Note: Descriptions are shown in the official language in which they were submitted.
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CLEANING IMPLEMENTS AND DISPOSABLE SUBSTRATES COMPRISING
SUSTAINABLE MATERIALS, AND SUSTAINABLE CLEANING
COMPOSITIONS FOR USE THEREWITH
TECHNICAL FIELD
implements, disposable substrates for the cleaning implements, and cleaning
compositions for
use with the cleaning implements and the disposable substrates, wherein the
cleaning implements
and/or the disposable substrates and/or the cleaning compositions include or
are made from
sustainable materials including one or more bio-derived source of carbon.
BACKGROUND
Consumer cleaning implements, their cleaning substrates, and cleaning
compositions for use with
the cleaning implements, typically comprise a number of organic ingredients
such as plastics,
fibers, surfactants, builders, polymers, and adjuncts. As used here, "organic
ingredients" refers
to ingredients containing chemical compositions having carbon atoms. In
typical commercial
In view of current global drivers to decrease reliance on petroleum sources,
owing at least in part
both to decreasing supplies of petroleum and also to increased concern about
global warming
caused from carbon dioxide emissions during petroleum capture and refining,
there is a constant
Thus, there remains a need for consumer products such as cleaning implements,
their cleaning
SUMMARY
In view of these needs, embodiments disclosed herein are directed to consumer
products, in
which a portion, a substantial portion, or all of the carbon atoms in the
products are bio-derived.
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In a first aspect, embodiments are directed to disposable surface cleaning
sheets, wipes, dusters,
and pads made from bio-derived polymers or bio-derived fibers.
In a second aspect, embodiments are directed to surface cleaning fibrous
substrates, for which a
substantial portion of the fibers in the substrates are bio-derived fibers or
petroleum-based fibers
formed from non-virgin petroleum-based sources such as post-consumer recycled
plastics, post-
industrial recycled plastics, and/or regrind plastics.
In a third aspect, embodiments are directed to surface cleaning pads that
contain absorbent
gelling materials derived at least in part from bio-acrylic acid.
In a fourth aspect, embodiments are directed to surface cleaning substrates
that include coatings
made from bio-derived paraffins, bio-derived polymers or natural coating, bio-
derived solvents,
or combinations thereof. One example of a coating may include microcrystalline
wax.
In a fifth aspect, embodiments are directed to cleaning implements made from
bio-derived
polymers such as, for example, bio-derived polyethylene (Bio-PE), bio-derived
high-density
polyethylene (Bio-HDPE), bio-derived polypropylene (Bio-PP), bio-derived
polyethylene
terephthalate (Bio-PET), or combinations thereof. In one embodiment, the
polymer is recycled
polymer such as a recycled PET (or "rPET"). In yet another embodiment, the
polymer is a
combination of recycled and bio-dervied materials. For example, the polmer may
be a
combination of Bio-PET and rPET.
In a sixth aspect, embodiments are directed to cleaning compositions for use
with the above
cleaning sheets, fibrous substrates, surface cleaning pads, surface cleaning
substrates, and
cleaning implements. The cleaning compositions may include at least one bio-
derived surfactant.
The cleaning compositions may further comprise one or more components selected
from bio-
derived solvents, bio-derived chelants, bio-derived thickeners, natural
thickeners in combination
with bio-derived thickeners, and additional non-bio-derived surfactants.
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.
Unless otherwise indicated, all numbers expressing quantities of ingredients,
properties such as
molecular weight, reaction conditions, and so forth as used in the
specification and claims are to
be understood as being modified in all instances by the term "about."
Accordingly, unless
otherwise indicated, the numerical properties set forth in the specification
and claims are
approximations that may vary depending on the desired properties sought to be
obtained in
embodiments of the present invention. Notwithstanding that the numerical
ranges and
parameters setting forth the broad scope of the invention are approximations,
the numerical
values set forth in the specific examples are reported as precisely as
possible. One of ordinary
skill in the art will understand that any numerical values inherently contain
certain errors
attributable to the measurement techniques used to ascertain the values.
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. Thus, "bio-derived compounds" typically are compounds produced from
a naturally
occurring substance obtained from a plant, animal, or microbe, and then
modified via chemical
reaction. Modification 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.
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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"; and "naturally-derived" are used synonymously herein.
petroleum or a petrochemical feedstock.
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. Conversely, "non-virgin petroleum-based"
refers to
"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
"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.
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",
"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 have few radioisotopes in their population. Carbon of fossil origin is
identifiable by means
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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
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 LCI.
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".
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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 14C/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.
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.
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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 (14C) 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
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.
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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.
By 'cleaning tool' it is meant any material used to clean surfaces. A cleaning
tool, as defined
herein, must directly contact the surface to be cleaned. Cleaning tool
materials include
conventional cleaning aids such as sponges, cloths, cellulose strings or
strips, paper or
commercially available paper towel, as well as novel cleaning tools including
disposable or
durable floor wipe cloths, cleaning sheets, laminates or other substrates and
absorbent disposable
cleaning pads.
By 'implement' or 'cleaning implement', it is meant any material used in
conjunction with
cleaning tools to make the cleaning job easier, more efficient or more
convenient. Cleaning
implements consist of handles, mop heads or other cleaning substrate
attachment heads, or short
or long pole or telescoping pole attachments with or without the attachment
heads, or other
means used to attach, in any manner possible, a cleaning tool.
By 'absorbent' it is meant any material or laminate that can absorb at least
about 1 gram of de-
ionized water per gram of said material.
By 'absorbent disposable cleaning pad' it is meant an absorbent pad that is
typically used for a
cleaning job and then disposed of. Absorbent disposable cleaning pads can
range from simple
dry absorbent non-woven structures to multi-layered absorbent composites.
While it is
understood that some pad designs can be used, stored and re-used, the amount
of re-use is limited
and is typically determined by the ability of the pad to continue to absorb
more liquid and/or dirt.
Unlike conventional systems such as sponge mops, strip and string mops, which
are considered
fully re-usable, once saturated, an absorbent disposable pad is not designed
to be reversed by the
consumer to get it back to its original state.
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Embodiments of the present invention include disposable substrates, cleaning
implements, and
cleaning compositions, any or each of which may comprise or be formed from a
sustainable
material, preferably a bio-derived material. The disposable substrates,
cleaning implements, and
cleaning compositions may be used together as part of a cleaning system, or
may be used
separately for any desired purpose. In a preferred embodiment, the cleaning
implements support
a disposable substrate. In another preferred embodiment, the cleaning
implement supports a
disposable substrate containing a liquid cleaning composition.
Cleaning Substrates
Dry Disposable Substrates
According to one aspect, the present invention relates to a cleaning sheet
useful for removing
dust, lint, hair, grass, sand, food crumbs and other matter of various size,
shape, consistency, etc.,
from a variety of surfaces. The cleaning sheet may be in the form of a simple
sheet, a wipe, a
duster, or a pad, for example. Relative to other products and practices for
similar cleaning
purposes, the sheets have an increased ability to contact and hold materials
such as dust, lint, and
other airborne matter. This ability to hold such materials reduces the levels
of such materials that
may be left on surfaces or dispersed into the atmosphere by the other products
or practices. This
ability is especially apparent in embodiments described herein, in which the
sheets contain
additives. In such embodiments, a low level of additive may be uniformly
attached on at least
one area of the sheet, preferably a continuous area of the sheet, to control
soil adherence. The
low level of additive may be attached in an amount effective to improve the
adherence of soils
such as particulates and/or common particulate allergens.
The cleaning sheets of the present invention can be made using either a woven
or nonwoven
process, or by forming operations using melted materials laid down on forms,
especially in belts,
and/or by forming operations involving mechanical actions/modifications
carried out on films.
The structures are made by any number of methods, once the essential three
dimensional
requirements are known. However, the preferred structures are nonwoven, and
especially those
formed by hydroentanglement as is well known in the art, since they provide
highly desirable
open structures.
