through
nozzles into a hollow,
heated preform mold. The preform mold forms the external shape of the
resulting container and
is clamped around a mandrel (the core rod) which forms the internal shape of
the preform. The
preform consists of a fully formed bottle/jar neck with a thick tube of
polymer attached, which
will form the body. The preform mold opens and the core rod is rotated and
clamped into the
hollow, chilled blow mold. The core rod opens and allows compressed air into
the preform,
which inflates it to the finished article shape. After a cooling period the
blow mold opens and the
core rod is rotated to the ejection position. The finished article is stripped
off the core rod and
leak-tested. Injection blow molding, as well as the other blow molding methods
described
herein, is useful for the formation of article components that have embedded
biodegradable
polymer. Injection blow molding can be used to produce containers that include
blends of
biodegradable polymers.
Injection stretch blow molding (ISBM) is a method for producing a plastic
container from
a preform or parison that is stretched in both the hoop direction and the
axial direction when the
preform is blown into its desired container shape. In the ISBM process, a
plastic is first molded
into a "preform" using the injection molding process. These preforms are
produced with the
necks of the containers, including threads. The preforms are packaged, and
after cooling, fed
into a reheat stretch blow molding machine. The preforms are heated above
their glass transition
temperature, then blown using high pressure air into containers using metal
blow molds.
Typically, the preform is stretched with a core rod as part of the process.
Injection stretch blow
molding can be used to produce the bio-HDPE, bio-PET, and bio-PP containers of
the invention.
Sustainable Closures
Compositions of Sustainable Closures
In some embodiments, the sustainable containers described above may comprise a
closure
that closes the container to seal in any consumer composition contained in the
container. In some
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22
embodiments the closure may be configured as a threaded cap, a snap-on cap, a
snap-shut cap
with a hinged portion connected to a cap body, an interlocking track that may
be sealed by a
user's fingers or with a zipper-type mechanism, and the like. The closure may
be used in
conjunction with the container according to any suitable means such as by
threads on the closure
that engage mating threads on the container, suitable sealing mechanisms,
child-proof
mechanisms known in the art, simple snap-on mechanisms, and the like.
In some embodiments, the closure is composed of a polymer selected from the
group
consisting of polypropylene that has a biobased content of at least 90%,
preferably at least 93%,
more preferably at least 95%, for example, about 100%; post-consumer recycled
polypropylene
(PCR-PP); post-industrial recycled polypropylene (PIR-PP); and a mixture
thereof. In some
embodiments, the closure is composed of a polymer selected from the group
consisting of linear
low density polyethylene (LLDPE) that has a biobased content of at least 90%,
preferably at least
93%, more preferably at least 95%, for example, about 100%; post-consumer
recycled LLDPE;
post-industrial recycled LLDPE; high density polyethylene (HDPE) that has a
biobased content
of at least 90%, preferably at least 93%, more preferably at least 95%, for
example, about 100%;
post-consumer recycled polyethylene (PCR-PE); post-industrial recycled
polyethylene (PIR-PE);
and a mixture thereof.
For example, the closure can be composed of (i) a polymer selected from the
group
consisting of bio-linear low density polyethylene (LLDPE), as described above;
post-consumer
recycled LLDPE; post-industrial recycled LLDPE, and a mixture thereof; or (ii)
a polymer
selected from the group consisting of bio-high density polyethylene (HDPE), as
described above;
post-consumer recycled HDPE; post-industrial recycled polyethylene HDPE; low
density
polyethylene (LDPE) that has a biobased content of at least 90%, preferably at
least 93%, more
preferably at least 95%, for example, about 100%; post-consumer recycled LDPE;
post-industrial
recycled LDPE; and a mixture thereof.
The closure in these embodiments may have a density of less than 1 g/mL to aid
separation during the floatation process of recycling, as previously
described. For example, the
closure can include a mixture of bio-polypropylene and recycled polypropylene;
recycled
polypropylene without bio-polypropylene; or bio-polypropylene without recycled
polypropylene.
Characterization of Sustainable Closures
Each component of the sustainable article has a shelf life of at least two
years. The
density of the closure can be determined using ASTM D792.
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A closure with a shelf life of at least two years can be characterized by at
least one of the
following expedients: its hinge life, if the closure design include a hinge,
stress crack resistance,
drop impact resistance, change in modulus with immersion in water, and Vicat
softening point.
Hinge life is the ability of a hinge to sustain multiple openings by a person
or a machine. If the
hinge life of the closure is tested manually, the closure of the invention can
sustain at least 150,
preferably at least 200, more preferably at least 300 openings by the person
at room temperature.
If the hinge life of the closure is tested by machine, it can sustain at least
1500, preferably at least
1700, more preferably at least 2000 openings by the machine at room
temperature. In some of
these embodiments, the closure is comprised of polypropylene. After each test,
the hinge region
is inspected for breakages. When the closure of the invention is placed in a
cold environment
(e.g., less than 5 C), it shows no breakages.
Stress crack resistance of the closure can be determined by the ESC methods
previously
described. For example, a closure of the invention can survive a 4.5 kilogram
load at about 50 C
for about fifteen days, preferably for about thirty days. Alternatively, under
ASTM D-5419, a
closure of the invention can withstand cracking at immersion stress crack
resistance (ISCR) and
exhibit no de-coloration for about 15 days, preferably for about 30 days.
Drop impact resistance is the ability of a closure to survive a fall. To
determine drop
impact resistance, a container that is free from damage and constructed as
intended is filled with
tap water to nominal fill capacity and left uncapped for 24 hours at 23 2 C
to achieve
normalized temperature. The container is capped and dropped from a specified
height. A
closure of the invention, when assembled on a container that is filled with
water, can survive a
side panel or horizontal drop and an upside-down drop from a height of about
1.2 m. A closure
of the invention, when assembled on a container that is filled with water, can
survive a vertical
bottom drop from a height of about 1.5 m.
Additionally or alternatively, the raw construction material comprising the
PP, LLDPE,
HDPE, and LDPE closure, as described above, used to produce the closure of the
invention
preferably has a change in modulus with immersion in water or Vicat softening
point as specified
below.
Change in modulus with immersion in water is tested with ASTM D-638, which
measures
the modulus of plastics. The modulus is compared before and after immersion in
product for two
weeks at room temperature and at 45 C. The raw construction material
comprising the closure
of the invention exhibits negligible change in modulus when it is immersed in
water, with less
than 1% reduction in modulus.
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The raw construction material comprising the closure of the invention exhibits
a Vicat
softening point of at least 75 C, preferably at least 125 C, according to
test method A50 of ISO
306, as previously described. For example, the raw construction material
comprising the closure
of the invention can exhibit a Vicat softening point of about 75 C to about
175 C, preferably
about 125 C to about 154 C. The closure of the invention exhibits a Vicat
softening point of at
least 50 C to about 95 C, preferably about 75 C to about 85 C, according
to test method B50
of ISO 306, as previously described.
Methods for Closures
The closures described above can be formed using injection molding. Injection
molding
is a manufacturing process for producing parts from thermoplastic materials,
thermosetting
plastic materials, or a mixture thereof. During injection molding, polymeric
material is fed into a
barrel, mixed, formed into a melt, and forced into a three-dimensional mold
cavity where it
solidifies into the configuration of the moldcavity via cooling, heating,
and/or chemical reaction.
Injection molding can be used to make single layer closures or multilayer
closures.
Sustainable Trigger Sprayer-Type Dispensers
In some embodiments, the sustainable article may comprise a spray-type
dispenser that
may be used in conjunction with the sustainable container according to one or
more embodiments
described above. For example, compositions for reducing malodor impression may
be placed
into a spray dispenser to be distributed onto the fabric. Said spray dispenser
may be any of the
manually activated means for producing a spray of liquid droplets as is known
in the art, e.g.
trigger-type, pump-type, non-aerosol self-pressurized, and aerosol-type spray
means. The spray
dispenser herein does not include those that will substantially foam a clear,
aqueous composition.
It may be preferred that at least 80%, more preferably, at least 90% of the
droplets have a particle
size of larger than 30 um.
The spray dispenser can be an aerosol dispenser. Said aerosol dispenser
comprises a
container which can be constructed of any of the conventional materials
employed in fabricating
aerosol containers. The dispenser must be capable of withstanding internal
pressure in the range
of from about 20 to about 110 p.s.i.g., more preferably from about 20 to about
70 p.s.i.g. The
one important requirement concerning the dispenser is that it be provided with
a valve member
which will permit the clear, aqueous odor absorbing composition contained in
the dispenser to be
dispensed in the form of a spray of very fine, or finely divided, particles or
droplets. The valve
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member may comprise or be made from a bio-derived plastic such as bio-derived
polyethylene or
bbe polyethylene terephthalate, for example.
The aerosol dispenser may utilize a pressurized sealed sustainable container
from which a
composition may be dispensed through a special actuator/valve assembly under
pressure. The
5 aerosol dispenser may be pressurized by incorporating therein a gaseous
component generally
known as a propellant. Common aerosol propellants, e.g., gaseous hydrocarbons
such as
isobutane, and mixed halogenated hydrocarbons, are not preferred but, if
present, may comprise
or consist of bio-derived hydrocarbons to increase sustainability of the
consumer product as a
whole. Halogenated hydrocarbon propellants such as chlorofluoro hydrocarbons
have been
10 alleged to contribute to environmental problems. Hydrocarbon propellants
can form complexes
with the cyclodextrin molecules thereby reducing the availability of
uncomplexed cyclodextrin
molecules for odor absorption. Preferred propellants are compressed air,
nitrogen, inert gases,
carbon dioxide, etc. A more complete description of commercially available
aerosol-spray
dispensers appears in U.S. Pat. No. 3,436,772, Stebbins, issued Apr. 8, 1969;
and U.S. Pat. No.
15 3,600,325, Kaufman et al., issued Aug. 17, 1971; both of said references
are incorporated herein
by reference. Because nitrogen and many inert gases do not contain carbon
atoms, they may be
regarded as "natural" according to the definitions provided herein, even if
they are not bio-
derived. As such, natural propellants such as nitrogen and inert gases that do
not contain carbon
are particularly preferred.
20 Preferably the spray dispenser can be a self-pressurized non-aerosol
container having a
convoluted liner and an elastomeric sleeve, either or both of which may be
formed from bio-
derived materials. Said self-pressurized dispenser comprises a liner/sleeve
assembly containing a
thin, flexible radially expandable convoluted plastic liner of from about
0.010 to about 0.020 inch
thick, inside an essentially cylindrical elastomeric sleeve. The liner/sleeve
is capable of holding a
25 substantial quantity of odor-absorbing fluid product and of causing said
product to be dispensed.
A more complete description of self-pressurized spray dispensers can be found
in U.S. Pat. No.
5,111,971, Winer, issued May 12, 1992, and U.S. Pat. No. 5,232,126, Winer,
issued Aug. 3,
1993; both of said references are herein incorporated by reference. Another
type of aerosol spray
dispenser is one wherein a barrier separates the odor absorbing composition
from the propellant
(preferably compressed air or nitrogen), as disclosed in U.S. Pat. No.
4,260,110, issued Apr. 7,
1981, and incorporated herein by reference. Such a dispenser is available from
EP Spray
Systems, East Hanover, N.J.
In some embodiments, the sustainable article may comprise a spray-type
dispenser that
may be used in conjunction with the sustainable container according to one or
more embodiments
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described above. Suitable spray-type dispensers may include aerosols as well
as manually-
operated foam trigger-type dispensers according to the design and operation
principles of those
sold by Specialty Packaging Products, Inc. or Continental Sprayers, Inc., for
example. These
types of dispensers are disclosed, for example, in U.S. Pat. No. 4,701,311 to
Dunnining et al. and
U.S. Pat. No. 4,646,973 and U.S. Pat. No. 4,538,745, both to Focarracci.
Particularly preferred
to be used herein are spray-type dispensers having the design and operation
principals of devices
such as T 8500 commercially available from Continental Spray International or
T 8100
commercially available from Canyon, Northern Ireland. In such a spray-type
dispenser the liquid
composition is divided in fine liquid droplets resulting in a spray that is
directed onto the surface
to be treated. Indeed, in such a spray-type dispenser the composition
contained in the body of
said dispenser is directed through the spray-type dispenser head via energy
communicated to a
pumping mechanism by the user as said user activates said pumping mechanism.
More
particularly, in said spray-type dispenser head the composition is forced
against an obstacle, e.g.
a grid or a cone or the like, thereby providing shocks to help atomize the
liquid composition, i.e.
to help the formation of liquid droplets.
Most preferably, the spray dispenser is a manually activated trigger-spray
dispenser.
Such a trigger-spray dispenser comprises a container and a trigger, both of
which can be
constructed of any of the conventional material employed in fabricating
trigger-spray dispensers,
including, but not limited to: polyethylene; polypropylene; polyacetal;
polycarbonate;
polyethyleneterephthalate; polyvinyl chloride; polystyrene; blends of
polyethylene, vinyl acetate,
and rubber elastomer. If these materials are used, most preferably all or a
portion thereof are bio-
derived materials such as bio-derived polyethylene; bio-derived polypropylene;
bio-derived
polyacetal; bio-derived polycarbonate; bio-derived polyethyleneterephthalate;
bio-derived
polyvinyl chloride; bio-derived polystyrene; blends of bio-derived
polyethylene, bio-derived
vinyl acetate, and bio-derived rubber elastomer; combinations thereof, and
mixtures thereof.
Other materials can include stainless steel and glass. A preferred container
is made of clear, e.g.
polyethylene terephthalate.
The trigger-spray dispenser does not incorporate a propellant gas into the
composition
contained therein, and preferably it does not include those that will foam the
odor-absorbing
composition. The trigger-spray dispenser herein is typically one which acts
upon a discrete
amount of the composition itself, typically by means of a piston or a
collapsing bellows that
displaces the composition through a nozzle to create a spray of thin liquid.
Such a trigger-spray
dispenser typically comprises a pump chamber having either a piston or bellows
which is
movable through a limited stroke response to the trigger for varying the
volume of said pump
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chamber. This pump chamber or bellows chamber collects and holds the product
for dispensing.
The trigger spray dispenser typically has an outlet check valve for blocking
communication and
flow of fluid through the nozzle and is responsive to the pressure inside the
chamber. For the
piston type trigger sprayers, as the trigger is compressed, it acts on the
fluid in the chamber and
the spring, increasing the pressure on the fluid. For the bellows spray
dispenser, as the bellows is
compressed, the pressure increases on the fluid. The increase in fluid
pressure in either trigger
spray dispenser acts to open the top outlet check valve. The top valve allows
the product to be
forced through the swirl chamber and out the nozzle to form a discharge
pattern. An adjustable
nozzle cap can be used to vary the pattern of the fluid dispensed.
For the piston spray dispenser, as the trigger is released, the spring acts on
the piston to
return it to its original position. For the bellows spray dispenser, the
bellows acts as the spring to
return to its original position. This action causes a vacuum in the chamber.
The responding fluid
acts to close the outlet valve while opening the inlet valve drawing product
up to the chamber
from the reservoir.
A more complete disclosure of commercially available dispensing devices
appears in U.S.
Pat. No. 4,082,223, Nozawa, issued Apr. 4, 1978; U.S. Pat. No. 4,161,288,
McKinney, issued Jul.
17, 1985; U.S. Pat. No. 4,434,917, Saito etal., issued Mar. 6, 1984; and U.S.
Pat. No. 4,819,835,
Tasaki, issued Apr. 11, 1989; U.S. Pat. No. 5,303,867, Peterson, issued Apr.
19, 1994; all of said
references are incorporated herein by reference.
Thus, in general, trigger-operated spray-type dispensers may comprise a neck
adapted to
fit on the sustainable container, for example by a thread fitting; a straw
having a first end that
reaches into a liquid contained in the sustainable container and a second end
in fluidic
communciation with a compression chamber; a trigger; a nozzle; and mechanical
components
that compress and deliver a liquid composition from the compression chamber
and through the
nozzle in a suitable spray pattern. In specific non-limiting embodiments, any
or all of the straw,
the compression chamber, the trigger, the nozzle, and/or the mechanical
components may
comprise or be formed from one or more bio-derived materials. In further non-
limiting
embodiments any or all of these components may comprise or be made from the
same materials
or combinations of materials of the sustainable containers or the sustainable
closures described
above. For example, the components of the spray-type dispenser may comprise or
be made from
bio-derived polyethylene, bio-derived high-density polyethylene, bio-derived
polypropylene, bio-
derived polyethylene terephthalic acid, combinations thereof, and mixtures
thereof.
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Sustainable Pump-Type Dispensers
In some embodiments, the sustainable article may comprise a pump-type
dispenser that
may be used in conjunction with the sustainable container according to one or
more embodiments
described above. In this sense, the pump-type dispenser may be a non-aerosol,
manually
activated, pump-spray dispenser. Such a pump-spray dispenser may comprise a
sustainable
container, as described above, and a pump mechanism that securely screws or
snaps onto the
container. The container comprises a vessel for containing the particular
composition to be
dispensed.
The pump mechanism may comprise a pump chamber of substantially fixed volume,
having an opening at the inner end thereof. Within the pump chamber is located
a pump stem
having a piston on the end thereof disposed for reciprocal motion in the pump
chamber. The
pump stem has a passageway there through with a dispensing outlet at the outer
end of the
passageway and an axial inlet port located inwardly thereof.
The container and the pump mechanism may be constructed of any conventional
material
employed in fabricating pump-spray dispensers, including, but not limited to:
polyethylene;
polypropylene; polyethyleneterephthalate; blends of polyethylene, vinyl
acetate, and rubber
elastomer. A preferred container is made of clear, e.g., polyethylene
terephthalate. Other
materials can include stainless steel. A more complete disclosure of
commercially available
dispensing devices appears in: U.S. Pat. No. 4,895,279, Schultz, issued Jan.
23, 1990; U.S. Pat.
No. 4,735,347, Schultz et al., issued Apr. 5, 1988; and U.S. Pat. No.
4,274,560, Carter, issued
Jun. 23, 1981; all of said references are herein incorporated by reference.
Most preferably, the
pump-spray dispensers comprise or are formed from bio-derived materials such
as: bio-derived
polyethylene; bio-derived polypropylene; bio-derived
polyethyleneterephthalate; blends of bio-
derived polyethylene, bio-derived vinyl acetate, and bio-derived rubber
elastomer; combinations
thereof; and mixtures thereof.
A broad array of designs for trigger sprayers or finger pump sprayers are
suitable for use
with the compositions of this invention. Suitable designs include those
available from suppliers
such as Calmar, Inc., City of Industry, Calif.; CSI (Continental Sprayers,
Inc.), St. Peters, Mo.;
Berry Plastics Corp., Evansville, Ind.--a distributor of Gualag sprayers; or
Seaquest Dispensing,
Cary, Ill., preferably made with components comprising bio-derived materials.
The preferred trigger sprayers are the blue inserted Guala sprayer, available
from Berry
Plastics Corp., or the Calmar TS800-1A sprayers, available from Calmar Inc.,
because of the fine
uniform spray characteristics, spray volume, and pattern size. Any suitable
bottle or container
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can be used with the trigger sprayer, the preferred bottle is a 17 fl-oz.
bottle (about 500 ml) of
good ergonomics similar in shape to the Cinch bottle. It can be made of any
materials such as
high density polyethylene, polypropylene, polyvinyl chloride, polystyrene,
polyethylene
terephthalate, glass, or any other material that forms bottles. Preferably, it
is made of high
density polyethylene or clear polyethylene terephthalate. Most preferably, the
container is a
sustainable container such as those described above.
For smaller four fl-oz. size (about 118 ml), a finger pump can be used with
canister or
cylindrical bottle. The preferred pump for this application is the cylindrical
Euromist II , from
Seaquest Dispensing.
The pump-type dispenser may further comprise a foam-generating dispenser for
generating a foam. When activated, the foam-generating dispenser generates
foam and
concurrently dispenses the foamed composition from the container. The foam-
generating
dispenser may be formed as either integral with, or separate from the
container. If formed
separately, the foam-generating dispenser may attach to the container via
methods known in the
art such as by employing a transition piece, corresponding threaded male and
female members,
pressurized and non-pressurized seals, locking and snap-on parts, and/or other
methods known in
the art. Preferably, the foam-generating dispenser is attached to the
container via a transition
piece and/or with corresponding threaded male and female members which allow
easy refilling.
The foam-generating dispenser may generate a foam via any method, such as a
chemical
reaction, an enzymatic reaction, and/or a mechanical action. However, a
mechanical action is
preferred herein, and typically involves a mechanism which imparts a gas, such
as air, nitrogen,
carbon dioxide, etc., directly into the dishwashing composition in a turbulent
manner as it
dispenses, so as to physically form the foam. Preferably, the foam-generating
dispenser includes
a gas imparting mechanism to form the foam, such as, for example, a propellant
or liquefied gas,
a pressurized gas, an aerosol gas, an air injection piston, foam-generating
aperture, an impinging
surface, a mesh or net, a pump, and/or a sprayer, more preferably, an air
injection piston, a pump,
an impinging surface, a mesh or net, and/or a sprayer which injects or imparts
air from the
atmosphere into the dishwashing composition.
The foam-generating dispenser also typically includes an activator, preferably
a manual
activator such as, for example, a trigger, a pressure-activated pumping
mechanism, a button,
and/or a slider, more preferably a trigger and/or a pressure-activated pumping
mechanism which
can be activated with a single finger. It is highly preferred that the
activator be designed such
that a consumer may easily activate it when their. hands are wet and/or
slippery. Such an
activator should allow the user to easily and conveniently control both the
speed of dispensing
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and the volume dispensed. For certain applications, such as in industry or in
public facilities,
other activators may be useful, such as an electronic activator, a computer-
controlled activator,
an electric eye or an infrared detection activator, a manual lever-assist
activator, etc. It may be
preferably that any or all of the components of the foam-generating dispenser
be formed from a
5 bio-derived material such as bio-PE, bio-HDPE, bio-PP, or bio-PET, for
example.
Sustainable Labels
The sustainable article, particularly any of the sustainable containers, the
sustainable
closures, the sustainable trigger spray dispensers, and the trigger pump
dispensers described
above, may be labeled with a suitable sustainable label that may contain
printed indicia.
10 In non-limiting embodiments, the label may be composed of a substrate
that includes a
polymer selected from the group consisting of polyethylene that has a biobased
content of at least
90%, preferably at least 93%, more preferably at least 95%, for example, about
100%; post-
consumer recycled polyethylene (PCR-PE); post-industrial recycled polyethylene
(PIR-PE);
paper; and a mixture thereof. The polyethylene can include LDPE, LLDPE, or
HDPE. In
15 alternative embodiments, the substrate includes a polymer selected from
the group consisting of
polyethylene terephthalate that has a biobased content of at least 90%,
preferably at least 93%,
more preferably at least 95%, for example, about 100%; post-consumer recycled
polyethylene
terephthalate (PCR-PET); post-industrial recycled polyethylene terephthalate
(PIR-PET); paper;
and a mixture thereof In other alternative embodiments, the substrate includes
a polymer
20 selected from the group consisting of polypropylene that has a biobased
content of at least 90%,
preferably at least 93%, more preferably at least 95%, for example, about
100%; post-consumer
recycled polypropylene (PCR-PP); post-industrial recycled polypropylene (PIR-
PP); paper; and a
mixture thereof.
In further embodiments, the label may be composed of a substrate that includes
a polymer
25 selected from the group consisting of polyethylene terephthalate that
has a biobased content of at
least 90%, preferably at least 93%, more preferably at least 95%, for example,
about 100%; post-
consumer recycled polyethylene terephthalate (PET); post-industrial recycled
PET; regrind PET;
paper, or a mixture thereof. In some alternative embodiments, the label is
composed of a
substrate that includes a polymer selected from the group consisting of
polyethylene that has a
30 biobased content of at least 90%, preferably at least 93%, more
preferably at least 95%, for
example, about 100%; post-consumer recycled polyethylene (PCR-PE); post-
industrial recycled
polyethylene (PIR-PE); paper; and a mixture thereof. In other alternative
embodiments, the
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substrate includes a polymer selected from the group consisting of
polypropylene that has a
biobased content of at least 90%, preferably at least 93%, more preferably at
least 95%, for
example, about 100%; post-consumer recycled polypropylene (PCR-PP); post-
industrial recycled
polypropylene (P1R-PP); paper; and a mixture thereof.
In still further embodiments, the label may be composed of a substrate that
includes a
polymer selected from the group consisting of polyethylene that has a biobased
content of at least
90%, preferably at least 93%, more preferably at least 95%, for example about
100%; post-
consumer recycled polyethylene (PCR-PE); post-industrial recycled polyethylene
(PIR-PE);
paper; and a mixture thereof. In alternative embodiments, the label is
composed of a substrate
that includes a polymer selected from the group consisting of polypropylene
that has a biobased
content of at least 90%, preferably at least 93%, more preferably at least
95%, for example, about
100%; post-consumer recycled polypropylene (PCR-PP), post-industrial recycled
polypropylene
(PIR-PP); regrind polypropylene; paper; and a mixture thereof. In other
alternative embodiments,
the substrate includes a polymer selected from the group consisting of
polyethylene terephthalate
that has a biobased content of at least 90%, preferably at least 93%, more
preferably at least 95%,
for example, about 100%; post-consumer recycled polyethylene terephthalate
(PCR-PET); post-
industrial recycled polyethylene terephthalate (PIR-PET); paper; and a mixture
thereof.
The label may further include printed indicia made from an ink. The ink can be
solvent-
based or water-based. In some embodiments, the ink is derived from a renewable
resource, such
as soy, a plant, or a mixture thereof. The ink can be cured using heat or
ultraviolet radiation
(UV). In some preferred embodiments, the ink is cured by UV, which results in
a reduction of
curing time and energy output. Nonlimiting examples of inks include ECO-
SURE!TM from Gans
Ink & Supply Co. and the solvent-based VUTEk and BioVuTM inks from EFI, which
are
derived completely from renewable resources (e.g., corn).
The label can be fixed to the sustainable container using adhesive. In some
preferred
embodiments, the adhesive is a renewable adhesive, such as BioTAK by
Berkshire Labels,
which is fully biodegradable and compostable, conforms to European standard EN
13432, and is
approved by the FDA, a shrink sleeve, or by melting the label onto the
container during
manufacturing. Alternatively, the label can be molded directly into the
plastic of the container.
The label can optionally comprise layers. For example, a metallization effect
results
when a layer composed of ink/metallization is flanked by outer layers composed
of polyethylene
in a trilayer label.
When the label is composed of polyethylene or polypropylene, it may have a
density of
less than 1 g/mL to aid separation during the floatation process of recycling,
as previously
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described. When the label is composed of polyethylene terephthalate it has a
density of greater
than 1 g/mL.
Characterization of Labels
Each component of the sustainable article has a shelf life of at least two
years. The
density of the label can be determined using ASTM D792.
A label with a shelf life of at least two years can be characterized by at
least one of the
following expedients: its chemical resistance, product resistance, shrinkage,
friction test, and rub
test. The chemical resistance of the label is determined by the Soak Squeeze
Test, which
assesses the label adhesion to the container, the label de-lamination
resistance, and the label
product or water resistance during a simulated shower or bath use. The results
of the test are
determined by the performance of the label after submerging containers filled
with a diluted soap
solution in a 38 C diluted soap solution bath (i.e., 5 grams per liter) for
one hour and squeezing
the container 10, 50, and 100 times. The labels of the invention exhibit no
change (e.g., creases
in the label, blisters, bubbles, flaking ink, changes in printing ink colors)
after the multiple
squeezes.
Product resistance is the ability of a label to resist its intended product.
To test product
compatibility, product is dropped on the printed side of label at about 20 to
24 C. After about 24
hours, the product is wiped off the label surface using a soft paper tissue,
and the label is
examined for traces of ink bleed, surface discoloration, and foil blocking.
The labels of the
invention exhibit no change in each of the examined parameters.
Shrinkage is the loss of label size. The labels of the invention exhibit less
than 0.2%,
preferably less than 0.1%, shrinkage 24 hours after their manufacture.
The friction test measures the level of friction of label surfaces to
determine the slip of the
product on a packing line's conveyors. In this test, a label is wrapped around
a 200 g steel block
and dragged at least 15 mm across a rubber mat at a rate of 150 mm/min. The
labels of the
invention remain unchanged when subjected to the friction test.
The rub test ensures that label artwork does not rub off or scratch during
manufacture or
use. In this test, a label is folded with printed side in and placed between
the thumb and
forefinger. The label is lightly rolled back and forth between the finger for
ten cycles. The label
of the invention remains unchanged after the rub test.
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Methods for Labels
The labels of the invention can be formed using film extrusion. In film
extrusion,
thermoplastic material is melted and formed into a continuous profile. In some
embodiments,
multilayer films are coextruded. Film extrusion and coextrusion can be
performed by any
method known to one skilled in the art.
Consumer Compositions
The sustainable container may be used in any suitable manner such as to
deliver to a
consumer, to contain, or to dispense for application, a consumer product that
may be beneficial
for fabric care, personal care, or home care. The type of consumer products
suitable for use
herein are limited generally only by the compatibility of the compositions
with the materials from
which the sustainable container is made. Without intent to be bound by theory,
it is believed that
compatibility issues with bio-derived materials will be substantially
identical to those
encountered with petroleum-derived counterparts. As such, it should be clear
to the person of
ordinary skill how to most appropriately select materials for the sustainable
container, in view of
what is already known about petroleum-derived containers.
The consumer products typically are liquids but may also be solids, semi-
solids, creams,
gels, compressed gases, or combinations thereof. In several embodiments,
compositions that
may be contained in the sustainable containers include, but are not limited
to, liquid laundry
detergents, liquid fabric softeners, laundry stain removers, dryer sheets,
toothpastes,
mouthwashes, hand dishwashing compositions, automatic dishwashing
compositions, fabric
freshening compositions, air freshening compositions including those used in
energized devices
(e.g., plug-in air fresheners and battery-powered air fresheners) and those
used in passive air-
freshening systems (e.g., air freshening systems activated by gravity,
actuated by a timer, or
intended for use over a moving air source such as found over a vent opening in
a vehicle cabin
such as the passenger compartment of a car), odor control compositions,
shaving creams,
shampoos, hair conditioners, hair colorants, deodorants, antiperspirants,
personal beauty
products, cosmetics, dental products, feminine hygiene products, colognes,
hand soaps, bath
soaps, hair-styling products, skin-care compositions, body washes, body
sprays, hard-surface
cleaning compositions, glass cleaning compositions, toilet cleaning
compositions, and carpet
cleaning compositions. In preferred embodiments, the consumer products suited
for the
sustainable containers described herein are hard-surface cleaners appropriate
for cleaning
household hard surfaces such as glass, ceramic tile, wood, stainless steel,
natural and synthetic
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countertops, stone surfaces, granite, baseboards, floors, and kitchen
appliances. In some
embodiments, the hard-surface cleaners may comprise one or more surfactants
compatible with
the bio-derived material of the sustainable container. In some embodiments,
the hard-surface
cleaners may further comprise one or more odor-reducing agents and/or
antibactierial agents.
Exemplary Embodiments of Sustainable Articles
The container of the sustainable articles described above, preferably when
composed of
polypropylene, can further include an impact modifier in an amount of about 2
wt.% to about 20
wt.%, preferably about 5 wt.% to about 10 wt.%. The impact modifier typically
includes LDPE
in an amount of about 5 wt.% to about 10 wt.%, an olefinic elastomer in an
amount of about 5
wt.% to about 15 wt.%, a styrenic elastomer in an amount of about 2 wt.% to
about 10 wt.%, or a
mixture thereof Examples of impact modifiers include Dow AFFINITYTm (i.e.,
polyolefin
plastomer), Exxon Mobil VISTAMAXXTm (i.e., polypropylene based elastomer), and
KRATON from GLS (i.e., styrenic based block-copolymer/elastomer), any of
which can vary in
the level of saturation of the olefinic portion. The impact modifier can be
derived wholly or
partly from oil, wholly or partially from a renewable resource, or wholly or
partially from
recycled material.
The closure of the sustainable article in any of the aspects can optionally
include up to 70
wt.%, preferably up to about 30 wt.%, more preferably up to about 40 wt.%,
even more
preferably up to about 50 wt.%. of regrind polypropylene, regrind
polyethylene, or a mixture
thereof, based on the total weight of the closure. In some embodiments, the
amount of regrind
polymer can be about 5 wt.% to about 75 wt.%, preferably about 25 wt.% to
about 50 wt.%,
based on the total weight of the closure. The incorporation of regrind
material in the closure
decreases the cost of the resulting article and prevents material waste within
plants, further
improving sustainability of the plant.
Additionally or alternatively, the closure of the sustainable article in any
of the aspects
can optionally include elastomer derived from a recycled material, for
example, from diaper
scrap, which contains an amount of elastomer. The presence of elastomer in the
closure
improves, for example, the stress crack resistance, and drop impact
resistance, of the closure.
Elastomer can be present in the closure in an amount of about 0.1 wt.% to
about 60 wt.%,
preferably about 0.1 wt.% to about 40 wt.%, more preferably about 0.1 wt.% to
about 20 wt.%,
depending on the exact performance needs. The elastomer also can be derived
wholly or partly
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from oil, wholly or partially from a renewable resource, or wholly or
partially from recycled
material.
At least one of the container, closure, or label of the sustainable article in
aspects where
the container, closure, and label are not composed of polyethylene
terephthalate, can optionally
5 include less than 70 wt.% of a biodegradable polymer, based on the total
weight of the container,
closure, or label, as long as the resulting container, closure, or label has a
density of less than 1
g/mL. The biodegradable polymer can be embedded into the polymer matrix of the
renewable,
recycled, or regrind material (e.g., by physical blending) to prevent the
biodegradable polymer
from being exposed to the surface of the article component, preventing it from
biodegrading
10 and/or deteriorating. Nonlimiting examples of biodegradable polymers
include aliphatic
polyesters, such as polylactic acid (PLA), polyglycolic acid (PGA),
polybutylene succinate
(PBS), and copolymers thereof; aliphatic-aromatic polyesters such as ECOFLEX
from BASF
(i.e., an aliphatic-aromatic copolyester based on terephthalic acid, adipic
acid, and 1,4-
butanediol), BIOMAX from DuPont (i.e., an aromatic copolyester with a high
terephthalic acid
15 content); polyhydroxyalkanoate (PHA), and copolymers thereof;
thermoplastic starch (TPS)
materials; cellulosics; and a mixture thereof. In some embodiments, the
biodegradable polymer
further includes an inorganic salt, such as calcium carbonate calcium sulfate,
talcs, clays (e.g.,
nanoclays), aluminum hydroxide, CaSiO3, glass fibers, crystalline silicas
(e.g., quartz, novacite,
crystallobite), magnesium hydroxide, mica, sodium sulfate, lithopone,
magnesium carbonate,
20 iron oxide, or a mixture thereof.
At least one of the container, closure, or label of the sustainable article in
any of the
aspects can optionally include a colorant masterbatch. As used herein, a
"colorant masterbatch"
refers to a mixture in which pigments are dispersed at high concentration in a
carrier material.
The colorant masterbatch is used to impart color to the final product. In some
embodiments, the
25 carrier is a biobased plastic or a petroleum-based plastic, while in
alternative embodiments, the
carrier is a biobased oil or a petroleum-based oil. The colorant masterbatch
can be derived
wholly or partly from a petroleum resource, wholly or partly from a renewable
resource, or
wholly or partly from a recycled resource. Nonlimiting examples of the carrier
include bio-
derived or oil derived polyethylene (e.g,. LLDPE, LDPE, HDPE), bio-derived oil
(e.g., olive oil,
30 rapeseed oil, peanut oil), petroleum-derived oil, recycled oil, bio-
derived or petroleum derived
polyethylene terephthalate, polypropylene, and a mixture thereof. The pigment
of the carrier,
which can be derived from either a renewable resource or a non-renewable
resource, can include,
for example, an inorganic pigment, an organic pigment, a polymeric resin, or a
mixture thereof.
Nonlimiting examples of pigments include titanium dioxide (e.g., rutile,
anatase), copper
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phthalocyanine, antimony oxide, zinc oxide, calcium carbonate, fumed silica,
phthalocyamine
(e.g., phthalocyamine blue), ultramarine blue, cobalt blue, monoazo pigments,
diazo pigments,
acid dye, base dye, quinacridone, and a mixture thereof. In some embodiments,
the colorant
masterbatch can further include one or more additives, which can either be
derived from a
renewable resource or a non-renewable resource. Nonlimiting examples of
additives include
slip agents, UV absorbers, nucleating agents, UV stabilizers, heat
stabilizers, clarifying agents,
fillers, brighteners, process aids, perfumes, flavors, and a mixture thereof.
In some embodiments, color can be imparted to the container, closure, or label
of the
sustainable article in any of the aspects by using direct compounding (i.e.,
in-line compounding).
In these embodiments, a twin screw compounder is placed at the beginning of
the injection
molding, blow molding, or film line and additives, such as pigments, are
blended into the resin
just before article formation.
At least one of the container or closure of the sustainable article in any of
the aspects can
further include about I wt.% to about 50 wt.%, preferably about 3 wt.% to
about 30 wt.%, more
preferably about 5 wt.% to about 15 wt.% of a filler, based on the total
weight of the container,
closure, or label. Nonlimiting examples of fillers include starches, renewable
fibers (e.g., hemp,
flax, coconut, wood, paper, bamboo, grass), inorganic materials (e.g., calcium
carbonate, mica,
talc), gases (e.g., high pressure gas), foaming agents, microspheres,
biodegradable polymers
(e.g., PLA, PHA, TPS), a renewable, but non-biodegradable polymer (e.g.,
particles of cellulose
acetate, polyaminde-11, alkyd resin), and mixtures thereof.
One or more of the container, closure, and label of the sustainable article in
any of the
aforementioned aspects can exhibit a single layer or multiple layers. When a
component of the
sustainable article exhibits multiple layers, the component can include 2, 3,
4, 5, 6, 7, 8, 9, or 10
layers. Preferably, the multilayer is a bilayer, trilayer, quadruple layer, or
a quintuple layer. In
some embodiments, the multilayer is a bilayer that has a weight ratio of outer
layer to inner layer
of about 99:1 to about 1:99, preferably about 10:90 to about 30:70, for
example, about 20:80. In
some embodiments, the multilayer is a trilayer that has a weight ratio of
outer layer to middle
layer to inner layer of about 1:98:1 to about 30:40:30, for example, about
5:90:5, 10:80:10 or
20:60:20. In some embodiments when a component of the article has at least
three layers,
recycled material, one or more biodegradable polymers (e.g., PLA, PHA, TPS,
cellulose), or a
mixture thereof comprises a middle layer. The middle layer composed of
recycled material,
biodegradable polymer, or a mixture thereof can further include an inorganic
salt, such as
calciUm carbonate calcium sulfate, talcs, clays (e.g., nanoclays), aluminum
hydroxide, CaSiO3,
glass fibers, crystalline silicas (e.g., quartz, novacite, crystallobite),
magnesium hydroxide, mica,
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sodium sulfate, lithopone, magnesium carbonate, iron oxide, or a mixture
thereof. A multilayer
component with recycled material or biodegradable polymer as the middle layer
can be achieved,
for example, by injection techniques (e.g., co-injection), a stretch blow
process, or an extrusion
blow molding process, as described herein. In some embodiments, a multilayer
component of
the sustainable article includes a barrier layer to gases (e.g., oxygen,
nitrogen, carbon dioxide,
helium). The barrier layer can be biobased or petroleum-based, and composed
of, for example,
ethyl vinyl alcohol copolymer (EVOH).
SUSTAINABLE COMPOSITIONS
The sustainable consumer product may comprise a sustainable composition
contained
within a sustainable container according to any of the embodiments described
above. The
sustainable composition may be any consumer product that may be beneficial for
fabric care,
personal care, or home care, provided that the consumer product comprises or
consists of one or
more bio-derived ingredients. The type of consumer products suitable for use
herein are limited
generally only by the compatibility of the compositions with the materials
from which the
sustainable container is made. Without intent to be bound by theory, it is
believed that
compatibility issues with bio-derived sustainable compositions and bio-derived
materials will be
substantially identical to those encountered with petroleum-derived
counterparts. As such, it
should be clear to the person of ordinary skill how to most appropriately
select materials for the
bio-derived sustainable composition in the sustainable container, in view of
what is already
known about petroleum-derived containers and petroleum-derived compositions.
The sustainable consumer compositions typically are liquids but may also be
solids, semi-
solids, creams, gels, compressed gases, or combinations thereof. In several
embodiments,
compositions that may be contained in the sustainable containers include, but
are not limited to,
liquid laundry detergents, liquid fabric softeners, laundry stain removers,
dryer sheets,
toothpastes, mouthwashes, hand dishwashing compositions, automatic dishwashing
compositions, fabric freshening compositions, odor control compositions, air
fresheners, shaving
creams, shampoos, hair conditioners, hair colorants, deodorants,
antiperspirants, personal beauty
products, cosmetics, dental products, feminine hygiene products, colognes,
hand soaps, bath
soaps, hair-styling products, skin-care compositions, body washes, body
sprays, hard-surface
cleaning compositions, glass cleaning compositions, toilet cleaning
compositions, and carpet
cleaning compositions. In preferred embodiments, the consumer products suited
for the
sustainable containers described herein are hard-surface cleaners appropriate
for cleaning
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38
household hard surfaces such as glass, ceramic tile, wood, stainless steel,
natural and synthetic
countertops, stone surfaces, granite, baseboards, floors, and kitchen
appliances. In some
embodiments, the hard-surface cleaners may comprise one or more surfactants
compatible with
the bio-derived material of the sustainable container. In some embodiments,
the hard-surface
cleaners may further comprise one or more odor-reducing agents and/or
antibactierial agents.
In exemplary embodiments, the sustainable composition comprises at least one
bio-
derived ingredient selected from the group consisting of sustainable bio-
derived low-residue
surfactants, sustainable bio-derived solvents, sustainable bio-derived
polymers, sustainable bio-
derived thickening agents, sustainable bio-derived fragrances and/or natural
essences, sustainable
bio-derived odor-control agents; optional additional sustainable bio-derived
surfactants; bio-
derived adjuncts; bio-derived builders; and/or enzymes.
Sustainable Low-Residue Surfactant
The sustainable compositions will normally have one of the preferred
surfactants present,
such as alkylpolysaccharides or nonionic surfactants, including alkyl
ethoxylates. The
surfactants may be petroluem-derived, bio-derived, or part petroleum-derived
and part bio-
derived. In a preferred embodiment, the composition according to the present
invention
comprises a low-residue surfactant or a mixture thereof.
By "low-residue surfactant" it is meant herein any surfactant that mitigates
the
appearance of either streaks or films upon evaporation of the aqueous
compositions comprising
said surfactant. A low residue surfactant-containing composition may be
identified using either
gloss-meter readings or expert visual grade readings. The conditions for the
determination of
what constitutes a low-residue surfactant are one of the following: (a) less
than 1.5% gloss loss
on black shiny porcelain tiles, preferably on black shiny Extracompa
porcelain tiles used in this
invention; or (b) lack of significant filming and/streaking as judged by one
skilled in the art. One
of the important advantages of the low residue surfactant is that it requires
less polymeric
biguanide compound for gloss enhancement, relative to non-low residue
surfactants. This can be
important in light of cost considerations, potential stickiness issues
delivered by higher
concentrations of the polymeric biguanide, and/or concerns over the ability to
completely strip a
more concentrated polymeric biguanide film.
As identified within this invention there are three classes of low-residue
surfactants:
selected non-ionic surfactants, and zwitterionic surfactants and amphoteric
surfactants and
mixtures thereof. One class of low residue surfactants is the group of non-
ionic surfactants that
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39
include a head group consisting of one or more sugar moieties. Examples
include alkyl
polyglycosides, especially poly alkyl glucosides, and sucrose esters. The
chain length of these
non-ionic surfactants is preferably about C6 to about C18, more preferably
from about C8 to
about C16. The hydrophilic component of these surfactants may comprise one or
more sugar
moieties liked by glycosidic linkages. In a preferred embodiment, the average
number of sugar
moieties per surfactant chain length is from about 1 to about 3, more
preferably from about 1.1 to
about 2.2.
The most preferred non-ionic low residue surfactants are the
alkylpolysaccharides that are
disclosed in U.S. Patents: U.S. Pat. No. 5,776,872, Cleansing compositions,
issued Jul. 7, 1998,
to Giret, Michel Joseph; Langlois, Anne; and Duke, Roland Philip; U.S. Pat.
No. 5,883,059,
Three in one ultra mild lathering antibacterial liquid personal cleansing
composition, issued Mar.
16, 1999, to Furman, Christopher Allen; Giret, Michel Joseph; and Dunbar,
James Charles; etc.;
U.S. Pat. No. 5,883,062, Manual dishwashing compositions, issued Mar. 16,
1999, to Addison,
Michael Crombie; Foley, Peter Robert; and Allsebrook, Andrew Micheal; and U.S.
Pat. No.
5,906,973, issued May 25, 1999, Process for cleaning vertical or inclined hard
surfaces, by
Ouzounis, Dimitrios and Nierhaus, Wolfgang.
The low-residue surfactants for use herein further may include, for example
alkylpolyglycosides having the formula:
R20(CõH2O)t (glycosyl),x
where R2 is selected from the group consisting of alkyl, alkyl-phenyl,
hydroxyallyl,
hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain
from about 10 to
about 18, preferably from about 12 to about 14, carbon atoms; n is 2 or 3,
preferably 2; t is from
0 to about 10, preferably 0; and x is from about 1.3 to about 10, preferably
from about 1.3 to
about 3, most preferably from about 1.3 to about 2.7. The glycosyl is
preferably derived from
glucose. Preferably, the alkylpolyglycosides are bio-derived.
To prepare these compounds, a bio-derived alcohol or bio-derived
alkylpolyethoxy
alcohol is formed first and then reacted with glucose, such as bio-derived
glucose, to form the
glucoside (attachment at the 1-position). The additional glycosyl units can
then be attached
between their 1-position and the preceding glycosyl units 2-, 3-, 4- and/or 6-
position, preferably
predominantly the 2-position.
Thus, alkyl polyglycosides (APGs), also called alkyl polyglucosides if the
saccharide
moiety is glucose, are naturally derived, nonionic surfactants. The alkyl
polyglycosides also may
fatty ester derivatives of saccharides or polysaccharides that are formed when
a carbohydrate is
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reacted under acidic condition with a bio-derived fatty alcohol through
condensation
polymerization. The APGs are typically derived from corn-based carbohydrates
and fatty
alcohols from natural oils in animals, coconuts and palm kernels. Such methods
for preparing
APGs are well known in the art. For example, U.S. Pat. No. 5,003,057 to
McCurry, et al.,
5 incorporated herein, describes methods for making APGs, along with their
chemical properties.
The alkyl polyglycosides that are preferred contain a hydrophilic group
derived from bio-
derived carbohydrates and are composed of one or more bio-derived
anhydroglucose units. Each
of the bio-derived glucose units can have two ether oxygen atoms and three
hydroxyl groups,
along with a terminal hydroxyl group, which together impart water solubility
to the glycoside.
10 The presence of the alkyl carbon chain leads to the hydrophobic tail to
the molecule. When
carbohydrate molecules react with fatty alcohol compounds, alkyl polyglycoside
molecules are
formed having single or multiple anhydroglucose units, which are termed
monoglycosides and
polyglycosides, respectively. The final alkyl polyglycoside product typically
has a distribution of
varying concentration of glucose units (or degree of polymerization).
15 The APGs for use in the sustainable composition preferably comprise
saccharide or
polysaccharide groups (i.e., mono-, di-, tri-, etc. saccharides) of hexose or
pentose, and a fatty
aliphatic group having 6 to 20 carbon atoms. Preferred alkyl polyglycosides
are represented by
the general formula, Gx¨O¨RI, where G is a moiety derived from reducing
saccharide containing
5 or 6 carbon atoms, e.g., pentose or hexose; RI is fatty alkyl group
containing 6 to 20 carbon
20 atoms; and x is the degree of polymerization of the polyglycoside,
representing the number of
monosaccharide repeating units in the polyglycoside. Generally, x is an
integer on the basis of
individual molecules, but because there are statistical variations in the
manufacturing process for
APGs, x may be a noninteger on an average basis when referred to APG used as
an ingredient for
the sustainable composition. For the APGs used in the sustainable
compositions, x preferably
25 has a value of less than 2.5, and more preferably is between 1 and 2.
Exemplary bio-derived
saccharides from which G can be derived are glucose, fructose, mannose,
galactose, talose,
gulose, allose, altrose, idose, arabinose, xylose, lyxose and ribose. Because
of the ready
availability of glucose, glucose is preferred in polyglycosides. The fatty
alkyl group is preferably
saturated, although unsaturated fatty chains may be used. Generally, the
commercially available
30 polyglycosides have C8 to C16 alkyl chains and an average degree of
polymerization of from 1.4
to 1.6.
Commercially available alkyl polyglycoside can be obtained as concentrated
aqueous
solutions ranging from 50 wt.% to 70wt% actives and are available from Cognis.
Most preferred
for use in the present compositions are APGs with an average degree of
polymerization of from
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41
1.4 to 1.7 and the chain lengths of the aliphatic groups, preferably bio-
derived aliphatic groups
are between C8 and C16. For example, one preferred APG for use herein has
chain length of Cg
and C10 (ratio of 45:55) and a degree of polymerization of 1.7.
The sustainable compositions of have the advantage of having less adverse
impact on the
environment than conventional sustainable compositions. Bio-derived alkyl
polyglycosides used
in the present invention exhibit low oral and dermal toxicity and irritation
on mammalian tissues.
These bio-derived alkyl polyglycosides are also biodegradable in both
anaerobic and aerobic
conditions and they exhibit low toxicity to plants, thus improving the
environmental
compatibility of the rinse aid of the present invention. Because of the
carbohydrate property and
the excellent water solubility characteristics, alkyl polyglycosides are
compatible in high caustic
and builder formulations. The sustainable compositions may include a
sufficient amount of alkyl
polyglycoside surfactant in an amount that provides a desired level of
cleaning, that being from
about 0.01% and about 10% by weight alkyl polyglycoside surfactant. Most
preferred is to
include an amount between about 0.5% and about 5% by weight actives.
Some alkyl glycosides and polyglycosides occur in nature, e.g. in
cyanobacteria such as
Anabaena cylindrica, Anamaeba torulosa and Cyanospira rippkae, where they may
take part in
cell protection. However, synthetic alkyl polyglycosides that may be used in
the sustainable
compositions may be practically conceived as fatty ester derivatives of
saccharides or
polysaccharides that are formed when a carbohydrate is reacted under acidic
conditions with a
fatty alcohol through condensation polymerization. The APGs may be derived
from corn-based
carbohydrates and fatty alcohols from natural oils found in animals, coconuts
and palm kernels.
However, these surfactants alternatively may be constructed with algae-derived
bioorganics. As
described above, glucose may be directly obtained from algae, or alternately
the sugars used to
synthesize APG surfactants may be derived from cellulose or other algal
polysaccharides. The
fatty alcohols may be obtained by hydrolysis or transesterification of algae
lipids followed by
hydrogenation of the intermediate fatty acids or fatty acid esters. Such
methods for deriving
APGs from vegetative sources are well known in the art and may be extrapolated
to algae-
sourced, rather than crop-sourced, bioorganic substances. The alkyl
polyglycosides that are
preferred for use in the sustainable composition contain a hydrophilic group
derived from
carbohydrates and are composed of one or more anhydroglucose units. Each of
the glucose units
may have two ether oxygen atoms and three hydroxyl groups, along with a
terminal hydroxyl
group, which together impart water solubility to the glycoside. The presence
of the alkyl carbon
chain leads to the hydrophobic tail of the molecule.
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42
When carbohydrate molecules react with fatty alcohol compounds, alkyl
polyglycoside
molecules are formed having single or multiple anhydroglucose units, which are
termed
monoglycosides and polyglycosides, respectively. The final alkyl polyglycoside
product
typically has a distribution of glucose units (i.e., degree of
polymerization).
As noted above, the APGs may comprise saccharide or polysaccharide groups
(i.e.,
mono-, di-, tri-, etc. saccharides) of hexose or pentose, and a fatty
aliphatic group having 6 to 20
carbon atoms. Exemplary saccharides from which G can be derived are glucose,
fructose,
mannose, galactose, talose, gulose, allose, aitrose, idose, arabinose, xylose,
lyxose and ribose.
Because of the ready availability of glucose from algae, polyglycosides having
glucose
substituents may be obtained from algae. The glucose may be obtained as a
metabolite from
certain cyanobacteria or may be obtained by cellulolysis (chemically or
enzymatically) of algal
cellulose. The fatty alkyl group is preferably saturated, although unsaturated
fatty chains may be
used. Generally, commercially available polyglycosides have C8 to C16 alkyl
chains and an
average degree of polymerization of from 1.4 to 1.6, and these may be readily
synthesized from
algae-derived intermediates rather than crop-based substances.
Bio-derived alkyl sulfate surfactants are another type of bio-derived anionic
surfactant of
importance for use herein. In addition to providing excellent overall cleaning
ability when used
in combination with polyhydroxy fatty acid amides (see below), including good
grease/oil
cleaning over a wide range of temperatures, wash concentrations, and wash
times, dissolution of
alkyl sulfates can be obtained, as well as improved formulability in
sustainable compositions are
water soluble salts or acids of the formula ¨ROSO3M, where R preferably is a
C10---C24
hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C10¨C20 alkyl
component, more
preferably a C12¨C18 alkyl or hydroxyalkyl, and M is H or a cation, e.g., an
alkali or alkaline
(Group IA or Group 1IA) metal cation (e.g., sodium, potassium, lithium,
magnesium, calcium),
substituted or unsubstituted ammonium cations such as methyl-, dimethyl-, and
trimethyl
ammonium and quaternary ammonium cations, e.g., tetramethyl-ammonium and
dimethyl
piperdinium, and cations derived from alkanolamines such as ethanolamine,
diethanolamine,
triethanolamine, and mixtures thereof, and the like. Typically, alkyl chains
of C12¨C16 are
preferred. For example, sodium octyl sulfate, preferably in which the octyl
chains thereof are
partially or wholly bio-derived, may be a preferred surfactant for use in the
sustainable
compositions herein.
Zwitterionic surfactants can also be incorporated into the sustainable
compositions as
low-residue surfactants. These surfactants can be broadly described as
derivatives of secondary
and tertiary amines, derivatives of heterocyclic secondary and tertiary
amines, or derivatives of
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43
quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds.
See U.S. Pat.
No. 3,929,678 to Laughlin et al., issued Dec. 30, 1975 at column 19, line 38
through column 22,
line 48 for examples of zwitterionic surfactants. Ampholytic and zwitterionic
surfactants are
generally used in combination with one or more anionic and/or nonionic
surfactants and most
preferably are formed from bio-derived carbon atoms obtained from natural
sources.
Other suitable, amphoteric surfactants being either cationic or anionic
depending upon the
pH of the system are represented by surfactants such as dodecylbeta-alanine, N-
alkyltaurines
such as the one prepared by reacting dodecylamine with sodium isethionate
according to the
teaching of U.S. Pat. No. 2,658,072, N-higher alkylaspartic acids such as
those produced
according to the teaching of U.S. Pat. No. 2,438,091, and the products sold
under the trade name
"Miranolg", and described in U.S. Pat. No. 2,528,378, said patents being
incorporated herein by
reference.
Low-residue surfactants contribute to the filming/streaking performance (i.e.,
low or
substantially no streaks- and/or film-formation) of the compositions according
to the present
invention.
Low-residue surfactants can be present in the compositions of this invention
at levels
from about 0.01% to about 15%, preferably of from about 0.01% to about 10%,
and more
preferably of from about 0.03% to about 0.75% by weight of the total
composition. At actual
product use levels, following recommended product dilution, if any, the low-
residue surfactants
are typically present at levels from about 0.01% to about 1.5%, more
preferably from about
0.01% to about 10%, and more preferably of from about 0.03% to about 0.75% by
weight of the
total composition. Importantly, the Applicant has found that the use of a low
residue surfactant
in combination with a conventional surfactant (i.e., non-low residue) can
mitigate filming and/or
streaking issues relative to similar compositions that only use the
conventional surfactant.
Solvents
The sustainable compositions can optionally contain limited amounts of organic
solvents.
Preferably, the organic solvents are bio-derived solved such as bio-derived
ethanol, bio-derived
sorbitol, bio-derived glycerol, bio-derived propylene glycol, bio-derived
glycerol, bio-derived
1,3-propanediol, and mixtures thereof. These solvents may be less than 10% of
the composition;
preferably less than 5% of the composition. It is preferred that the
sustainable compositions
described herein be non-flammable, and/or have relatively high flash points,
and/or have
relatively low amounts of volatile organic compounds (VOCs) meeting,
exceeding, or preferably
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substantially exceeding environmental guidelines recommended or established by
law or other
guideline in the jurisdictions in which the sustainable compositions may be
used. The
incorporation of these solvents in sustainable compositions is useful for
controlling aesthetic
factors of the undiluted products, such as viscosity, and/or for controlling
the stability of
Alternatively, the sustainable compositions may also be substantially devoid
of solvents
and may include solvent-free surfactants such as Berol CLF by AkzoNobel. The
sustainable
Bio-derived solvents can be produced from renewable resources, even if not
directly
available from the renewable resource. In cases where the bio-solvent is not
directly available
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from the renewable resource, the component that can be derived from the
renewable resource
may need to undergo one or more chemical reactions and/or purification steps
to form the desired
bio-derived solvent. For example, two or more chemical components, at least
one of which is
derived from bio-derived sources, may be used to produce the desired bio-
derived solvent. As an
5 example, the esterification of bio-derived acetic acid with bio-derived
butanol, can form bio-
derived butyl acetate. Preferably, any bio-derived solvent present in the
sustainable composition
derives greater than 50%, grater than 75%, greater than 90%, or even 100% of
its carbon from
renewable resources.
The renewably resourcing of solvents is an area of the chemical industry that
has a large
10 potential for displacing petroleum-derived solvents. Commonly used
solvents include alcohols,
esters, ketones, ethers and hydrocarbons. Many of these materials are not
available as pure
compounds from bio-mass sources, but the reaction of two or more compounds
available via bio-
transformation processes can result in useful solvents. Classes of bio-derived
solvents include
alcohols, esters, ketones and aldehydes, ethers, alkanes, aromatics,
15 Bio-derived alcohols that can be produced via renewable resources
include mono-, di-,
tri- and higher alcohols having one or more carbon atoms. For example, bio-
derived methanol,
bio-derived ethanol, isomers of bio-derived propanol, isomers of bio-derived
butanol, isomers of
bio-derived pentanol, isomers of bio-derived hexanol, bio-derived
cyclopentanol, bio-derived
ethylene glycol, bio-derived 1,3-propanediol, bio-derived 1,2-propanediol, bio-
derived 1,4-
20 butane diol, bio-derived 2-methyl-1,4-butanediol, bio-derived 1,4-
pentanediol, bio-derived 1,5-
pentanediol, bio-derived glycerol, bio-derived isobomyl alcohol, and others.
Bio-derived
methanol, bio-derived ethanol and bio-derived butanol can be formed by well-
known
fermentation process. Other alcohols can be produced as well, see for example,
US 4,536,584.
Ester-based solvents can be produced from the reaction of a bio-derived
carboxylic acid
25 and a bio-derived alcohol. Suitable acids that can be produced via
renewable resources include,
for example, formic acid, acetic acid, propionic acid, butyric acid, lactic
acid, malonic acid, and
adipic acid. See US 5,874,263; WO 95/07996; Biotechnology Letters Vol. 1 1
(3), pages 189-
194, 1989; and Green Chemistry 2008, DOI: 10.1039/b802076k. Bio-derived esters
can be
formed from a bio-derived acid and a bio-derived alcohol via the well-known
esterification
30 industrial process of these generic components. For example, bio-derived
acetic acid can be
reacted under esterification reaction conditions with bio-derived butanol to
form bio-derived
butyl acetate. Bio-derived butyl acetate can be used in the synthesis of
polyacrylates and as a
reducer. As an additional example, bio-derived tert-butyl acetate can be
produced using indium
catalysts, see Journal of Molecular Catalysis, volume 235, page 150-153, 2005.
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46
Ketone-based and aldehyde-based solvents can be produced by the oxidation of
many of
the above listed bio-derived alcohols. Bio-derived acetone, bio-derived methyl
ethyl ketone, bio-
derived cyclopentanone, bio-derived cyclohexanone, bio-derived 2-pentanone,
bio-derived 2,5-
hexanedione, and the various isomers of 4 to 6 carbon bio-derived ketones are
useful as solvents
in many chemical reactions, such as, for example, free radical polymerization
and also can also
be used in the preparation of ingredients for sustainable compositions. See
for example, US
4,536,584.
Bio-derived ethers, including bio-derived polyethers, can be produced from
biomass or
via the condensation of bio-derived alcohols with bio-derived ketones and bio-
derived aldehydes
according to known ether forming reaction processes. Examples include, bio-
derived
diethoxymethane and bio-derived tetrahydrofuran. See for example, US
4,536,584. Other
methods to produce bio-derived polyethers can include the polymerization of
bio-derived
ethylene oxide. Bio-derived ethylene oxide can be produced from the
epoxidation of bio-derived
ethylene. Bio-derived low molecular-weight polyethers, especially bio-derived
alkyl capped-
polyethers, may be used as solvents in the sustainable compositions.
Alkane hydrocarbon solvents are commonly used in free radical polymerizations.
Bio-
derived hydrocarbons having in the range of from 1 to 15 carbon atoms can be
produced from
bio-mass according to the procedures given in US 6,180,845 or Chemistry and
Sustainable
Chemistry, Volume 1, pages 417-424, 2008. Distillation or other purification
procedures can
provide pure fractions of bio-derived hydrocarbons, such as, for example, bio-
derived hexane
that can be used in, for example, free radical polymerization processes.
Aromatics, such as, toluene and xylene, are also commonly used in
polymerization
reactions. Using fast-pyrolosis techniques and certain zeolites, it is
possible to produce bio-
derived aromatics that can be used for polymerization. See, for example,
Chemistry and
Sustainable Chemistry, Volume 1, pages 397-400, 2008.
The compositions, optionally, can also contain one, or more, organic cleaning
solvents at
effective levels, typically no less than 0.25%, and, at least 0.5%, preferably
at least 3.0%, and no
more than about 7%, preferably no more than about 5%, by weight of the
composition.
Preferably such solvents are bio-derived.
The surfactant, described below, provides cleaning and/or wetting even without
an
organic cleaning solvent present. However, the cleaning can normally be
further improved by
the use of the right organic cleaning solvent. By organic cleaning solvent, it
is meant an agent
which assists the surfactant to remove soils such as those commonly
encountered in the
bathroom. The organic cleaning solvent also can participate in the building of
viscosity, if
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needed, and in increasing the stability of the composition. The compositions
containing C8-16
alkyl polyglucosides, preferably bio-derived, and/or C8-14 alkylethoxylates,
preferably bio-
derived, also have lower sudsing when the solvent is present. Thus, the suds
profile can be
controlled in large part by simply controlling the level of hydrophobic
solvent in the formulation.
The amount of organic cleaning solvent can vary depending on the amount of
other
ingredients present in the composition. The hydrophobic cleaning solvent is
normally helpful in
providing good cleaning, such as in floor cleaner applications. For cleaning
in enclosed spaces,
the solvent can cause the formation of undesirably small respirable droplets,
so
compositions/solutions for use in treating such spaces are desirably
substantially free, more
preferably completely free, of such solvents.
For purposes of soap scum and hard water stain removal, the sustainable
compositions
can be made acidic with a pH of from about 2 to about 5, more preferably about
3. Acidity is
accomplished, at least in part, through the use of one or more organic acids
that have a pKa of
less than 5, preferably less than 4. Such organic acids also can assist in
phase formation for
thickening, if needed, as well as provide hard water stain removal properties.
It is found that
organic acids are very efficient in promoting good hard water removal
properties within the
framework of the compositions of the present invention. Lower pH and use of
one or more
suitable acids is also found to be advantageous for disinfectancy benefits.
The organic acids may
be bio-derived organic acids.
Examples of suitable mono-carboxylic acids include acetic acid, glycolic acid
or f3-
hydroxy propionic acid and the like. Examples of suitable polycarboxylic acids
include citric
acid, tartaric acid, succinic acid, glutaric acid, adipic acid, and mixtures
thereof. Such acids are
readily available in the trade. Examples of more preferred polycarboxylic
acids, especially non-
polymeric polycarboxylic acids, include citric acid (available from Aldrich
Corporation, 1001
West Saint Paul Avenue, Milwaukee, Wis.), a mixture of succinic, glutaric and
adipic acids
available from DuPont (Wilmington, Del.) sold as "refined AGS di-basic acids",
maleic acid
(also available from Aldrich), and mixtures thereof. Citric acid is most
preferred, particularly for
applications requiring cleaning of soap scum. Glycolic acid and the mixture of
adipic, glutaric
and succinic acids provide greater benefits for hard water removal. The amount
of organic acid
in the compositions herein can be from about 0.01% to about 1%, more
preferably from about
0.01% to about 0.5%, most preferably from about 0.025% to about 0.25% by
weight of the
composition. Most preferably all, or a portion of the acids, are bio-derived.
Suitable bio-derived
acids, natural-based analogs of acids described above, are available and/or
may be prepared as
described above, for example.
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48
Polymer
The sustainable composition may comprise a polymer. The polymer, if present,
is used in
any suitable amount from about 0.1% to about 50%, preferably from 0.5% to
about 20%, more
preferably from 1% to 10% by weight of the sustainable composition.
In one example, sulfonated/carboxylated polymers are particularly suitable for
the
sustainable composition of the invention.
Preferred sustainable compositions may contain a dispersant polymer typically
in the
range from 0 to about 25%, preferably from about 0.5% to about 20%, more
preferably from
about 1% to about 7% by weight of the sustainable composition.
One dispersant polymer suitable for use in the present composition includes an
ethoxylated cationic diamine comprising the formula (III):
C113 CH3
X¨f-OCH2C112-t--N"¨CH2¨CH2¨(-CH2t7-N'¨ (C112CH20t X
(CH2CII29),,¨X (CH2CH20),¨X
(III)
where X of formula (III) is a nonionic group selected from the group
consisting of H, C1-C4 alkyl
or hydroxyalkyl ester or ether groups, and mixtures thereof n is at least 6;
and a is from 0 to 4 (e.
g. ethylene, propylene, hexamethylene). For preferred ethoxylated cationic
diamines, n of
formula (III) is at least 12 with a typical range of from about 12 to about
42. See U.S. Pat. No.
4,659,802 for further information regarding the ethoxylated cationic diamines.
The alkylene
oxide components in all regards are preferably obtained from bio-derived
ethylene oxide.
Further suitable dispersant polymers suitable for use herein are illustrated
by formula
(IV):
COONa
COON4 COON('
0
OH
803Na
(IV)
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Formula IV is an Acrylic acid (AA), maleic acid (MA) and sodium 3-allyloxy-2-
hydroxy-
I -propanesulfonate (HAPS) copolymer, preferably comprising about 45 wt% of
the polymer of
AA, about 45 wt % of the polymer of MA and about 10 wt% of the polymer HAPS.
Molecular
weight may be from about 8000 to about 15000. In one embodiment, dispersant
polymers of
formula (IV) have a molecular weight of about 8000 to about 8500. In another
embodiment
dispersant polymers of formula (IV) have a molecular weight of about 12500 to
about 13300.
Salts of formula (IV) may be selected from any water soluble salt such as
sodium or potassium
salt.
Further suitable dispersant polymers suitable for use herein are illustrated
by the film-
forming polymers. Suitable for use as dispersants herein are co-polymers
synthesized from bio-
derived acrylic acid, bio-derived maleic acid and bio-derived methacrylic
acid. Such polymers
may be bio-derived analogs of commercial products such as ACUSOL 480N
supplied by Rohm
& Haas and polymers containing both carboxylate and sulfonate monomers, such
as
ALCOSPERSE polymers (supplied by Alco). In one embodiment an ALCOSPERSE
polymer sold under the trade name ALCOSPERSE 725, is a co-polymer of Styrene
and Acrylic
Acid.
In certain embodiments, a dispersant polymer may be present in an amount in
the range
from about 0.01% to about 25%, or from about 0.1% to about 20%, and
alternatively, from about
0.1% to about 7% by weight of the sustainable composition.
Further suitable dispersant polymers include polyacrylic phosphono end group
polymers
or acrylic-maleic phosphono end group copolymers according to the general
formula H2P03¨
(CH2¨CHCOOH)n¨(CHCOOH-CHCOOH)m¨where n is an integer greater than 0, m is an
integer of 0 (for polyacrylic polymers) or greater (for acrylic¨maleic
copolymers) and n and m
are integers independently selected to give a molecular weight of the polymer
of between 500
and 200,000, preferably of between 500 and 100,000, and more preferably
between 1,000 and
50,000. For polyacrylates, m is zero. Suitable polyacrylic phosphono end group
polymers or
acrylic-maleic phosphono end group copolymers for use herein are available
from Rohm &Haas
under the tradenames ACUSOLO E 420 or 470 or 425. In one embodiment Acusol
425N is
used. Acusol 425N is an acrylic-maleic (ratio 80/20) phosphono end group
copolymers and is
available from Rohm &Haas.
Particularly preferred dispersant polymers are low molecular weight modified
polyacrylate copolymers, most preferably obtained from bio-derived sources of
carbon. Such
copolymers contain as monomer units: (a) from about 90% to about 10%,
preferably from about
80% to about 20% by weight bio-derived acrylic acid or its salts and (b) from
about 10% to about
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90%, preferably from about 20% to about 80% by weight of a substituted bio-
derived acrylic
monomer or its salt and having the general formula ¨[(C(R2)C(RI)(C(0)0R3)]---
where the
incomplete valencies inside the square braces are hydrogen and at least one of
the substituents
RI, R2 or R3, preferably RI or R2, is a C1 to C4 alkyl or hydroxyalkyl group,
RI or R2 canbe a
The low molecular-weight polyacrylate dispersant polymer preferably has a
molecular
weight of less than 15,000, preferably from about 500 to about 10,000, most
preferably from
about 1,000 to about 5,000. The most preferred polyacrylate copolymer for use
herein has a
The sulfonated/carboxylated polymers may comprise (a) at least one structural
unit
derived from at least one carboxylic acid monomer having the general formula
(I):
RI R3
_______________________________________ C 2 R4
(I)
R
where RI to R4 are independently hydrogen, methyl, carboxylic acid group or
¨CH2COOH and
R5
H2C ________________________________________ (II)
X
where R5 is hydrogen, CI to C6 alkyl, or CI to C6 hydroxyalkyl, and X is
either aromatic (with R5
being hydrogen or methyl when X is aromatic) or X is of the general formula
(III):
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51
C ¨0
(III)
R6
where R6 is (independently of R5) hydrogen, C1 to C6 alkyl, or C1 to C6
hydroxyalkyl, and Y is 0
or N; and at least one structural unit derived from at least one sulfonic acid
monomer having the
general formula (IV):
R7
(A)1
(IV)
(B)t
SO3- M+
where R7 is a group comprising at least one sp2 bond, A is 0, N, P, S. or an
amido or ester
linkage; B is a monocyclic or polycyclic aromatic group or an aliphatic group;
each t is
independently 0 or 1; and M+ is a cation. In one aspect, le is a C2 to C6
alkene. In another
aspect, R7 is ethene, butene or propene.