Therefore, preferred cleaning sheets useful herein are nonwoven structures
having the
characteristics described herein. Materials particularly suitable for forming
the preferred
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nonwoven cleaning sheet of the present invention include, for example, natural
cellulosics as
well as synthetics such as polyolefins (e.g., polyethylene and polypropylene),
polyesters,
polyamides, synthetic cellulosics (e.g., RAYON), and blends thereof. Also
useful are natural
fibers, such as cotton or blends thereof and those derived from various
cellulosic sources.
Preferably, the cleaning sheet, any additives therein, and/or any coatings
thereon are made from
or comprise bio-derived materials such as bio-derived polymers, bio-derived
fibers, or bio-
derived compositions. Thus, particularly suitable synthetic fibers include,
without limitation,
bio-derived polyolefins (e.g., bio-derived polyethylene and bio-derived
polypropylene), bio-
derived polyesters, bio-derived polyamides, and blends thereof. In one
embodiment, the cleaning
sheet is made from recycled PET (rPET), alternatively contains rPET. In yet
another
embodiment the cleaning sheet contains a natural coating (to assist in soil
retention). In one
example, the sheet contains microcrystalline wax as a coating.
The cleaning sheets can be formed from a single fibrous layer, but preferably
are a composite of
at least two separate layers. Preferably, the sheets are nonwovens made via a
hydroentangling
process. In this regard, prior to hydroentangling discrete layers of fibers,
it may be desired to
slightly entangle each of the layers prior to joining the layers by
entanglement.
In a particularly preferred embodiment of the present invention, to enhance
the integrity of the
final sheet, it is preferred to include a polymeric net (referred to herein as
a "scrim" material) that
is arranged with the fibrous material, e.g., though lamination via heat or
chemical means such as
adhesives, through hydroentanglement, etc. Scrim materials useful herein are
described in detail
in U.S. Pat. No. 4,636,419, which is incorporated by reference herein. The
scrims can be formed
directly at the extrusion die or can be derived from extruded films by
fibrillation or by
embossing, followed by stretching and splitting. The scrim can be derived from
a polyolefin
such as polyethylene or polypropylene, copolymers thereof, poly(butylene
terephthalate),
polyethylene terephthalate, Nylon 6, Nylon 66, and the like. Scrim materials
are available from
various commercial sources. A preferred scrim material useful in the present
invention is a
polypropylene scrim, available from Conwed Plastics (Minneapolis, Minn.).
Many suitable bio-derived polymers are known or commercially available. For
example, a
biomass, such as terpenes and terpenoids, and mixtures thereof, may be
converted to bio-based
terephthalic acid (TPA) and bio-based di-methyl terephthalate (DMT). In
particular, both a- and
11-pinene, the main component of turpentine oil, and limonene, the main
component of lemon
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essential oil, posses a six member hydrocarbon ring. These terpenes are an
available biomass
source, and may be transformed into six member ring aromatic compounds such as
para-cymene,
which is then converted to bio-based terephthalic acid (bio-TPA) and bio-based
di-methyl
terephthalate (bio-DMT). The bio-TPA and bio-DMT may be subsequently
polymerized to form
bio-based polyesters, such as bio-based poly(ethylene terephthalate) (bio-
PET), bio-based
poly(trimethylene terephthalate) (bio-P'FT), and bio-based poly(butylene
terephthalate) (bio-
PBT). A biomass may also be converted to bio-based cyclohexane di-methanol and
polymerized
with bio-based terephthalic acid or bio-based di-methyl terephthalate (bio-
DMT) to produce bio-
based poly(cyclohexylene dimethyl terephthalate) (bio-PCT). These bio-derived
materials may
be prepared from bio-derived sources as described in detail in Berti, et al.,
U.S. Pat. Appl. Pub.
No. 2010/0168371, entitled "Bio-Based Terephthalate Polymers," for example.
Suitable bio-derived Nylon or bio-derived polyamide fibers may be made from
natural sources as
well. For example, Vestamid fibers, registered trademark of Fujitsu, are 100%
bio-derived
fibers formed from the polycondensation product of 1,10-decamethylene diamine
and
1,10-decanedioic acid (sebacic acid) monomers that are both extracted from
castor oil. Such bio-
derived polyamide fibers may be well suited in applications to replace
petrochemical-derived
Nylon 6 or Nylon 66.
In preferred embodiments, the above-described surface cleaning substrate
comprises some
portion of bio-derived fibers and/or petroleum-based fibers derived from non-
virgin petroleum
sources such as post-consumer recycled materials, post-industrial recycled
materials, and/or
regrind materials, for example. In some embodiments, the surface cleaning
substrate may
comprise or be formed from fibers, wherein greater than 1% by weight, greater
than 5% by
weight, greater than 10% by weight, greater than 15% by weight, greater than
20% by weight,
greater than 25% by weight, greater than 30% by weight, greater than 35% by
weight, greater
than 40% by weight, greater than 45% by weight, greater than 50% by weight,
greater than 55%
by weight, greater than 60% by weight, greater than 65% by weight, greater
than 70% by weight,
greater than 75% by weight, greater than 80% by weight, greater than 85% by
weight, greater
than 90% by weight, greater than 95% by weight, greater than 99% by weight,
greater than
99.9% by weight, or even 100% by weight of the fibers, based on the total
weight of fibers in the
surface cleaning substrate, are bio-derived fibers, petroleum-based fibers
derived from non-virgin
petroleum sources, or combinations thereof.
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In an example embodiment, the cleaning substrate can be composed of suitable
unmodified
and/or modified naturally occurring fibers including cotton, Esparto grass,
bagasse, hemp, flax,
silk, wool, wood pulp, chemically modified wood pulp, jute, ethyl cellulose,
and/or cellulose
acetate. Suitable synthetic fibers can comprise fibers of one, or more, of bio-
derived polyvinyl
chloride, bio-derived polyvinyl fluoride, bio-derived polytetrafluoroethylene,
bio-derived
polyvinylidene chloride, bio-derived polyacrylics, bio-derived polyvinyl
acetate, bio-derived
polyethylvinyl acetate, non-soluble or soluble bio-derived polyvinyl alcohol,
bio-derived
polyolefins such as bio-derived polyethylene and bio-derived polypropylene,
bio-derived
polyamides such as nylon, bio-derived polyesters, bio-derived polyurethanes,
bio-derived
polystyrenes, and the like, including fibers comprising bio-derived polymers
containing more
than one bio-derived monomer. The absorbent layer can comprise solely
naturally occurring
fibers, solely synthetic fibers, or any compatible combination of naturally
occurring and synthetic
fibers.
The fibers and bio-derived fibers useful herein can be hydrophilic,
hydrophobic, or can be a
combination of both hydrophilic and hydrophobic fibers. The particular
selection of hydrophilic
or hydrophobic fibers depends upon the other materials included in the
absorbent (and to some
degree) the scrubbing layer described herein. Suitable hydrophilic fibers for
use in the present
invention include cellulosic fibers, modified cellulosic fibers, rayon,
cotton, polyester fibers such
as hydrophilic nylon (HYDROFILO). Suitable hydrophilic fibers can also be
obtained by
hydrophilizing hydrophobic fibers, such as surfactant-treated or silica-
treated thermoplastic fibers
derived from, for example, bio-derived polyolefins such as bio-derived
polyethylene, bio-derived
polypropylene, bio-derived polyacrylics, bio-derived polyamides, bio-derived
polystyrenes, bio-
derived polyurethanes and the like.
Suitable wood pulp fibers can be obtained from well-known chemical processes
such as the Kraft
and sulfite processes. It is especially preferred to derive these wood pulp
fibers from southern
soft woods due to their premium absorbency characteristics. These wood pulp
fibers can also be
obtained from mechanical processes, such as ground wood, refiner mechanical,
thermomechanical, chemimechanical, and chemi-thermomechanical pulp processes.
Recycled or
secondary wood pulp fibers, as well as bleached and unbleached wood pulp
fibers, can be used.
Wood-pulp fibers are desirable as inherently bio-derived.