Preferred carboxylic acid monomers include one or more of the following: bio-
derived
acrylic acid, bio-derived maleic acid, bio-derived itaconic acid, bio-derived
methacrylic acid, or
ethoxylate esters of bio-derived acrylic acids, acrylic and methacrylic acids
being more preferred.
Preferred sulfonated monomers include one or more of the following: bio-
derived sodium (meth)
allyl sulfonate, bio-derived vinyl sulfonate, bio-derived sodium phenyl (meth)
ally! ether
sulfonate, or bio-derived 2-acrylamido-methyl propane sulfonic acid ("AMPS"),
or bio-derived
sodium 3-allyloxy-2-hydroxy-l-propanesulfonate ("HAPS"). Preferred non-ionic
monomers
include one or more of the following: bio-derived methyl (meth) acrylate, bio-
derived ethyl
(meth) acrylate, bio-derived t-butyl (meth) acrylate, bio-derived methyl
(meth) acrylamide, bio-
derived ethyl (meth) acrylamide, bio-derived t-butyl (meth) acrylamide, bio-
derived styrene, or
bio-derived a-methyl styrene. Preferably, the polymer comprises the following
levels of
monomers: from about 40% to about 90%, preferably from about 60% to about 90%
by weight of
the polymer of one or more bio-derived carboxylic acid monomer; from about 5%
to about 50%,
preferably from about 10% to about 40% by weight of the polymer of one or more
sulfonic acid
monomer; and optionally from about 1% to about 30%, preferably from about 2%
to about 20%
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52
by weight of the polymer of one or more non-ionic monomer. An especially
preferred polymer
comprises about 70% to about 80% by weight of the polymer of at least one bio-
derived
carboxylic acid monomer and from about 20% to about 30% by weight of the
polymer of at least
one bio-derived sulfonic acid monomer.
The polymers for use in the sustainable compositions preferably are derived
from a
renewable resource via an indirect route involving one or more intermediate
compounds.
Suitable intermediate compounds derived from renewable resources include
sugars. Suitable
sugars include monosaccharides, disaecharides, trisaccharides, and
oligosaccharides. Sugars
such as sucrose, glucose, fructose, maltose may be readily produced from
renewable resources
such as sugar cane and sugar beets. Sugars may also be derived (e.g., via
enzymatic cleavage)
from other agricultural products such as starch or cellulose. For example,
glucose may be
prepared on a commercial scale by enzymatic hydrolysis of corn starch. While
corn is a
renewable resource in North America, other common agricultural crops may be
used as the base
starch for conversion into glucose. Wheat, buckwheat, arracaha, potato,
barley, kudzu, cassava,
sorghum, sweet potato, yam, arrowroot, sago, and other like starchy fruit,
seeds, or tubers are
may also be used in the preparation of glucose.
Other suitable intermediate compounds derived from renewable resources include
monofunctional alcohols such as methanol or ethanol and polyfunctional
alcohols such as
glycerol. Ethanol may be derived from many of the same renewable resources as
glucose. For
example, cornstarch may be enzymatically hydrolysized to yield glucose and/or
other sugars.
The resultant sugars can be converted into ethanol by fermentation. As with
glucose
production, corn is an ideal renewable resource in North America; however,
other crops may be
substituted. Methanol may be produced from fermentation of biomass. Glycerol
is commonly
derived via hydrolysis of triglycerides present in natural fats or oils, which
may be obtained from
renewable resources such as animals or plants.
Other intermediate compounds derived from renewable resources include organic
acids
(e.g., citric acid, lactic acid, alginic acid, amino acids etc.), aldehydes
(e.g., acetaldehyde), and
esters (e.g., cetylpalmitate, methyl stearate, methyl oleate, etc.).
Additional intermediate compounds such as methane and carbon monoxide may also
be
derived from renewable resources by fermentation and/or oxidation processes.
Intermediate compounds derived from renewable resources may be converted into
polymers (e.g., glycerol to polyglycerol) or they may be converted into other
intermediate
compounds in a reaction pathway which ultimately leads to a polymer useful in
the sustainable
compositions. An intermediate compound may be capable of producing more than
one
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53
secondary intermediate compound. Similarly, a specific intermediate compound
may be derived
from a number of different precursors, depending upon the reaction pathways
used.
Particularly desirable intermediates include bio-derived (meth)acrylic acids
and their
esters and salts; and olefins. In particular embodiments, the intermediate
compound may be bio-
derived acrylic acid, bio-derived ethylene, or bio-derived propylene.
For example, acrylic acid is a monomeric compound that may be derived from
renewable
resources via a number of suitable routes. Examples of such routes are
provided below.
Acrylic and methacrylic monomers represent a large portion of the monomers
that are
used to produce the acrylic polymers. For example, both bio-derived 3-
hydroxypropionic acid
and bio-derived 2-hydroxyisobutyric acids are available via bio-transformation
pathways, see for
example, Biotechnology Journal, volume 1, pages 756-769, 2006 and Applied
Microbiological
Biotechnology, volume 66, pages 131-142, 2004. These bio-derived acids can be
dehydrated to
form bio-derived acrylic acid and bio-derived methacrylic acid.
The bio-derived acrylic acid and bio-derived acrylic acid monomers, and
derivatives
thereof, can be used to form numerous bio-derived methacrylic acid, bio-
derived alkyl acrylate
and bio-derived alkyl methacrylate esters as well as bio-derived acrylamides,
bio-derived
methacrylami des, bio-derived acrylonitrile and bio-derived methacrylonitrile.
Bio-derived
acrylate and bio-derived methacrylate esters can be produced, via
esterification reactions with
bio-derived alcohols. By incorporating an excess of bio-derived diols into the
esterification
reaction, hydroxy functional bio-derived acrylate and bio-derived methacrylate
esters can be
formed. Using at least two equivalents excess of the bio-derived acrylic acid
and bio-derived
methacrylic acid with bio-derived diols, bio-derived diacrylates and bio-
derived dimethacrylates
can be formed. These types of monomers find widespread use in the acrylic
polymers suitable
for use in the sustainable compositions.
A representative sample of bio-derived alcohol, bio-derived acrylic acid, bio-
derived
acrylic acid, and derivatives thereof, includes, but is not limited to: bio-
derived methanol, bio-
derived methylacrylate, bio-derived methylmethacrylate, bio-derived ethanol,
bio-derived ethyl
acrylate, bio-derived ethylmethacrylate, bio-derived 1-propanol, bio-derived
propyl acrylate, bio-
derived propyl methacrylate, bio-derived 2-propanol, bio-derived isopropyl
acrylate, bio-derived
isopropyl methacrylate, bio-derived 1-butanol, bio-derived butyl acrylate, bio-
derived butyl
methacrylate, bio-derived 2-butanol, bio-derived isobutyl acrylate, bio-
derived isobutyl
methacrylate, bio-derived ethylene glycol, bio-derived 2-hydroxyethyl
acrylate, bio-derived 2-
hydroxyethyl methacrylate, bio-derived 1,2-propylene glycol, bio-derived 2-
hydroxypropyl
acrylate, bio-derived 2-hydroxypropyl methacrylate, bio-derived 1,3-propylene
glycol, bio-
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54
derived 3-hydroxypropyl acrylate, bio-derived 3-hydroxypropyl methacrylate,
bio-derived 1,4-
butane diol, bio-derived 4-hydroxybutyl acrylate, bio-derived 4-hydroxybutyl
methacrylate, bio-
derived 1,2-butane diol, bio-derived 2-hydroxybutyl acrylate, bio-derived 2-
hydroxybutyl
methacrylate, bio-derived isobornyl alcohol, bio-derived isobornyl acrylate,
and bio-derived
isobornyl methacrylate.
Bio-epichlorhydrin is also available from bio-derived glycerol via the
EPLCEROLTM
process developed by Solvay. Bio-derived epichlorohydrin allows the formation
of bio-glycidyl
acrylate and bio-glycidyl methacrylate monomers.
While bio-derived acrylic and bio-derived methacrylic esters monomers make up
the
majority of the monomers that are used to produce bio-derived acrylic
polymers, other monomers
can be copolymerized with these ester monomers to modify the properties of the
polymer. These
monomers can include, for example, bio-derived acrylamide, bio-derived
methacrylamide, bio-
derived acrylonitrile and bio-derived methacrylonitrile, bio-derived styrene
and styrene
derivatives, or combinations thereof are often used. Bio-acrylamides and bio-
methacrylamides
can be derived from the corresponding bio-derived acrylic acid and bio-derived
methacrylic acid,
for example, by the formation of bio-derived acid chlorides, followed by
amination with
ammonia or other primary and/or secondary amines.
Bio-derived acrylonitrile and bio-derived methacrylonitrile can be produced by
the
dehydration of bio-derived acrylamide and bio-derived methacrylamide using,
for example,
phosphorus pentoxide. Bio-derived styrene can be produced from phenylalanine
by the
deamination using phenylalanine ammonia lyase, which results in the formation
of cinnamic
acid. The formed cinnamic acid can then be decarboxylated using a variety of
methods,
including bio-synthetic pathways. See for example, The Chemical and
Pharmaceuticals Bulletin,
Volume 49(5), pages 639-641 , 2001. Another group of monomers that are
important to the for
formation of bio-derived polymers are the bio-derived monomers that produce
polyesters. These
bio-derived monomers include monoalcohols, diols, triols and higher polyols;
bio-derived
monocarboxylic acids, bio-derived dicarboxylic acids, and bio-derived higher
carboxylic acids;
as well as bio-derived hydroxy-functional carboxylic acids, for example, bio-
derived 12-hydroxy
stearic acid. There exist processes for many of these monomers to be produced
from bio-mass
sources, thereby providing a route to bio-derived monomers that can be used to
form bio-derived
polyesters. Bio-derived alcohols and some bio-derived acids have been
discussed above. Bio-
derived diacids are also available. References can be found to produce bio-
derived adipic acid as
well as other diacids; see for example, US 4,400,468 and US .4,965,201. It is
preferable for the
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sustainable compositions that all of the carbon atoms of the monomers used to
form the polymer
components to be bio-derived.
As an example route to obtaining bio-derived acrylic acid, glycerol starting
material may
be derived from a renewable resource (e.g., via hydrolysis of soybean oil and
other triglyceride
15 Alternatively, glucose derived from a renewable resource (e.g., via
enzmatic hydrolysis of
corn starch) may be converted into acrylic acid via a two step process with
lactic acid as an
intermediate product. In the first step, glucose may be biofermented to yield
lactic acid. Any
suitable microorganism capable of fermenting glucose to yield lactic acid may
be used including
members from the genus Lactobacillus such as Lactobacillus lactis as well as
those identified in
Another suitable reaction pathway for converting glucose into acrylic acid
involves a two
step process with 3-hydroxypropionic acid as an intermediate compound. In the
first step,
glucose may be biofermented to yield 3-hydroxypropionic acid. Microorganisms
capable of
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56
production of the recombinant organism may be found in U.S. Patent No.
6,852,517. In the
second step, the 3-hydroxypropionic acid may be dehydrated to produce acrylic
acid.
Glucose derived from a renewable resource (e.g., via enzymatic hydrolysis of
corn starch
obtained from the renewable resource of corn) may be converted into acrylic
acid by a multistep
reaction pathway. Glucose may be fermented to yield ethanol, which itself may
be obtained from
bio-derived sources of carbon. Ethanol may be dehydrated to yield ethylene. At
this point,
ethylene may be polymerized to form polyethylene. However, ethylene may be
converted into
prop ionaldehyde by hydroformylation of ethylene using carbon monoxide and
hydrogen in the
presence of a catalyst such as cobalt octacarbonyl or a rhodium complex.
Propan-l-ol may be
= formed by catalytic hydrogenation of propionaldehyde in the presence of a
catalyst such as
sodium borohydride and lithium aluminum hydride. Propan-l-ol may be dehydrated
in an acid
catalyzed reaction to yield propylene. At this point, propylene may be
polymerized to form
polypropylene. However, propylene may be converted into acrolein by catalytic
vapor phase
oxidation. Acrolein may then be catalytically oxidized to form acrylic acid in
the presence of a
molybdenum- vanadium catalyst.
While the above reaction pathways yield acrylic acid, a skilled artisan will
appreciate that
acrylic acid may be readily converted into an ester (e.g., methyl acrylate,
ethyl acrylate, etc.) or
salt. Thereby, the bio-derived acrylic acid becomes an intermediate in a
pathway to bio-derived
esters such as bio-derived methyl acrylate and bio-derived ethyl acrylate.
Scale formation is sometimes a problem, particularly in nil-phosphate
formulation. Anti-
sealants include polyacrylates and polymers based on acrylic acid combined
with other moieties,
preferably from bio-derived sources. Sulfonated varieties of these polymers
are particular
effective in nil phosphate formulation executions. Examples of anti-scalants
include those
described in US 5,783,540, column 15, line 20 through column 16, line 2; and
EP 0 851 022 A2,
page 12, lines 1-20. Commercially available examples may include Acusol series
(e.g., Acusol
588) of polymers from Dow and sulfonated polymers from Nippon Shukobai.
Olefins such as ethylene and propylene may be derived from renewable
resources. For
example, methanol derived from fermentation of biomass may be converted to
ethylene and/or
propylene, which are both suitable monomeric compounds, as described in U.S.
Patent Nos.
4,296,266 and 4,083,889. Ethanol derived from fermentation of a renewable
resource may be
converted into monomeric compound of ethylene via dehydration as described in
U.S. Patent No.
4,423,270. Similarly, propanol or isopropanol derived from a renewable
resource can be
dehydrated to yield the monomeric compound of Propylene as exemplified in U.S.
Patent No.
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5,475,183. Propanol is a major constituent of fusel oil, a by-product formed
from certain amino
acids when potatoes or grains are fermented to produce ethanol.
Charcoal derived from biomass can be used to create syngas (i.e., CO/H2) from
which
hydrocarbons such as ethane and propane can be prepared (Fischer-Tropsch
Process). Ethane
and propane can be dehydrogenated to yield the monomeric compounds of ethylene
and
propylene.
Acrylic acid having a 100% bio-derived carbon isotope ratio may be produced
from
bioderived glycerol, bio-derived lactic acid, and/or bio-derived lactate
esters, as described in U.S.
Pat. Appl. Pub. No. 2009/0018300. In turn, the bioderived glycerol may be
converted to other
useful chemical feedstocks, such as, acrylic acid (2-propenoic acid), allyl
alcohol (2-propen-1-
ol), and 1,3-propanediol, having a 100% biobased carbon isotope ratio. For
example, bioderived
glycerol may be dehydrated to give acrolein (2-propenal). The acrolein may be
oxidized to
afford acrylic acid (2-propenoic acid). Alternatively, acrolein may be reduced
to give ally'
alcohol (2-propen-1-01). Suitable methods for the conversion of acrolein to
allyl alcohol include,
but are not limited to, reactions catalyzed by a silver indium catalyst as
described by Lucas et al.
in Chemie Ingenieur Technik, 2005, 77, 110-113, the disclosure of which is
incorporated by
reference herein in its entirety. Further, acrolein may be converted to 1,3-
propanediol. One
suitable method for the conversion of acrolein to 1,3-propanediol includes
hydration followed by
hydrogenation as described in U.S. Pat. No. 5,171,898, the disclosure of which
is incorporated by
reference herein in its entirety. The industrial/chemical feedstocks produced
from glycerol, via
acrolein, as set forth herein, will have a carbon isotope ratio that can be
identified as being
derived from biomass (i.e., bio-derived). Bio-derived 1,3-propanediol may be
prepared as
disclosed in U.S. Pat. Appl. Pub. No. 2007/0213247. Moreover, sustainable
compositions herein
may comprise bio-derived 1,3-propanediol prepared as disclosed in U.S. Pat.
Appl. Pub. No.
2007/0213247.
Alternatively, bio-derived acrylic acid or acrylate esters may be synthesized
from bio-
derived lactic acid or lactate esters. Biobased lactic acid derivatives may be
bio-synthesized, for
example, by fermentation of a carbohydrate material. Conversion of lactic acid
and lactate esters
into acrylic acid and acrylate esters, respectively, may be accomplished by
dehydration of the
alcohol group of the lactate moiety. Suitable methods for the conversion of
lactic acid and
lactate esters, for example, lactic acid/lactate esters from the fermentation
of carbohydrate
material in the presence of ammonia, into an acrylate ester or acrylic acid
are disclosed in U.S.
Pat. Nos. 5,071,754 and 5,252,473, the disclosures of which are incorporated
by reference herein
in their entirety.
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The bio-derived monomers described herein may be used for the synthesis of
polymers
having up to a 100% bio-derived carbon isotope ratio. Thus, the bio-derived
monomers may be
used for the synthesis of polymers having from 1% to 99.9% bio-derived carbon.
The bio-
derived polymers, then, are suited for use in the sustainable composition.
According to other
embodiments, the bio-derived monomers may be used for the synthesis of
polymers having from
50% to 99.9% biobased carbon. Thus, the glycerol and carbohydrate starting
materials described
herein will necessarily be derived from biological sources. For example, bio-
derived glycerol
containing 100% bio-derived carbon, as determined by ASTM Method D 6866, may
be obtained
from triglycerides (triacylglycerols) from biological sources, for example, a
vegetable oil or an
animal fat, by splitting the triglyceride into the corresponding fatty acids
and glycerol.
Triglycerides may be converted into the corresponding fatty acids and glycerol
by acidic
hydrolysis, basic hydrolysis (saponification) or by a catalytic de-
esterification. Suitable
triglycerides for use in the formation of bio-derived glycerol include, but
are not limited to, corn
oil, soybean oil, canola oil, vegetable oil, safflower oil, sunflower oil,
nasturtium seed oil,
mustard seed oil, olive oil, sesame oil, peanut oil, cottonseed oil, rice bran
oil, babassu nut oil,
castor oil, palm oil, palm kernel oil, rapeseed oil, low erucic acid rapeseed
oil, lupin oil, jatropha
oil, coconut oil, flaxseed oil, evening primrose oil, jojoba oil, tallow, beef
tallow, butter, chicken
fat, lard, dairy butterfat, shea butter, biodiesel, used frying oil, oil
miscella, used cooking oil,
yellow trap grease, hydrogenated oils, derivatives of these oils, fractions of
these oils, conjugated
derivatives of these oils, and mixtures of any thereof.
Suitable bioderived olefins include, but are not limited to monoacrylates,
diacrylates, and
allyl esters.
Alternatively, bio-derived glycerol may be produced as a co-product of
biodiesel
production. Glycerol produced by these methods will have a carbon isotope
ratio consistent with
a 100% bio-derived product and will provide a renewable source of acrolein and
acrylic acid that
may be used as a feedstock for the bio-derived monomers and polymers for use
in the sustainable
compositions. Non-limiting examples of methods and processes for producing
biodiesel may be
found in U.S. Pat. No. 5,354,878; U.S. Patent Application Publication Nos.
20050245405A1;
2007-0181504; and 20070158270A1; Provisional Patent Application Ser. No.
60/851,575, the
disclosures of which are incorporated in their entirety by reference herein.
The monomers and polymers, as set forth herein, may have up to 100% biobased
carbon
isotope ratio as determined by ASTM Method D 6866. The monomers and polymers
may be
differentiated from, for example, similar monomers and polymers comprising
petroleum derived
components by comparison of the carbon isotope ratios, for example, the
14C/12C or the 13C/'2C
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carbon isotope ratios, of the materials. As described herein, isotopic ratios
may be determined,
for example, by liquid scintillation counting, accelerator mass spectrometry,
or high precision
isotopic ratio mass spectrometry.
Bio-derived acrylic acid (or acrylate esters), for example acrylic acid and
esters
synthesized by any of the embodiments described herein, may be esterified (or
transesterified)
with other bio-derived alcohols, diols, or polyols. Non-limiting suitable bio-
derived alcohols and
diols include, for example, methanol; ethanol; n-butanol, for example from an
acetone/butanol
fermentation; fusel oil alcohols (n-propanol, isobutyl alcohol, isoamyl
alcohol, and/or furfural);
and alcohol and diol derivatives derived from carbohydrates or their
derivatives.
Non-limiting examples of carbohydrate derived diols include
hydroxymethylfurfuryl, 2,5-
bis(hydroxymethyl)furan, 2,5-bis(hydroxymethyl)tetrahydrofuran, and isosorbide
(dianhydrohexitol), isomannide, mannitol, xylitol, maltitol, maltitol syrup,
lactitol, erythritol,
isomalt, isoidide (the dianhydrohexitol of iditol), or ethoxylated or
propoxylated derivatives of
these.
Diacrylate esters may be produced from carbohydrate derived diols and may act
as
monomers or co-monomers having 100% bio-derived carbons, as determined by ASTM
Method
D 6866, for the synthesis of polymers having up to 100% biobased carbon and
being suitable for
use in the sustainable compositions.
Other embodiments of bio-derived diols suitable for producing diacrylate
esters having
100% biobased carbon may be produced from fatty acids, such as, for example,
unsaturated fatty
acids. For example, hydroformylation of unsaturated fatty acids and their
derivatives to produce
fatty acid derivatives having a hydroxymethylene group is described in U.S.
Pat. No. 3,210,325
to De Witt et al., the disclosure of which is incorporated in its entirety by
reference herein.
Reduction of the carbonyl of the fatty acid derivative, for example, by
hydrogenation, produces a
biobased diol suitable for esterification or transesterification with acrylic
acid or an acrylate ester,
as produced herein, to form a biobased diacrylate monomer.
Additionally, bio-derived diols suitable for producing diacrylate esters
having 100% bio-
derived carbon may be produced by epoxidation of at least one of the double
bonds of an
unsaturated fatty acid/ester or unsaturated fatty alcohol. One non-limiting
example of the
epoxidation procedure is described by Rao et al., Journal of the American Oil
Chemists' Society,
(1968), 45(5), 408, the disclosure of which is incorporated in its entirety by
reference herein.
The epoxidation may be followed by reduction, for example, by hydrogenation,
to open the
epoxide to the alcohol, which May also include reduction of the carbonyl of
the fatty acid/ester to
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the alcohol. Any biobased diol may then be esterified or transesterified with
acrylic acid or an
acrylate ester, as produced herein, to form a diacrylate monomer having 100%
biobased carbon.
Still further, diols suitable for producing diacrylate esters having 100%
biobased carbon
may be produced by reduction of cc,o)-dicarboxylic acids. As used herein, the
term a,o)-
5 dicarboxylic acid" includes organic molecules comprising a carbon chain
of at least 1 carbon
atom and two carboxylic acid functional groups, each of which is positioned at
opposite ends of
the carbon chain. For example, a,w-dicarboxylic acids may be produced by a
fermentation
process involving biobased fatty acids, such as, by a fermentation process as
described in Craft,
et al., Applied and Environmental Microbiology, (2003), 69(10), 5983-5991
and/or U.S. Pat. No.
10 6,569,670 to Anderson et al., the disclosures of which are incorporated
in their entirety by
reference herein. Other a,w-dicarboxylic acids from biobased sources, such as,
for example,
maleic acid, fumaric acid, oxalic acid, malonic acid, adipic acid, succinic
acid, and glutaric acid,
adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid may
also be used in the
sustainable compositions. According to certain embodiments, the a,w-
dicarboxylic acid may be
15 an unsaturated a,w-dicarboxylic acid or a saturated a,co-dicarboxylic
acid. Reduction of the
carbonyls of the a,co-dicarboxylic acids provides a biobased diol which may
then be esterified or
transesterified with acrylic acid or an acrylate ester, as produced herein, to
form a biobased
diacrylate monomer.
Still further, bioderived diacrylamide derivatives may serve as monomers for
the
20 polymerization reactions described herein. For example, according to
certain embodiments, the
diol component in the formation of the diacrylate esters described herein, may
be chemically
converted to a bio-derived diamine, for example, by a double Mitsunobu-type
reaction. Non-
limiting examples of resulting biobased diamines may include, for example, his-
amino
isosorbide, 2,5-bisaminomethyltetrahydrofuran, 2,5-bisaminomethylfuran.
Alternatively,
25 naturally occurring bioderived diamines, such as, for example, 1,4-
diaminobutane, 1,5-
diaminopentane, or other alkyldiamines or diamine containing alkaloid
derivatives, may be
replace the diol reactant in the reaction with the bioderived acrylate
derivative to form a diacryl
amide compound. Further, it is also contemplated that bioderived amino
alcohols may replace
the diol component in the formation of the biobased monomers. According to
these
30 embodiments, the bioderived amino alcohols may be reacted with the
bioderived acrylic acid or
bioderived acrylate esters to form a bioderived monomer possessing both an
acrylate ester and an
acrylamide functionality.
Bioderived diacryl derivatives, such as the diacrylate esters, diacrylamides,
and
acrylate/acrylamide monomers may serve as monomers or co-monomers in a
polymerization
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reaction to produce a bio-derived polymer for inclusion in the sustainable
compositions. For
example, an olefin metathesis polymerization reaction may be used to produce
the biobased
polymer. As used herein, the term "metathesis polymerization" includes an
olefin metathesis
reaction involving a metal carbene acting as a catalyst to metathesize alkene
monomers or co-
monomers into a polyunsaturated polymer through a metallocyclobutane
intermediate. Thus, a
polymer comprising a product from an olefin metathesis polymerization reaction
of a bioderived
olefin and a diacrylate ester of a bioderived diol may be used, wherein the
diacrylate ester is
produced by reacting a bioderived diol with at least two equivalents of bio-
derived acrylic acid or
an acrylate ester derived from a bioderived glycerol. The olefin metathesis
polymerization
reaction may be catalyzed by an olefin metathesis catalyst, such as a metal
carbene catalyst, for
example, metal carbenes of molybdenum or ruthenium. Commercially available
olefin
metathesis catalysts suitable for use in the polymerization reactions of the
present disclosure
include, but are not limited to, the "Schrock catalyst" (i.e.,
[Mo(=CHMe2Ph)(=N¨
Ar)(0CMe(CF3)2)2]), the "1st generation Grubb's catalyst" (i.e.,
[Ru(=CHPh)C12(PCy3)2]), and
the "2nd generation Grubb's catalyst" (i.e, [Ru(¨CHPh)C12PCy3(N,1\11-diary1-2-
imidazolidiny1)])
(Me¨methyl, Ph¨phenyl, Ar=aryl, and Cy=cyclohexyl). Other olefin metathesis
catalysts that
may be suitable include those catalysts set forth in U.S. Pat. 7,034,096 to
Choi et al. at column
12, line 27 to column 19, line 2, the disclosure of which is incorporated in
its entirety by
reference herein. It should be noted that the polymers and polymerization
process described in
the present disclosure are not limited to a particular olefin metathesis
catalyst(s) and that any
olefin metathesis catalyst, either currently available or designed in the
future, may be suitable for
use in various embodiments of the present disclosure.
Additionally, the bio-derived olefin component of the metathesis
polymerization may be a
bioderived cyclic olefin, wherein the metathesis polymerization reaction is a
ring opening
metathesis polymerization ("ROMP") reaction. As used herein, the term "ring
opening
metathesis polymerization reaction" includes olefin metathesis polymerization
reactions wherein
at least one of the monomer alkene units comprises a cyclic olefin. Thus, the
ROMP reaction
may react a bioderived diacryl derivative with a bioderived cyclic olefin to
produce a polymer
that is up to 100% biobased as determined by ASTM Method D 6866. Bio-derived
cyclic olefins
may be prepared, for example, from palmitoleic acid, oleic acid, erucic acid,
linoleic acid,
linolenic acid, arachidonic acid, eicosapentaenoic acid, docosahexaenoic acid,
and other
unsaturated fatty acids.
Further processes for producing bio-derived acrylic acid, acrylic acid esters,
and acrylate
polymers are disclosed in WO 2011/002284; US 7,928,148; US 2009/0018300; EP
1710227, and
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Xu et al, "Advances in the Research and Development of Acrylic Acid Production
from
Biomass," Chinese J. Chem. Eng., vol. 14, pp. 419-427 (2006), all of which are
incorporated
herein in their entirety.
In example embodiments of the sustainable compositions comprising a carboxylic
acid
polymer, the carboxylic acid is preferably bio-derived (meth)acrylic acid.
Sulfonic acids, when
present in the sustainable compositions, preferably are derived from a monomer
selected from:
bio-derived 2-acrylamido methyl-l-propanesulfonic acid, bio-derived 3-allyloxy-
2-hydroxy-1-
propanesulfonic acid ("HAPS"), bio-derived 2-methacrylamido-2-methyl-1-
propanesulfonic
acid, bio-derived 3-methacrylamido-2-hydroxypropanesulfonic acid, bio-derived
allylsulfonic
acid, bio-derived methallylsulfonic acid, bio-derived allyloxybenzenesulfonic
acid, bio-derived
methallyloxybenzensulfonic acid, bio-derived 2-hydroxy-3-(2-
propenyloxy)propanesulfonic acid,
bio-derived 2-methyl-2-propene-1-sulfonic acid, bio-derived styrene sulfonic
acid, bio-derived
vinylsulfonic acid, bio-derived 3-sulfopropyl acrylate, bio-derived 3-
sulfopropyl methacrylate,
bio-derived sulfomethylacrylamide, bio-derived sulfomethylmethacrylamide, and
water soluble
salts thereof. The unsaturated sulfonic acid monomer is most preferably 2-
acrylamido-2-
propanesulfonic acid (AMPS).
In the polymers, all or some of the carboxylic or sulfonic acid groups can be
present in
neutralized form, i.e. the acidic hydrogen atom of the carboxylic and/or
sulfonic acid group in
some or all acid groups can be replaced with metal ions, preferably alkali
metal ions and in
particular with sodium ions. Preferably, at least 50%, at least 60%, at least
70%, at least 80%, at
least 90%, at least 95%, at least 99%, or 100% of the carbon atoms in the
polymers are bio-
derived.
Hydrophilic Polymer
In some of the embodiments of the invention, the sustainable composition may
comprise
a polymeric material that improves the hydrophilicity of the surface being
treated. This increase
in hydrophilicity provides improved final appearance by providing "sheeting"
of the water from
the surface and/or spreading of the water on the surface, and this effect is
preferably seen when
the surface is rewetted and even when subsequently dried after the rewetting.
In the context of a
product intended to be used as a daily shower product, the "sheeting" effect
is particularly
noticeable because most of the surfaces treated are vertical surfaces. Thus,
benefits have been
noted on glass, ceramic and even tougher to wet surfaces such as porcelain
enamel. When the
water "sheets" evenly off the surface and/or spreads on the surface, it
minimizes the formation
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of, e.g., "hard water spots" that form upon drying. For a product intended to
be used in the
context of a floor cleaner, the polymer improves surface wetting and assists
cleaning
performance.
Many materials can provide the sheeting and anti-spotting benefits, but the
preferred
materials are polymers that contain amine oxide hydrophilic groups. Polymers
that contain other
hydrophilic groups such a sulfonate, pyrrolidone, and/or carboxylate groups
can also be used.
Examples of desirable poly-sulfonate polymers include polyvinylsulfonate, and
more preferably
polystyrene sulfonate, such as those sold by Monomer-Polymer Dajac (1675
Bustleton Pike,
Feasterville, Pa. 19053). A typical formula is as follows.
¨[CH(C6H4S03Na)¨CH2]¨CH(C6H5)¨CH2¨
wherein n is a number to give the appropriate molecular weight as disclosed
below.
Polyvinylpyrrolidones may be preferred, particularly bio-derived
polyvinylpyrrolidones.
Typical molecular weights are from about 10,000 to about 1,000,000, preferably
from
about 200,000 to about 700,000. Preferred polymers containing pyrrolidone
functionalities
include polyvinyl pyrrolidone, quaternized pyrrolidone derivatives (such as
Gafquat 755N from
International Specialty Products), and co-polymers containing pyrrolidone,
such as
polyvinylpyrrolidone /dimethylaminoethylmethacrylate (available from ISP) and
polyvinyl
pyrrolidone/acrylate (available from BASF). Other materials can also provide
substantivity and
hydrophilicity including cationic materials that also contain hydrophilic
groups and polymers that
contain multiple ether linkages. Cationic materials include cationic sugar
and/or starch
derivatives and the typical block copolymer detergent surfactants based on
mixtures of
polypropylene oxide and ethylene oxide are representative of the polyether
materials.
Some non-limiting examples of homopolymers and copolymers which can be used as
water-soluble polymers of the present invention are: adipic acid/
dimethylaminohydroxypropyl
diethylenetriamine copolymer; adipic acid/epoxypropyl diethylenetriamine
copolymer; polyvinyl
alcohol; methacryloyl ethyl betaine/methacrylates copolymer; ethyl
acrylate/methyl
methacrylate/methacrylic acid/acrylic acid copolymer; polyamine resins;
polyquatemary amine
resins; poly(ethenylformamide); poly(vinylamine) hydrochloride; poly(vinyl
alcohol-co-6%
vinylamine); poly(vinyl alcohol-co-12% vinylamine); poly(vinyl alcohol-co-6%
vinylamine
hydrochloride); poly(vinyl alcohol-co-12% vinylamine hydrochloride); and
mixtures thereof.
Preferably, said copolymer and/or homopolymers are selected from the group
consisting of
adipic acid/dimethylaminohydroxypropyl diethylenetriamine copolymer;
poly(vinylpyrrolidone/dimethylaminoethyl methacrylate); polyvinyl alcohol;
ethyl
acrylate/methyl methacrylate/methacrylic acid/acrylic acid copolymer;
methacryloyl ethyl
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betaine/methacrylates copolymer; polyquatemary amine resins;
poly(ethenylformamide);
poly(vinylamine) hydrochloride; poly(vinyl alcohol-co-6% vinylamine);
poly(vinyl alcohol-co-
12% vinylamine); poly(vinyl alcohol-co-6% vinylamine hydrochloride);
poly(vinyl alcohol-co-
12% vinylamine hydrochloride); and mixtures thereof. Preferably, the all or a
portion of the
polymer used is bio-derived.
Polymers useful in the present invention can be selected from the group
consisting of
copolymers of hydrophilic monomers. The polymer can be linear random or block
copolymers,
and mixtures thereof. Preferably the polymers are formed from bio-derived
monomers. The
term "hydrophilic" is used herein consistent with its standard meaning of
having affinity for
water. As used herein in relation to monomer units and polymeric materials,
including the
copolymers, "hydrophilic" means substantially water soluble. In this regard,
"substantially water
soluble" shall refer to a material that is soluble in distilled (or
equivalent) water, at 25 C., at a
concentration of about 0.2% by weight, and are preferably soluble at about 1%
by weight. The
terms "soluble", "solubility" and the like, for purposes hereof, correspond to
the maximum
concentration of monomer or polymer, as applicable, that can dissolve in water
or other solvents
to form a homogeneous solution, as is well understood to those skilled in the
art.
Nonlimiting examples of useful hydrophilic monomers are unsaturated organic
mono-
and polycarboxylic acids such as acrylic acid, methacrylic acid, crotonic
acid, maleic acid and its
half esters, and itaconic acid; unsaturated alcohols, such as vinyl alcohol
and allyl alcohol; polar
vinyl heterocyclics such as vinyl caprolactam, vinyl pyridine, and vinyl
imidazole; vinyl amine;
vinyl sulfonate; unsaturated amides such as acrylamides, e.g., N,N-
dimethylacrylamide and N-t-
butyl acrylamide; hydroxyethyl methacrylate; dimethylaminoethyl methacrylate;
salts of acids
and amines listed above; and the like; and mixtures thereof. Some preferred
hydrophilic
monomers are bio-derived acrylic acid, bio-derived methacrylic acid, bio-
derived N,N-dimethyl
acrylamide, bio-derived N,N-dimethyl methacrylamide, bio-derived N-t-butyl
acrylamide, bio-
derived dimethylamino ethyl methacrylate, and mixtures thereof.
Polycarboxylate polymers are those formed by polymerization of monomers, at
least
some of which contain carboxylic functionality. Common monomers include bio-
derived acrylic
acid, bio-derived maleic acid, bio-derived ethylene, bio-derived vinyl
pyrrolidone, bio-derived
methacrylic acid, bio-derived methacryloylethylbetaine, and the like.
Some polymers, especially polycarboxylate polymers, thicken the compositions
that are
aqueous liquids. This can be desirable. However, when the compositions are
placed in
Containers with trigger spray devices, the compositions are desirably not so
thick as to require
excessive trigger pressure. Typically, the viscosity under shear should be
less than 200 cp,
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preferably less than 100 cp, more preferably less than 50 cp. It can be
desirable, however, to
have thick compositions to inhibit the flow of the composition off the
surface, especially vertical
surfaces.
The level of polymeric material will normally be less than 0.5%, preferably
from about
5 0.01% to about 0.4%, more preferably from about 0.01% to about 0.3%. In
general, lower
molecular weight materials such as lower molecular weight poly(acrylic acid),
e.g., those having
molecular weights below about 10,000, and especially about 2,000, do not
provide good anti-
spotting benefits upon rewetting, especially at the lower levels, e.g., about
0.02%.
The polymers for use in the sustainable compositions preferably are derived
from a
10 renewable resource via an indirect route involving one or more
intermediate compounds.
Suitable intermediate compounds derived from renewable resources include
sugars. Suitable
sugars include monosaccharides, disaecharides, trisaccharides, and
oligosaccharides. Sugars
such as sucrose, glucose, fructose, maltose may be readily produced from
renewable resources
such as sugar cane and sugar beets. Sugars may also be derived (e.g., via
enzymatic cleavage)
15 from other agricultural products such as starch or cellulose. For
example, glucose may be
prepared on a commercial scale by enzymatic hydrolysis of corn starch. While
corn is a
renewable resource in North America, other common agricultural crops may be
used as the base
starch for conversion into glucose. Wheat, buckwheat, arracaha, potato,
barley, kudzu, cassava,
sorghum, sweet potato, yam, arrowroot, sago, and other like starchy fruit,
seeds, or tubers are
20 may also be used in the preparation of glucose.
Other suitable intermediate compounds derived from renewable resources include
monofunctional alcohols such as methanol or ethanol and polyfunctional
alcohols such as
glycerol. Ethanol may be derived from many of the same renewable resources as
glucose. For
example, cornstarch may be enzymatically hydrolysized to yield glucose and/or
other sugars.
25 The resultant sugars can be converted into ethanol by fermentation. As
with glucose
production, corn is an ideal renewable resource in North America; however,
other crops may be
substituted. Methanol may be produced from fermentation of biomass. Glycerol
is commonly
derived via hydrolysis of triglycerides present in natural fats or oils, which
may be obtained from
renewable resources such as animals or plants.
30 Other intermediate compounds derived from renewable resources include
organic acids
(e.g., citric acid, lactic acid, alginic acid, amino acids etc.), aldehydes
(e.g., acetaldehyde), and
esters (e.g., cetyl palmitate, methyl stearate, methyl oleate, etc.).
Additional intermediate compounds such as methane and carbon monoxide may also
be
derived from renewable resources by fermentation and/or oxidation processes.
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66
Intermediate compounds derived from renewable resources may be converted into
polymers (e.g., glycerol to polyglycerol) or they may be converted into other
intermediate
compounds in a reaction pathway which ultimately leads to a polymer useful in
the sustainable
compositions. An intermediate compound may be capable of producing more than
one
secondary intermediate compound. Similarly, a specific intermediate compound
may be derived
from a number of different precursors, depending upon the reaction pathways
used.
Particularly desirable intermediates include bio-derived (meth)acrylic acids
and their
esters and salts; and olefins. In particular embodiments, the intermediate
compound may be bio-
derived acrylic acid, bio-derived ethylene, or bio-derived propylene.
For example, acrylic acid is a monomeric compound that may be derived from
renewable
resources via a number of suitable routes. Examples of such routes are
provided below.
Acrylic and methacrylic monomers represent a large portion of the monomers
that are
used to produce the acrylic polymers. For example, both bio-derived 3-
hydroxypropionic acid
and bio-derived 2-hydroxyisobutyric acids are available via bio-transformation
pathways, see for
example, Biotechnology Journal, volume 1, pages 756-769, 2006 and Applied
Microbiological
Biotechnology, volume 66, pages 131-142, 2004. These bio-derived acids can be
dehydrated to
form bio-derived acrylic acid and bio-derived methacrylic acid.
The bio-derived acrylic acid and bio-derived acrylic acid monomers, and
derivatives
thereof, can be used to form numerous bio-derived methacrylic acid, bio-
derived alkyl acrylate
and bio-derived alkyl methacrylate esters as well as bio-derived acrylamides,
bio-derived
methacrylamides, bio-derived acrylonitrile and bio-derived methacrylonitrile.
Bio-derived
acrylate and bio-derived methacrylate esters can be produced, via
esterification reactions with
bio-derived alcohols. By incorporating an excess of bio-derived diols into the
esterification
reaction, hydroxy functional bio-derived acrylate and bio-derived methacrylate
esters can be
formed. Using at least two equivalents excess of the bio-derived acrylic acid
and bio-derived
methacrylic acid with bio-derived diols, bio-derived diacrylates and bio-
derived dimethacrylates
can be formed. These types of monomers find widespread use in the acrylic
polymers suitable
for use in the sustainable compositions.
A representative sample of bio-derived alcohol, bio-derived acrylic acid, bio-
derived
acrylic acid, and derivatives thereof, includes, but is not limited to: bio-
derived methanol, bio-
derived methylacrylate, bio-derived methylmethacrylate, bio-derived ethanol,
bio-derived ethyl
acrylate, bio-derived ethylmethacrylate, bio-derived I-propanol, bio-derived
propyl acrylate, bio-
.
derived propyl methacrylate, bio-derived 2-propanol, bio-derived isopropyl
acrylate, bio-derived
isopropyl methacrylate, bio-derived 1-butanol, bio-derived butyl acrylate, bio-
derived butyl
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methacrylate, bio-derived 2-butanol, bio-derived isobutyl acrylate, bio-
derived isobutyl
methacrylate, bio-derived ethylene glycol, bio-derived 2-hydroxyethyl
acrylate, bio-derived 2-
hydroxyethyl methacrylate, bio-derived 1,2-propylene glycol, bio-derived 2-
hydroxypropyl
acrylate, bio-derived 2-hydroxypropyl methacrylate, bio-derived 1,3-propylene
glycol, bio-
derived 3-hydroxypropyl acrylate, bio-derived 3-hydroxypropyl methacrylate,
bio-derived 1,4-
butane diol, bio-derived 4-hydroxybutyl acrylate, bio-derived 4-hydroxybutyl
methacrylate, bio-
derived 1,2-butane diol, bio-derived 2-hydroxybutyl acrylate, bio-derived 2-
hydroxybutyl
methacrylate, bio-derived isobornyl alcohol, bio-derived isobornyl acrylate,
and bio-derived
isobornyl methacrylate.
Bio-epichlorhydrin is also available from bio-derived glycerol via the
EPICEROLTM
process developed by Solvay. Bio-derived epichlorohydrin allows the formation
of bio-glycidyl
acrylate and bio-glycidyl methacrylate monomers.
While bio-derived acrylic and bio-derived methacrylic esters monomers make up
the
majority of the monomers that are used to produce bio-derived acrylic
polymers, other monomers
can be copolymerized with these ester monomers to modify the properties of the
polymer. These
monomers can include, for example, bio-derived acrylamide, bio-derived
methacrylamide, bio-
derived acrylonitrile and bio-derived methacrylonitrile, bio-derived styrene
and styrene
derivatives, or combinations thereof are often used. Bio-acrylamides and bio-
methacrylamides
can be derived from the corresponding bio-derived acrylic acid and bio-derived
methacrylic acid,
for example, by the formation of bio-derived acid chlorides, followed by
amination with
ammonia or other primary and/or secondary amines.
Bio-derived acrylonitrile and bio-derived methacrylonitrile can be produced by
the
dehydration of bio-derived acrylamide and bio-derived methacrylamide using,
for example,
phosphorus pentoxide. Bio-derived styrene can be produced from phenylalanine
by the
deamination using phenylalanine ammonia lyase, which results in the formation
of cinnamic
acid. The formed cinnamic acid can then be decarboxylated using a variety of
methods,
including bio-synthetic pathways. See for example, The Chemical and
Pharmaceuticals Bulletin,
Volume 49(5), pages 639-641 , 2001. Another group of monomers that are
important to the for
formation of bio-derived polymers are the bio-derived monomers that produce
polyesters. These
bio-derived monomers include monoalcohols, diols, triols and higher polyols;
bio-derived
monocarboxylic acids, bio-derived dicarboxylic acids, and bio-derived higher
carboxylic acids;
as well as bio-derived hydroxy-functional carboxylic acids, for example, bio-
derived I2-hydroxy
stearic acid. There exist processes for many of these monomers to be produced
from bio-mass
sources, thereby providing a route to bio-derived monomers that can be used to
form bio-derived
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68
polyesters. Bio-derived alcohols and some bio-derived acids have been
discussed above. Bio-
derived diacids are also available. References can be found to produce bio-
derived adipic acid as
well as other diacids; see for example, US 4,400,468 and US 4,965,201. It is
preferable for the
sustainable compositions that all of the carbon atoms of the monomers used to
form the polymer
components to be bio-derived.
As an example route to obtaining bio-derived acrylic acid, glycerol starting
material may
be derived from a renewable resource (e.g., via hydrolysis of soybean oil and
other triglyceride
oils) and converted into acrylic acid according to a two-step process. In a
first step, the glycerol
may be dehydrated to yield acrolein. A particularly suitable conversion
process involves
subjecting glycerol in a gaseous state to an acidic solid catalyst such as
H3PO4 on an aluminum
oxide carrier (which is often referred to as solid phosphoric acid) to yield
acrolein. Specifics
relating to dehydration of glycerol to yield acrolein are disclosed, for
instance, in U.S. Patent
Nos. 2,042,224 and 5,387,720. In a second step, the acrolein is oxidized to
form acrylic acid. A
particularly suitable process involves a gas phase interaction of acrolein and
oxygen in the
presence of a metal oxide catalyst. A molybdenum and vanadium oxide catalyst
may be used.
Specifics relating to oxidation of acrolein to yield acrylic acid are
disclosed, for instance, in U.S.
Patent No. 4,092,354.
Alternatively, glucose derived from a renewable resource (e.g., via enzmatic
hydrolysis of
corn starch) may be converted into acrylic acid via a two step process with
lactic acid as an
intermediate product. In the first step, glucose may be biofermented to yield
lactic acid. Any
suitable microorganism capable of fermenting glucose to yield lactic acid may
be used including
members from the genus Lactobacillus such as Lactobacillus lactis as well as
those identified in
U.S. Patent Nos. 5,464,760 and 5,252,473. In the second step, the lactic acid
may be dehydrated
to produce acrylic acid by use of an acidic dehydration catalyst such as an
inert metal oxide
carrier which has been impregnated with a phosphate salt. This acidic
dehydration catalyzed
method is described in further detail in U.S. Patent 4,729,978. In an
alternate suitable second
step, the lactic acid may be converted to acrylic acid by reaction with a
catalyst comprising solid
aluminum phosphate. This catalyzed dehydration method is described in further
detail in U.S.
Patent 4,786,756.
Another suitable reaction pathway for converting glucose into acrylic acid
involves a two
step process with 3-hydroxypropionic acid as an intermediate compound. In the
first step,
glucose may be biofermented to yield 3-hydroxypropionic acid. Microorganisms
capable of
fermenting glucose to yield 3-hydroxypropionic acid have been genetically
engineered to express
the requisite enzymes for the conversion. For example, a recombinant
microorganism expressing
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69
the dhaB gene from Klebsiella pneumoniae and the gene for an aldehyde
dehydrogenase has been
shown to be capable of converting glucose to 3-hydroxypropionic acid.
Specifics regarding the
production of the recombinant organism may be found in U.S. Patent No.
6,852,517. In the
second step, the 3-hydroxypropionic acid may be dehydrated to produce acrylic
acid.
Glucose derived from a renewable resource (e.g., via enzymatic hydrolysis of
corn starch
obtained from the renewable resource of corn) may be converted into acrylic
acid by a multistep
reaction pathway. Glucose may be fermented to yield ethanol, which itself may
be obtained from
bio-derived sources of carbon. Ethanol may be dehydrated to yield ethylene. At
this point,
ethylene may be polymerized to form polyethylene. However, ethylene may be
converted into
prop ionaldehyde by hydroformylation of ethylene using carbon monoxide and
hydrogen in the
presence of a catalyst such as cobalt octacarbonyl or a rhodium complex.
Propan-l-ol may be
formed by catalytic hydrogenation of propionaldehyde in the presence of a
catalyst such as
sodium borohydride and lithium aluminum hydride. Propan-l-ol may be dehydrated
in an acid
catalyzed reaction to yield propylene. At this point, propylene may be
polymerized to form
polypropylene. However, propylene may be converted into acrolein by catalytic
vapor phase
oxidation. Acrolein may then be catalytically oxidized to form acrylic acid in
the presence of a
molybdenum- vanadium catalyst.
While the above reaction pathways yield acrylic acid, a skilled artisan will
appreciate that
acrylic acid may be readily converted into an ester (e.g., methyl acrylate,
ethyl acrylate, etc.) or
salt. Thereby, the bio-derived acrylic acid becomes an intermediate in a
pathway to bio-derived
esters such as bio-derived methyl acrylate and bio-derived ethyl acrylate.
Scale formation is sometimes a problem, particularly in nil-phosphate
formulation. Anti-
sealants include polyacrylates and polymers based on acrylic acid combined
with other moieties,
preferably from bio-derived sources. Sulfonated varieties of these polymers
are particular
effective in nil phosphate formulation executions. Examples of anti-scalants
include those
described in US 5,783,540, column 15, line 20 through column 16, line 2; and
EP 0 851 022 A2,
page 12, lines 1-20. Commercially available examples may include Acusol series
(e.g., Acusol
588) of polymers from Dow and sulfonated polymers from Nippon Shukobai.
Olefins such as ethylene and propylene may be derived from renewable
resources. For
example, methanol derived from fermentation of biomass may be converted to
ethylene and/or
propylene, which are both suitable monomeric compounds, as described in U.S.
Patent Nos.
4,296,266 and 4,083,889. Ethanol derived from fermentation of a renewable
resource may be
converted into monomeric compound of ethylene via dehydration as described in
U.S. Patent No.
4,423,270. Similarly, propanol or isopropanol derived from a renewable
resource can be
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dehydrated to yield the monomeric compound of propylene as exemplified in U.S.
Patent No.
5,475,183. Propanol is a major constituent of fusel oil, a by-product formed
from certain amino
acids when potatoes or grains are fermented to produce ethanol.
Charcoal derived from biomass can be used to create syngas (i.e., CO/H2) from
which
5 hydrocarbons such as ethane and propane can be prepared (Fischer-Tropsch
Process). Ethane
and propane can be dehydrogenated to yield the monomeric compounds of ethylene
and
propylene.
Acrylic acid having a 100% bio-derived carbon isotope ratio may be produced
from
bioderived glycerol, bio-derived lactic acid, and/or bio-derived lactate
esters, as described in U.S.
10 Pat. App!. Pub. No. 2009/0018300. In turn, the bioderived glycerol may
be converted to other
useful chemical feedstocks, such as, acrylic acid (2-propenoic acid), allyl
alcohol (2-propen-1-
01), and 1,3-propanediol, having a 100% biobased carbon isotope ratio. For
example, bioderived
glycerol may be dehydrated to give acrolein (2-propenal). The acrolein may be
oxidized to
afford acrylic acid (2-propenoic acid). Alternatively, acrolein may be reduced
to give ally!
15 alcohol (2-propen-1-o1). Suitable methods for the conversion of acrolein
to ally! alcohol include,
but are not limited to, reactions catalyzed by a silver indium catalyst as
described by Lucas et al.
in Chemie Ingenieur Technik, 2005, 77, 110-113, the disclosure of which is
incorporated by
reference herein in its entirety. Further, acrolein may be converted to 1,3-
propanediol. One
suitable method for the conversion of acrolein to 1,3-propanediol includes
hydration followed by
20 hydrogenation as described in U.S. Pat. No. 5,171,898, the disclosure of
which is incorporated by
reference herein in its entirety. The industrial/chemical feedstocks produced
from glycerol, via
acrolein, as set forth herein, will have a carbon isotope ratio that can be
identified as being
derived from biomass (i.e., bio-derived). Bio-derived 1,3-propanediol may be
prepared as
disclosed in U.S. Pat. App!. Pub. No. 2007/0213247. Moreover, sustainable
compositions herein
25 may comprise bio-derived 1,3-propanediol prepared as disclosed in U.S.
Pat. App!. Pub. No.
2007/0213247.
Alternatively, bio-derived acrylic acid or acrylate esters may be synthesized
from bio-
derived lactic acid or lactate esters. Biobased lactic acid derivatives may be
bio-synthesized, for
example, by fermentation of a carbohydrate material. Conversion of lactic acid
and lactate esters
30 into acrylic acid and acrylate esters, respectively, may be accomplished
by dehydration of the
alcohol group of the lactate moiety. Suitable methods for the conversion of
lactic acid and
lactate esters, for example, lactic acid/lactate esters from the fermentation
of carbohydrate
material in the presence of ammonia, into an acrylate ester or acrylic acid
are disclosed in U.S.
=
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71
Pat. Nos. 5,071,754 and 5,252,473, the disclosures of which are incorporated
by reference herein
in their entirety.
The bio-derived monomers described herein may be used for the synthesis of
polymers
having up to a 100% bio-derived carbon isotope ratio. Thus, the bio-derived
monomers may be
used for the synthesis of polymers having from 1% to 99.9% bio-derived carbon.
The bio-
derived polymers, then, are suited for use in the sustainable composition.
According to other
embodiments, the bio-derived monomers may be used for the synthesis of
polymers having from
50% to 99.9% biobased carbon. Thus, the glycerol and carbohydrate starting
materials described
herein will necessarily be derived from biological sources. For example, bio-
derived glycerol
containing 100% bio-derived carbon, as determined by ASTM Method D 6866, may
be obtained
from triglycerides (triacylglycerols) from biological sources, for example, a
vegetable oil or an
animal fat, by splitting the triglyceride into the corresponding fatty acids
and glycerol.
Triglycerides may be converted into the corresponding fatty acids and glycerol
by acidic
hydrolysis, basic hydrolysis (saponification) or by a catalytic de-
esterification. Suitable
triglycerides for use in the formation of bio-derived glycerol include, but
are not limited to, corn
oil, soybean oil, canola oil, vegetable oil, safflower oil, sunflower oil,
nasturtium seed oil,
mustard seed oil, olive oil, sesame oil, peanut oil, cottonseed oil, rice bran
oil, babassu nut oil,
castor oil, palm oil, palm kernel oil, rapeseed oil, low erucic acid rapeseed
oil, lupin oil, jatropha
oil, coconut oil, flaxseed oil, evening primrose oil, jojoba oil, tallow, beef
tallow, butter, chicken
fat, lard, dairy butterfat, shea butter, biodiesel, used frying oil, oil
miscella, used cooking oil,
yellow trap grease, hydrogenated oils, derivatives of these oils, fractions of
these oils, conjugated
derivatives of these oils, and mixtures of any thereof.
Suitable bioderived olefins include, but are not limited to monoacrylates,
diacrylates, and
ally' esters.
Alternatively, bio-derived glycerol may be produced as a co-product of
biodiesel
production. Glycerol produced by these methods will have a carbon isotope
ratio consistent with
a 100% bio-derived product and will provide a renewable source of acrolein and
acrylic acid that
may be used as a feedstock for the bio-derived monomers and polymers for use
in the sustainable
compositions. Non-limiting examples of methods and processes for producing
biodiesel may be
found in U.S. Pat. No. 5,354,878; U.S. Patent Application Publication Nos.
20050245405A1;
2007-0181504; and 20070158270A1; Provisional Patent Application Ser. No.
60/851,575, the
disclosures of which are incorporated in their entirety by reference herein.
The monomers and polymers, as set forth herein, may have up to 100% biobased
carbon
isotope ratio as determined by ASTM Method D 6866. The monomers and polymers
may be
-
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72
differentiated from, for example, similar monomers and polymers comprising
petroleum derived
components by comparison of the carbon isotope ratios, for example, the
14C/12C or the 13c/12c
carbon isotope ratios, of the materials. As described herein, isotopic ratios
may be determined,
for example, by liquid scintillation counting, accelerator mass spectrometry,
or high precision
isotopic ratio mass spectrometry.
Bio-derived acrylic acid (or acrylate esters), for example acrylic acid and
esters
synthesized by any of the embodiments described herein, may be esterified (or
transesterified)
with other bio-derived alcohols, diols, or polyols. Non-limiting suitable bio-
derived alcohols and
diols include, for example, methanol; ethanol; n-butanol, for example from an
acetone/butanol
fermentation; fusel oil alcohols (n-propanol, isobutyl alcohol, isoamyl
alcohol, and/or furfural);
and alcohol and diol derivatives derived from carbohydrates or their
derivatives.
Non-limiting examples of carbohydrate derived diols include
hydroxymethylfurfuryl, 2,5-
bis(hydroxymethyl)furan, 2,5-bis(hydroxymethyl)tetrahydrofuran, and isosorbide
(dianhydrohexitol), isomannide, mannitol, xylitol, maltitol, maltitol syrup,
lactitol, erythritol,
isomalt, isoidide (the dianhydrohexitol of iditol), or ethoxylated or
propoxylated derivatives of
these.
Diacrylate esters may be produced from carbohydrate derived diols and may act
as
monomers or co-monomers having 100% bio-derived carbons, as determined by ASTM
Method
D 6866, for the synthesis of polymers having up to 100% biobased carbon and
being suitable for
use in the sustainable compositions.
Other embodiments of bio-derived diols suitable for producing diacrylate
esters having
100% biobased carbon may be produced from fatty acids, such as, for example,
unsaturated fatty
acids. For example, hydroformylation of unsaturated fatty acids and their
derivatives to produce
fatty acid derivatives having a hydroxymethylene group is described in U.S.
Pat. No. 3,210,325
to De Witt et al., the disclosure of which is incorporated in its entirety by
reference herein.
Reduction of the carbonyl of the fatty acid derivative, for example, by
hydrogenation, produces a
biobased diol suitable for esterification or transesterification with acrylic
acid or an acrylate ester,
as produced herein, to form a biobased diacrylate monomer.
Additionally, bio-derived diols suitable for producing diacrylate esters
having 100% bio-
derived carbon may be produced by epoxidation of at least one of the double
bonds of an
unsaturated fatty acid/ester or unsaturated fatty alcohol. One non-limiting
example of the
epoxidation procedure is described by Rao et al., Journal of the American Oil
Chemists' Society,
(1968), 45(5), 408, the disclosure of which is incorporated in its entirety by
reference herein.
The epoxidation may be followed by reduction, for example, by hydrogenation,
to open the
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73
epoxide to the alcohol, which may also include reduction of the carbonyl of
the fatty acid/ester to
the alcohol. Any biobased diol may then be esterified or transesterified with
acrylic acid or an
acrylate ester, as produced herein, to form a diacrylate monomer having 100%
biobased carbon.
Still further, diols suitable for producing diacrylate esters having 100%
biobased carbon
may be produced by reduction of a,w-dicarboxylic acids. As used herein, the
term a,w-
dicarboxylic acid" includes organic molecules comprising a carbon chain of at
least 1 carbon
atom and two carboxylic acid functional groups, each of which is positioned at
opposite ends of
the carbon chain. For example, a,w-dicarboxylic acids may be produced by a
fermentation
process involving biobased fatty acids, such as, by a fermentation process as
described in Craft,
et al., Applied and Environmental Microbiology, (2003), 69(10), 5983-5991
and/or U.S. Pat. No.
6,569,670 to Anderson et al., the disclosures of which are incorporated in
their entirety by
reference herein. Other a,co-dicarboxylic acids from biobased sources, such
as, for example,
maleic acid, fumaric acid, oxalic acid, malonic acid, adipic acid, succinic
acid, and glutaric acid,
adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid may
also be used in the
sustainable compositions. According to certain embodiments, the a,w-
dicarboxylic acid may be
an unsaturated a,w-dicarboxylic acid or a saturated a,w-dicarboxylic acid.
Reduction of the
carbonyls of the a,w-dicarboxylic acids provides a biobased diol which may
then be esterified or
transesterified with acrylic acid or an acrylate ester, as produced herein, to
form a biobased
diacrylate monomer.
Still further, bioderived diacrylamide derivatives may serve as monomers for
the
polymerization reactions described herein. For example, according to certain
embodiments, the
diol component in the formation of the diacrylate esters described herein, may
be chemically
converted to a bio-derived diamine, for example, by a double Mitsunobu-type
reaction. Non-
limiting examples of resulting biobased diamines may include, for example, bis-
amino
isosorbide, 2,5-bisaminomethyltetrahydrofuran, 2,5-bisaminomethylfuran.
Alternatively,
naturally occurring bioderived diamines, such as, for example, 1,4-
diaminobutane, 1,5-
diaminopentane, or other alkyldiamines or diamine containing alkaloid
derivatives, may be
replace the diol reactant in the reaction with the bioderived acrylate
derivative to form a diacryl
amide compound. Further, it is also contemplated that bioderived amino
alcohols may replace
the diol component in the formation of the biobased monomers. According to
these
embodiments, the bioderived amino alcohols may be reacted with the bioderived
acrylic acid or
bioderived acrylate esters to form a bioderived monomer possessing both an
acrylate ester and an
acrylamide functionality.
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Bioderived diacryl derivatives, such as the diacrylate esters, diacrylamides,
and
acrylate/acrylamide monomers may serve as monomers or co-monomers in a
polymerization
reaction to produce a bio-derived polymer for inclusion in the sustainable
compositions. For
example, an olefin metathesis polymerization reaction may be used to produce
the biobased
polymer. As used herein, the term "metathesis polymerization" includes an
olefin metathesis
reaction involving a metal carbene acting as a catalyst to metathesize alkene
monomers or co-
monomers into a polyunsaturated polymer through a metallocyclobutane
intermediate. Thus, a
polymer comprising a product from an olefin metathesis polymerization reaction
of a bioderived
olefin and a diacrylate ester of a bioderived diol may be used, wherein the
diacrylate ester is
produced by reacting a bioderived diol with at least two equivalents of bio-
derived acrylic acid or
an acrylate ester derived from a bioderived glycerol. The olefin metathesis
polymerization
reaction may be catalyzed by an olefin metathesis catalyst, such as a metal
carbene catalyst, for
example, metal carbenes of molybdenum or ruthenium. Commercially available
olefin
metathesis catalysts suitable for use in the polymerization reactions of the
present disclosure
include, but are not limited to, the "Schrock catalyst" (i.e.,
[Mo(=CHMe2Ph)(=N¨
Ar)(0CMe(CF3)2)21), the "1st generation Grubb's catalyst" (i.e.,
[Ru(=CHPh)C12(PCy3)2]), and
the "2nd generation Grubb's catalyst" (i.e, [Ru(=CHPh)C12PCy3(N,N'-diary1-2-
imidazolidiny1)])
(Me=methyl, Ph=phenyl, Ar=aryl, and Cy=cyclohexyl). Other olefin metathesis
catalysts that
may be suitable include those catalysts set forth in U.S. Pat. 7,034,096 to
Choi et al. at column
12, line 27 to column 19, line 2, the disclosure of which is incorporated in
its entirety by
reference herein. It should be noted that the polymers and polymerization
process described in
the present disclosure are not limited to a particular olefin metathesis
catalyst(s) and that any
olefin metathesis catalyst, either currently available or designed in the
future, may be suitable for
use in various embodiments of the present disclosure.
Additionally, the bio-derived olefin component of the metathesis
polymerization may be a
bioderived cyclic olefin, wherein the metathesis polymerization reaction is a
ring opening
metathesis polymerization ("ROMP") reaction. As used herein, the term "ring
opening
metathesis polymerization reaction" includes olefin metathesis polymerization
reactions wherein
at least one of the monomer alkene units comprises a cyclic olefin. Thus, the
ROMP reaction
may react a bioderived diacryl derivative with a bioderived cyclic olefin to
produce a polymer
that is up to 100% biobased as determined by ASTM Method D 6866. Bio-derived
cyclic olefins
may be prepared, for example, from palmitoleic acid, oleic acid, erucic acid,
linoleic acid,
linolenic acid, arachidonic acid, eicosapentaenoic acid, docosahexaenoic acid,
and other
unsaturated fatty acids.
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Further processes for producing bio-derived acrylic acid, acrylic acid esters,
and acrylate
polymers are disclosed in WO 2011/002284; US 7,928,148; US 2009/0018300; EP
1710227, and
Xu et al, "Advances in the Research and Development of Acrylic Acid Production
from
Biomass," Chinese J. Chem. Eng., vol. 14, pp. 419-427 (2006), all of which are
incorporated
5 herein in their entirety.
Thickening Agent
The sustainable compositions may comprise a thickener system. A particularly
preferred
thickener for use in the compositions herein comprises xanthan gum or similar
material and a co-
thickener such as an associative polymer or water soluble silicates. The
thickener system may
10 constitute from about 0.1% to about 15% by weight of the composition.
Suitable thickening agents are viscoelastic, thixotropic thickening agents.
The
viscoelastic, thixotropic thickening agent in the compositions of the present
invention is from
about 0.1% to about 10%, preferably from about 0.25% to about 8%, most
preferably from about
0.5% to about 5%, by weight of the detergent composition. Preferably, the
thickening agents are
15 bio-derived.
Suitable thickeners which can be used in this composition include natural
gums, such as
xanthan gum, locust bean gum, guar gum, and the like. In one embodiment,
xanthan gums are
utilized. Xanthan gums are biopolysaccharides and suitable xanthan gums
include, without
limitation, products sold by Kelco Corporation under the trade names KELTROL ,
such as
20 KETROL RD and KELTROL CG-SFT and KELZAN as well as products sold by
Rhodia
under the trade names RHODIPOL , RHODIGEL" and RHODICARE", such as
RHODICAREe T.
The cleaning detergent composition may comprise water-soluble silicates. Water-
soluble
silicates herein are any silicates which are soluble to the extent that they
do not adversely affect
25 spotting/filming characteristics of the sustainable composition.
Aluminosilicate builders can be
used in the present compositions though are not preferred for automatic
dishwashing detergents.
The soluble silicate is typically used in an amount of about 0.4% to about
4.0% by
weight; more preferably is present in an amount of about 0.75% to about 3% by
weight and most
preferably present in an amount of about 1% to about 2% by weight, based on
the total weight of
30 the composition.
The associative thickener is typically an addition polymer of three
components: (1) an
alpha-beta-monoethylenically unsaturated monocarboxylic acid or dicarboxylic
acid of from 3 to
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8 carbon atoms such as bio-derived acrylic acid or bio-derived methacrylic
acid to provide water
solubility; (2) a monoethylenically unsaturated copolymerizable monomer
lacking surfactant
capacity such as bio-derived methyl acrylate or bio-derived ethyl acrylate to
obtain the desired
polymer backbone and body characteristics; and (3) a monomer possessing
surfactant capacity
which provides the pseudo plastic properties to the polymer and is the
reaction product of a
monoethylenically unsaturated monomer with a nonionic surfactant compound
wherein the
monomer is copolymerizable with the foregoing monomers such as the reaction
product of bio-
derived methacrylic acid with a monohydric nonionic surfactant to obtain a
monomer such as
CH3(CH2)is-17(OCH2CH2)e0OCC(CH3)=CH2, where "e" has an average value of about
10 or 20.
Optionally, up to about 2.0% of a polyethylenically unsaturated monomer sloth
as bio-derived
ethylene glycol diacrylate or dimethacrylate or divinylbenzene can be included
if a higher
molecular weight polymer is desired.
Additional associative thickeners include bio-derived maleic anhydride
copolymers
reacted with nonionic surfactants such as bio-derived ethoxylated C12-C14
primary alcohol,
similar to the compounds available under the tradename Surfonic L Series from
Texaco
Chemical Co. and the tradename Gantrez AN-119 from ISP.
The associative thickeners may include C10¨C22 alkyl groups in an alkali-
soluble acrylic
emulsion polymer such as those available under the trademark AcusoI from Rohm
& Haas
Co. of Philadelphia, Pa. The most preferred associative thickeners are Acusol
820 ("820") and
1206A ("1206A"). Acusol 820 is a 30.0% active emulsion polymer of 40.0%
methacrylic acid,
50% ethyl acrylate and 10.0% stearyl oxypoly ethyl methacrylic emulsion
polymer having
approximately 20 moles of ethylene oxide. Acusol 1206A is a 30% active
emulsion polymer
with 44% methacrylic acid, 50% ethyl acrylate and 6% stearyl methacrylate
polymer having
about 10 moles of ethylene oxide. These polymers are described in U.S. Pat.
No. 4,351,754 to
Dupre. Most preferably, the associative thickeners are provided as 100% bio-
derived analogs of
these commercially available products.
The associative thickener is typically used in an amount of about 0.01% to
about 1.0% by
weight; more preferably is present in an amount of about 0.05% to about 0.5%
by weight and
most preferably present in an amount of about 0.1% to about 0.3% by weight,
based on the total
weight of the sustainable composition.
In addition to the xanthan gum thickener, other thickeners may be utilized.
Suitable are
various carboxyvinyl polymers, homopolymers and copolymers are commercially
available from
B. F. Goodrich Company, New York, N.Y., under the trade name CARBOPOLe. These
polymers are also known as carbomers or polyacrylic acids. Carboxyvinyl
polymers useful in
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formulations of the present invention include CARBOPOL 910 having a molecular
weight of
about 750,000, CARBOPOL 941 having a molecular weight of about 1,250,000, and
CARBOPOLe 934 and 940 having molecular weights of about 3,000,000 and
4,000,000,
respectively. More preferred are the series of CARBOPOL which use ethyl
acetate and
cyclohexane in the manufacturing process, for example, CARBOPOL 981, 2984,
980, and
1382. Analogous compounds may be produced from bio-derived carbon sources and
may be
used in the sustainable compositions in preferred embodiments.
Further suitable additional thickeners include polycarboxylate polymers of the
invention
are non-linear, water-dispersible, polyacrylic acid cross-linked with a
polyalkenyl polyether and
having a molecular weight of at lease 750,000, preferably from about 750,000
to about
4,000,000, all preferably bio-derived. Suitable examples of these
polycarboxylate polymers
include are SOKALAN PHC-25 , a polyacrylic acid available from BASF
Corporation and the
POLYGEL series available from 3-V Chemical Corporation. Mixtures of
polycarboxylate
polymers may also be used.
Semi-synthetic thickeners such as the cellulosic type thickeners: hydroxyethyl
and
hydroxymethyl cellulose (ETHOCEL and METHOCEL available from Dow Chemical)
can
also be used. Preferably the semi-synthetic thickeners are obtained from bio-
derived sources of
carbon. Mixtures of inorganic clays (e.g., aluminum silicate, bentonite, fumed
silica) are also
suitable for use as a thickener herein. The preferred clay thickening agent
can be either naturally
occurring or synthetic. An example of a suitable synthetic clay is disclosed
in the U.S. Pat. No.
3,843,598. Naturally occurring clays further include some smectite and
attapulgite clays as
disclosed in U.S. Pat. No. 4,824, 590.