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Another type of hydrophilic fibers for use in the present invention are
chemically stiffened
cellulosic fibers. As used herein, the term "chemically stiffened cellulosic
fibers" means
cellulosic fibers that have been stiffened by chemical means to increase the
stiffness of the fibers
under both dry and aqueous conditions. Such means can include the addition of
a chemical
stiffening agent that, for example, coats and/or impregnates the fibers. Such
means can also
include the stiffening of the fibers by altering the chemical structure, e.g.,
by crosslinking
polymer chains. Preferred stiffening agents comprise or consist of bio-derived
polymers.
Where fibers are used as the absorbent layer (or a constituent component
thereof), the fibers can
optionally be combined with a thermoplastic material, preferably a
thermoplastic that is bio-
derived or partially bio-derived. Upon melting, at least a portion of this
thermoplastic material
migrates to the intersections of the fibers, typically due to interfiber
capillary gradients. These
intersections become bond sites for the thermoplastic material. When cooled,
the thermoplastic
materials at these intersections solidify to form the bond sites that hold the
matrix or substrate of
fibers together in each of the respective layers. This can be beneficial in
providing additional
overall integrity to the cleaning wipe.
Thermoplastic materials useful in the present invention can be in any of a
variety of forms
including particulates, fibers, or combinations of particulates and fibers.
Bio-derived
thermoplastic fibers are a particularly preferred form because of their
ability to form numerous
interfiber bond sites. Suitable bio-derived thermoplastic materials can be
made from any bio-
derived thermoplastic polymer that can be melted at temperatures that will not
extensively
damage the fibers that comprise the primary substrate or matrix of each layer.
Preferably, the
melting point of this bio-derived thermoplastic material will be less than
about 190 C., and
preferably between about 75 C. and about 175 C. In any event, the melting
point of this bio-
derived thermoplastic material should be no lower than the temperature at
which the thermally
bonded absorbent structures, when used in the cleaning pads, are likely to be
stored. The melting
point of the bio-derived thermoplastic material is typically no lower than
about 50 C.
The bio-derived thermoplastic materials, and in particular the bio-derived
thermoplastic fibers,
can be made from a variety of bio-derived thermoplastic polymers, including
bio-derived
polyolefins such as bio-derived polyethylene and bio-derived polypropylene,
bio-derived
polyesters, bio-derived copolyesters, bio-derived polyvinyl acetate, bio-
derived polyethylvinyl
acetate, bio-derived polyvinyl chloride, bio-derived polyvinylidene chloride,
bio-derived
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polyacrylics, bio-derived polyamides, bio-derived copolyamides, bio-derived
polystyrenes, bio-
derived polyurethanes and bio-derived copolymers of any of the foregoing such
as bio-derived
vinyl chloride/vinyl acetate, and the like. Depending upon the desired
characteristics for the
resulting thermally bonded absorbent member, suitable thermoplastic materials
include
hydrophobic fibers that have been made hydrophilic, such as surfactant-treated
or silica-treated
thermoplastic fibers derived from, for example, bio-derived polyolefins such
as bio-derived
polyethylene or bio-derived polypropylene, bio-derived polyacrylics, bio-
derived polyamides,
bio-derived polystyrenes, bio-derived polyurethanes and the like. The surface
of the hydrophobic
bio-derived thermoplastic fiber can be rendered hydrophilic by treatment with
a surfactant, such
as a nonionic or anionic surfactant, e.g., by spraying the fiber with a
surfactant, by dipping the
fiber into a surfactant or by including the surfactant as part of the polymer
melt in producing the
thermoplastic fiber. Upon melting and resolidification, the surfactant will
tend to remain at the
surfaces of the bio-derived thermoplastic fiber. Suitable surfactants include
nonionic surfactants
such as Brij 76 manufactured by ICI Americas, Inc. of Wilmington, Del., and
various
surfactants sold under the Pegosperse trademark by Glyco Chemical, Inc. of
Greenwich, Conn.
Besides nonionic surfactants, anionic surfactants can also be used. These
surfactants can be
applied to the thermoplastic fibers at levels of, for example, from about 0.2
to about 1 gram per
square centimeter of thermoplastic fiber.
Suitable thermoplastic fibers can be made from a single polymer (monocomponent
fibers), or can
be made from more than one polymer (e.g., bicomponent fibers). As used herein,
"bicomponent
fibers" refers to thermoplastic fibers that comprise a core fiber made from
one polymer that is
encased within a thermoplastic sheath made from a different polymer. The
polymer comprising
the sheath often melts at a different, typically lower, temperature than the
polymer comprising
the core. As a result, these bicomponent fibers provide thermal bonding due to
melting of the
sheath polymer, while retaining the desirable strength characteristics of the
core polymer.
Suitable bicomponent fibers for use in the present invention can include
sheath/core fibers having
the following polymer combinations: polyethylene/polypropylene, polyethylvinyl
acetate/polypropylene, polyethylene/polyester, polypropylene/polyester,
copolyester/polyester,
and the like. Particularly suitable bicomponent thermoplastic fibers for use
herein are those
having a polypropylene or polyester core, and a lower melting copolyester,
polyethylvinyl acetate
or polyethylene sheath (e.g., those available from Danaklon a/s, Chisso Corp.,
and CELBOND ,
available from Hercules). These bicomponent fibers can be concentric or
eccentric. As used
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herein, the terms "concentric" and "eccentric" refer to whether the sheath has
a thickness that is
even, or uneven, through the cross-sectional area of the bicomponent fiber.
Eccentric
bicomponent fibers can be desirable in providing more compressive strength at
lower fiber
thicknesses. Preferably, the sheath, the core, or both, are formed from bio-
derived polymers or
combinations of bio-derived polymers.
Methods for preparing thermally bonded fibrous materials are described in U.S.
Pat. No.
5,766,874 and U.S. Pat. No. 5,549,589. The absorbent layer can also comprise a
HIPE-derived
hydrophilic, polymeric foam. Such foams and methods for their preparation are
described in
U.S. Pat. No. 5,550,167 (DesMarais) and U.S. Pat. No. 5,563,179.
In one embodiment, the dry fibrous substrate can be an airlaid nonwoven
substrate comprising a
combination of natural fibers, staple length synthetic fibers, and a latex
binder. The dry fibrous
substrate can be from about 20% to about 80%, by weight, of wood pulp fibers,
from about 10%
to about 60%, by weight, of staple length polyester fibers, and from about 10%
to about 25%, by
weight, of binder.
The dry, fibrous substrate can have a basis weight of between about 30 g/m2
and about 100 g/m2.
The density of the dry substrate can be measured after evaporating the liquid
from the
premoistened wipe, and the density can be less than about 0.15 g/cm3. The
density is the basis
weight of the dry substrate divided by the thickness of the dry substrate,
measured in consistent
units, and the thickness of the dry substrate is measured using a circular
load foot having an area
of about 2 square inches and which provides a confining pressure of about 95
grams per square
inch. In one embodiment, the dry substrate can have a basis weight of about 64
g/m2, a thickness
of about 0.06 cm, and a density of about 0.11 g/cm3.
The following patents are incorporated herein by reference for their
disclosure related to
substrates: U.S. Pat. No. 3,862,472 issued Jan. 28, 1975; U.S. Pat. No.
3,982,302 issued Sep. 28,
1976; U.S. Pat. No. 4,004,323 issued Jan. 25, 1977; U.S. Pat. No. 4,057,669
issued Nov. 8, 1977;
U.S. Pat. No. 4,097,965 issued Jul. 4, 1978; U.S. Pat. No. 4,176,427 issued
Dec. 4, 1979; U.S.
Pat. No. 4,130,915 issued Dec. 26, 1978; U.S. Pat. No. 4,135,024 issued Jan.
16, 1979; U.S. Pat.
No. 4,189,896 issued Feb. 26, 1980; U.S. Pat. No. 4,207,367 issued Jun. 10,
1980; U.S. Pat. No.
4,296,161 issued Oct. 20, 1981; U.S. Pat. No. 4,309,469 issued Jan. 25, 1982;
U.S. Pat. No.
-
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4,682,942 issued Jul. 28, 1987; and U.S. Pat. Nos. 4,637,859; 5,223,096;
5,240,562; 5,556,509;
and 5,580,423.
The art recognizes the use of dusting sheets such as those in U.S. Pat. No.
3,629,047, U.S. Pat.
No. 3,494,421, U.S. Pat. No. 4,144,370, U.S. Pat. No. 4,808,467, U.S. Pat. No.
5,144,729, and
U.S. Pat. No. 5,525,397, as effective for picking up and retaining particulate
dirt. These sheets
require a structure that provides reinforcement yet free fibers in order to be
effective. It has been
found that similar structures used dry for dusting can also be advantageously
used when pre-
moistened with liquid at levels of at least about 0.5 gram of chemical
solution per gram of dry
substrate or greater. These levels are significantly higher than the levels
used for chemical
additives such as mineral oils, waxes, and the like, often applied to
conventional dusting sheets to
enhance performance. In particular, the wipes of this invention are
specifically intended to be
used pre-moistened with aqueous compositions.
In one embodiment, the cleaning sheet will have, in addition to regions which
differ with regard
to basis weight, substantial macroscopic three-dimensionality. The term
"macroscopic three-
dimensionality", when used to describe three dimensional cleaning sheets means
a three
dimensional pattern is readily visible to the naked eye when the perpendicular
distance between
the viewer's eye and the plane of the sheet is about 12 inches. In other
words, the three
dimensional structures of the pre-moistened sheets of the present invention
are cleaning sheets
that are non-planar, in that one or both surfaces of the sheets exist in
multiple planes. By way of
contrast, the term "planar", refers to sheets having fine-scale surface
aberrations on one or both
sides, the surface aberrations not being readily visible to the naked eye when
the perpendicular
distance between the viewer's eye and the plane of the sheet is about 12
inches. In other words,
on a macro scale the observer will not observe that one or both surfaces of
the sheet will exist in
multiple planes so as to be three-dimensional.
In another alternative embodiment, the substrate can comprise a laminate of
two outer
hydroentangled substrates, such as nonwoven substrates of polyester, rayon
fibers or blends,
preferably bio-derived polyester or bbe polyester blends, having a basis
weight of about 10 g/m2
to about 60 g/m2, joined to an inner constraining layer, which can be in the
form of net like scrim
material which contracts upon heating to provide surface texture in the outer
layers.
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In one embodiment, a dry cleaning sheet is provided, and to enhante the
integrity of
the final sheet, it is preferred to include a center layer of polymeric
material that is arranged with
the fibrous material, e.g., though lamination via heat or chemical means such
as adhesives,
through hydroentanglement, etc. A preferred option is a polymeric net
(referred to herein as a
"scrim" material). Scrim materials useful herein are described in detail in
U.S. Pat. No.
4,636,419, which is incorporated by reference herein. The scrims can be formed
directly at the
extrusion die or can be derived from extruded films by fibrillation or by
embossing, followed by
stretching and splitting. The scrim can be derived from a polyolefin such as
bio-derived or
recycled: polyethylene or polypropylene, copolymers thereof, poly(butylene
terephthalate),
polyethylene terephthalate, Nylon 6, Nylon 66, and the like. Scrim materials
are available from
various commercial sources. A preferred scrim material useful in the present
invention is a
polypropylene scrim, available from Conwed Plastics (Minneapolis, Minn.).
In another embodiment, a low basis weight continuous web as a center layer,
most
preferably as a selection of spunmelt material. The spunmelt materials can be
derived from a
bio-derived or recycled: polyolefin such as polyethylene or polypropylene,
copolymers thereof,
poly(butylene terephthalate), polyethylene terephthalate, Nylon 6, Nylon 66,
and the like. The
center layer can also be selected from bioderived or non-virgin petroleum
materials. A preferred
spunbond material is a 12 gsm polypropylene from First Quality Nonwovens
(Hazelton, PA).
Wet Disposable Substrates
If desired, the cleaning sheet may be pre-moistened. If the cleaning sheet is
pre-moistened, it is
preferably pre-moistened with a liquid which provides for cleaning of the
target surface, such as
a floor, but yet does not require a post-cleaning rinsing operation.
The pre-moistened cleaning sheet may comprise natural or synthetic fibers. The
fibers may be
hydrophilic, hydrophobic or a combination thereof, provided that the cleaning
sheet is generally
absorbent to hold, and express upon demand, a cleaning solution. In one
embodiment, the
cleaning sheet may comprise at least 50 weight percent or at least 70 weight
percent cellulose
fibers, such as air laid SSK fibers. If desired, the cleaning sheet may
comprise plural layers to
provide for scrubbing, liquid storage, and other particularized tasks for the
cleaning operation.
Preferably a substantial portion of the fibers are bio-derived. Preferably,
the cleaning solution
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contains one or more bio-derived ingredients or consists entirely of bio-
derived ingredients.
Cleaning solutions are described below in further detail.
The cleaning pad may comprise or consist of one or more layers including an
optional scrub layer
for maximum cleaning efficiency. For pre-moistened wipes that use a single
substrate, the
substrate preferably contains fibers comprising of some combination of
hydrophilic and
hydrophobic fibers, and more preferably fibers comprising at least about 30%
hydrophobic fibers
and even more preferably at least about 50% of hydrophobic fibers in a
hydroentangled substrate.
The term "hydrophobic fibers" includes polyester fibers as well as fibers
derived from
polyolefins such as polyethylene, polypropylene, and the like, including all
bio-derived
polyesters and all bio-derived polyolefins. The combination of hydrophobic
fibers and absorbent
hydrophilic fibers represents a particularly preferred embodiment for the
single substrate pre-
moistened wipe since the absorbent hydrophilic fibers, typically cellulose,
aid in the sequestering
and removal of dust and other soils present on the surface. The hydrophobic
fibers are
particularly useful in cleaning greasy soils, in improving the pre-moistened
wipe and in lowering
the friction between substrate and hard surface (glide). Various forming
methods can be used to
form a suitable fibrous substrate for the premoistened wipes of the present
invention. For
instance, the substrate can be made by nonwoven dry forming techniques, such
as air-laying, or
alternatively by wet laying, such as on a paper-making machine. Other non-
woven
manufacturing techniques, including but not limited to techniques such as melt
blown,
spunbonded, needle punched, and hydroentanglement methods, can also be used.
A pre-moistened wipe may be made by wetting the dry substrate with at least
about 1.0 gram of
cleaning composition per gram of dry fibrous substrate. Preferably, the dry
substrate is wetted
with at least about 1.5 and more preferably at least about 2.0 grams of liquid
composition per
gram of the dry fibrous substrate. The exact amount of solution impregnated on
the wipe will
depend on the product's intended use. For pre-moistened wipes intended to be
used for cleaning
counter tops, stove tops, glass, and the like, optimum wetness is from about 1
to about 5 grams of
solution per gram of substrate. In the context of a floor cleaning wipe, the
pre-moistened wipe
can preferably include an absorbent core reservoir with a large capacity to
absorb and retain
fluid. Preferably, the absorbent reservoir has a fluid capacity of from about
5 grams to about 15
grams per gram of absorptive material. Pre-moistened wipes intended to be used
for the cleaning
of walls, exterior surfaces, etc. will have a capacity of from about 2 grams
to about 10 grams of
dry fibrous substrate. The cleaning composition may comprise a surfactant,
such as alkyl
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polyglucoside surfactant which minimizes streaking since there is typically
not a rinsing =
operation, agglomerating chemicals, disinfectants, bleaching solutions,
perfumes, or secondary
surfactants, for example. Preferably, at least one and, more preferably, all
of the ingredients of
the cleaning composition is bio-derived.
Optionally, the pre-moistened cleaning sheet may further comprise a scrubbing
strip. A
scrubbing strip is a portion of the cleaning sheet which provides for more
aggressive cleaning of
the target surface. A suitable scrubbing strip may comprise a polyolefinic
film, such as LDPE,
and have outwardly extending perforations, etc.
A suitable pre-moistened cleaning sheet may be made according to the teachings
of commonly
assigned US patents 6,716,805; D551,409 S and/or D614,408 S.