Other suitable organic polymer for use herein includes a polymer comprising an
acrylic
acid backbone and alkoxylated side chains, the polymer having a molecular
weight of from about
2,000 to about 20,000, and said polymer having from about 20 wt% to about 50
wt% of an
alkylene oxide, preferably a bio-derived alkylene oxide. The polymer should
have a molecular
weight of from about 2,000 to about 20,000, or from about 3,000 to about
15,000, or from about
5,000 to about 13,000. The alkylene oxide (AO) component of the polymer is
generally
propylene oxide (PO) or ethylene oxide (E0), preferably bio-derived EO and/or
bio-derived PO,
and generally comprises from about 20 wt% to about 50 wt%, or from about 30
wt% to about
45 wt%, or from about 30 wt% to about 40 wt% of the polymer. The alkoxylated
side chains of
the water soluble polymers may comprise from about 10 to about 55 AO units, or
from about 20
to about 50 AO units, or from about 25 to 50 AO units. The polymers,
preferably water. soluble,
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may be configured as random, block, graft, or other known configurations.
Methods for forming
alkoxylated acrylic acid polymers are disclosed in U.S. Patent No. 3,880,765.
Further methods for producing bio-based glycol compositions as synthetic
feedstocks for
bio-derived monomers and bio-derived polymers are disclosed in WO 2008/057220,
incorporated
herein by reference.
Polyvalent Metal Compounds
The sustainable composition may comprise a polyvalent metal compound. Any
suitable
polyvalent metal compound may be used in any suitable amount or form. Suitable
polyvalent
metal compounds include, but are not limited to: polyvalent metal salts,
oxides, hydroxides, and
mixtures thereof. Suitable polyvalent metals include, but are not limited to:
Groups IIA, IIIA,
IVA, VA, VA, VIIA, IIB, IIIB, IVB, VB and VIII of the Periodic Table of the
Elements. For
example, suitable polyvalent metals may include Al, Mg, Co, Ti, Zr, V, Nb, Mn,
Fe, Ni, Cd, Sn,
Sb, Bi, and Zn. These polyvalent metals may be used in any suitable oxidation
state. Suitable
oxidation states are those that are stable in the cleaning sustainable
compositions described
herein.
Any suitable polyvalent metal salt may be used in any suitable amount or form.
Suitable
salts include but are not limited to: organic salts, inorganic salts, and
mixtures thereof. For
example, suitable polyvalent metal may include: water-soluble metal salts,
slightly water-soluble
metal salts, water-insoluble metal salts, slightly water-insoluble metal
salts, and mixtures thereof.
Suitable water-soluble aluminum salts may include, but are not limited to:
aluminum
acetate, aluminum ammonium sulfate, aluminum chlorate, aluminum chloride,
aluminum
chlorohydrate, aluminum diformate, aluminum fluoride, aluminum formoacetate,
aluminum
lactate, aluminum nitrate, aluminum potassium sulfate, aluminum sodium
sulfate, aluminum
sulfate, aluminum tartrate, aluminum triformate, and mixtures thereof.
Suitable water-insoluble
aluminum salts may include, but are not limited to: aluminum silicates,
aluminum salts of fatty
acids (e.g., aluminum stearate and aluminum laurate), aluminum metaphosphate,
aluminum
monostearate, aluminum oleate, aluminum oxylate, aluminum oxides and
hydroxides (e.g.,
activated alumina and aluminum hydroxide gel), aluminum palmitate, aluminum
phosphate,
aluminum resinate, aluminum salicylate, aluminum stearate, and mixtures
thereof.
Suitable water-soluble magnesium salts may include, but are not limited to:
magnesium
acetate, magnesium acetylacetonate, magnesium ammonium phosphate, magnesium
benzoate,
magnesium biophosphate, magnesium borate, magnesium borocitrate, magnesium
bromate,
magnesium bromide, magnesium calcium chloride, magnesium chlorate, magnesium
chloride,
magnesium citrate, magnesium fluosilicate, magnesium formate, magnesium
gluconate,
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magnesium glycerophosphate, magnesium lauryl sulfate, magnesium nitrate,
magnesium
phosphate monobasic, magnesium salicylate, magnesium stannate, magnesium
stannide,
magnesium sulfate, magnesium sulfite, and mixtures thereof. Suitable water-
insoluble
inagnesium salts may include, but are not limited to: magnesium aluminate,
magnesium fluoride,
magnesium oleate, magnesium perborate, magnesium phosphate dibasic, magnesium
phosphate
tribasic, magnesium pyrophosphate, magnesium silicate, magnesium trisilicate,
magnesium
sulfide, magnesium tripolyphosphate, and mixtures thereof.
Suitable water-soluble zinc salts may include, but are not limited to: zinc
acetate, zinc
benzoate, zinc borate, zinc bromate, zinc bromide, zinc chlorate, zinc
chloride, zinc ethysulfate,
zinc fluorosilicate, zinc formate, zinc gluconate, zinc hydrosulfite, zinc
lactate, zinc linoleate,
zinc malate, zinc nitrate, zinc perborate, zinc salicylate, zinc sulfate, zinc
sulfamate, zinc tartrate,
and mixtures thereof. Suitable water-insoluble zinc salts may include, but are
not limited to: zinc
bacitracin, zinc carbonate, zinc basic carbonate or basic zinc carbonate,
hydrozincite, zinc
laurate, zinc phosphate, zinc tripolyphosphate, sodium zinc tripolyphosphate,
zinc silicate, zinc
stearate, zinc sulfide, zinc sulfite, and mixtures thereof.
Any suitable polyvalent metal oxide and/or hydroxide may be used in any
suitable
amount or form. Suitable polyvalent metal oxides may include, but are not
limited to: aluminum
oxide, magnesium oxide, and zinc oxide. Suitable polyvalent metal hydroxides
may include, but
are not limited to: aluminum hydroxide, magnesium hydroxide, and zinc
hydroxide.
In certain non-limiting embodiments, polyvalent metal compounds may be used in
their
water-insoluble form. The presence of the polyvalent metal compounds in an
essentially
insoluble but dispersed form may inhibit the growth of large precipitates from
within cleaning
detergent product and/or wash liquor solution. Not to be bound by theory, it
is believed that
because the water-insoluble polyvalent metal compound is in a form in product
that is essentially
insoluble, the amount of precipitate, which will form in the wash liquor of
the dishwashing
process, is greatly reduced. Although the insoluble polyvalent metal compound
will dissolve
only to a limited extent in the wash liquor, the dissolved metal ions are in
sufficient concentration
to impart the desired glasscare benefit to treated dishware. Hence, the
chemical reaction of
dissolved species that produce precipitants in the dishwashing process is
controlled. Thus, use of
water-insoluble polyvalent metal compounds allows for control of the release
of reactive metal
species in the wash liquor, as well as, the control of unwanted precipitants.
In certain non-limiting embodiments, the amount of polyvalent metal compound
may be
provided in a range of from about 0.01% to about 60%, from about 0.02% to
about 50%, from
about 0.05% to about 40%, from about 0.05% to about 30%, from about 0.05% to
about 20%,
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from about 0.05% to about 10%, and alternatively, from about 0.1% to about 5%,
by weight, of
the sustainable composition.
Natural Thickener
The sustainable compositions can also comprise an auxiliary nonionic or
anionic
5 polymeric thickening component, especially cellulose thickening polymers,
especially a water-
soluble or water dispersible polymeric materials, having a molecular weight
greater than 20,000.
The cellulose thickening polymers preferably contain bio-derived cellulose. By
"water-soluble
or water dispersible polymer" is meant that the material will form a
substantially clear solution in
water at a 0.5 to 1 weight percent concentration at 25 C and the material
will increase the
10 viscosity of the water either in the presence or absence of surfactant.
Examples of water-soluble
polymers which may desirably be used as an additional thickening component in
the present
compositions, are hydroxyethylcellulose, hydroxypropyl cellulose,
hydroxypropyl
methylcellulose, dextrans, for example Dextran purified crude Grade 2P,
available from D&O
Chemicals, carboxymethyl cellulose, plant exudates such as acacia, ghatti, and
tragacanth,
15 seaweed extracts such as sodium alginate, and sodium carrageenan.
Preferred as the additional
thickeners for the present compositions are bio-derived polysaccharide or
cellulose materials.
Examples of such materials include, but are limited to, guar gum, locust bean
gum, xanthan gum
and mixtures thereof. The sustainable composition also may contain an anti-
redeposition
polymer. Examples of anti- redeposition polymers include, but are not limited
to, inulin,
20 derivatized inulin, guar and derivatized guar. Also suitable for use in
the sustainable
compositions is hydroxyethyl cellulose, preferably bio-derived, having a
molecular weight of
about 700,000. The thickeners are generally present in amounts of about 0.05
to about 2.0
weight percent, or about 0.1 to about 2.0 weight percent.
Low levels of polymer can also be used to thicken the preferred aqueous
compositions of
25 the present invention. In general, the level of thickening polymer is
kept as low as possible so as
not to hinder the product's end result properties. Xanthan gum is a
particularly preferred
thickening agent as it can also enhance end result properties, particularly
when used in low
concentrations. Moreover, xanthan gum is bio-derived. The thickening polymer
agent is present
in from about 0.001% to about 0.1%, more preferably from about 0.0025% to
about 0.05%, most
30 preferably from about 0.005% to about 0.025%, by weight of the
composition.
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81
=
Natural Essence
The sustainable compositions of the present invention may include a bio-
derived "natural
essence". As used herein, "natural essence" is intended to include a broader
class of natural
products comprising natural oils extracted from plants and trees and their
fruits, nuts and seeds,
(for example by steam or liquid extraction of ground-up plant/tree material),
natural products that
may be purified by distillation, (i.e., purified single organic molecules or
close boiling point
"cuts" of organic materials such as terpenes and the like), and synthetic
organic materials that are
the synthetic versions of naturally occurring materials (e.g., either
identical to the natural
material, or the optical isomer, or the racemic mixture). Synthetic versions
of naturally occurring
materials preferably are synthesized from bio-derived carbon sources. An
example of the
synthetic essence is D,L-limonene that is synthetically prepared and is a good
and eco-friendly
substitute for natural orange oil (mostly D-limonene) when citrus is
expensive, for example,
because of crop freezes.
Thus, it should be understood that "natural essence" incorporates a wide range
of pure
organic materials either natural or synthetic versions thereof, mixtures of
these previously
purified individual materials or distillate cuts of materials, and complex
natural mixtures directly
extracted from plant/tree materials through infusion, steam extraction, etc.
Also, it should be
understood that these natural essence ingredients may double as fragrance
materials for the
sustainable composition, and in fact many natural extracts, oils, essences,
infusions and such are
very fragrant materials. However, for use in the present sustainable
compositions, these
materials are used at higher levels than would be typical for fragrance
purposes, and it should be
also understood that depending on optical isomers used, there may be no smell
or a reduced
smell, or even a masking effect to the human sensory perception. Thus by
judicious choice of
natural essence mixtures, performance boosting may be effected without making
the
compositions overwhelmingly scented. Also, actual fragrance masking materials
(such as used
for household cleaners and available from the fragrance supply houses such as
International
Flavors & Fragrances, Symrise, Givaudan, Firmenich, and others) may be added
to mask the
smells of the natural essences.
Some of the naturally derived essences for use in the sustainable compositions
include,
but are not limited to, musk, civet, ambergis, castoreum and similar animal
derived oils; abies oil,
ajowan oil, almond oil, ambrette seed absolute, angelic root oil, anise oil,
basil oil, bay oil,
benzoin resinoid, bergamot oil, birch oil, bois de rose oil, broom abs.,
cajeput oil, cananga oil,
capsicum oil, caraway oil, cardamon oil, carrot seed oil, cassia oil, cedar
leaf oil, cedar wood oil,
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celery seed oil, cinnamon bark oil, citronella oil, clary sage oil, clove oil,
cognac oil, coriander
oil, cubeb oil, cumin oil, camphor oil, dill oil, elemi gum, estragon oil,
eucalyptol nat., eucalyptus
oil, fennel sweet oil, galbanum res., garlic oil, geranium oil, ginger oil,
grapefruit oil, hop oil,
hyacinth abs., jasmin abs., juniper berry oil, labdanum res., lavender oil,
laurel leaf oil, lavender
Synthetic essences include but are not limited to pinene, limonene and like
hydrocarbons;
3,3,5-trimethylcyclohexanol, linalool, geraniol, nerol, citronellol, menthol,
borneol, borneyl
methoxy cyclohexanol, benzyl alcohol, anise alcohol, cinnamyl alcohol, 3-
phenyl ethyl alcohol,
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83
acetate, methyl anthranilate, methyl dihydrojasmonate, nopyl acetate, P-
phenylethyl acetate,
trichloromethylphenyl carbinyl acetate, terpinyl acetate, vetiveryl acetate,
and the like.
Suitable essence mixtures may produce synergistic performance attributes for
the
sustainable composition and may help to impart an overall fragrance perception
as well to the
composition including but not limited to, fruity, musk, floral, herbaceous
(including mint), and
woody, or perceptions that are in-between (fruity-floral for example).
Typically these essence or
essential oil mixtures may be compounded by mixing a variety of these active
extract or synthetic
materials along with various solvents to adjust cost, viscosity, flammability,
ease of handling, etc.
Since many natural extract ingredients are compounded into fragrances, the
essential oils,
infusions, distillates, etc. that are considered "natural essences" are also
available from the
fragrance companies such as International Flavors & Fragrances, Givaudan,
Symrise, Firmenich,
Robertet, and many others. The natural essences are preferably incorporated at
a level of from
about 0.1% to about 5% as the 100% neat substance or mixture of substances. It
is important to
note that these levels tend to be greater than those levels used for scenting
a product with a
perfume.
Fragrances
The sustainable compositions can contain fragrances, especially fragrances
containing
essential oils, and especially fragrances containing D-limonene or lemon oil;
or natural essential
oils or fragrances containing D-limonene or lemon oil. Lemon oil and D-
limonene compositions
which are useful in the sustainable compositions include mixtures of terpene
hydrocarbons
obtained from the essence of oranges, e.g., cold-pressed orange terpenes and
orange terpene oil
phase from fruit juice, and the mixture of terpene hydrocarbons expressed from
lemons and
grapefruit. The essential oils may contain minor, non-essential amounts of
hydrocarbon carriers.
Suitably, the fragrance contains essential oil or lemon oil or D-limonene in
the sustainable
composition in an amount ranging from about 0.01 wt.% to about 5.0 wt.%, from
about
0.01 wt.% to about 4.0 wt.%, from about 0.01 wt.% to about 3.0 wt.%, from
about 0.01 wt.% to
about 2.0 wt.%, from about 0.01 wt.% to about 1.0 wt.%, or from about 0.01
wt.% to about
0.50 wt.%, or from about 0.01 wt.% to about 0.40 wt.%, or from about 0.01 wt.%
to about
0.30 wt.%, or from about 0.01 wt.% to about 0.25 wt.%, or from about 0.01 wt.%
to about
0.20 wt.%, or from about 0.01 wt.% to about 0.10 wt.%, or from about 0.05 wt.%
to about
2.0 wt.%, or from about 0.05 wt.% to about 1.0 wt.%, or from about 0.5 wt.% to
about 1.0 wt.%,
or from about 0.05 wt.% to about 0.40 wt.%, or from about 0.05 wt.% to about
0.30 wt.%, or
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from about 0.05 wt.% to about 0.25 wt.%, or from about 0.05 wt.% to about 0.20
wt.%, or from
about 0.05 wt.% to about 0.10 wt.%.
The sustainable compositions may further comprise a perfume. In a particularly
preferred
embodiment the sustainable compositions comprise different perfumes such that
the user will
gain a different olfactory experience, for example, when the sustainable
compositions are
contained within different types of dosing devices such as pouches.
The sustainable compositions may also comprise a blooming perftime. A blooming
perfume composition is one which comprises blooming perfume ingredients. A
blooming
perfume ingredient may be characterized by its boiling point (B.P.) and its
octanol/water partition
coefficient (P). As used in this context, "boiling point" refers to boiling
point measured under
normal standard pressure of 760 mmHg. The boiling points of many perfume
ingredients, at
standard 760 mm Hg are given in, e.g., "Perfume and Flavor Chemicals (Aroma
Chemicals),"
Steffen Arctander, published by the author, 1969, incorporated herein by
reference.
The octanol/water partition coefficient of a perfume ingredient is the ratio
between its
equilibrium concentrations in octanol and in water. The partition coefficients
of the preferred
perfume ingredients may be more conveniently given in the form of their
logarithm to the base
10, logP. The logP values of many perfume ingredients have been reported; for
example, the
Pomona92 database, available from Daylight Chemical Information Systems, Inc.
(Daylight
CIS), Irvine, Calif., contains many, along with citations to the original
literature. However, the
logP values are most conveniently calculated by the "CLOGP" program, also
available from
Daylight CIS. This program also lists experimental logP values when they are
available in the
Pomona92 database. The "calculated logP" (ClogP) is determined by the fragment
approach of
Hansch and Leo (cf., A. Leo, in Comprehensive Medicinal Chemistry, Vol. 4, C.
Hansch, P. G.
Sammens, J. B. Taylor and C. A. Ramsden, Eds., p. 295, Pergamon Press, 1990,
incorporated
herein by reference). The fragment approach is based on the chemical structure
of each perfume
ingredient, and takes into account the numbers and types of atoms, the atom
connectivity, and
chemical bonding. The ClogP values, which are the most reliable and widely
used estimates for
this physicochemical property, are preferably used instead of the experimental
logP values in the
selection of perfume ingredients which are useful in sustainable compositions.
The perfume, if present in the sustainable composition, may preferably
comprise at least
two perfume ingredients. The first perfume ingredient is characterized by a
boiling point of
250 C or less and ClogP of 3.0 or less. More preferably the first perfume
ingredient has boiling
point of 240 C or less, most preferably 235 . C or less. More preferably the
first perfume
ingredient has a ClogP value of less than 3.0, more preferably 2.5 or less.
The first perfume
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ingredient is present at a level of at least 7.5% by weight of the
composition, more preferably at
least 8.5% and most preferably at least 9.5% by weight of the composition.
The second perfume ingredient, if present in the sustainable composition, may
be
characterized by a boiling point of 250 C or less and ClogP of 3.0 or more.
More preferably the
5 second perfume ingredient has boiling point of 240 C or less, most
preferably 235 C or less.
More preferably the second perfume ingredient has a ClogP value of greater
than 3.0, even more
preferably greater than 3.2. The second perfume ingredient is present at a
level of at least 35%
by weight of the composition, more preferably at least 37.5% and most
preferably greater than
40% by weight of the perfume composition.
10 More preferably the perfume, when present in the sustainable
composition, may comprise
a plurality of ingredients chosen from the first group of perfume ingredients
and a plurality of
ingredients chosen from the second group of perfume ingredients. In addition
to the above, it is
the sustainable composition may comprise at least one perfume ingredient
selected from either
first and/or second perfume ingredients, which are present in an amount of at
least 7% by weight
15 of the perfume composition, preferably at least 8.5% of the perfume
composition, and most
preferably, at least 10% of the perfume composition.
The first and second perfume ingredients may be selected from the group
consisting of
esters, ketones, aldehydes, alcohols, derivatives thereof and mixtures
thereof. Preferred
examples of the first and second perfume ingredients can be found in PCT
application number
20 US00/19078 (Applicants case number CM2396F). Preferably, the perfume
ingredients comprise
or consist of natural or bio-derived substances.
In the perfume art, some auxiliary materials having no odor, or a low odor,
are used, e.g.,
as solvents, diluents, extenders or fixatives. Non-limiting examples of these
materials are ethyl
alcohol, carbitol, diethylene glycol, dipropylene glycol, diethyl phthalate,
triethyl citrate,
25 isopropyl myristate, and benzyl benzoate, any or all of which may be bio-
derived substances.
These materials are used for, e.g., solubilizing or diluting some solid or
viscous perfume
ingredients to, e.g., improve handling and/or formulating. These materials are
useful in the
blooming perfume compositions, but are not counted in the calculation of the
limits for the
definition/formulation of the blooming perfume compositions of the present
invention.
30 It can be desirable to use blooming and delayed blooming perfume
ingredients and even
other ingredients, preferably in small amounts, in the blooming perfume
compositions of the
present invention, that have low odor detection threshold values. The odor
detection threshold of
an odorous material is the lowest vapor. concentration of that material which
can be detected. The
odor detection threshold and some odor detection threshold values are
discussed in, e.g.,
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86
"Standardized Human Olfactory Thresholds", M. Devos et al, IRL Press at Oxford
University
Press, 1990, and "Compilation of Odor and Taste Threshold Values Data", F. A.
Fazzalari,
editor, ASTM Data Series DS 48A, American Society for Testing and Materials,
1978, both of
said publications being incorporated by reference. The use of small amounts of
non-blooming
perfume ingredients that have low odor detection threshold values can improve
perfume odor
character, without the potential negatives normally associated with such
ingredients, e.g.,
spotting and/or filming on, e.g., dish surfaces. Non-limiting examples of
perfume ingredients
that have low odor detection threshold values useful in the present invention
include coumarin,
vanillin, ethyl vanillin, methyl dihydro isojasmonate, 3-hexenyl salieylate,
isoeugenol, lyral,
gamma-undecalactone, gamma-dodecalactone, methyl beta naphthyl ketone, and
mixtures
thereof. These materials are preferably present at low levels in addition to
the blooming and
optionally delayed blooming ingredients, typically less than 5%, preferably
less than 3%, more
preferably less than 2%, by weight of the blooming perfume compositions of the
present
invention. Preferably, these materials are obtained from sources of bio-
derived carbon.
The perfumes suitable for use in the sustainable compositions herein can be
formulated
from known fragrance ingredients and for purposes of enhancing environmental
compatibility,
the perfume compositions used herein are preferably substantially free of
halogenated fragrance
materials and nitromusks.
Alternatively the perfume ingredients or a portion thereof, when present in
the sustainable
composition, may be complexed with a complexing agent. Complexing agents may
include any
compound which encapsulate or bind perfume raw materials in aqueous solution.
Binding can
result from one or more of strong reversible chemical bonding, reversible weak
chemical
bonding, weak or strong physical absorption or adsorption and, for example,
may take the form
of encapsulation, partial encapsulation, or binding. Complexes formed can be
1:1, 1:2, 2:1
complexant:perfume ratios, or can be more complex combinations. It is also
possible to bind
perfumes via physical encapsulation via coating (e.g. starch coating), or
coacervation. Key to
effective complexation for controlled perfume release is an effective de-
complexation
mechanism, driven by use of the product for washing dishes or hard surfaces.
Suitable de-
complexation mechanisms can include dilution in water, increased or decreased
temperature,
increased or decreased ionic strength. It is also possible to chemically or
physically decompose a
coated perfume, eg via reaction with enzyme, bleach or alkalinity, or via
solubilization by
surfactants or solvents. Preferred complexing agents include cyclodextrin,
zeolites, coacervates
starch coatings, and mixtures thereof.
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Cyclodextrin molecules are known for their ability to form complexes with
perfume
ingredients and have typically been taught as a perfume carrier. In addition,
cyclodextrin
molecules also appear to be surprisingly effective at reducing malodors
generated by nitrogenous
compounds, such as amines. Cyclodextrins for use herein preferably are bio-
derived molecules
and may be obtained, for example, by enzymatic conversion of natural or plant-
derived starches.
Suitable cyclodextrins are discussed in U.S. Pat. No. 5,578,563, issued Nov.
26, 1996, to
Trinh et al., which is hereby incorporated by reference. The cavity of a
cyclodextrin molecule
has a substantially conical shape. It is preferable in the present invention
that the cone-shaped
cavity of the cyclodextrins have a length (altitude) of 8 A and a base size of
from 5 A to 8.5 A.
Thus the preferred cavity volume for cyclodextrins of the present invention is
from 65 A3 to
210 A3.
Suitable cyclodextrin species include any of the known cyclodextrins such as
unsubstituted cyclodextrins containing from six to twelve glucose units,
especially, alpha-
cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin and/or their derivatives
and/or mixtures
thereof. The alpha-cyclodextrin consists of six glucose units, the beta-
cyclodextrin consists of
seven glucose units, and the gamma-cyclodextrin consists of eight glucose
units arranged in a
donut-shaped ring. The specific coupling and conformation of the glucose units
give the
cyclodextrins a rigid, conical molecular structure with a hollow interior of a
specific volume.
The "lining" of the internal cavity is formed by hydrogen atoms and glycosidic
bridging oxygen
atoms, therefore this surface is fairly hydrophobic. The unique shape and
physical-chemical
property of the cavity enable the cyclodextrin molecules to absorb (form
inclusion complexes
with) organic molecules or parts of organic molecules which can fit into the
cavity. Many
perfume molecules can fit into the cavity.
The cyclodextrin molecules are preferably water-soluble. The water-soluble
cyclodextrins preferably have a water solubility of at least 10 g in 100 mL
water, more preferably
at least 25 g in 100 mL of water at standard temperature and pressure.
Examples of preferred
water-soluble cyclodextrin derivative species are hydroxypropyl alpha-
cyclodextrin, methylated
alpha-cyclodextrin, methylated beta-cyclodextrin, hydroxyethyl beta-
cyclodextrin, and
hydroxypropyl beta-cyclodextrin. Hydroxyalkyl cyclodextrin derivatives
preferably have a
degree of substitution of from 1 to 14, more preferably from 1.5 to 7, wherein
the total number of
OR groups per cyclodextrin is defined as the degree of substitution.
Methylated cyclodextrin
derivatives typically have a degree of substitution of from 1 to 18,
preferably from 3 to 16. A
known methylated beta-cyclodextrin is heptakis-2,6-di-O-methyl-,13-
cyclodextrin, commonly
known as DIMEB, in which each glucose unit has 2 methyl groups with a degree
of substitution
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88
of 14. A preferred, more commercially available methylated beta-cyclodextrin
is a randomly
methylated beta-cyclodextrin having a degree of substitution of 12.6. The
preferred
cyclodextrins are available, e.g., from American Maize-Products Company and
Wacker
Chemicals (USA), Inc. Preferably, the cyclodextrins themselves, as well as any
alkyl
functionality, contain only bio-derived carbon.
Further cyclodextrin species suitable for use in the present invention include
alpha-
cyclodextrin and derivatives thereof, gamma-cyclodextrin and derivatives
thereof, derivatized
beta-cyclodextrins, and/or mixtures thereof. Other derivatives of cyclodextrin
suitable for use in
the sustainable compositions are discussed in U.S. Pat. No. 5,578,563,
incorporated above. It
should be noted that two or more different species of cyclodextrin may be used
in the same liquid
detergent composition.
The complexes may be formed in any of the ways known in the art. Typically,
the
complexes are formed either by bringing the fragrance materials and the
cyclodextrin together in
a suitable solvent e.g. water and ethanol mixtures, propylene glycol,
preferably bio-derived
propylene glycol. Additional examples of suitable processes as well as further
preferred
processing parameters and conditions are disclosed in U.S. Pat. No. 5,234,610,
to Gardlik et al.,
issued Aug. 10, 1993, which is hereby incorporated by reference. After the
cyclodextrin and
fragrance materials are mixed together, this mixture is added to the
sustainable composition.
Generally, only a portion (not all) of the fragrance materials mixed with the
cyclodextrin
will be encapsulated by the cyclodextrin and form part of the
cyclodextrin/perfume complex; the
remaining fragrance materials will be free of the cyclodextrin and when the
cyclodextrin/perfume
mixture is added to the detergent composition they will enter the detergent
composition as free
perfume molecules. A portion of free cyclodextrin molecules which are not
complexed with the
fragrance materials may also be present. In an alternative embodiment of the
present invention,
the fragrance materials and cyclodextrins are added uncomplexed and separately
to the liquid
sustainable compositions. Consequently, the cyclodextrins and fragrance
materials will come
into the presence of each other in the composition, and a portion of each will
combine to form the
desired fragrance materials/cyclodextrin complex.
In general, perfume/cyclodextrin complexes have a molar ratio of perfume
compound to
cyclodextrin of 1:1. However, the molar ratio can be either higher or lower,
depending on the
size of the perfume compound and the identity of the cyclodextrin compound.
For example, the
the molar ratio of fragrance materials to cyclodextrin may be from 4:1 to 1:4,
preferably from
1.5:1 to 1:2, more preferably from 1:1 to 1:1.5. The molar ratio can be
determined easily by
forming a saturated solution of the cyclodextrin and adding the perfume to
form the complex. In
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89
general the complex will precipitate readily. If not, the complex can usually
be precipitated by
the addition of electrolyte, change of pH, cooling, etc. The complex can then
be analyzed to
determine the ratio of perfume to cyclodextrin.
The actual complexes are determined by the size of the cavity in the
cyclodextrin and the
size of the perfume molecule. Although the normal complex is one molecule of
perfume in one
molecule of cyclodextrin, complexes can be formed between one molecule of
perfume and two
molecules of cyclodextrin when the perfume molecule is large and contains two
portions that can
fit in the cyclodextrin. Highly desirable complexes can be formed using
mixtures of
cyclodextrins since perfumes are normally mixtures of materials that vary
widely in size. It is
usually desirable that at least a majority of the material be beta- and/or
gamma-cyclodextrin.
Odor Control Agents
The sustainable compositions may comprise one or more odor control agents, of
which all
or a substantial portion of the carbon atoms in the odor control agents are
bio-derived.
Cyclodextrins are particularly preferred, and may be bio-derived from sources
such as those
described above with respect to the cyclodextrins for complexing perfumes.
For the odor control agents, the term "cyclodextrin" includes any of the known
cyclodextrins such as unsubstituted cyclodextrins containing from six to
twelve glucose units,
especially, alpha-cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin and/or
their derivatives
and/or mixtures thereof. The alpha-cyclodextrin consists of six glucose units,
the beta-
cyclodextrin consists of seven glucose units, and the gamma-cyclodextrin
consists of eight
glucose units arranged in donut-shaped rings. The specific coupling and
conformation of the
glucose units give the cyclodextrins rigid, conical molecular structures with
hollow interiors of
specific volumes. The "lining" of each internal cavity is formed by hydrogen
atoms and
glycosidic bridging oxygen atoms; therefore, this surface is fairly
hydrophobic.
The unique shape and physical-chemical properties of the cavity enable the
cyclodextrin
molecules to absorb (form inclusion complexes with) organic molecules or parts
of organic
molecules which can fit into the cavity. Many odorous molecules can fit into
the cavity
including many malodorous molecules and perfume molecules. Therefore,
cyclodextrins, and
especially mixtures of cyclodextrins with different size cavities, can be used
to control odors
caused by a broad spectrum of organic odoriferous materials, which may, or may
not, contain
reactive functional groups. The complexation between cyclodextrin and odorous
molecules
occurs rapidly in the presence of water. However, the extent of the complex
formation also
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depends on the polarity of the absorbed molecules. In an aqueous solution,
strongly hydrophilic
molecules (those which are highly water-soluble) are only partially absorbed,
if at all. Therefore,
cyclodextrin does not complex effectively with some very low molecular weight
organic amines
and acids when they are present at low levels on wet surfaces. As the water is
being removed
5 however, e.g., the surface is being dried off, some low molecular weight
organic amines and
acids have more affinity and will complex with the cyclodextrins more readily.
The cavities within the cyclodextrin in the solution of the present invention
should remain
essentially unfilled (the cyclodextrin remains uncomplexed) while in solution,
in order to allow
the cyclodextrin to absorb various odor molecules when the solution is applied
to a surface.
10 Non-derivatised (normal) beta-cyclodextrin can be present at a level up
to its solubility limit of
about 1.85% (about 1.85g in 100 grams of water) at room temperature. Beta-
cyclodextrin is not
preferred in compositions which call for a level of cyclodextrin higher than
its water solubility
limit. Non-derivatised beta-cyclodextrin is generally not preferred when the
composition
contains surfactant since it affects the surface activity of most of the
preferred surfactants that are
15 compatible with the derivatised cyclodextrins.
Preferably, the compositions of the present invention are clear. The term
"clear" as
defined herein means transparent or translucent, preferably transparent, as in
"water clear," when
observed through a layer having a thickness of less than 10 cm.
Preferably, the cyclodextrins used in the present invention are highly water-
soluble such
20 as, alpha-cyclodextrin and/or derivatives thereof, gamma-cyclodextrin
and/or derivatives thereof,
derivatised beta-cyclodextrins, and/or mixtures thereof. The derivatives of
cyclodextrin consist
mainly of molecules wherein some of the OH groups are converted to OR groups.
Cyclodextrin
derivatives include, e.g., those with short chain alkyl groups such as
methylated cyclodextrins,
and ethylated cyclodextrins, wherein R is a methyl or an ethyl group; those
with hydroxyalkyl
25 substituted groups, such as hydroxypropyl cyclodextrins and/or
hydroxyethyl cyclodextrins;
branched cyclodextrins such as maltose-bonded cyclodextrins; cationic
cyclodextrins such as
those containing 2-hydroxy-3-(dimethylamino)propyl ether; quaternary
ammonium,; anionic
cyclodextrins such as carboxymethyl cyclodextrins, cyclodextrin sulfates, and
cyclodextrin
succinylates; amphoteric cyclodextrins such as carboxymethyliquaternary
ammonium
30 cyclodextrins; cyclodextrins wherein at least one glucopyranose unit has
a 3-6-anhydro-
cyclomalto structure, e.g., the mono-3-6-anhydrocyclodextrins.
Highly water-soluble cyclodextrins are those having water solubility of at
least 10 g in
100 ml Of water at room temperature, preferably at least 20 g in 100 mL of
water, more
preferably at least 25 g in 100 mL of water at room temperature. The
availability of solubilized,
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uncomplexed cyclodextrins is essential for effective and efficient odor
control performance.
Solubilized, water-soluble cyclodextrin can exhibit more efficient odor
control performance than
non-water-soluble cyclodextrin when deposited onto surfaces.
Examples of preferred water-soluble cyclodextrin derivatives suitable for use
herein are
hydroxypropyl alpha-cyclodextrin, methylated alpha-cyclodextrin, methylated
beta-cyclodextrin,
hydroxyethyl beta-cyclodextrin, and hydroxypropyl beta-cyclodextrin.
Hydroxyalkyl
cyclodextrin derivatives preferably have a degree of substitution of from
about 1 to about 14,
more preferably from about 1.5 to about 7, wherein the total number of OR
groups per
cyclodextrin is defined as the degree of substitution. Methylated cyclodextrin
derivatives
typically have a degree of substitution of from about 1 to about 18,
preferably from about 3 to
about 16. A known methylated beta-cyclodextrin is heptakis-2,6-di-O-methyl-f3-
cyclodextrin,
commonly known as DIMEB, in which each glucose unit has about 2 methyl groups
with a
degree of substitution of about 14. A preferred, more commercially available,
methylated beta-
cyclodextrin is a randomly methylated beta-cyclodextrin, commonly known as
RAMEB, having
different degrees of substitution, normally of about 12.6. RAMEB is more
preferred than
DIMEB, since DIMEB affects the surface activity of the preferred surfactants
more than
RAMEB. The preferred cyclodextrins are available, e.g., from Cerestar USA,
Inc. and Wacker
Chemicals (USA), Inc.
It is also preferable to use a mixture of cyclodextrins. Such mixtures absorb
odors more
broadly by complexing with a wider range of odoriferous molecules having a
wider range of
molecular sizes. Preferably at least a portion of the cyclodextrin is alpha-
cyclodextrin and/or its
derivatives, gamma-cyclodextrin and/or its derivatives, and/or derivatised
beta-cyclodextrin,
more preferably a mixture of alpha-cyclodextrin, or an alpha-cyclodextrin
derivative, and
derivatised beta-cyclodextrin, even more preferably a mixture of derivatised
alpha-cyclodextrin
and derivatised beta-cyclodextrin, most preferably a mixture of hydroxypropyl
alpha-
cyclodextrin and hydroxypropyl beta-cyclodextrin, and/or a mixture of
methylated alpha-
cyclodextrin and methylated beta-cyclodextrin.
It is preferable that the usage compositions of the present invention contain
low levels of
cyclodextrin so that no visible residue appears at normal usage levels.