In some embodiments, the cleaning solution comprises a detergent surfactant
that is preferably
linear, e.g., branching and aromatic groups should not be present, and is
preferably relatively
water soluble, e.g., having a hydrophobic chain containing preferably from
about 8 to about 16,
carbon atoms, and, for nonionic detergent surfactants, having an HLB of from
about 9 to about
15, more preferably from about 10 to about 13.5. The most preferred
surfactants are
alkylpolyglucosides described in detail below. Other preferred surfactants are
the alkyl
ethoxylates comprising from about 9 to about 12 carbon atoms, and from about 4
to about 8
ethylene oxide units. These surfactants offer excellent cleaning benefits and
work synergistically
with the required hydrophilic polymers. Most preferably, the surfactants are
made from
compositions, or contain compositions having some bio-derived carbon atoms or
all bio-derived
carbon atoms.
The invention also comprises a detergent composition as disclosed herein in a
container in
association with instructions to use it. This container can have an assembly
of one or more units,
either packaged together or separately. For example, the container can include
a pad or a dry
wipe with cleaning solution. A second example is a container with pad or dry
wipe, implement
and solution. A third example is a container with concentrated refill, ready
to use solution and
pads with or without superabsorbent gelling. Yet another example is a
container with a pre-
moistened wipe, either with or without an implement, with or without a handle.
The detergent composition, (cleaning solution) may comprise an aqueous-based
solution
comprising a hydrophilic polymer, optionally, but preferably, and optionally
one or more
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detergent surfactants, the preferred alkylpolyglycosides being present if the
hydrophilic polymer
isn't present, optional solvents, builders, chelants, suds suppressors,
enzymes, etc. Suitable
polymers are those previously described herein. Bio-derived polymers or
polymers formed from
bio-derived monomers are preferred.
A suitable preferred cleaning solution for use in the context of floors,
counters, walls, either as a
stand-alone or in conjunction with conventional sponges, mops, rags, or with
disposable pre-
moistened wipes, pads, mops etc. comprises: from about 0.001% to about 0.25%,
preferably from
about 0.005% to about 0.15%, more preferably from about 0.01% to about 0.07%
of the
hydrophilic polymer. The level of polymer chosen will depend on the
application.
One embodiment of the invention also preferably comprises a detergent
composition as disclosed
herein in a container in association with instructions to use it with an
absorbent structure
comprising an effective amount of a superabsorbent material, and, optionally,
in a container
comprising the implement, or, at least, a disposable cleaning pad comprising a
superabsorbent
material. This invention also relates to the use of a composition with
hydrophilic polymer and a
cleaning pad comprising a superabsorbent material to effect cleaning of soiled
surfaces, i.e., the
process of cleaning a surface comprising applying an effective amount of a
detergent
composition, typically containing no more than about 1% detergent surfactant;
a level of
hydrophobic materials, including solvent, that is less than about 5%; and
having a pH of more
than about 9 and absorbing the composition in an absorbent structure
comprising superabsorbent
material. The container may be appropriately labeled to indicate that a
substantial portion of the
composition contained therein, or a substantial portion of the ingredients
thereof, is bio-derived
or naturally-based.
Wet Jet Approach
Optionally, and most preferably, convenience and performance can be maximized
by using a
system composed of a disposable cleaning pad and a mode for applying fresh
solution onto the
floor. The pad may be composed of a laminate of non-wovens, cellulose and
super-absorbent
polymer. Preferably at least a portion of the materials composing the
laminates are bio-derived.
This pad is attached to a device comprising a pad attachment head and handle.
In such a system,
solution application can be achieved via a separate squirt bottle or spray
trigger system, or can be
directly attached or built-in to the device (i.e., on the attachment head or
the handle). The
delivery mechanism can be actuated by the operator, or can be battery-induced
or electrical.
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This system provides multiple benefits versus conventional cleaning modes. It
reduces time to
clean the floor, because the pad sucks up dirty solution. It eliminates the
need to carry heavy,
messy buckets. Due to the absorbent pad which absorbs and locks away dirty
solution, a single
pad can clean large surface areas. Additionally, since a fresh pad is used
every time, germs and
dirt are trapped, removed and thrown away, promoting better hygiene and
malodor control.
Conventional mops, which are re-usable, can harbor dirt and germs, which can
be spread
throughout the household and create persistent bad odors in the mop and in the
home.
Additionally, because the cleaning process involves use of low levels of
solution in contact with
the floor for much shorter periods of time relative to conventional cleaning
systems, (less
solution is applied on the floor and the super-absorbent polymer absorbs most
of it such that
volume left behind with the disposable pad and mop is only from about 1 mL to
about 5 mL of
solution per square meter), the system provides improved surface safety on
delicate surfaces.
This is particularly important for the cleaning of wood, which tends to expand
and then contract
when treated with excess water.
Finally, this system is well suited for pre-treating tough soil spots prior to
full floor cleaning
because of the controlled dosing of solution. Unlike conventional mops, this
system is more
effective and more convenient for removal of spills. For example, conventional
mops actually
wet the floor in attempting to control spills, while absorbent paper towels or
cloths require the
user to bend down to achieve spill removal. Finally, the implement plus pad
can be designed to
allow easy access to tough to clean and hard to reach areas, e.g., under
appliances, tables,
counters, and the like. The use of super-absorbent polymer allows a reduction
in volume of the
pad, i.e., the pad is thin though highly absorbent due to the super-absorbent
structure being able
to absorb 100 times its weight; this is achievable with conventional mops,
which require greater
bulk for absorption purposes (cellulose or a synthetic structures absorb only
up to about from 5 to
about 10 times their weight).
The pads are versatile in that they can be used for multiple cleanings and
multiple surfaces. Each
pad is designed to clean one average size floor (i.e., from about 10 to about
20 square meters)
with an average soil load. Pads can need to be changed sooner if floors are
larger than average,
or especially dirty. To determine if the pad needs changing, look at the back
of the pad and
ascertain if the back absorbent layer is saturated with liquid and/or dirt.
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=
The use of the compositions herein, where no rinsing is desirable, as opposed
to the types of
compositions sold heretofore for treating non-bathtub/shower area surfaces
including floor
surfaces, walls and counter tops, provides improved performance.
Cleaning Substrate Absorbent Layer
The cleaning pads according to any of the embodiments described above may
comprise an
absorbent layer. The absorbent layer serves to retain any fluid and soil
absorbed by the cleaning
pad during use. While the scrubbing layer has some effect on the pad's ability
to provide the
requisite fluid absorption rates, the absorbent layer plays the major role in
achieving the
absorption rates and overall absorbency of the cleaning pad.
The absorbent layer will be capable of removing fluid and soil from the
scrubbing layer so that
the scrubbing layer will have capacity to continually remove soil from the
surface. The
absorbent layer also should be capable of retaining absorbed material under
typical in-use
pressures to avoid "squeeze-out" of absorbed soil, cleaning solution, etc.
The absorbent layer may comprise any material that is capable of absorbing
fluids at the requisite
rates, and retaining such fluids during use. To achieve desired total fluid
capacities, it will be
preferred to include in the absorbent layer a material having a relatively
high capacity (in terms
of grams of fluid per gram of absorbent material). As used herein, the term
"superabsorbent
material" means any absorbent material having a g/g capacity for water of at
least about 15 g/g,
when measured under a confining pressure of 0.3 psi. Because a majority of the
cleaning fluids
useful with the present invention are aqueous based, it is preferred that the
superabsorbent
materials have a relatively high g/g capacity for water and water-based
fluids.
Further representative superabsorbent materials include water insoluble, water-
swellable
superabsorbent gelling polymers which are well known in the literature. These
materials
demonstrate very high absorbent capacities for water. The superabsorbent
gelling polymers
useful in the present invention can have a size, shape and/or morphology
varying over a wide
range. These polymers can be in the form of particles that do not have a large
ratio of greatest
dimension to smallest dimension (e.g., granules, flakes, pulverulents,
interparticle aggregates,
interparticle crosslinked aggregates, and the like) or they can be in the form
of fibers, sheets,
films, foams, laminates, and the like. The use of superabsorbent gelling
polymers in fibrous form
provides the benefit of providing enhanced retention of the superabsorbent
material, relative to
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particles, during the cleaning process. While their capacity is generally
lower for aqueous-based
mixtures, these materials still demonstrate significant absorbent capacity for
such mixtures. The
patent literature is replete with disclosures of water-swellable materials.