Preferably, the solution
used to treat the surface under usage conditions is virtually not discernible
when dry. Typical
levels of cyclodextrin in usage compositions for usage conditions are from
about 0.01% to about
1%, preferably from about 0.05% to about 0.75%, more preferably from about
0.1% to about
0.5% by weight of the composition. Compositions with higher concentrations can
leave
unacceptable visible residues.
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Optional Additional Sustainable Surfactants
Optionally, additional surfactants, in addition to the low-residue surfactant,
may be
present in the sustainable composition. Additional surfactants suitable for
use herein may
include bio-derived surfactants and, optionally, non-bio-derived surfactants.
The bio-derived
surfactants may include bio-derived anionic surfactants, bio-derived nonionic
surfactants, bio-
derived cationic surfactants, or combinations thereof. Additional surfactants
may be present in
amounts from 0% to 10% by weight, preferably from 0.1% to 10%, and most
preferably from
0.25% to 6% by weight of the total composition. Of all the surfactants in the
sustainable
composition, preferably at least 50% by weight, at least 60% by weight, at
least 70% by weight,
at least 80% by weight, at least 90% by weight, at least 99% by weight, or
100% by weight are
bio-derived surfactants.
Surfactants generally comprise at least one hydrophilic portion and one
hydrophobic
portion. In the surfactants in the sustainable composition, either or both
portions may be
biobased. Bio-derived surfactants containing biologically derived carbon may
include, without
limitation, glycosides of fatty acids and alcohols, polyether glycosidic
ionophores, macrocyclic
glycosides, carotenoid glycosides, isoprenoid glycosides, fatty acid amide
glycosides and
analogues and derivatives thereof, glycosides of aromatic metabolites,
alkaloid glycosides,
hemiterpenoid glycosides, monoterpenoid glycosides, phospholipids,
lysophospholipids,
ceramides, gangliosides, sphingolipids, fatty acid amides,
alkylpolyglucosides, polyol alkyl
ethoxylates, anhydrohexitol alkyl ethoxylates, and combinations of any
thereof.
The hydrophilic portions of bio-derived surfactants in the sustainable
compositions
include, without limitation, a polyol alkyl ethoxylate containing biobased
carbon (bioderived
polyol alkyl ethoxylate). The polyol portions of polyol alkyl ethoxylates may
be biologically
derived polyols from biological or botanical sources. Biobased polyols
suitable as a starting
material for polyols suitable for use in polyol alkyl ethoxylates include, but
are not limited to,
anhydrohexitols, saccharides, such as monosaccharides including but not
limited to dioses, such
as glycolaldehyde; trioses, such as glyceraldehyde and dihydroxyacetone;
tetroses, such as
erythrose and threose; aldo-pentoses such as arabinose, lyxose, ribose,
deoxyribose, xylose; keto-
pentoses, such as ribulose and xylulose; aldo-hexoses such as allose, altrose,
galactose, glucose
(dextrose), gulose, idose, mannose, talose; keto-hexoses, such as fructose,
psicose, sorbose,
tagatose; heptoses, such as mannoheptulose and sedoheptulose; octoses, such as
octolose and 2-
. keto-3-deoxy-manno-octonate; and nonoses, such as sialose; disaccharides
including but not
limited to sucrose (table sugar, cane sugar, saccharose, or beet sugar),
lactose (milk sugar),
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93
maltose, trehalose cellobiose; oligosaccharides, such as raffinose (melitose),
stachycose, and
verbascose, sorbitol, glycerol, sorbitan, isosorbide; polyglycerols; hexoses;
pentoses; polyols;
hydrogenated sugars; hydroxymethylfurfural; refined sugars; crude sugars;
products of the
breakdown of cellulose; products of the breakdown of hemicellulose; products
of the breakdown
of lignin; plant fiber hydrolyzates; fermented plant fiber hydrolyzates;
carbohydrate
hydrogenolyzates; and combinations of any of these.
The bio-derived polyol feedstock may be a side product or co-product from the
synthesis
of biodiesel or the saponification of vegetable oils and/or animal fats (i e ,
triacylglycerols), such
as glycerol. According to further embodiments, the polyol portion of polyol
alkyl ethoxylate
containing biobased carbon may be derived from polyol feedstocks obtained as
mixed polyols
from hydrolyzed natural (biobased) fibers. Natural fibers may be hydrolyzed
(producing a
hydrolyzate) to provide bioderived polyol feedstock comprising plant fiber
hydrolyzate, such as
mixtures of polyols. Fibers suitable for this purpose include, without
limitation, corn fiber from
corn wet mills, dry corn gluten feed which may contain corn fiber from wet
mills, wet corn
gluten feed from wet corn mills, distiller dry grains solubles (DDGS) and
Distiller's Grain
Solubles (DGS) from dry corn mills, canola hulls, rapeseed hulls, peanut
shells, soybean hulls,
cottonseed hulls, cocoa hulls, barley hulls, oat hulls, wheat straw, corn
stover, rice hulls, starch
streams from wheat processing, fiber streams from corn mesa plants, edible
bean molasses,
edible bean fiber, and mixtures of any of these. Plant fiber hydrolyzates,
such as hydrolyzed corn
fiber, may be enriched in bio-derived polyol compositions suitable for use as
a feedstock in the
hydrogenation reaction described herein, including, but not limited to,
arabinose, xylose, sucrose,
maltose, isomaltose, fructose, mannose, galactose, glucose, and mixtures of
any of these.
The bio-derived surfactants may be derived from a polyol feedstock obtained
from
biobased fibers which have been hydrolyzed and subjected to fermentation. The
fermentation of
plant fiber hydrolyzates may provide new biobased polyol feedstocks, or may
alter the amounts
of residues of polysaccharides or polyols obtained from hydrolyzed fibers.
After fermentation, a
fermentation broth may be obtained and residues of polysaccharides or polyols
can be recovered
and/or concentrated from the fermentation broth to provide a biobased polyol
feedstock suitable
for use as a starting material for polyols suitable for use in polyol alkyl
ethoxylates, as described
herein.
According to certain embodiments, the bio-derived surfactant may be prepared
from bio-
derived propylene glycol or bio-derived ethylene glycol, such as through
reaction with one or
more bio-derived substances such as bio-derived methanol, bio-derived 2-
propanol, bio-derived
glycerol, bio-derived lactic acid, bio-derived glyceric acid, bio-derived
sodium lactate, and/or
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94
bio-derived sodium glycerate. Reaction products or intermediates during
preparation of the bio-
derived surfactants may include butanediols (BDO) such as bio-derived 1,2-
butanediol, bio-
derived 1,3-butanediol, bio-derived 1,4-butanediol, bio-derived 2,3-butanediol
and bio-derived
2,4-Pentanediol (2,4-PeD0).
Bio-derived 6-carbon sugars (hexoses), such as mannose, can be converted to
mannitol,
which can be converted to mannitan, which can be converted to isomannide for
use in polyol
alkyl ethoxylates. In certain embodiments, biobased surfactants may contain
portions derived
from hydrogenolysis of biobased polyol feed stocks, such as a carbohydrate
having been
subjected to hydrogenolysis, where the carbonyl group (aldehyde or ketone) of
the carbohydrate
has been reduced to a primary or secondary hydroxyl group to provide a
carbohydrate
hydrogenolyzate. The anhydrohexitol portion of anhydrohexitol alkyl
ethoxylates may be
derived from sorbitan Sorbitan (IUPAC name (3S)-2-(1,2-
Dihydroxyethyl)tetrahydrofuran-3,4-
diol) may comprise a mixture of chemical compounds derived from the
dehydration of sorbitol.
The sorbitan mixture can vary, but may include, without limitation: 1,4-
anhydrosorbitol;
1,5-anhydrosorbitol; and 1,4,3,6-dianhydrosorbitol. Sorbitan is used in the
production of
surfactants such as polysorbates. As a further example, a nonionic sorbitan
fatty acid ethoxylate
may be employed.
The alkyl portion of polyol alkyl ethoxylates may be derived from bio-derived
fatty acids
or biobased or bio-derived fatty alcohols. Bio-derived carboxylic acids may
include, without
limitation, animal or vegetable fatty acids selected from the group consisting
of butyric acid,
caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic
acid, stearic acid,
arachic acid, behenic acid, lignoceric acid, hexacosanoic acid, octacosanoic
acid, triacontanoic
acid and n-dotriacontanoic acid; fatty acids having an odd number of carbon
atoms, such as
propionic acid, n-valeric acid, enanthic acid, pelargonic acid, henadecanoic
acid, tridecanoic acid,
pentadecanoic acid, heptadecanoic acid, nonadecanoic acid, heneicosanoic acid,
tricosanoic acid,
pentacosanoic acid, and heptacosanoic acid; branched fatty acids such as
isobutyric acid,
isocaproic acid, isocaprylic acid, isocaprilic acid, isolauric acid, 11-
methyldodecanoic acid,
isomyristic acid, 13-methyl- tetradecanoic acid, isopalmitic acid, 15-methyl-
hexadecanoic acid,
isostearic acid, I7-methyloctadecanoic acid, isoarachic acid, 19-methyl-
eicosanoic acid, a-ethyl-
hexanoic acid, a-hexyldecanoic acid, a-heptylundecanoic acid, 2-
decyltetradecanoic acid, 2-
undecyltetradecanoic acid, 2-decylpentadecanoic acid, 2-undecylpentadecanoic
acid, 6-methyl-
octanoic acid, 8-methyl-decanoic acid, 10-methyl-dodecanoic acid, 12-methyl-
tetradecanoic acid,
14-methyl-hexadecanoic acid, 16-methyl-octadecanoic acid, 18-methyl-eicosanoic
acid, 20-
methyl-docosanoic acid, 22-methyl-tetracosanoic acid, 24-methyl-hexacosanoic,
26-
. _
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methyloctacosanoic acid; unsaturated fatty acids, such as 4-decenoic acid,
caproleic acid, 4-
dodecenoic acid, 5-dodecenoic acid, lauroleic acid, 4-tetradecenoic acid, 5-
tetradecenoic acid, 9-
tetradecenoic acid, palmitoleic acid, 6-octadecenoic acid, oleic acid, 9-
octadecenoic acid, 11-
octadecenoic acid, 9-eicosenoic acid, cis-11-eicosenoic acid, cetoleic acid,
13-docosenoic acid,
5 15-tetracosenoic acid, 17-hexacosenoic acid, 6,9,12,15-
hexadecatetraenoic acid, linoleic acid,
linolenic acid, gamma linolenic acid, a-eleostearic acid, gadoleic acid, a-
eleostearic acid, punicic
acid, 6,9,12,15-octadecatetraenoic acid, parinaric acid, 5,8,1 1 ,14-
eicosatetraenoic acid, erucic
acid, 5,8,11,14,17-eicosapentaenoic acid (EPA), 7,10,13,16,19-docosapentaenoic
acid,
4,7,10,13,16,19-docosahexaenoic acid (DHA); hydroxylated fatty acids, such as
a-hydroxylauric
10 acid, a-hydroxymyristic acid, a-hydroxypalmitic acid, a-hydroxystearic
acid, co-hydroxylauric
acid, a-hydroxyarachic acid, 9-hydroxy-12-octadecenoic acid, ricinoleic acid,
a-hydroxybehenic
acid, 9-hydroxy-trans-10,12-octadecadienic acid, kamolenic acid, ipurolic
acid, 9,10-
dihydroxystearic acid, 12-hydroxystearic acid, the corresponding alcohol of
any thereof,
derivatives of any thereof, and combinations of any thereof. These fatty acids
may be reduced to
15 their corresponding fatty alcohols.
The alkyl portion of the polyol alkyl ethoxylate may comprise a bio-derived
fatty acid
alkyl portion, such as from the group consisting of animal oil, vegetable oil,
biodiesel,
triacylglycerols, diacylglycerols, monoacylglycerols, fatty acids, fatty
alcohols, branched
dicarboxylic acids, dicarboxylic acid ethers, phospholipids, soapstock,
deodorizer distillate, acid
20 oil, polymerized oil, heat-bodied oil, blown oil, derivatives of any
thereof, and combinations of
any thereof. Fatty acids may comprise a mixture of bio-derived fatty acids,
such as from the
group consisting of animal fat, beef tallow, biodiesel, borne tallow,
butterfat, camelina oil,
candlefish oil, canola oil, castor oil, ceramides, cocoa butter, cocoa butter
substitutes, coconut oil,
cod-liver oil, coriander oil, corn oil, cottonseed oil, diacylglycerols, flax
oil, float grease from
25 wastewater treatment facilities, hazelnut oil, hempseed oil, herring
oil, illipe fat, jatropha oil,
kokum butter, lanolin, lard, linseed oil, mango kernel oil, marine oils,
meadowfoam oil,
menhaden oil, milk fat, monoacylglycerols, mowrah fat, mustard oil, mutton
tallow, neat's foot
oil, olive oil, orange roughy oil, palm oil, palm kernel oil, palm kernel
olein, palm kernel stearin,
palm olein, palm stearin, peanut oil, phospholipids, phulwara butter, pile
herd oil, pork lard,
30 rapeseed oil, rice bran oil, safflower oil, sal fat, sardine oil,
sasanqua oil, shea fat, shea butter,
soybean oil, sphingolipids, sunflower seed oil, tall oil, tallow, tsubaki oil,
tung oil,
triacylglycerols, triolein, used cooking oil, vegetable oil, whale oil, white
grease, yellow grease,
and derivatives, conjugated derivatives, genetically-modified derivatives, and
mixtures of any
thereof.
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The alkyl portion of the polyol alkyl ethoxylate may comprise a bio-derived
branched
dicarboxylic acid. Bio-derived branched dicarboxylic acids may be obtained by
subjecting fatty
acid-containing compositions containing one or more double bonds to cross-
linking, such as by
industrial processes including but not limited to heat bodying, oxidation,
polymerization, and
blowing. For example, soybean oil may be cross-linked by blowing, wherein
polymerization is
carried out by bubbling air through a triacylglycerol oil while heating to
temperatures of about
110 C. Typical oils include but are not limited to, drying oils, such as
linseed oil, and semi-
drying oils, such as soybean oil.
Carbon¨carbon and ether cross-linkages are formed between fatty acids of fatty
acid-
containing compositions during the blowing process of a fatty acid-containing
composition
containing unsaturated fatty acid. Double bonds in the cross-linked molecule
may be cis or trans
double bonds, or may become single bonds in the blowing process. The
carbon¨carbon and ether
linkages formed as a result of the blowing process polymerize a portion of the
monounsaturated
fatty acids, such as oleic acid, and/or a portion of the polyunsaturated fatty
acids, such as linoleic
acid and linolenic acid, cross-linking the fatty acid-containing compositions.
In the case of
triacylglycerol oils, dimers or polymers of fatty acid alkyl chains linked to
glycerol molecules are
formed. The heat- bodying of fatty acid-containing compositions also forms
cross linkages but
tends to form more carbon-carbon linkages and fewer ether linkages.
When one or more of the resulting cross-linked fatty acids is joined to one or
more
alcohols through an ester bond, the ester bonds can be broken to form cross-
linked acids having
two carboxylic acid groups. For example, hydrolysis of the ester bonds of a
cross-linked
triacylglycerol oil results in breaking the ester bonds holding each of the
three fatty acids to the
glycerol backbone of the triacylglycerol units, while cross-linkages between
the fatty acids
remain intact. Hydrolysis can be carried out with heat and pressure, and under
conditions which
minimize the isomerization of remaining cis double bonds to trans double
bonds, for example as
described in US Patent No. 7,126,019 issued Oct. 24, 2006. Hydrolysis of the
ester bonds of the
cross-linked triacylglycerols yields a mixture of dicarboxylic acids and cross-
linked dicarboxylic
ethers. Selection of suitable starting fatty acid-containing compositions and
cross-linking
reaction designs will allow a portion of double bonds to remain in the cross-
linked fatty acids
The dicarboxylic acids and dicarboxylic ethers are biobased and can be reacted
to form
ABA type bio-derived surfactants, wherein the polar anhydrohexitol and
ethoxylate chains are
represented by A and the nonpolar cross-linked alkyl chain are represented by
B. Because the
melting points of branched-chain fatty acids are lower than the straight-chain
counterparts, these
branched B fatty acid chains of the surfactant molecules should crystallize at
lower temperatures
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than the non-cross- linked counterparts. Bio-derived dicarboxylic acids or bio-
derived cross-
linked dicarboxylic ethers can be used to form AB type bio-derived
surfactants. Blends of bio-
derived AB and ABA surfactants may be synthesized from bio-derived
dicarboxylic acids,bio-
derived cross-linked dicarboxylic ethers, mixtures of bio-derived dicarboxylic
acids and bio-
derived unsaturated fatty acids, or mixtures of any thereof
An ABA type surfactant comprises at least one polyol, at least one ethoxylate
group, and
at least one dicarboxylic acid derived from cross-linked fatty acids. A bio-
derived ABA type
surfactant may comprise at least two polyols, at least two ethoxylate groups,
and at least one
cross-linked dicarboxylic acid derived from polymerized fatty acids. A bio-
derived ABA type
surfactant may comprise at least two polyols, at least two ethoxylate groups,
and at least one
cross-linked dicarboxylic acid ether derived from polymerized fatty acids.
In some embodiments, a bio-derived surfactant is an polyol alkyl ethoxylate
containing
biologically derived carbon.
Bio-derived surfactants described herein may be synthesized, for example,
using a
glycerol feedstock. The glycerol feedstock may include a diluent, such as
water, or a non-
aqueous solvent. Non-aqueous solvents that may be used include, but are not
limited to,
methanol, ethanol, ethylene glycol, propylene glycol, n-propanol and iso-
propanol, preferably
bio-derived methanol, bio-derived ethanol, bio-derived ethylene glycol, bio-
derived propylene
glycol, bio-derived n-propanol and bio-derived iso-propanol. Glycerol feed
stocks are
commercially available, or can be obtained as a byproduct of commercial
biodiesel production.
The bio-derived polyol feedstock may be a side product or co-product from the
synthesis of bio-
diesel or the saponification of vegetable oils and/or animal fats (i.e.,
triacylglycerols). For
instance, the glycerol feedstocks may be obtained through fats and oils
processing or generated
as a byproduct in the manufacture of soaps. The feedstock may be provided, for
example, as
glycerol byproduct of primary alcohol alcoholysis of a bio-derived glyceride,
such as a bio-
derived mono-, di- or tri glyceride. These bio-derived glycerides may be
obtained from refining
edible and non-edible plant feedstocks including without limitation butterfat,
cocoa butter, cocoa
butter substitutes, illipe fat, kokum butter, milk fat, mowrah fat, phulwara
butter, sal fat, shea fat,
borneo tallow, lard, lanolin, beef tallow, mutton tallow, tallow, animal fat,
canola oil, castor oil,
coconut oil, coriander oil, corn oil, cottonseed oil, hazelnut oil, hempseed
oil, jatropha oil,
linseed oil, mango kernel oil, meadowfoam oil, mustard oil, neat's foot oil,
olive oil, palm oil,
palm kernel oil, peanut oil, rapeseed oil, rice bran oil, safflower oil,
sasanqua oil, shea butter,
soybean oil, sunflower seed oil, tall oil, tsubaki oil, tung oil, vegetable
oils, marine oils,
menhaden oil, candlefish oil, cod-liver oil, orange roughy oil, pile herd oil,
sardine oil, whale
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oils, herring oils, triglyceride, diglyceride, monoglyceride, triolein palm
olein, palm stearin, palm
kernel olein, palm kernel stearin, triglycerides of medium chain fatty acids,
and derivatives,
conjugated derivatives, genetically-modified derivatives and mixtures of any
thereof.
Glycerol feedstocks are known to those of ordinary skill in the art and can be
used either
in pure or crude form. The purity of United States Pharmacopeia grade glycerol
is greater than
99%. However, the purity of the glycerol having utility in the present
invention may be between
10% and 99% by weight. The glycerol also may contain other constituents such
as water,
triglycerides, free fatty acids, soap stock, salt, and unsaponifiable matter.
In some examples, the
glycerol feedstocks may comprise from 20% to 80% by weight of bio-derived
glycerol.
The bio-derived surfactants also may be derived from natural lipids, such as
vegetable
oils and naturally occurring fatty acids or their naturally occurring
derivatives such as mono-, di-,
or triglycerides or phospholipids. The bio-derived surfactants may be
obtained, for example,
from natural oils such as soybean and castor oils, wherein the bio-derived
surfactants are
obtained by processes that typically include esterification of the oils to add
alkoxy groups such as
methoxy, ethoxy, or propoxy groups. In one version, the bio-derived
surfactants are obtained by
reactions that include hydrolysis, esterification of the liberated fatty acids
with methanol, and
then hydrogenation to create a bio-derived fatty acid alcohol. Bio-derived
datty alcohols can be
prepared from natural fatty acids with a variety of other technologies. In any
case, the alcohols
may then be further modified by reaction with ethylene oxide, such as bio-
derived ethylene
oxide, to add a plurality of ethoxy groups, forming a polyethoxy ether.
Polyoxy ethers with
relatively high HLB values can be formed from fatty alcohols via reaction with
other known
reactants as well to form, for example, bio-derived surfactants with multiple
propoxy groups,
butoxy groups, etc. In other cases, transesterification of a bio-derived fatty
acid ester with a
variety of bio-derived linear chain or other alcohols may be involved,
followed by conversion of
the ester to an alcohol. In some embodiments, the bio-derived surfactants have
aliphatic chains
with relatively high carbon numbers, such as 14 or more carbons, 16 or more
carbons, or 18 or
more carbons. For example, the carbon number may be from 16 to 18.
The bio-derived surfactant may comprise a bio-derived ethoxylated fatty acid
or a bio-
derived fatty alcohol, wherein the fatty acid or alcohol has a carbon number
of sixteen or greater
and at least 5 ethoxy groups, specifically at least 10 ethoxy groups, and more
specifically at least
20 ethoxy groups, such as between 5 and 80 ethoxy groups, or between 10 and 60
ethoxy groups,
or between 15 and 55 ethoxy groups. Such bio-derived surfactants may be
obtained by
esterification or epoxidation of soybean oil or castor oil, or of fatty
alcohols obtained from either
of these.
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More generally, but by way of example only, the bio-derived surfactants may be
derived
from any of the following lipids: soybean oil, castor oil, cottonseed oil,
linseed oil, canola oil,
safflower oil, sunflower oil, peanut oil, olive oil, sesame oil, coconut oil,
walnut oil or other nut
oils, flax oil, neem oil, meadowfoam oil, other seed oils, fish oils, animal
fats, and the like.
Exemplary fatty acids include omega-3 fatty acids such as alpha-linolenic
acid, stearidonic acid,
eicosapentaenoic acid, docosahexaenoic acid, and so forth; omega-6 fatty acids
such as linoleic
acid, gamma-linolenic acid, dihomo-gamma-linolenic acid, arachidonic acid,
calendic acid, and
the like; omega-9 fatty acids such as oleic acid, erucic acid, elaidic acid,
and the like; saturated
fatty acids such as myristic acid, palmitic acid, stearic acid,
dihydroxystearic acid, arachidic acid
(eicosanoic acid), behenic acid (docosanoic acid), lignoceric acid; and other
fatty acids including
various conjugated linoleic acids; and omega-5 fatty acids such as myristoleic
acid, malvalic
acid, sterculic acid. Natural waxes or the fatty acids therefrom may also be
used, particularly
ester waxes such as straight chain ester waxes; examples include jojoba oil,
carnauba wax,
beeswax, candellia wax, and the like. Fatty alcohols can be obtained from any
of these fatty
acids by any known method, including catalytic conversion, esterification plus
hydrogenation,
etc.
The bio-derived surfactants may be obtained from two or more vegetable oil
sources,
such as from mixtures of any two or more of the vegetable oils mentioned
herein. Alternatively,
two or more vegetable oils may be reconstituted to form a reconstituted oil
according to known
methods such as those described in U.S. Pat. No. 6,258,965, "Reconstituted
Meadowfoam Oil,"
issued July 10, 2001 to A.J. O'Lenick, Jr., and U.S. Pat. No. 6,013,818,
"Reconstituted
Meadowfoam Oil," issued Jan. 11 , 2001 to A.J. O'Lenick, Jr. The O'Lenick
patents describe
processes in which one or more oils of natural origin are transesterified
under conditions of high
temperature in the presence of a catalyst to make a "reconstituted product"
having an altered
alkyl distribution and consequently altered chemical and physical properties.
While bio-derived
surfactants obtained from natural lipids are useful, it is recognized that
identical materials
obtained from synthetic raw materials can be created and, in some embodiments,
may be suitable
for use in the sustainable compositions described herein.
Bio-derived surfactants also may be obtained, in whole or in significant part,
from
bioorganic substances directly obtainable from algae (from direct extraction
for example), and/or
through standard synthetic organic transformations starting from bioorganic
molecules that are in
turn obtainable from algae. Some of the more practical starting materials
directly obtainable
from algae include lipids and polysaccharides, which are useful bio-derived
feedstocks for bio-
derived surfactants. High yield, lipid-rich algae can be grown in water-ponds
in temperature and
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environmentally controlled greenhouses and bioreactors. Through autotrophic
and/or
heterotrophic processes, the lipid oil can be extracted through known
mechanical, chemical, and
biological techniques. Through algae strain selection, and technologies to
influence the algae
metabolic pathways, algae is also capable of producing high percentages of
starch and cellulose
via autotrophic and heterotrophic routes, giving additional feedstocks for
specialty chemicals
such as bio-derived for use in consumer products. In particular,
hydrogenolysis, hydrolysis,
amidation, esterification, ethoxylation and transesterification processes from
algal lipid starting
materials, along with the hydrolysis, enzymolysis, and/or fermentation of
algal polysaccharides
are available routes to the production of the bio-derived surfactants. Also
the direct production
of glucose, cellulose, and sucrose as metabolites from living cyanobacteria
give useful bioorganic
ingredients and bio-feedstock for bio-derived surfactants.
Algae that may be used to produce bioorganic substances that are directly
incorporable
into bio-derived surfactants, or which are useful as precursors to bio-derived
surfactants include,
but are not limited to, Chlorophyta (green algae), Charophyta (Stoneworts and
Brittleworts),
Euglenophyta (Euglenoids), Chrysophyta (golden-brown and yellow-green algae
and diatoms),
Phaeophyta (brown algae), Rhodophyta (red algae), Cyanophyta (blue-green
algae, same as blue-
green bacteria or cyanobacteria), and the Pyrrhophyta (dinoflagellates). Most
algae are
photoautotrophs, and most dried algae mass, wet algae colonies, or algae
metabolites will provide
some levels of lipid, saccharidic substances including polysaccharides and
sulfated materials
(cellulose, hemicellulose, pectin, alginic acid, carrageenan, agarose,
porphyran, fucelleran,
funoran, starch, simple sugars, and the like), glycoproteins, and a variety of
photosynthetic
pigments (chlorophyll, astaxanthin, etc).
For algal lipid feedstock, some species of algae and diatom algae that may
produce
commercially significant levels of lipids include, but are not limited to;
Actinastnim;
Actinochloris; Anabaena; Ankistrodesnnis; Apatococcus; Asterarcys;
Auzenochlorella;
Bacilliarophy; Botrydiopsis; Botiyococciis; Bracteacoccus; Biimilleriopsis;
Chaetophorcr, Chant
ransia; Charachtm; Chlamydomonas', Chlorella; Chlorideilcr, Chlorobotrys;
Chlorococcum;
Chlorokybns; Chloroliimula; Chlormonas; Chlorophyceae; Chlorosarcinopsis;
Chlorotetraedron;
Chloricystis; Coccomyxa; Coelasirella; Coelastropsis; Coelastrum;
Coenochloris; Coleochlemys;
Cosmarivm; Crucigenia; Crucigeniella; Desmodesmus; Diadesmis; Dictyococciis;
Dictyosphaenum; Dipfosphaera; Dunaliella; Ellipsoidion; Ena/lax; Ettlia;
Euglena; Fortiea;
Geminella; Gonium; Graesiella; Haematococcus; Heterococcus; Interfilum;
Isochrysis;
Kentrosphaera; Keratococcus; Klebsormidium; Koliella; Lagerheimia;
Lobosphaera;
Macrochloris; Microthamnion; Monodus; Monoraphidium; Mougeotia; Muriel la;
Mychonastes;
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Myrmecia; Nannochlolis; Nannochloropsis; Nautococcus; navicular, Navioua;
Neochloris;
Neodesmus; Neospongiococcum; Nephrochlamys; Oocyst is; Oonephris;
Orthotrichum;
Pediastrum; Phaeodactylum; Pithophora; Pleurastrum; Pleurochrysis;
Porphyridium; Possonia;
Prasiolopsis; Protosiphon; Prymnesium, Pseudollipsoidion; Pseudendoclonium;
Pseudocharaciopsis; Pseudococcomyxa; Pseudoendoclonium; Raphidocelis;
Raphidonema;
Rhexinema; Rhopalocystis; Scenedesmus; Schroederiella; Scotiella;
Scotiellopsis; Selenastrum,
Sphaerocystis; Spirogyra; Spirulina; Spongiochloris; Stichococcus;
Stigeoclonium; Synechoccus;
Tetradesmus; Tetrahedron; Tetraselmis; Tetrastrum; Tribonema; Vischeria;
Willea; Xanthonema;
and Zygnema.
From these and other algae and diatom algae may be obtained lipid (or "algal
fat") high in
C14 through C22 triglycerides including saturated and unsaturated fatty acid
chains. Other lipid
and oil producing algae include blue algae, green algae, blue-green algae, and
golden-brown
algae, often collectively referred to as micro-algae. This lipid constitution
is similar to fresh
water fish oils. Brown algae and red algae produce longer chain triglycerides,
for example with
carbon chains greater than 24-carbons.
The algae-derived lipid oils (triglycerides), starch, and cellulose may be
converted to
algae-derived surfactants through established chemical synthetic routes, such
as:
(1) Algae ¨> Lipid Triglycerides ¨> Surfactants;
(2) Algae ¨> Starch or Cellulose ¨> Sugar ¨> Surfactants;
(3) Algae ¨> Starch or Cellulose ¨> Surfactants; and, combinations of the
intermediates
and end molecules obtainable from these basic routes, (e.g., a sugar from
route 2 combined with
a fatty acid from route I to produce an alkylpolyglycoside surfactant).
Examples of bio-derived surfactants having carbon chains traceable back to
algae may
include, but are not limited to, alkyl glycosides and alkyl polyglycosides,
fatty alcohol
ethoxylates, fatty acid soaps, fatty acid amides and alkanolamides, fatty
amines and ethoxylated
amines, quaternary ammonium compounds (cationic surfactants), fatty acid
esters and
ethoxylated esters, alpha-sulfonated fatty acid esters, fatty acid phosphates,
glyceryl esters,
glucamides, polyglycerol esters, lecithins, lignin sulfonates, proteins and
protein derivatives,
saponins, sorbitol and sorbitan esters, sucroglycerides, sucrose esters, alkyl
sulfates and alcohol
ether sulfates.
Some bioorganic materials, such as alkylglycoside, lignin, saponins,
glycolipids (such as
ascarosides, simplexides, plakopolyprenos ides, and the like), etc. may or may
not be found in
algae species currently known to date; however, some of these materials are
known to be plant
derived and may eventually be sourced from alga species that are currently
undiscovered or not
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yet bio-engineered. For example, certain alkylglycosides are found naturally
in cyanobacteria,
but lignin is primarily found in wood.
Anionic Surfactants¨In view of the above-mentioned sources and production
methods
for obtaining bio-derived surfactants generally, bio-derived anionic
surfactants useful in the
present sustainable composition are preferably selected from the group
consisting of, bio-derived
linear alkylbenzene sulfonate, bio-derived alpha olefin sulfonate, bio-derived
paraffin sulfonates,
bio-derived methyl ester sulfonates, bio-derived alkyl sulfates, bio-derived
alkyl alkoxy sulfate,
bio-derived alkyl sulfonates, bio-derived alkyl alkoxy carboxylate, bio-
derived alkyl alkoxylated
sulfates, bio-derived sarcosinates, bio-derived taurinates, and mixtures
thereof. An effective
amount, typically from 0% to 10%, preferably from 0.1% to 10%, and most
preferably from
0.25% to 6% by weight of the total sustainable composition, of anionic
surfactant can be used.
Of all the anionic surfactants in the sustainable composition, preferably at
least 50% by weight,
at least 60% by weight, at least 70% by weight, at least 80% by weight, at
least 90% by weight,
at least 99% by weight, or 100% by weight are bio-derived anionic surfactants.
The anionic surfactant may include alkyl ester sulfonates. These are desirable
because
they can be made with renewable, non-petroleum resources. Preparation of alkyl
ester sulfonate
surfactants can be effected according to known methods disclosed in the
technical literature. For
example, linear esters of C8-C2ocarboxylic acids can be sulfonated with
gaseous SO3 according to
"The Journal of the American Oil Chemists Society," vol. 52, pp. 323-329
(1975). Suitable
starting materials include natural fatty substances as derived from tallow
oils, palm oils, and
coconut oils, for example.
Preferred alkyl ester sulfonate surfactant comprise alkyl ester sulfonate
surfactants of the
structural formula:
0
R3¨al¨C¨OR4
SO3M
where R3 is a C8 -C20 hydrocarbyl, preferably an alkyl, or combination
thereof, R4 is a C1¨C6
hydrocarbyl, preferably an alkyl, or combination thereof, and M is a soluble
salt-forming cation.
Suitable salts include metal salts such as sodium, potassium, and lithium
salts, and substituted or
unsubstituted ammonium salts, such as methyl-, dimethyl, -trimethyl, and
quaternary ammonium
cations, e.g. tetramethyl-ammonium and dimethyl piperdinium, and cations
derived from
alkanolamines, e.g. monoethanol-amine, diethanolamine, and triethanolamine.
Preferably, R3 is
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C10¨C16 alkyl, and R4 is methyl, ethyl, or isopropyl. Especially preferred are
the methyl ester
sulfonates wherein R3 is C14¨C16 alkyl.
Bio-derived alkyl sulfate surfactants are another type of bio-derived anionic
surfactant of
importance for use herein. In addition to providing excellent overall cleaning
ability when used
in combination with polyhydroxy fatty acid amides (see below), including good
grease/oil
cleaning over a wide range of temperatures, wash concentrations, and wash
times, dissolution of
alkyl sulfates can be obtained, as well as improved formulability in
sustainable compositions are
water soluble salts or acids of the formula ¨ROSO3M, where R preferably is a
Cio¨C24
hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C10¨C20 alkyl
component, more
preferably a C12¨C18 alkyl or hydroxyalkyl, and M is H or a cation, e.g., an
alkali or alkaline
(Group IA or Group IIA) metal cation (e.g., sodium, potassium, lithium,
magnesium, calcium),
substituted or unsubstituted ammonium cations such as methyl-, dimethyl-, and
trimethyl
ammonium and quaternary ammonium cations, e.g., tetramethyl-ammonium and
dimethyl
piperdinium, and cations derived from alkanolamines such as ethanolamine,
diethanolamine,
triethanolamine, and mixtures thereof, and the like. Typically, alkyl chains
of C12¨C15 are
preferred.
Bio-derived alpha-sulfonated alkyl esters may be include linear esters of C6-
C22
carboxylic acids sulfonated with gaseous S03. Alpha, (or a-, used
interchangeably herein),
pertains to the first position on the carbon chain adjacent to the carboxylate
carbon, as per
standard organic chemistry nomenclature. The alpha-sulfonated alkyl esters may
be pure alkyl
ester or a blend of (1) a mono-salt of an alpha-sulfonated alkyl ester of a
fatty acid having from 8
to 20 carbon atoms where the alkyl portion forming the ester is straight alkyl
chain of 1 to 6
carbon atoms; and (2) a di-salt of an alpha-sulfonated fatty acid, the ratio
of mono-salt to di-salt
being at least 2:1. The alpha-sulfonated alkyl esters useful herein are
typically prepared by
sulfonating an alkyl ester of a fatty acid with a sulfonating agent such as
S03. As an example,
the bio-derived fatty acid esters are readily available by transesterification
of algae lipids, or
alternatively by esterification of the fatty acids obtained by hydrolysis of
the algae lipids. When
prepared by sulfonation of fatty acid esters, the alpha-sulfonated alkyl
esters normally contain a
minor amount, (typically less than 33% by weight), of the di-salt of the alpha-
sulfonated fatty
acid which results from saponification of the ester. Preferred alpha-
sulfonated alkyl esters
contain less than 10% by weight of the di-salt of the corresponding alpha-
sulfonated fatty acid.