See, for example, U.S.
Pat. No. 3,699,103 (Harper et al.), issued Jun. 13, 1972; U.S. Pat. No.
3,770,731 (Harmon),
issued Jun. 20, 1972; U.S. Reissue Pat. No. 32,649 (Brandt etal.), reissued
Apr. 19, 1989; U.S.
Pat. No. 4,834,735 (Alemany et al.), issued May 30, 1989. In preferred
embodiments, the
superabsorbent gelling polymers are bio-derived.
Superabsorbent gelling polymers useful in the present invention include a
variety of water-
insoluble, but water-swellable polymers capable of absorbing large quantities
of fluids. Such
polymeric materials are also commonly referred to as "hydrocolloids", and can
include
polysaccharides such as carboxymethyl starch, carboxymethyl cellulose, and
hydroxypropyl
cellulose; nonionic types such as polyvinyl alcohol, and polyvinyl ethers;
cationic types such as
polyvinyl pyridine, polyvinyl morpholinione, and N,N-dimethylaminoethyl or N,N-
diethylaminopropyl acrylates and methacrylates, and the respective quaternary
salts thereof,
many of which are substantially bio-derived. Typically, superabsorbent gelling
polymers useful
in the present invention have a multiplicity of anionic functional groups,
such as sulfonic acid,
and more typically carboxy, groups. Examples of polymers suitable for use
herein include those
which are prepared from polymerizable, unsaturated, acid-containing monomers.
Thus, such
monomers include the olefinically unsaturated acids and anhydrides that
contain at least one
carbon to carbon olefinic double bond. More specifically, these monomers can
be selected from
olefinically unsaturated carboxylic acids and acid anhydrides, olefinically
unsaturated sulfonic
acids, and mixtures thereof. Preferably, such monomers are attained from
partially or wholly
bio-derived sources of carbon.
Some non-acid monomers can also be included, usually in minor amounts, in
preparing the
superabsorbent gelling polymers useful herein. Such non-acid monomers can
include, for
example, the water-soluble or water-dispersible esters of the acid-containing
monomers, as well
as monomers that contain no carboxylic or sulfonic acid groups at all.
Optional non-acid
monomers can thus include monomers containing the following types of
functional groups:
carboxylic acid or sulfonic acid esters, hydroxyl groups, amide-groups, amino
groups, nitrile
groups, quaternary ammonium salt groups, aryl groups (e.g., phenyl groups,
such as those
derived from styrene monomer). These non-acid monomers are well-known
materials and are
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described in greater detail, for example, in U.S. Pat. No. 4,076,663 (Masuda
et al), issued Feb.
28, 1978, and in U.S. Pat. No. 4,062,817 (Westerman), issued Dec. 13, 1977.
Olefinically unsaturated carboxylic acid and carboxylic acid anhydride
monomers include the
acrylic acids typified by acrylic acid itself, methacrylic acid, ethacrylic
acid, a-chloroacrylic acid,
a-cyanoacrylic acid, P-methylacrylic acid (crotonic acid), a-phenylacrylic
acid, 13-
acryloxypropionic acid, sorbic acid, a-chlorosorbic acid, angelic acid,
cinnamic acid, p-
chlorocinnamic acid, p-sterylacrylic acid, itaconic acid, citroconic acid,
mesaconic acid,
glutaconic acid, aconitic acid, maleic acid, fumaric acid, tricarboxyethylene
and maleic acid
anhydride.
Old-mically unsaturated sulfonic acid monomers include aliphatic or aromatic
vinyl sulfonic
acids such as vinylsulfonic acid, ally! sulfonic acid, vinyl toluene sulfonic
acid and styrene
sulfonic acid; acrylic and methacrylic sulfonic acid such as sulfoethyl
acrylate, sulfoethyl
methacrylate, sulfopropyl acrylate, sulfopropyl methacrylate, 2-hydroxy-3-
methacryloxypropyl
sulfonic acid and 2-acrylamide-2-methylpropane sulfonic acid.
Preferred superabsorbent gelling polymers for use in the present invention
contain carboxy
groups. These polymers include hydrolyzed starch-acrylonitrile graft
copolymers, partially
neutralized hydrolyzed starch-acrylonitrile graft copolymers, starch-acrylic
acid graft
copolymers, partially neutralized starch-acrylic acid graft copolymers,
saponified vinyl acetate-
acrylic ester copolymers, hydrolyzed acrylonitrile or acrylamide copolymers,
slightly network
crosslinked polymers of any of the foregoing copolymers, partially neutralized
polyacrylic acid,
and slightly network crosslinked polymers of partially neutralized polyacrylic
acid. These
polymers can be used either solely or in the form of a mixture of two or more
different polymers.
Examples of these polymer materials are disclosed in U.S. Pat. No. 3,661,875,
U.S. Pat. No.
4,076,663, U.S. Pat. No. 4,093,776, U.S. Pat. No. 4,666,983, and U.S. Pat. No.
4,734,478.
Most preferred polymer materials for use in making the superabsorbent gelling
polymers are
slightly network crosslinked polymers of partially neutralized polyacrylic
acids and starch
derivatives thereof. Most preferably, the hydrogel-forming absorbent polymers
comprise from
about 50 to about 95%, preferably about 75%, neutralized, slightly network
crosslinked,
polyacrylic acid (i.e. poly (sodium acrylate/acrylic acid)). Network
crosslinking renders the
polymer substantially water-insoluble and, in part, determines the absorptive
capacity and
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extractable polymer content characteristics of the superabsorbent gelling
polymers. Processes for
network crosslinking these polymers and typical network crosslinking agents
are described in
greater detail in U.S. Pat. No. 4,076,663.
While the superabsorbent gelling polymers is preferably of one type (i.e.,
homogeneous),
In addition to the contribution to overall fluid absorbency, the
superabsorbent material also
directly affects the rate of absorbency by the pad. As such, where
superabsorbent gelling
Other useful superbsorbent materials include hydrophilic polymeric foams, such
as those
described in U.S. Pat. No. 5,650,222 (DesMarais et al.) and U.S. Pat. No.
5,387,207 (Dyer et al.).
Where superabsorbent material is included in the absorbent layer, the
absorbent layer will
preferably comprise at least about 15%, by weight of the absorbent layer, more
preferably at least
about 20%, still more preferably at least about 25%, of the superabsorbent
material.
Preferably, at least a portion of, or even all of, the carbon atoms in the
superabsorbent polymers
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polymers are often divided into two main classes; i.e., synthetic
(petrochemical-based) and
natural. The latter can be divided into two main groups, i.e., the hydrogels
based on
polysaccharides and others based on polypeptides (proteins). The natural-based
superabsorbent
polymers are usually prepared through addition of some synthetic parts onto
the natural
substrates, e.g., graft copolymerization of vinyl monomers on polysaccharides.
A variety of bio-derived monomers, mostly acrylics, may be employed to prepare
superabsorbent
polymers. Acrylic acid (AA) and its sodium or potassium salts, and acrylamide
(AM) are most
often used in the industrial production of superabsorbent polymers. The AA
monomer is
inhibited by methoxyhydroquinone (MHC) to prevent spontaneous polymerization
during
storage. In industrial production, the inhibitor is not usually removed due to
some technical
reasons. Meanwhile, AA is converted to an undesired dimer that must be removed
or minimized.
The minimization of acrylic acid dimer (DAA) in the monomer is important due
to its indirect
adverse effects on the final product specifications, typically soluble
fraction and the residual
monomer. As soon asAA is produced, diacrylic acid (0-acryloxypropionic acid)
is formed
spontaneously in the bulk of AA via a sluggish Michael-addition reaction.
Since temperature,
water content, and pH have impact on the rate of DAA formation, the rate can
be minimized by
controlling the temperature of stored monomer and excluding the moisture.
Increasing water
concentration has a relatively small impact on the DAA formation rate.
Nevertheless, the rate
roughly doubles for every 5 C increase in temperature. For example, in an AA
sample having
0.5% water, the dimerization rate is 76 and 1672 ppm/day at 20 C and 40 C,
respectively.
DAA, however, can be hydrolyzed in alkaline media to produce AA and P-
hydroxypropionic
acid(HPA). Since the latter is unable to be polymerized, it remains as part of
the SAP soluble
fraction. Fortunately, alkaline media used conventionally for AA
neutralization with NaOH
favors this hydrolytic reaction. For instance, in an 80% neutralized AA, the
dimerization rate at
23 C and 40 C has been determined to be 125 and 770 ppm/day, respectively.
DAA can also
be polymerized to go into the SAP network. It may be then thermally cleaved
through a retro-
Michael reaction in the course of heating in the drying step of the final
product. As a result, free
AA will be released and will cause the enhancement of the level of residual
monomer.
On laboratory scales, however, a number of monomers such as methacrylic acid
(MAA),methacrylamide (MAM), acrylonitrile (AN), 2-hydroxyethylmethacrylate
(HEMA), 2-
acrylamido-2-methylpropane sulfonic acid (AMPS), N-vinylpyrrolidone (NVP),
vinyl sulfonic
acid (VSA) and vinyl acetate (VAc) are also used. In the modified natural-
based superabsorbent
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polymers (i.e., hybrid superabsorbents), trunk biopolymers such as cellulose,
starch, chitosan,
gelatin and some of their possible derivatives e.g., carboxymethyl cellulose
(CMC) are also used
as the modifying substrate (polysaccharide based SAPs section). The
bifunctional compound
N,N'-methylenebisacrylamide (MBA) is most often used as a water soluble cross-
linking agent.
Ethyleneglycoledimethacrylate (EGDMA), 1,1,1-trimethylolpropanetriacrylate
(TMPTA), and
tetraalyloxy ethane (TAOE) are known examples of two-, three- and four-
functional cross-
linkers, respectively. Potassium persulfate (KPS) and ammonium persulfate
(APS) are water
soluble thermal initiators used frequently in both solution and inverse-
suspension methods of
polymerization (discussed in the snapshot section of production processes).
Redox pair initiators
such as Fe2+-H202 (Fenton reagent) and APS sodium sulfite are also employed
particularly in the
solution method.
Although the majority of the commericially available superabsorbents are
nowadays
manufactured from synthetic polymers (essentially acrylics) due to their
superior price-to-
efficiency balance, the world's firm decision for environmental protection
potentially support the
ideas of partially/totally replacing the synthetics by "greener" alternatives.
Carbohydrate
polymers (polysaccharides) are the cheapest and most abundant, available, and
renewable
organic materials. Chitin, cellulose, starch, and natural gums (such as
xanthan gum, guar gum
and alginates) are some of the most important polysaccharides. Generally, the
reported reactions
for preparing the polysaccharide-based SAPs are held in two main groups; (a)
graft
copolymerization of suitable vinyl monomer(s) on polysaccharide in the
presence of a cross-
linker, and (b) direct cross-linking of polysaccharide. In graft
copolymerization, generally a
polysaccharide enters reaction with initiator by either of two separate ways.
First, the
neighbouring OHs on the saccharide units and the initiator (commonly Cen
interact to form
redox pair-based complexes. These complexes are subsequently dissociated to
produce carbon
radicals on the polysaccharide substrate via homogeneous cleavage of the
saccharide C¨C bonds.
These free radicals initiate the graft polymerization of the vinyl monomers
and cross-linker on
the substrate. In the second way of initiation, an initiator such as
persulfate may abstract
hydrogen radicals from the OHs of the polysaccharide to produce the initiating
radicals on the
polysaccharide backbone. Due to employing a thermal initiator, this reaction
is more affected by
temperature compared to previous method. The earliest commercial SAPs were
produced from
starch and AN monomer by the first mentioned method without employing a cross-
linker. The
mechanism of in-situ cross-linking during the alkaline hydrolysis of
polysacchride-g-PAN
copolymer to yield superabsorbing hybrid material alkaline medium to produce a
hybrid SAP,
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hydrolyzed SPAN (H-SPAN) while an in-situ cross-linking occurred
simultaneously. This
fascinating approach has been employed to convert various polysaccharides into
SAP hydrogel
hybrids. In the method direct cross-linking of polysaccharides, polyvinylic
compounds (e.g.,
divinyl sulfone, DVS) or polyfunctional compounds (e.g.,
glycerol,epichlorohydrin and glyoxal)
are often employed. POC13 is also used for the cross-linking. Fully natural
SAP hydrogels may
be synthesized also via crosslinking of the cellulosics by citric acid.
Bio-derived superabsorbent polymer hydrogels may comprise polypeptides as the
main or part of
their structure. Proteins from soybean, fish, and collagen-based proteins are
the most frequently
used hetero-polypeptides for preparation of proteinaceous super-swelling
hydrogels. The most
Madison, USA. They converted soy and fish proteins to superabsorbent polymers
through
modification by ethylenediamine tetraaceticdianhydride (EDTAD) in the first
stage. EDTAD has
low toxicity because the only reactive group introduced into the network is
the carboxyl group,
In the second stage, the remaining amino groups of the hydrophilized protein
are lightly cross-
linked by glutaraldehyde to yield a hydrogel network with superabsorbing
properties. The
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= The swelling capacity of a 76% EDTAD modifiedFP is reported to be 540 g/g
at 214 g, assumed
to be dependent on pH and ionic strength ofthe swelling media, similar to what
observed for
EDTAD-modified SPI hydrogels. When glutaraldehyde (GA) was employed as a
crosslinker, the
SAP swelling ability was diminished to 150-200 g/g, whereas the gel rigidity
was enhanced.
Therefore, these superabsorbent polymers are preferred to be used for water
absorption under
pressure in real applications, such as absorbent cleaning sheets disclosed
herein.
Proteins can also be modified by either polysaccharides or synthetics to
produce hybrid
hydrogels with super-swelling properties. For instance, the researchers have
studied the water
swelling propertyof binary polymer networks (frequently as interpenetrated
polymer networks,
IPNs) of modified proteins with some water-soluble, hydrophilic,
biodegradable,and non-toxic
polymers, e.g., modified soy protein, gelatin, sodium carboxymethyl cellulose
(CMC),
poly(ethylene glycol) (PEG), poly(vinyl alcohol), guar gum, chitosan, and
carboxymethyl
chitosan.
Collagen-based proteins including gelatin and hydrolyzed collagen (H-collagen;
very low
molecular weight products of collagen hydrolysis) have been used for preparing
SAP materials.
For example, gelatin-g-poly (NaAA-co-AM) hydrogel have been synthesized
through
simultaneous cross-linking and graft polymerization of AAJAM mixtures onto
gelatin.
Homo-poly(amino acid)s of poly(aspartic acid)s, poly(L-lysine) and poly(y-
glutamic acid)s have
also been employed to prepare superabsorbent polymer materials. In 1999, Rohm
and Haas
Company's researchers reported lightly cross-linked high MW sodium
polyaspartateswith
superabsorbing, pH- and electrolyte-responsiveness properties. They used
ethylene glycol
diglycidyl ether (EGDGE) as a cross-linker. Polyethylene glycol diglycidyl
ether (PEG-
diepoxide) with different MWs has also been employed to synthesize
biodegradable poly(aspartic
acid) hydrogels with super-swelling behavior. To enhance the swelling
capacity, several
hydrophilic polymers (i.e., starch, ethyl cellulose, carrageenan, PAM, P-
cyclodextrin, and CMC)
were incorporated into the hydrogels (after or before the hydrolysis step) to
attain modified
superabsorbent polymer composites. Super-swelling hydrogels based on poly(y-
glutamicacid),
PGA, has been prepared by cross-linking reactions via both irradiation and
chemical approaches.