The alpha-sulfonated fatty acid ester surfactants that may be incorporated
into the
sustainable compositions may comprise alkyl ester sulfonate surfactants of the
structural formula
R3¨CH(S03M)¨0O2R4, where R3 is a C8¨C20 algae-sourced carbon chain, R4 is a
straight or
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branched chain C1¨C6 alkyl group, and M is a cation that forms a water-soluble
salt with the alkyl
ester sulfonate, including sodium, potassium, magnesium, and ammonium cations.
Preferably,
R3 is C10¨C16 fatty alkyl, and R4 is ethyl, in turn indirectly derived from
algal polysaccharides
(transesterification of the algae-lipid with ethanol obtained through algae
cellulose fermentation).
Other anionic surfactants that may be included in the sustainable compositions
herein
include bio-derived alkyl sulfates, also known as alcohol sulfates. These bio-
derived surfactants
have the general formula R¨O¨SO3Na, where R is a hydrocarbyl having from about
10 to 18
carbon atoms, and these materials may also be denoted as sulfuric monoesters
of C10¨C18
alcohols, examples being sodium decyl sulfate, sodium palmityl alkyl sulfate,
sodium myristyl
alkyl sulfate, sodium dodecyl sulfate, sodium tallow alkyl sulfate, sodium
coconut alkyl sulfate,
and mixtures of these surfactants, or of C10¨C20 oxo alcohols, and those
monoesters of secondary
alcohols of this chain length. The alkyl sulfates are readily obtainable by
sulfonation of the bio-
derived fatty alcohols described above, which can be directly synthesized
through hydrogenolysis
of algae lipids, or less directly through transesterification of algae lipids
and hydrogenation of the
intermediate fatty acid esters.
Fatty alkylamidopropyl betaines may be present in the sustainable compositions
and
represent an important class of mild detergents. For example, cocamidopropyl
betaine, with or
without sodium laureth sulfate as co-surfactant, is the surfactant system of
choice for most
shampoo and bodywash compositions. The synthesis of betaines is well known and
is described
in U.S. Patent No. 5,354,906 (Weitemeyer, et al.) incorporated herein in its
entirety by reference.
The amidoamine intermediates described by Weitemeyer as obtainable from
coconut fatty acid
are just as easily be obtainable from a fatty acid blend derived from
hydrolysis or hydrogenolysis
of algal lipids. Alternatively, algae lipids may be directly amidated using
bio-derived 1,3-
propanediamine to give fatty amidoamines that then may be converted to
alkylamidopropyl
betaines using the methods described in the '906 patent.
The bio-derived anionic surfactants may include alkyl alkoxylated sulfate
surfactants.
These surfactants are water-soluble salts or acids typically of the formula
RO(A)1,S03M, where
R is an unsubstituted C10¨C24 alkyl or hydroxyalkyl group having a C10¨C24
alkyl component,
preferably a C12¨C20 alkyl or hydroxyalkyl, more preferably C12¨C18 alkyl or
hydroxyalkyl; A is
an ethoxy or propoxy unit; m is greater than zero, typically between about 0.5
and about 6, more
preferably between about 0.5 and about 3; and M is H or a cation which can be,
for example, a
metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.),
ammonium or
substituted-ammonium cation. Alkyl ethoxylated sulfates as well as alkyl
propoxylated sulfates
are contemplated herein. Specific examples of substituted ammonium cations
include methyl-,
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dimethyl-, trimethyl-ammonium and quaternary ammonium cations, such as
tetramethyl-
ammonium, dimethyl piperidinium and cations derived from alkanolamines, e.g.
monoethanolamine, diethanolamine, and triethanolamine, and mixtures thereof.
Exemplary
surfactants include C12-C18 alkyl polyethoxylate (1.0) sulfate, C12-C18
alkylpolyethoxylate (2.25)
sulfate, C12¨C18 alkyl polyethoxylate (3.0) sulfate, and C12-C18 alkyl
polyethoxylate (4.0) sulfate
where M is selected from sodium and potassium. Surfactants for use herein can
be made from
natural or synthetic alcohol feedstocks. Chain lengths represent average
hydrocarbon
distributions, including branching.
Preferred anionic surfactants for use in the sustainable composition include
the alkyl ether
sulfates, also known as alcohol ether sulfates. Alcohol ether sulfates are the
sulfuric monoesters
of the straight chain or branched alcohol ethoxylates and have the general
formula
R¨(OCH2CH2)x¨O¨S03M, where R preferably comprises C7¨C21 alcohol ethoxylated
with from
about 0.5 mol to about 9 mol of ethylene oxide (i.e., x=0.5 to 9 EO), such as
C12¨C18 alcohols
containing from 0.5 to 9 EO, and where M is alkali metal or ammonium, alkyl
ammonium or
alkanol ammonium counterion. Preferred alkyl ether sulfates are C8¨C18 alcohol
ether sulfates
with a degree of ethoxylation of from about 0.5 to about 9 ethylene oxide
moieties and most
preferred are the C12¨C15 alcohol ether sulfates with ethoxylation from about
4 to about 9
ethylene oxide moieties, with 7 ethylene oxide moieties being most preferred.
In another
embodiment, the C12-C15 alcohol ether sulfates with ethoxylation from about
0.5 to about 3
ethylene oxide moieties are preferred. In keeping with the spirit of only
using natural feedstock
for ingredients for the sustainable composition, the fatty alcohol portion of
the surfactant is
preferably animal or vegetable derived, rather than petroleum derived.
Therefore the fatty
alcohol portion of the surfactant will comprise distributions of even number
carbon chains, e.g.
C12, C14, C16, C18, and so forth. It is understood that when referring to
alkyl ether sulfates, these
substances are already salts (hence "sulfate" nomenclature), and most
preferred and most readily
available are the sodium alkyl ether sulfates (also referred to as NaAES, or
simply FAES).
Commercially available alkyl ether sulfates include the CALFOAM alcohol ether
sulfates from Pilot Chemical, the EMAL , LEVENOL and LATEMAL products from
Kao
Corporation, and the POLYSTEP products from Stepan, most of these with fairly
low EO
content (e.g., average 3 or 4-E0). Alternatively, the alkyl ether sulfates may
be prepared by
sulfonation of alcohol ethoxylates (i.e., nonionic surfactants) if the
commercial alkyl ether sulfate
with the desired chain lengths and EO content are not easily found, but
perhaps where the
nonionic alcohol ethoxylate starting material may be. For example, sodium
lauryl ether sulfate
("sodium laureth sulfate", having about 2-3 ethylene oxide moieties) is very
readily available
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commercially and quite common in shampoos and detergents. Depending on the
degree of
ethoxylation desired, it may be more practical to sulfonate a commercially
available nonionic
surfactant such as Neodol 25-7 Primary Alcohol Ethoxylate (a C12-C15/7E0
nonionic from
Shell) to obtain for example the C12-C15/7E0 alkyl ether sulfate that may have
been more
include the alpha-sulfonated alkyl esters of C12-C16 fatty acids. The alpha-
sulfonated alkyl esters
may be pure alkyl ester or a blend of (1) a mono-salt of an alpha- sulfonated
alkyl ester of a fatty
acid having from 8 to 20 carbon atoms where the alkyl portion forming the
ester is straight or
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However, the methyl esters are derived from methanol sources. Thus, the ethyl
esters, which are
currently not commercially available, would be the most preferred alpha-
sulfonated fatty acid
esters. When used in the present sustainable compositions, the alpha-
sulfonated alkyl ester is
preferably incorporated at from about 3% to about 15% by weight actives.
The sustainable compositions may also include bio-derived fatty acid soaps as
an anionic
surfactant ingredient. The fatty acids that may be represented by the general
formula R¨COOH,
where R represents a linear or branched alkyl or alkenyl group having between
about 8 and 24
carbons. It is understood that within the sustainable compositions, the free
fatty acid form (the
carboxylic acid) will be converted to the carboxylate salt in-situ (that is,
to the fatty acid soap),
by the excess alkalinity present in the composition from added alkaline
builder. As used herein,
"soap" means salts of fatty acids. Thus, after mixing and obtaining the
compositions of the
present invention, the fatty acids will be present in the composition as
R¨COOM, where R
represents a linear or branched alkyl or alkenyl group having between about 8
and 24 carbons
and M represents an alkali metal such as sodium or potassium.
The fatty acid soap, which is often a desirable component having suds-reducing
effect in
the dishwasher, is preferably comprised of higher fatty acid soaps. The fatty
acids that are added
directly into the sustainable compositions may be derived from natural fats
and oils, such as those
from animal fats and greases and/or from vegetable and seed oils, for example,
tallow,
hydrogenated tallow, whale oil, fish oil, grease, lard, coconut oil, palm oil,
palm kernel oil, olive
oil, peanut oil, corn oil, sesame oil, rice bran oil, cottonseed oil, babassu
oil, soybean oil, castor
oil, and mixtures thereof. Although fatty acids can be synthetically prepared,
for example, by the
oxidation of petroleum, or by hydrogenation of carbon monoxide by the Fischer-
Tropsch
process, the naturally obtainable fats and oils are preferred. The fatty acids
of particular use in
the sustainable compositions are linear or branched and contain from about 8
to about 24 carbon
atoms, preferably from about 10 to about 20 carbon atoms and most preferably
from about 14 to
about 18 carbon atoms. Preferred fatty acids include coconut, tallow or
hydrogenated tallow
fatty acids, and most preferred is to use entirely coconut fatty acid.
Preferred salts of the fatty
acids are alkali metal salts, such as sodium and potassium or mixtures thereof
and, as mentioned
above, preferably the soaps generated in-situ by neutralization of the fatty
acids with excess
alkali from the silicate. Other useful soaps are ammonium and alkanol ammonium
salts of fatty
acids, with the understanding that these soaps would necessarily be added to
the compositions as
the preformed ammonium or alkanol ammonium salts and not neutralized in-situ
within the
added alkaline builders of the present invention. The bio-derived fatty acids
that may be
included in the present compositions will preferably be chosen to have
desirable detergency and
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suds-reducing effect. Fatty acid soaps may be incorporated in the sustainable
compositions of
the present invention at from about 1% to about 10% by weight of the
sustainable composition.
The sustainable compositions may also include alkyl sulfate as the sole
anionic surfactant
component, or in combination with one of more other anionic surfactants
mentioned above. Fatty
alkyl sulfates have the general formula R-S03M, where R preferably comprises a
C7-C21 fatty
alkyl chain, and where M is alkali metal or ammonium, alkyl ammonium or
alkanol ammonium
counterion. Preferred alkyl sulfates for use in the present invention are
C8¨C18 fatty alkyl sulfate.
Most preferred is to incorporate sodium lauryl sulfate, such as Standapol WAQ-
LC marketed by
Cognis, and to have from about 1% to about 10% by actives weight basis in the
cleaningcomposition.
Other Anionic Surfactants¨Other anionic surfactants useful for detersive
purposes can
also be included in the sustainable compositions. These can include salts
(including, for
example, sodium, potassium, ammonium, and substituted ammonium salts such as
mono-, di-
and triethanolamine salts) of soap, C9-C20 linear alkylbenzenesulfonates, C8-
C22 primary or
secondary alkanesulfonates, Cg ¨C24olefinsulfonates, sulfonated polycarboxylic
acids prepared
by sulfonation of the pyrolyzed product of alkaline earth metal citrates,
e.g., as described in
British patent specification No. 1,082,179, alkyl glycerol sulfonates, fatty
acyl glycerol
sulfonates, fatty ()ley] glycerol sulfates, alkyl phenol ethylene oxide ether
sulfates, paraffin
sulfonates, alkyl phosphates, isothionates such as the acyl isothionates, N-
acyl taurates, fatty acid
amides of methyl tauride, alkyl succinamates and sulfosuccinates, monoesters
of sulfosuccinate
(especially saturated and unsaturated C12¨C18 monoesters) diesters of
sulfosuccinate (especially
saturated and unsaturated C6¨C14 diesters), N-acyl sarcosinates, sulfates of
alkylpolysaccharides
such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds
being described
below), branched primary alkyl sulfates, alkyl polyethoxy carboxylates such as
those of the
formula RO(CH2CH20)kCH2COOM4- , where R is a C8-C22 alkyl, k is an integer
from 0 to 10,
and M is a soluble salt-forming cation, and fatty acids esterified with
isethionic acid and
neutralized with sodium hydroxide. Resin acids and hydrogenated resin acids
are also suitable,
such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin
acids present in or
derived from tall oil. Further examples are given in "Surface Active Agents
and Detergents"
(Vol. I and II by Schwartz, Perry and Berch). A variety of such surfactants
are also generally
disclosed in U.S. Pat. No. 3,929,678, issued Dec. 30, 1975 to Laughlin, et al.
at Column 23, line
58 through Column 29, line 23. Preferably, the other anionic surfactants are
bio-derived.
Specific examples of bio-derived anionic surfactants suitable herein include
Caflon
2L28U by Univar, a sodium lauryl ether sulfate from bio-derived C12¨C14
alcohols; Akypo LF I
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and Akypo LF 2 by Kao, low-foaming bio-derived anionic surfactants from palm
kernal oil and
comprising capryleth carboxylic acids; and Akypo RLM bio-derived surfactants
by Kao, laureth
carboxylic acids from bio-derived C12¨C14 alcohols.
Secondary Surfactants¨Secondary detersive surfactants can be selected from the
group
consisting of nonionics, cationics, ampholytics, zwitterionics, and mixtures
thereof. By selecting
the type and amount of detersive surfactant, along with other adjunct
ingredients disclosed
herein, the present sustainable compositions can be formulated to be used in
the context of
dishwashing. The particular surfactants used can therefore vary widely
depending upon the
particular end-use envisioned. Suitable secondary surfactants are described
below.
Nonionic Detergent Surfactants¨Suitable nonionic detergent surfactants are
generally
disclosed in U.S. Pat. No. 3,929,678, Laughlin et at., issued Dec. 30, 1975,
at column 13, line 14
through column 16, line 6, incorporated herein by reference. Exemplary, non-
limiting classes of
useful nonionic surfactants include: alkyl dialkyl amine oxide, alkyl
ethoxylate, alkanoyl glucose
amide, the so-called narrow peaked alkyl ethoxylates, C 6-C 12 alkyl phenol
alkoxylates
(especially ethoxylates and mixed ethoxy/propoxy) and mixtures thereof. In the
present
sustainable compositions, preferably the nonionic surfactants are bio-derived.
The nonionic surfactants for use herein may include, for example, the
polyethylene,
polypropylene, and polybutylene oxide condensates of alkyl phenols. In
general, the
polyethylene oxide condensates are preferred. These compounds include the
condensation
products of alkyl phenols having an alkyl group containing from about 6 to
about 12 carbon
atoms in either a straight-chain or branched-chain configuration with the
alkylene oxide. In a
preferred embodiment, the ethylene oxide is present in an amount equal to from
about 5 to about
moles of ethylene oxide per mole of alkyl phenol. Commercially available
nonionic
surfactants of this type include Igepal CO-630, marketed by the GAF
Corporation; and Triton
25 X-45, X-114, X-100, and X-102, all marketed by the Rohm & Haas Company.
These
compounds are commonly referred to as alkyl phenol alkoxylates, (e.g., alkyl
phenol
ethoxylates).
Specific examples of bio-derived nonionic surfactants suitable herein include
Ecosurf SA
surfactants by Dow, alcohol ethoxylates made from bio-derived modified seed
oils; Amidet N by
Kao, a bio-derived amine surfactant made from polyethylene glycol and rapeseed
oil; Levenol by
Kao, glycereth cocoate surfactants made from bio-derived glycerine of
vegetable origin; Emanon
XLf by Kao, comprising vegetable-derived glycereth caprylate; Caflon SP20 by
Kao/Univar,
vegetable-derived sorbitan laurate; Canon SP60 by Kao/Univar, vegetable-
derived sorbitan
stearate; Kaopan SP-010, vegetable-derived sorbitan oleate; Kaopan TX and
Caflon TW
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surfactants, vegetable-derived polyethylene glycol¨sorbitan surfactants; and
Caflon LF, Triton
BG, and Triton CG by Univar/Dow, all vegetable-derived alkyl polyglucoside
surfactants.
The nonionic surfactants for use herein further may include, for example, the
condensation products of bio-derived aliphatic alcohols with from about 1 to
about 25 moles of
bio-derived ethylene oxide. The alkyl chain of the aliphatic alcohol can
either be straight or
branched, primary or secondary, and generally contains from about 8 to about
22 carbon atoms.
Particularly preferred are the condensation products of alcohols having an
alkyl group containing
from about 10 to about 20 carbon atoms with from about 2 to about 18 moles of
ethylene oxide
per mole of alcohol. Examples of commercially available nonionic surfactants
of this type
include Tergitol 15-S-9 (the condensation product of Cu¨Cis linear secondary
alcohol with 9
moles ethylene oxide), Tergitol 24-L-6 NMW (the condensation product of
C12¨C14 primary
alcohol with 6 moles ethylene oxide with a narrow molecular weight
distribution), both marketed
by Union Carbide Corporation; Neodol 45-9 (the condensation product of
C14¨C15 linear
alcohol with 9 moles of ethylene oxide), Neodol 23-6.5 (the condensation
product of C12¨C13
linear alcohol with 6.5 moles of ethylene oxide), Neodol 45-7 (the
condensation product of
C14¨C15 linear alcohol with 7 moles of ethylene oxide), Neodol el 45-4 (the
condensation product
of C14¨C15 linear alcohol with 4 moles of ethylene oxide), marketed by Shell
Chemical
Company, and Kyro BOB (the condensation product of C13-C15 alcohol with 9
moles ethylene
oxide), marketed by The Procter & Gamble Company. Other commercially available
nonionic
surfactants include Dobanol 91-80 marketed by Shell Chemical Co. and Genapol
UD-080
marketed by Hoechst. This category of nonionic surfactant is referred to
generally as "alkyl
ethoxylates." Preferably, the alkyl ethoxylates are bio-derived and may be
obtained according to
the methods described herein.
The nonionic surfactants for use herein may include, for example the
condensation
products of bio-derived ethylene oxide with a hydrophobic base formed by the
condensation of
bio-derived propylene oxide with bio-derived propylene glycol. The hydrophobic
portion of
these compounds preferably has a molecular weight of from about 1500 to about
1800 and
exhibits water insolubility. The addition of polyoxyethylene moieties to this
hydrophobic portion
tends to increase the water solubility of the molecule as a whole, and the
liquid character of the
product is retained up to the point where the polyoxyethylene content is about
50% of the total
weight of the condensation product, which corresponds to condensation with up
to about 40
moles of bio-derived ethylene oxide. Examples of compounds of this type
include certain of the
commercially-available Pluronic surfactants, marketed by BASF.
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The sustainable compositions may also include bio-derived amide type nonionic
surfactants, for example alkanolamides that are condensates of algae-derived
fatty acids with
alkanolamines such as bio-derived monoethanolamine (MEA), bio-derived
diethanolamine
(DEA) and bio-derived monoisopropanolamine (MIPA), that have previously found
widespread
use in cosmetic, personal care, household and industrial formulations. Useful
alkanolamides
include bin-derived ethanolamides and/or bin-derived isopropanolamides such as
monoethanolamides, diethanolamides and isopropanolamides in which the fatty
acid acyl radical
typically contains from 8 to 18 carbon atoms. Especially satisfactory
alkanolamides have been
mono- and diethanolamides such as those derived from mixed fatty acids or
special fractions
containing, for instance, predominately C12 to C14 fatty acids. For example,
bio-derived fatty
acids may be obtained from algae lipids through a number of routes, and these
may be amidated
with the required alkanolamine. Alternatively, and more directly, the nonionic
alkanolamides
may be obtained by direct amidation of the algae lipid (e.g., the crude algae
fat).
Additional classes of bio-derived nonionic surfactants that may be used in the
sustainable
compositions herein include bio-derived ethoxylated fatty acid alkyl esters,
preferably having 1
to 4 carbon atoms in the alkyl chain, especially bio-derived fatty acid ethyl
esters. An algae-
sourced fatty acid ester may be ethoxylated, for example, with bio-derived
ethylene oxide, such
as ethylene oxide obtained from algae-sourced ethanol. Additionally,
ethoxylated fatty amines
may be obtained by ethoxylation of fatty amines, wherein these starting
materials are obtained
from bio-derived ethanol and algae lipid, respectively.
Further examples of suitable nonionic surfactants are alcohol ethoxylates
containing
linear radicals from alcohols of natural origin having 12 to 18 carbon atoms,
e.g., from coconut,
palm, tallow fatty or oley1 alcohol and on average from 4 EO to about 12 EO
per mole of alcohol.
Also useful as a nonionic surfactant is the C12¨C14 alcohol ethoxylate-7E0,
and the C12¨C14
alcohol ethoxylate-12E0 incorporated in the composition at from about 1 wt% to
about 10 wt%.
Preferred nonionic surfactants for use in this invention include for example,
Neodol 45-7,
Neodol 25-9, or Neodol 25-12 from Shell Chemical Company and most preferred
are
Surfonic L24-7, which is a CU- CI4 alcohol ethoxylate-7E0, and Surfonic L24-
12, which is a
C12¨C14 alcohol ethoxylate-12E0, both available from Huntsman. Combinations of
more than
one alcohol ethoxylate surfactant may also be desired in the sustainable
composition to maximize
cleaning performance.
The nonionic surfactants for use herein further may include, for example, the
condensation products of bio-derived ethylene oxide with the product resulting
from the reaction
of bio-derived propylene oxide and bio-derived ethylenediamine. The
hydrophobic moiety of
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these products consists of the reaction product of bio-derived ethylenediamine
and excess bio-
derived propylene oxide, and generally has a molecular weight of from about
2500 to about
3000. This hydrophobic moiety is condensed with bio-derived ethylene oxide to
the extent that
the condensation product contains from about 40% to about 80% by weight of bio-
derived
polyoxyethylene and has a molecular weight of from about 5,000 to about
11,000. Examples of
this type of nonionic surfactant include bio-derived analogs of the
commercially available
Tetronice compounds, marketed by BASF.
Fatty alcohol ethoxylates may be obtained additionally through synthetic
organic
transformations starting from algae bioorganic materials. Algae-derived
examples may include
alcohol ethoxylates containing linear radicals from bio-derived alcohols
having 14 to 24 carbon
atoms, e.g., from the hydrogenation of fatty acids and/or fatty acid esters
that are in turn derived
from algal lipids through hydrolysis or transesterification, respectively.
Fatty alcohols may also
be obtained by direct high-pressure hydrogenation of the algae lipid mass and
separation of the
fatty alcohols from the propane diol. The ethoxylation or the propoxylation
(preferably on
average from 4 to about 12 EO, PO, or E0/P0 per mole of alcohol) does not
necessarily have to
come from bio-sources, although that would be preferred. So for example, a
fatty alcohol with
carbon chain directly from algae sources may be conventionally ethoxylated
with ethylene oxide
obtained from petroleum sources (cracked ethylene and oxygen). In this way, a
preferred
detergent surfactant such as C14¨C16 alcohol ethoxylate-7E0 would at least
have about 50% of
the carbon (the C14¨C16 chain) obtained from algae, and about 50% of the
carbon from petroleum
sources (the 7E0, or 14-carbons from the 7-moles of ethylene oxide). More
preferred is to
incorporate bio-derived ethylene oxide as the building blocks for the
ethoxylate (EC)) chains of
these nonionic surfactants to create molecules having all of the carbon bio-
derived. In known
processes, bio-derived ethanol may be dehydrated to ethylene, which may in
turn be oxidized to
ethylene oxide with oxygen. Additionally, once fatty alcohols are obtained
from algae lipids, the
alcohols may be reacted in a Guerbet Reaction ("Guerbetization") to produce
the branched
"Guerbet Alcohols", which then may be ethoxyIated to give bio- derived
branched chain alcohol
ethoxylate surfactants.
Semi-polar nonionic surfactants are a special category of nonionic surfactants
that include
water-soluble amine oxides containing one alkyl moiety of from about 10 to
about 18 carbon
atoms and 2 moieties selected from the group consisting of alkyl groups and
hydroxyalkyl groups
containing from about I to about 3 carbon atoms; water-soluble phosphine
oxides containing one
alkyl moiety of from about 10 to about 1 8 carbon atoms and 2 moieties
selected from the group
consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to
about 3 carbon
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atoms; and water-soluble sulfoxides containing one alkyl moiety of from about
10 to about 18
carbon atoms and a moiety selected from the group consisting of alkyl and
hydroxyalkyl moieties
of from about 1 to about 3 carbon atoms.
Semi-polar nonionic detergent surfactants include the amine oxide surfactants
having the
formula
0\
R3(0R4)11N(R5)2
where R3 is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures thereof
containing from
about 8 to about 22 carbon atoms; R4 is an alkylene or hydroxyalkylene group
containing from
about 2 to about 3 carbon atoms or mixtures thereof; x is from 0 to about 3;
and each R5 is an
alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms or
a polyethylene
oxide group containing from about 1 to about 3 ethylene oxide groups. The R5
groupscan be
attached to each other, e.g., through an oxygen or nitrogen atom, to form a
ring structure.
Preferably, a substantial portion or, more preferably, all of the carbon atoms
in these groups are
bio-derived.
The amine oxide surfactants in particular include C10¨C18 alkyl dimethyl amine
oxides
and C8¨C12 alkoxy ethyl dihydroxy ethyl amine oxides. Spectic examples of bio-
derived amine
oxide surfactants suitable herein include ChemoxideTM SO Surfactant by
Lubrizol, a soy-based
amine oxide, and Genaminox CHE by Clariant.
The nonionic surfactants for use herein further may include, for example, bio-
derived
analogs of alkylpolysaccharides disclosed in U.S. Pat. No. 4,565,647, Llenado,
issued Jan. 21,
1986, having a hydrophobic group containing from about 6 to about 30 carbon
atoms, preferably
from about 10 to about 16 carbon atoms and a polysaccharide, e.g., a
polyglycoside, hydrophilic
group containing from about 1.3 to about 10, preferably from about 1.3 to
about 3, most
preferably from about 1.3 to about 2.7 saccharide units. Any reducing
saccharide containing 5 or
6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties
can be substituted
for the glucosyl moieties. (Optionally the hydrophobic group is attached at
the 2-, 3-, 4-, etc.
positions thus giving a glucose or galactose as opposed to a glucoside or
galactoside.) The
intersaccharide bonds can be, e.g., between the one position of the additional
saccharide units and
the 2-, 3-, 4-, and/or 6- positions on the preceding saccharide units. The
sacchrides may be bio-
derived, such as from algae or from another renewable resource.
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Optionally, and less desirably, there can be a polyalkylene-oxide chain
joining the
hydrophobic moiety and the polysaccharide moiety. The preferred alkyleneoxide
is ethylene
oxide, such as bio-derived ethylene oxide. Typical hydrophobic groups include
alkyl groups,
either saturated or unsaturated, branched or unbranched containing from about
8 to about 18,
preferably from about 10 to about 16, carbon atoms. Preferably, the alkyl
group is a straight
chain saturated alkyl group. The alkyl group can contain up to about 3 hydroxy
groups and/or
the polyalkyleneoxide chain can contain up to about 10, preferably less than
5, alkyleneoxide
moieties. Suitable alkyl polysaccharides are octyl, nonyl, decyl,
undecyldodecyl, tridecyl,
tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl, di-, tri-, tetra-
, penta-, and
hexaglucosides, galactosides, lactosides, glucoses, fructosides, fructoses
and/or galactoses.
Suitable mixtures include coconut alkyl, di-, tri-, tetra-, and
pentaglucosides and tallow alkyl
tetra-, penta-, and hexa-glucosides. Preferably, these groups are obtained
from natural sources so
as to produce bio-derived surfactants.
Polyhydroxy Fatty Acid Amide Surfactant¨The sustainable compositions may also
contain an effective amount of polyhydroxy fatty acid amide surfactant. By
"effective amount"
is meant that the formulator of the composition can select an amount of
polyhydroxy fatty acid
amide to be incorporated into the compositions that will improve the cleaning
performance of the
detergent composition. In general, for conventional levels, the incorporation
of about 1%, by
weight, polyhydroxy fatty acid amide will enhance cleaning performance.
The sustainable compositions herein may comprise about 1% weight basis,
polyhydroxy
fatty acid amide surfactant, preferably from about 3% to about 30%, of the
polyhydroxy fatty
acid amide. The polyhydroxy fatty acid amide surfactant component comprises
compounds of
the structural formula:
0 R1
II I
R2¨C¨N¨Z
where: R1 is H, C1¨C4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, or a
mixture thereof,
preferably C1 -C4 alkyl, more preferably C1 or C2 alkyl, most preferably C1
alkyl (i.e., methyl);
and R2 is a C5¨C31 hydrocarbyl, preferably straight-chain C7¨C19 alkyl or
alkenyl, more
preferably straight chain C9¨C17 alkyl or alkenyl, most preferably straight
chain C11¨C15 alkyl or
alkenyl, or mixtures thereof; and Z is a polyhydroxyhydrocarbyl having a
linear hydrocarbyl
chain with at least 3 hydroxyls directly connected to the chain, or an
alkoxylated derivative
(preferably ethoxylated or propoxylated) thereof. Z preferably will be derived
from a reducing
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sugar in a reductive amination reaction; more preferably Z will be a glycityl.
Suitable reducing
sugars include glucose, fructose, maltose, lactose, galactose, mannose, and
xylose. As raw
materials, high dextrose corn syrup, high fructose corn syrup, and high
maltose corn syrup can be
utilized as well as the individual sugars listed above. These corn syrups may
yield a mix of sugar
components for Z. It should be understood that it is by no means intended to
exclude other
suitable raw materials. Z preferably will be selected from the group
consisting of
¨CH2¨(CHOH)õ¨CH2OH; ¨CH(CH2OH)¨(CHOH)n; ¨CH2OH,
¨CH2¨(CHOH)2(CHOR')(CHOH) ¨CH2OH, and alkoxylated derivatives thereof, where n
is an
integer from 3 to 5, inclusive, and R' is H or a cyclic or aliphatic
monosaccharide. Most
preferred are glycityls wherein n is 4, particularly ¨CH2¨(CHOH)4CH2OH. RI can
be, for
example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-2-hydroxyethyl,
or N-
2-hydroxypropyl. R2¨CO¨N< can be, for example, cocamide, stearamide, oleamide,
lauramide,
myristamide, capricamide, palmitamide, tallowamide, etc. Z can be 1-
deoxyglucityl,
2-deoxyfructityl, 1-deoxymaltityl, 1-deoxylactityl, 1-deoxygalactityl, 1-
deoxymannityl,
1-deoxymaltotriotityl, etc.
Methods for making polyhydroxy fatty acid amides are known in the art. In
general, they
can be made by reacting an alkyl amine with a reducing sugar in a reductive
anation reaction to
form a corresponding N-alkyl polyhydroxyarine, and then reacting the N-alkyl
polyhydroxyamine with a fatty aliphatic ester or triglyceride in a
condensation/amidation step to
form the N-alkyl, N-polyhydroxy fatty acid amide product. Processes for making
compositions
containing polyhydroxy fatty acid amides are disclosed, for example, in G.B.
Patent Specification
809,060, published Feb. 18, 1959, by Thomas Hedley & Co., Ltd.; U.S. Pat. No.
2,965,576,
issued Dec. 20, 1960 to E. R. Wilson; and U.S. Pat. No. 2,703,798, Anthony M.
Schwartz, issued
Mar. 8, 1955; and U.S. Pat. No. 1,985,424, issued Dec. 25, 1934 to Piggott,
each of which is
incorporated herein by reference.
Fatty acid surfactants are also derivable from algae sources. For example, the
fatty acid
surfactants that may be used here have general formula R¨0O2M, where R
represents an algae-
derived linear alkyl (saturated or unsaturated) group having between about 8
and 24 carbons and
M represents an alkali metal such as sodium or potassium or ammonium or alkyl-
or dialkyl- or
trialkyl-ammonium or alkanolammonium cation. The fatty acids of particular use
in the
sustainable compositions include carbon chains of from about 8 to about 24
carbon atoms,
preferably from about 10 to about 20 carbon atoms and most preferably from
about 14 to about
18 carbon atoms. Preferred fatty acids should have similar structure to the
animal derived tallow
or hydrogenated tallow fatty acids and their preferred salts (soaps) are
alkali metal salts, such as
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sodium and potassium or mixtures thereof. That being said, hydrolysis of algae
lipids will
produce a mixture of unsaturated fatty acids and glycerol and the unsaturated
fatty acids may in
turn be hydrogenated as necessary to arrive at more saturated fats. Well known
are purification
processes such as distillation to arrive at particular fatty acid
distribution. So for example, crude
algae triglyceride may be transesterified with methanol and the resulting
fatty acid methyl esters
mixture may be fractionally distilled. The resulting methyl ester distillate
"cuts" may then be
hydrolyzed to yield fatty acids with narrower carbon chain distributions.
Cationic Surfactants¨Cationic detersive surfactants can also be included in
sustainable
compositions of the present invention. Cationic surfactants include the
ammonium surfactants
such as alkyldimethylammonium halogenides, and those surfactants having the
formula:
{R2(0R3)3,}[R4(0R3)5,12R5N+X-
where R2 is an alkyl or alkyl benzyl group having from about 8 to about 18
carbon atoms in the
alkyl chain; each R3 isselected from the group consisting of ¨CH2CH2¨,
¨CH2CH(CH3)
¨CH2CH(CH2OH) ¨CH2CH2CH2¨, and mixtures thereof; each R4 is selected from the
group
consisting of Ci-Caalkyl, CI-Ca hydroxyalkyl, benzyl, ring structures formed
by joining the two
R4 groups, ¨CH2CHOHCHOHCOR6CHOH¨CH 20H wherein R6 is any hexose or hexose
polymer having a molecular weight less than 1000, and hydrogen when y is not
0; R5 is the same
as R4 or is an alkyl chain wherein the total number of carbon atoms of R2 plus
R5 is not more
than about 18; each y is from 0 to about 10 and the sum of the y values is
from 0 to about 15; and
X is any compatible anion. Preferably at least 50%, more preferably all of the
carbon atoms in
the cationic surfactants are bio-derived.
Other cationic surfactants useful herein are also described in U.S. Pat. No.
4,228,044,
Cambre, issued Oct. 14, 1980, incorporated herein by reference.
Other Surfactants¨In addition to the above-mentioned surfactants, ampholytic
surfactants can be incorporated into the sustainable compositions hereof.
These surfactants can
be broadly described as aliphatic derivatives of secondary or tertiary amines,
or aliphatic
derivatives of heterocyclic secondary and tertiary amines in which the
aliphatic radical can be
straight chain or branched. One of the aliphatic substituents contains at
least 8 carbon atoms,
typically from about 8 to about 18 carbon atoms, and at least one contains an
anionic water-
solubilizing group, e.g., carboxy, sulfonate, sulfate. See U.S. Pat. No.
3,929,678 to Laughlin et
al., issued Dec. 30, 1975 at column 19, lines 18-35 for examples of ampholytic
surfactants.
Preferred amphoteric include C12-C18 betaines and sulfobetaines ("sultaines"),
C fo -C 18 amine
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oxides, and mixtures thereof. The ampholytic surfactants preferably contain
carbon atoms that
are bio-derived.
The bio-derived surfactants described above may be formed from a naturally
occurring
lipid by any known method such as by esterification, Fischer esterification,
epoxidation, etc.
Prior to the formation of a bio-derived surfactant, bio-derived fatty acids
may be liberated from
natural lipids by, for example, triglyceride hydrolysis, which separates the
fatty acids from
glycerol. The fatty acids may then be reacted to yield the bio-derived
surfactants, including fatty
alcohol ethoxylates or other high HLB-value surfactants derived from fatty
alcohols. In one
version, a reaction is performed of fatty acids is with an alcohol or an
epoxide. Exemplary
alcohols include methanol, ethanol, propanol, and other primary or secondary
alkyl alcohols.
In ethoxylation, bio-derived ethylene oxide is added to bio-derived fatty
acids or fatty
alcohols, typically in the presence of potassium hydroxide, resulting in the
addition of multiple
ethoxy groups to the molecule. To obtain a bio-derived surfactant with a
relatively high HLB
value that is the product of a natural lipid, ethoxylation is a useful
technique because a chain of
hydrophilic ethoxy groups can be readily added to the molecule. Thus, the bio-
derived
surfactants are preferably obtained through a simple operation or small number
of operations
from the natural raw materials themselves, such as via hydrolysis and
esterification (e.g.,
ethoxylation) or via esterification alone. A hydrogenation step may also be
included prior to or
after esterification (e.g, in the formation of alcohols, hydrogenation may
follow methylation of a
fatty acid). Bio-derived surfactants may be produced from any known method of
ethoxylating
triglycerides such as vegetable oils, including the methods discussed in U.S.
Pat. No. 6,268,517,
"Method for Producing Surfactant Compositions."
For example, if the bio-derived surfactant is an ethoxylated mono-, di-, or
triglyceride, it
may be prepared by the condensation of bio-derived ethylene oxide with a mono-
, di-, or
triglyceride. The reaction may be performed using from 5 to 70 moles, 10 to 50
moles, or 20 to
50 moles of preferably bio-derived ethylene oxide per mole of mono-, di-, or
triglyceride. The
resulting condensation product may have a melting point of at least 15 C, at
least 25 C, or at
least 30 C. As discussed by Ernst W. Flick in Industrial Surfactants, 2nd
ed., p. 230,
ethoxylated fatty acids and polyethylene glycol fatty acid esters are nonionic
mono and diesters
of various fatty acids, typically prepared by the condensation or addition of
ethylene oxide to a
fatty acid at the site of the active hydrogen or by esterification of the
fatty acid with polyethylene
glycol. The chemical structure of the monoester product is generally
R¨00¨(0¨CH2CH2)n¨OH
where R:CO represents the hydrophobic base and n denotes the mole ratio of
oxyethylene to the
base. The diester product has a chemical structure of R¨00¨(0¨CH2CH2)n¨O¨CO¨R.
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U.S. Pat. No. 6,300,508, "Thickened Aqueous Surfactant Solutions," issued Oct.
9, 2001
to Raths, Milstein, and Seipel, herein incorporated by reference to the extent
it is compatible
herewith, describes a method for the production of fatty acid esters of an
ethylene-propylene
glycol of the formula RICOO(E0)õ(PO)y(E0),H where RICO is a linear aliphatic,
saturated or
unsaturated acyl group, or a combination thereof, having from about 6 to about
22 carbon atoms
(though a more specific range of 14 to 22 or 16 to 22 carbon atoms may be
considered), EO is
¨CH2CH2¨, and PO is ¨CH2CH(CH3)0¨ or ¨CH2CH2CH20¨ or a combination thereof.
The
method of U.S. Pat. No. 6,300,508 comprises reacting a fatty acid having from
about 6 to about
22 carbon atoms with an alkylene oxide selected from the group consisting of
propylene oxide,
ethylene oxide or a combination thereof, in the presence of an alkanolamine.
For some
embodiments of the present invention, the use of additional moles of alkylene
oxide reactants
relative to the recommendations of U.S. Pat. No. 6,300,508 may be considered
to increase the
degree of ethoxylation or propoxylaytion and thereby increase HLB. Preferably,
each of the
reactants in these processes is bio-derived.
U.S. Pat. No. 6,221 ,919, "Utilization of Ethoxylated Fatty Acid Esters as
Self-
Emulsifiable Compounds," issued April 24, 2001, to G. Trouve, herein
incorporated by reference
to the extent that it is noncontradictory herewith, discloses methods of
producing ethoxylated
fatty acid esters that may have one or more of the following three formulas:
(A) RI¨00¨ (0¨CH2¨CH2)k-0R2
(B) R3¨00¨ (0¨CH2¨CH2)10R40¨ (CH2¨CH2-0),,¨CO¨R5
(C) R6¨00¨ (0¨CH2¨CH2)n¨O¨R7¨CHRI I¨R9-0¨ (CH2¨CH2-0)q¨CO¨RI
where R" is ¨0¨((0¨CH2¨CH2)n¨CO¨R8; RI , R3, R5, R6, R8 and RI each represent
a linear or
branched, saturated or unsaturated hydrocarbon chain having from 5 to 30
carbon atoms,
preferably from 14 to 30 carbon atoms; and R2, R4, R7 and R9 each represent a
linear or branched,
saturated or unsaturated hydrocarbon chain having from 1 to 5 carbon atoms. US
6,221 ,919
teaches that the values of k, l+m, and n+p+q should be adapted to give HLB
values between
about 4 and about 10, preferably neighboring 5, although higher HLB values are
within the scope
of the present invention, so elevated values of k, l+m, and n+p+q may be
useful.
Example 2 described by U.S. 6,221,919 is specifically incorporated herein by
reference,
for it describes ethoxylation of rapeseed oil via a process that may be useful
for a variety of other
vegetable oils. Ethoxylation is most easily performed by direct condensation
reactions with
ethylene oxide with fatty acids or fats themselves. Ethoxylation can also be
carried out on fatty
acid methyl esters if the appropriate catalysts are used, as described by I.
Hama, T. Okamoto and
H. Nakamura of Lion Corporation, Tokyo, Japan, in "Preparation and Properties
of Ethoxylated
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Fatty Methyl Ester Nonionics," Journal of the American Oil Chemists' Society,
Vol. 72, No. 7,
July, 1995, pp. 781-784. Their method directly inserts EO into fatty methyl
esters (RCOOCH3)
to give [RCO(OCH2CH2)õOCH3] using a solid catalyst modified by metal cations.
Ethoxylates
of fatty methyl esters obtained by this method were homogeneous monoesters and
had good
properties as nonionic surfactants.
Fischer esterification involves forming an ester by refluxing a carboxylic
acid and an
alcohol in the presence of an acid catalyst. Typical catalysts for a Fischer
esterification include
sulfuric acid, tosic acid, and lewis acids such as scandium(III) triflate or
dicyclohexylcarbodiimide.
Vegetable oils, after basic purification, can be processed to produce
methylated or
ethylated seed oils, commonly referred by the abbreviations MSO and ESO,
respectively, which
typically have a single moiety added, unlike epoxidation reactions which can
add numerous
groups. MSOs and ESOs are created by hydrolysis of the glycerol molecule from
the fatty acids,
and the acids are then esterified with methanol or ethanol. Such compounds can
be used as bio-
derived surfactants in the sustainable composition, but when higher HLB values
are desired,
additional hydrophilic groups should be added.
Examples of commercially available compositions comprising bio-derived
surfactants
that may be used within the sustainable compositions described herein include,
without
limitation, the following:
SC-1000TM, a surface washing agent marketed by GemTek Products (Phoenix, AZ).
SC1000TM is part of GemTek's SAFE CARE product series, that are said to
contain alcohols,
fatty acids, esters, waxes, saponifiers, chelators, enzymes and other
fractions from soy, corn,
palm kernel, peanut, walnut, safflower, sunflower, Canola, and cotton seed.
SoyFastTM Manufacturer's Base marketed by Soy Technologies (Nicholasville,
Kentucky)
as a soy-based biodegradable all-purpose cleaner, and related soy-based
products such as
SoyFastTM Cleaner and SoyGreenTM Solvents. Manufacturer's Base, according to
its MSDS,
comprises two bio-derived surfactants, ethoxylated castor oil (average degree
of ethoxylation
said to be about 30) and soybean oil methyl ester (formed by reaction of
soybean oil with
methanol, resulting in hydrolysis of the triglyceride to yield methylated
fatty acids and glycerol).
It also comprises pentanedioic acid, dimethyl ester; butanedioic acid,
dimethyl ester; hexanedioic
acid, dimethyl ester; and polyoxyethylene tridecyl ester.
Soy-Dex Plus marketed by Helena Chemical Co. (Memphis, Tennessee), said to be
a
proprietary blend of vegetable oil, polyol fatty acid ester, polyethoxylated
esters thereof, and
ethoxylated alkylaryl phosphate ester.
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Esterified vegetable oils, for example from Cognis Corp. (Monheim, Germany),
including
AGNIQUE SBO-10 Ethoxylated Soybean Oil, POE 10; AGNIQUE SBO-30 Ethoxylated
Soybean Oil POE 30; AGNIQUE SBO-42 (Trylox 5919-C) Ethoxylated Soybean Oil,
POE 42;
AGNIQUE SBO- 60 Ethoxylated Soybean Oil POE 60; AGNIQUE CSO-44 (Mergital EL
44)
Ethoxylated Castor Oil, POE (polyoxyethylene) 44; AGNIQUE CSO-60H (Eumulgin
HRE 60)
Hydrogenated Ethoxylated Castor Oil, POE 60; AGNIQUE CSO-200 (Etilon R 200)
Ethoxylated
Castor Oil, POE 200; AGNIQUE RS0-0303 (Eumulgin CO 3522) Alkoxylated Rapeseed
Oil,
POE 3, POP (polyoxypropylene) 3; AGNIQUE RSO-2203 (Eumulgin CO 3526)
Alkoxylated
Rapeseed Oil, POE 3, POP 22; AGNIQUE RSO-30 (Eumulgin CO 3373) Ethoxylated
Rapeseed
Oil, POE 30. Also, Ethoxolated Soybean Oil, marketed by Adjuvants Unlimited of
Memphis,
TN, as AU970 could be used.
TOXIMUL ethoxylated castor oils from Stepan Chemical (Northfield, Illinois),
including TOXIMUL 8240 (P0E-36), TOXIMUL 8241 (POE- 30), and TOXIMUL 8242
(P0E-40).
Genapol surfactants by Hoechst Chemical, such as Genapol OXD-080, a fatty
alcohol
polyglycol ether.
Ethoxylated castor oil is available as Shree Chem-Co 35 from Shree Vallabh
Chemicals
(Gujarat, India). In Shree Chem-Co 35, the hydrophobic constituents comprise
about 83% of the
total mixture, the main component being glycerol polyethylene glycol
ricinoleate. Other
hydrophobic constituents include fatty acid esters of polyethylene glycol
along with some
unchanged castor oil. The hydrophilic part (17%) consists of polyethylene
glycols and glycerol
ethoxylates. In a related compound, Shree Chem-Co 40, approximately 75% of the
components
of the mixture are hydrophobic. These comprise mainly fatty acid esters of
glycerol polyethylene
glycol and fatty acid esters of polyethylene glycol. The hydrophilic portion
consists of
polyethylene glycols and glycerol ethoxylates.
Ethoxylated castor oil and hydrogenated castor oil products marketed by Global
Seven
Corp. (Franklin, NJ). These products, marketed as emulsifiers, solubilizers,
and conditioners,
include HETOXIDE C-200, a PEG-200 castor oil compound having an HLB of 18.1;
HETOXIDE C-81, a PEG-81 castor oil compound said to have an HLB of 15.9;
HETOXIDE C-
40, a PEG-40 castor oil compound having an HLB of 13.0; HETOXIDE C-30, a PEG-
30 castor
oil compound having an HLB of 11.8; HETOXIDE C25, a PEG-25 castor oil compound
having
an HLB of 10.8; HETOXIDE C-16, a PEG-16 castor oil compound having an HLB of
8.6; and
I IETOXIDE C-5, a PEG-5 castor oil compound having an HLB of 4Ø
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In an example embodiment, the bio-derived surfactants of the present
sustainable
compositions comprise surfactants obtained by esterification of vegetable
lipids. In a particular
embodiment, the lipids are selected from soybean oil and castor oil. These may
also be derived
from single cell organisms, such as bacteria, algae, yeast, and fungi. The
major unsaturated fatty
acids in soybean oil triglycerides are 7% linolenic acid (C-18:3); 51%
linoleic acid (C-18:2); and
23% oleic acid (C-18:1). Castor oil is a triglyceride in which about 85% to
95% of the fatty acids
are ricinoleic acid (C18:1-0H), about 2% to 6% are oleic acid (C-18:1), about
1% to 5% is
linoleic acid (C-18:2), with there being about 0.3% to 1% each of linolenic
acid (C18:3), stearic
acid (C18:0), palmitic acid (C16:0), and dihydroxystearic acid, with small
amounts of some other
acids.
Additional steps, such as hydrogenation and dehydrogenation may be
contemplated. In
one embodiment, the bio-derived compound comprises an ester of a fatty acid,
wherein the fatty
acid has not been chemically modified apart from the formation of an ester
bond to join the fatty
acid to a hydrophilic moiety. Alternatively, a bio-derived surfactant may be
the ethoxylated
product of a naturally occurring fatty acid or lipid.
Other bio-derived or natural surfactants may be included in the sustainable
composition,
such as the rhamnolipids and rhamnolipid derivatives marketed by Jeneil
Biosurfactant Company
(Saukville, Wisconsin), such as JBR425 (CAS Number: 147858-26-2) as well as
those described
in U.S. Pat. No. 5,455,232, "Pharmaceutical Preparation Based in Rhamnolipid,"
issued Oct. 3,
1995 to Piljac and Piljac, or in U.S. Pat. No. 7,129,218, "Use of Rhamnolipids
in Wound
Healing, Treatment and Prevention of Gum Disease and Periodontal
Regeneration," issued Oct.
31, 2006 to Stipcevic et al. Lipopeptide biosurfactants such as those produced
by Bacillus
species may also be included. Natural plant oils may be provided in the form
of oil cakes that
can be used.
Adjuncts
The sustainable compositions optionally contain one or more of the following
adjuncts:
enzymes such as protease, amylase, mannanase, and lipase, stain and soil
repellants, lubricants,
odor control agents, perfumes, builders, fragrances and fragrance release
agents, reducing agents
such as sodium sulfite, and bleaching agents. Other adjuncts include, but are
not limited to,
acids, pH adjusting agents, electrolytes, dyes and/or colorants, solubilizing
materials, stabilizers,
thickeners, defoamers, hydrotropes, cloud point modifiers, preservatives, and
other polymers.
Electrolytes, when used, include, calcium, sodium and potassium chloride.
Preferably the
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adjuncts are bio-derived. Optional pH adjusting agents include inorganic acids
and bases such as
sodium hydroxide, and organic agents such as monoethanolamine, diethanolamine,
and
triethanolamine, preferably bio-derived. Thickeners, when used, include, but
are not limited to,
polyacrylic acid, xanthan gum, calcium carbonate, aluminum oxide, alginates,
guar gum, methyl,
ethyl, clays, and/or propyl hydroxycelluloses, preferably bio-derived.
Defoamers, when used,
include, but are not limited to, silicones, aminosilicones, silicone blends,
and/or
silicone/hydrocarbon blends, all preferably bio-derived. Bleaching agents,
when used, include,
but are not limited to, peracids, hypohalite sources, hydrogen peroxide,
and/or sources of
hydrogen peroxide. In a preferred embodiment, the sustainable composition
includes a builder
such as ethylenediamine disuccinate. In a suitable embodiment the compositions
contain an
effective amount of one or more of the following bio-derived enzymes:
protease, lipase, amylase,
cellulase, and mixtures thereof Suitable enzymes are available from
manufacturers including,
but not limited to, Novozymese and Genencor .
Any suitable adjunct ingredient in any suitable amount may be used in the
cleaning
detergent composition. Suitable adjunct ingredients as described herein may be
substantially
sodium ion-free. Suitable adjunct ingredients may include, but are not limited
to: co-surfactants;
suds suppressors; builders; enzymes; bleaching systems; dispersant polymers;
carrier media;
thickeners and mixtures thereof.
Other suitable adjunct ingredients may include, but are not limited to: enzyme
stabilizers,
such as calcium ion, boric acid, bio-derived propylene glycol, bio-derived
short-chain carboxylic
acids, boronic acids, and mixtures thereof chelating agents, such as, alkali
metal bio-derived
ethane 1-hydroxy diphosphonates (HEDP), bio-derived alkylene poly (alkylene
phosphonate), as
well as, amino phosphonate compounds, including amino aminotri(methylene
phosphonic acid)
(ATMP), bio-derived nitrilo trimethylene phosphonates (NTP), bio-derived
ethylene diamine
tetra methylene phosphonates, and bio-derived diethylene triamine penta
methylene
phosphonates (DTPMP); alkalinity sources; water softening agents; secondary
solubility
modifiers; soil release polymers; hydrotropes; binders; antibacterial actives,
such as bio-derived
citric acid, bio-derived benzoic acid, bio-derived benzophenone, bio-derived
thymol, bio-derived
eugenol, bio-derived menthol, bio-derived geraniol, bio-derived vertenone, bio-
derived
eucalyptol, bio-derived pinocarvone, bio-derived cedrol, bio-derived anethol,
bio-derived
carvacrol, bio-derived hinokitiol, bio-derived berberine, bio-derived ferulic
acid, bio-derived
cinnamic acid, bio-derived methyl salicylic acid, bio-derived methyl
salicylate, bio-derived
terpineol, bio-derived limonene, and halide-containing compounds; detergent
fillers, such as
potassium sulfate; abrasives, such as, quartz, pumice, pumicite, titanium
dioxide, silica sand,
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calcium carbonate, zirconium silicate, diatomaceous earth, whiting, and
feldspar; anti-
redeposition agents, such as organic phosphate; anti-oxidants; metal ion
sequestrants; anti-tarnish
agents, such as benzotriazole; anti-corrosion agents, such as, aluminum-,
magnesium-, zinc-
containing materials (e.g. hydrozincite and zinc oxide); processing aids;
plasticizers, such as, bio-
derived propylene glycol, and bio-derived glycerine; thickening agents, such
as bio-derived
cross-linked polycarboxylate polymers with a weight-average molecular weight
of at least
500,000 (e.g. CARBOPOLO 980 from B. F. Goodrich), naturally occurring or
synthetic clays,
bio-derived starches, bio-derived celluloses, bio-derived alginates, and
natural gums, (e.g.
xanthum gum); aesthetic enhancing agents, such as bio-derived dyes, bio-
derived colorants, bio-
derived pigments, bio-derived speckles, bio-derived perfume, and bio-derived
oils; preservatives;
and mixtures thereof. Suitable adjunct ingredients may contain low levels of
sodium ions by way
of impurities or contamination. In certain non-limiting embodiments, adjunct
ingredients may be
added during any step in the process in an amount from about 0.0001% to about
91.99%, by
weight of the composition.
Adjunct ingredients suitable for use are disclosed, for example, in U.S. Pat.
Nos.:
3,128,287; 3,159,581; 3,213,030; 3,308,067; 3,400,148; 3,422,021; 3,422,137;
3,629,121;
3,635,830; 3,835,163; 3,923,679;3,929,678; 3,985,669; 4,101,457; 4,102,903;
4,120,874;
4,141,841; 4,144,226; 4,158,635; 4,223,163; 4,228,042; 4,239,660; 4,246,612;
4,259,217;
4,260,529; 4,530,766; 4,566,984; 4,605,509; 4,663,071; 4,663,071; 4,810,410;
5,084,535;
5,114,611; 5,227,084; 5,559,089; 5,691,292; 5,698,046; 5,705,464; 5,798,326;
5,804,542;
5,962,386; 5,967,157; 5,972,040; 6,020,294; 6,113,655; 6,119,705; 6,143,707;
6,326,341;
6,326,341; 6,593,287; and 6,602,837; European Patent Nos.: 0,066,915;
0,200,263; 0332294;
0414 549; 0482807; and 0705324; PCT Pub. Nos.: WO 93/08876; and WO 93/08874.
Builders
The sustainable compositions optionally may comprise one or more builders.
Builders
for use in the sustainable compositions include non-phosphate builders. If
present, builders are
used in a level of from 5% to 60%, preferably from 10% to 50% by weight of the
sustainable
composition. In another embodiment, the builders are present in an amount of
up to 50%, more
preferably up to 45%, even more preferably up to 40%, and especially up to 35%
by weight of
the composition. The compositions of the present invention are preferably
phosphate free or
essentially free, and most preferably comprise carbon atoms that are bio-
derived.
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One example of a builder is an aminocarboxylic builder. Preferably the
aminocarboxylic
builder is an aminopolycarboxylic builder, more preferably a glycine-N,N-
diacetic acid or
derivative of general formula MO0C-CHR-N(CH2COOM)2, where R is a C1-12 alkyl
and M is
alkali metal. Aminocarboxylic builders may include MGDA (methyl-glycine-
diacetic acid),
GLDA (glutamic-N,N-diacetic acid), iminodisuccinic acid (IDS), carboxymethyl
inulin and salts
and derivatives thereof. MGDA (salts and derivatives thereof) is especially
preferred according
to the invention, with the tri-sodium salt thereof being preferred and a
sodium/potassium salt
being specially preferred for the low hygroscopicity and fast dissolution
properties of the
resulting particle. Preferably, the aminocarboxylic acid builders are obtained
from bio-derived
sources of carbon.
Other suitable aminocarboxylic builders include; for example, aspartic acid-N-
monoacetic
acid (ASMA), aspartic acid-N,N-diacetic acid (ASDA), aspartic acid-N-
monopropionic acid
(ASMP) , iminodisuccinic acid (IDA), N-(2-sulfomethyl) aspartic acid (SMAS), N-
(2-sulfoethyl)
aspartic acid (SEAS), N-(2-sulfomethyl) glutamic acid (SMGL), N-(2-sulfoethyl)
glutamic acid
(SEGL), IDS (iminodiacetic acid) and salts and derivatives thereof such as N-
methyliminodiacetic acid (MIDA), alpha-alanine-N,N-diacetic acid (alpha-ALDA),
serine-N,N-diacetic acid (SEDA), isoserine-N,N-diacetic acid (ISDA),
phenylalanine-N,N-diacetic acid (PHDA), anthranilic acid-N,N-diacetic acid
(ANDA), sulfanilic
acid-N,N-diacetic acid (SLDA), taurine-N,N-diacetic acid (TUDA) and
sulfomethyl-N,N-diacetic
acid (SMDA), and alkali metal salts and derivative thereof.
In addition to the aminocarboxylic builders in the sustainable article, the
composition can
comprise carbonate and/or citrate.
Other non-phosphate builders include homopolymers and copolymers of
polycarboxylic
acids and their partially or completely neutralized salts, monomeric
polycarboxylic acids and
hydroxycarboxylic acids and their salts. Preferred salts of the abovementioned
compounds are
the ammonium and/or alkali metal salts, i.e. the lithium, sodium, and
potassium salts, and
particularly preferred salts are the sodium salts.
Suitable polycarboxylic acids are acyclic, alicyclic, heterocyclic and
aromatic carboxylic
acids, in which case they contain at least two carboxyl groups which are in
each case separated
from one another by, preferably, no more than two carbon atoms.
Polycarboxylates which
comprise two carboxyl groups include, for example, water-soluble salts of,
malonic acid,
(ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid,
tartronic acid and
fumaric acid. Polycarboxylates which contain three carboxyl groups include,
for example, water-
soluble citrate. Correspondingly, a suitable hydroxycarboxylic acid is, for
example, citric acid.
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Another suitable polycarboxylic acid is the homopolymer of acrylic acid. Other
suitable builders
are disclosed in WO 95/01416. Carboxylic acids and, particularly acrylic acid
derivatives,
preferably are obtained from bio-derived sources.
Enzymes
Enzymes may be included in the sustainable compositions. One such enzyme
includes a
protease. Suitable proteases include metalloproteases and serine proteases,
including neutral or
alkaline microbial serine proteases, such as subtilisins (EC 3.4.21.62).
Suitable proteases include
those of animal, vegetable or microbial origin. Another enzyme for use herein
includes alpha-
amylases, including those of bacterial or fungal origin. Chemically or
genetically modified
mutants (variants) are included. Additional enzymes suitable for use in the
sustainable
composition can comprise one or more enzymes selected from the group
comprising
hemicellulases, cellulases, cellobiose dehydrogenases, peroxidases, proteases,
xylanases, lipases,
phospholipases, esterases, cutinases, pectinases, mannanases, pectate lyases,
keratinases,
reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases,
tannases,
pentosanases, malanases,13-glucanases, arabinosidases, hyaluronidase,
chondroitinase, laccase,
amylases, and mixtures thereof.
SUSTAINABLE CONSUMER PRODUCTS
A sustainable consumer product may comprise a sustainable container, as
described
above, and a sustainable composition, as also described above. The sustainable
consumer
product may further comprise secondary packaging around the sustainable
container having the
sustainable composition therein. The secondary packaging, as well as any label
on the
sustainable container, may comprise a suitable consumer message in the form of
printed indicia,
for example.
Secondary Packaging
The sustainable article as a whole or, alternatively, components of the
sustainable article
such as the sustainable container, the sustainable closure, the sustainable
dispenser, or
combinations thereof, may be packaged within a secondary packaging such as a
tub, a bag, a
shrink-wrapped bundle, a display pack comprising an outer package such as a
see-through
container, for example a transparent or translucent carton or bottle which
contains a plurality of
sustainable containers or other associated products (such as a cleaning
implement having a
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cleaning pad for spreading the sustainable composition, for example) in a
multiplicity of visually
or otherwise sensorially distinctive groups. By visually distinctive herein is
meant that the
groups can be distinguished in terms of shape, color, size, pattern, ornament,
etc. Otherwise the
groups are distinctive in terms of providing a unique sensorial signal such as
smell, sound, feel,
etc.
The secondary packaging can be made of plastic or any other suitable material,
provided
the material is strong enough to protect the sustainable container during
transport. Preferably, the
plastic or other suitable material comprises at least 50%, at least 75%, at
least 90%, at least 95%,
at least 99%, or even 100% bio-derived material. Alternatively, the pack can
have non-see-
through outer packaging, perhaps with indicia or artwork representing the
contents of the pack.
In further embodiments, when multiple sustainable containers are stored in a
container or
containers through at least a portion of which the sustainable containers
contained therein may be
seen, preferably as images on the printed material. Preferably the optional
image is linked
conceptually to graphic on the portions of the container through which the
sustainable container
may not be seen through. For example, the printed image may be of a lemon the
graphic on the
outside of the container may include images of lemons or odor-control
functionality and/or a
written reference to the lemon or citrus themes or odor-control functionality.
This provides a
strong and reinforced message to the consumer about the benefits of using the
product.
The printed images preferably are formed with bio-derived inks. The inks can
be solvent-
based or water-based. In some embodiments, the ink is derived from a renewable
resource, such
as soy, a plant, or a mixture thereof. The ink can be cured using heat or
ultraviolet radiation
(UV). In some preferred embodiments, the ink is cured by UV, which results in
a reduction of
curing time and energy output. Nonlimiting examples of bio-derived inks
include ECO-
SURE!TM from Gans Ink & Supply Co. and the solvent-based VUTEke and BioVuTM
inks
from EFI, all of which are derived completely from renewable resources (e.g.,
corn).
The secondary packaging or containers preferably are made from bio-derived
and/or
biodegradable products such as from bio-derived paper or bio-derived plastic,
and from
biodegradable or bioplastic resins. Bioplastic resins may include bio-derived
polyhydroxyalkanoate (PHA), bio-derived poly 3-hydroxybutrate-co-3-
hydroxyhexanote
(PHBH), bio-derived polyhydroxybutyrate-co -valerate (PHB/V), bio-derived poly-
3-
hydroxybutyrate (PHB), chemical synthetic polymer such as bio-derived
polybutylene succinate
(PBS), bio-derived polybutylene succinate adipate (PBSA), bio-derived
polybutylene succinate
carbonate, bio-derived polycaprolactone (PCL), bio-derived cellulose acetate
(PH), bio-derived
polylactic acid/chemical synthetic polymer such as bio-derived polylactic
polymer (PLA) or bio-
.
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derived copoly-L-lactide (CPLA), and naturally occurring polymer, such as
starch modified
PVA+aliphatic polyester, or corn starch.
Polylactic acid (PLA) is a transparent bioplastic produced from corn, beet and
cane sugar.
It not only resembles conventional petrochemical mass plastics, such as
polyethelene (PE),
polyethylene terephthalate (PET or PETE), high density polyethylene (HDPE) and
polypropene
(PP) in its characteristics, but it can also be processed easily on standard
equipment that already
exists for the production of conventional plastics. PLA and PLA-blends
generally come in the
form of PA010-103 granulates with various properties and are used in the
plastic processing
industry for the production of foil, molds, cups, bottles and other packaging.
The bio-derived polymer poly-3-hydroxybutyrate (PHB) is polyester produced by
certain
bacteria processing glucose or starch. Its characteristics are similar to
those of the petro plastic
polypropylene. The South American sugar industry, for example, has decided to
expand PHB
production to an industrial scale. PHB is distinguished primarily by its
physical characteristics.
It produces transparent film at a melting point higher than 130 C, and is
biodegradable without
residue.
Biodegradable resins may be made into products that are relatively rigid with
good
transparency, and thus use of these resins may be appropriate for rigid molded
products, such as
the secondary packaging described above.
The bio-derived plastic material may include a single, composite layer of
bioplastic resin
mixed with plasticizer. This material may be provided as a resin, which can be
formed into the
desired shape. Here, the plasticizer and resin cooperate to form a bio-derived
plastic material
that may be generally impermeable to fluids. The bioplastic resin may, for
example, be PLA,
PHA, PUB, PHBH, PBS, PBSA, PCL, PH, CPLA or PVA. The plasticizer may be a
silicone
such as, but not limited to, polydimethyl siloxane with filler and auxiliary
agents, alkylsilicone
resin with alkoxy groups with filler and auxiliary agents and
isooctyltrimethoxysilane or silicone
oxide, and silicone dioxide. The bioplastic resin and silicone may be mixed to
form a new resin.
This resin may have been shown to have improved barrier properties, resulting
in permeability
rates to less than or equal to from 0.5 to 3 units for water vapor, oxygen
from 75 to 1400 units,
and carbon dioxide from 200 to! 800 units, measured; at g-mil/100 square inch
per day for water
at 100% RH, and cc-mill/100 sq inch day atm at 20 C and 0% RH for at 100%
oxygen and
carbon dioxide.
Additionally, bio-derived paper and bio-derived plastic resins (namely, for
example, PLA,
PHA, PHB, PHBH, PBS, PBSA, PCL, PH, CPLA and PVA) may be coated with
ultraviolet
curable acrylates, preferably bio-derived acrylates, to form a bio degradable
container. Some of
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these ultraviolet curable acrylates are suitable for storing consumable
materials and are Food and
Drug Administration (FDA) approved, namely tripropylene glycol diacrylate,
trimethylolpropane
triacrylate, and bisphenol A diglycidal ether diacrylate. Other ultraviolet
cured materials might
not be FDA approved, but could still be used to coat a biodegradable
container.
In some embodiments, one or more sustainable articles described herein and
packaged in
a sustainable secondary packaging material may be further packaged or bundled
in a sustainable
tertiary packaging, for example, in a multi-pack or in a suitable shipping
container. In such
embodiments, the materials for the tertiary packaging preferably are bio-
derived and are made
from one or more of the materials described above with regard to the secondary
packaging. The
material of the tertiary packaging may be the same as or different from the
material of the
secondary packaging. The tertiary packaging can be labeled independently from
the secondary
packaging, preferably using the sustainable labels described above, the bio-
derived inks
described above, or both.
Consumer Message
The sustainable article or container, the sustainable label thereon, the
secondary
pacakging, or a combination thereof, may further comprise a related
environmental message that
communicates a related environmental message to a consumer. The related
environmental
message may convey the benefits or advantages of the sustainable composition
contained in the
sustainable article or container, particularly that the sustainable
composition, the packaging, or
both, comprise or consist of a polymer derived from a renewable resource. The
related
environmental message may identify the sustainable composition and its
packaging as: being
environmentally friendly or Earth friendly; having reduced petroleum (or oil)
dependence or
content; having reduced foreign petroleum (or oil) dependence or content;
having reduced
petrochemicals or having components that are petrochemical free; and/or being
made from
renewable resources or having components made from renewable resources. This
communication is of importance to consumers that may have an aversion to
petrochemical use
(e.g., consumers concerned about depletion of natural resources or consumers
who find
petrochemical based products unnatural or not environmentally friendly) and to
consumers that
are environmentally conscious. Without such a communication, the benefit of
the present
invention maybe lost on some consumers.
The communication may be effected in a variety of communication forms.
Suitable
communication forms include store displays, posters, billboard, computer
programs, brochures,
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package literature, shelf information, videos, advertisements, Internet web
sites, pictograms,
iconography, or any other suitable form of communication. The information
could be available
at stores, on television, in a computer-accessible form, in advertisements, or
any other
appropriate venue. Ideally, multiple communication forms may be employed to
disseminate the
related environmental message.
The communication may be written, spoken, or delivered by way of one or more
pictures,
graphics, or icons. For example, a television or Internet based-advertisement
may have narration,
a voice-over, or other audible conveyance of the related environmental
message. Likewise, the
related environmental message may be conveyed in a written form using any of
the suitable
communication forms listed above. It may be desirable to quantify the
reduction of
petrochemical usage of the sustainable composition compared to other
sustainable compositions
that are presently commercially available. The communication form may be one
or more icons,
such as those shown in FIGS. 3A-3F of WO 2007/109128, hereby incorporated by
reference.
The one or more icons may be used to convey the related environmental message
of reduced
petrochemical usage. Icons communicating the related environmental message of
environmental
friendliness or renewable resource may be used. The icons may be located on
the unit-dose
pouch, on the secondary packaging, or both. Preferably, the icons and any
graphics on the pouch
or packaging are printed with biodegradable and/or bio-derived inks.
The related environmental message may also include a message of petrochemical
equivalence. Because many renewable, naturally occurring, bio-derived, or non-
petroleum
derived polymers often are perceived to lack the performance characteristics
that consumers have
come to expect when used in absorbent articles, a message of petroleum
equivalence may be
necessary to educate consumers that the polymers derived from renewable
resources, as
described above, exhibit equivalent or better performance characteristics as
compared to
petroleum derived polymers. Thus, a suitable petrochemical equivalence message
can include
comparison to a sustainable composition that does not have a polymer derived
from a renewable
resource. For example, a suitable combined message may be, "Sustainable
Composition A with
bio-derived ingredients is just as effective as Petroleum-Derived Composition
B." This message
conveys both the related environmental message and the message of
petrochemical equivalence.
The dimensions and values disclosed herein are not to be understood as being
strictly
limited to the exact numerical values recited. Instead, unless otherwise
specified, each such
dimension is intended to mean both the recited value and a functionally
equivalent range
surrounding that value. For example, a dimension disclosed as "40 mm" is
intended to mean
"about 40 mm".
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Every document cited herein, including any cross referenced or related patent
or
application, is hereby incorporated herein by reference in its entirety unless
expressly excluded or
otherwise limited. The citation of any document is not an admission that it is
prior art with
respect to any invention disclosed or claimed herein or that it alone, or in
any combination with
any other reference or references, teaches, suggests or discloses any such
invention. Further, to
the extent that any meaning or definition of a term in this document conflicts
with any meaning
or definition of the same term in a document incorporated by reference, the
meaning or definition
assigned to that term in this document shall govern.
While particular embodiments of the present invention have been illustrated
and
described, it would be obvious to those skilled in the art that various other
changes and
modifications can be made without departing from the spirit and scope of the
invention. It is
therefore intended to cover in the appended claims all such changes and
modifications that are
within the scope of this invention.