Similar to PGA, highly swollen hydrogels based on L-lysine homopolymer have
been also
prepared simply by y-irradiation of their aqueous solutions.
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= To prepare the bio-derived superabsorbent polymers, acrylic acid (AA) and
its sodium or
potassium salts, and acrylamide (AM) are most frequently used. AM, a white
powder, is pure
enough to be often used without purification. AA, a colorless liquid with
vinegar odor, however,
has a different story due to its ability to convert intoits dimer (sub-section
main starting
materials). In this regard, the DAA level must be minimized to prevent the
final product
deficiencies, e.g., yield reduction, loss of soluble fraction, residual
monomers, etc. Due to the
potential problems originating from the inherent nature of AA to dimerize over
time,
manufacturers work properly with AA, such as timely order placement, just-in-
time delivery,
moisture exclusion, and temperature-controlled storage (typically 17-18 C).
In the laboratory
scale syntheses, however, AA is often distilled before use, to purify and
remove the impurities
including the inhibitor and DAA. AA salt solutions are usually produced by
slow addition of
appropriate solution of a desired metal hydroxide (NaOH or KOH) to cooled AA
while stirring
mild. The temperature of this extremely exothermic neutralization reaction
must be precisely
controlled to prevent undesired polymerization.
The superabsorbent polymer materials are often synthesized through free-
radically-initiated
polymerization of acrylic monomers. The resins are prepared either in aqueous
medium using
solution polymerization or in a hydrocarbon medium where themonomers are well-
dispersed.
Some additional treatments, such as modified gel-drying methods and,
particularly, surface cross-
linking and porosity generating techniques are important approaches for
altering and fine-tuning
the SAP morphology and physicochemical properties.
Free-radical initiated polymerization of AA and its salts (and AM), with a
cross-linker is
frequently used for superabsorbent polymer preparation. The carboxylic acid
groups of the
product are partially neutralized before or after the polymerization step.
Initiation is most often
carried out chemically with free-radical azo or peroxide thermal dissociative
species or by
reaction of a reducing agent with anoxidizing agent (redox system). In
addition, radiation is
sometimes used for initiating the polymerization.
The solution polymerization of AA and/or its salts with a water-soluble cross-
linker, e.g., MBA
in an aqueous solution is a straightforward process. The reactants are
dissolved in water at
desired concentrations, usually about 10-70%. A fast exothermic reaction
yields a gel-like elastic
product which is dried and the macro-porous mass is pulverized and sieved to
obtain the required
particle size. This preparative method usually suffers from the necessity to
handle a
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rubbery/solid reaction product, lack of a sufficient reaction control, non-
exact particle size
distribution, and increasing the sol content mainly due to undesired effects
of hydrolytic and
thermal cleavage. However, for a general production of a SAP with acceptable
swelling
properties, the less expensive and faster technique, i.e., solution method may
often be preferred.
Dispersion polymerization is an advantageous method since the products are
obtained as powder
or microspheres (beads), and thus grinding is not required. Since water-in-oil
(W/0) process is
chosen instead of the more common oil-in-water (0/W) the polymerization is
referred to as
"inverse-suspension". In this technique, the monomers and initiator are
dispersed in the
hydrocarbon phase as a homogenous mixture. The viscosity of the monomer
solution, agitation
speed, rotor design, and dispersant type mainly govern the resin particle size
and shape.
The dispersion is thermodynamically unstable and requires both continuous
agitation and
addition of a low hydrophilic-lipophilic-balance (HLB) suspending agent. The
inverse-
suspension is a highly flexible and versatile technique to produce SAPs with
high swelling ability
and fast absorption kinetics. A water-soluble initiator shows a better
efficiency than the oil-
soluble type. When the initiator dissolves in the dispersed (aqueous) phase,
each particle
contains all the reactive species and therefore behaves like an isolated micro-
batch
polymerization reactor. The resulting microspherical particles are easily
removed by filtration or
centrifugation from the continuous organic phase. Upon drying, these particles
or beads will
directly provide a free flowing powder. In addition to the unique flowing
properties of these
beads, the inverse-suspension process displays additional advantages compared
to the solution
method. These include a better control of the reaction heat removal, ab initio
regulation of
particle-size distribution, and further possibilities for adjusting particle
structure or morphology
alteration.
Cleaning Substrate Treatments and Additives
The cleaning sheet according to the present invention may comprise a nonwoven.
The nonwoven
may be synthetic and/or have cellulosic fibers therein. The synthetic fibers
may comprise carded,
staple, wet laid, air laid and/or spunbond fibers. The nonwoven cleaning sheet
may be made
according to a hydro-entangling process to provide a texture and a basis
weight of about 20 to
about 120 gsm. Optionally, the cleaning sheet may further comprise an
additive, to improve
cleaning performance and/or enhance the cleaning experience. The additive may
comprise wax,
such as microcrystalline wax, oil, adhesive, perfume and combinations thereof.
In particular, the
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additive may be a coating on the cleaning sheet and, preferably, the coating
contains at least
10%, at least 25%, at least 40%, at least 50%, at least 75%, at least 90%, at
least 95%, or 100%
bio-derived materials.
The cleaning performance of any of the cleaning sheets of the present
invention can be enhanced
by treating the fibers of the sheet, especially surface treating, with any of
a variety of additives,
including surfactants or lubricants, that enhance adherence of soils to the
sheet. When utilized,
such additives are added to the cleaning sheet at a level sufficient to
enhance the ability of the
sheet to adhere soils. Such additives are preferably applied to the cleaning
sheet at an add-on
level of at least about 0.01%, more preferably at least about 0.1%, more
preferably at least about
0.5%, more preferably at least about 1%, still more preferably at least about
3%, still more
preferably at least about 4%, by weight. Typically, the add-on level is from
about 0.1% to about
25%, more preferably from about 0.5% to about 20%, more preferably from about
1% to about
15%, still more preferably from about 3% to about 10%, still more preferably
from about 4% to
about 8%, and most preferably from about 4% to about 6%, by weight. In
preferred
embodiments, at least a portion of, or all of, the additives on the cleaning
sheet are bio-derived
additives or contain carbon atoms, wherein at least 10%, at least 50%, or at
least 75% of the
carbon atoms are bio-derived.
A preferred additive is a wax or a mixture of an oil (e.g., mineral oil,
petroleum jelly, etc.) and a
wax. Suitable waxes include various types of hydrocarbons, as well as esters
of certain fatty
acids (e.g., saturated triglycerides) and fatty alcohols. They can be derived
from natural sources
(i.e., animal, vegetable or mineral) or can be synthesized, but preferably are
bio-derived.
Mixtures of these various waxes can also be used. Some representative animal
and vegetable
waxes that can be used in the present invention include beeswax, carnauba,
spermaceti, lanolin,
shellac wax, candelilla, and the like. Representative waxes from mineral
sources that can be used
in the present invention include petroleum-based waxes such as paraffin,
petrolatum and
microcrystalline wax, and fossil or earth waxes such as white ceresine wax,
yellow ceresine wax,
white ozokerite wax, and the like. Representative synthetic waxes that can be
used in the present
invention include ethylenic polymers such as polyethylene wax, chlorinated
naphthalenes such as
"Halowax," hydrocarbon type waxes made by Fischer-Tropsch synthesis, and the
like.
When a mixture of mineral oil and wax is utilized, the components will
preferably be mixed in a
ratio of oil to wax of from about 1:99 to about 7:3, more preferably from
about 1:99 to about 1:1,
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still more preferably from about 1:99 to about 3:7, by weight. In a
particularly preferred
embodiment, the ratio of oil to wax is about 1:1, by weight, and the additive
is applied at an add-
on level of about 5%, by weight. A preferred mixture is a 1:1 mixture of
mineral oil and paraffin
wax. Preferably the paraffin wax is substantially bio-derived.
Particularly enhanced cleaning performance is achieved when macroscopic three-
dimensionality
and additive are provided in a single cleaning sheet. As discussed
hereinbefore, these low levels
are especially desirable when the additives are applied at an effective level
and preferably in a
substantially uniform way to at least one discrete continuous area of the
sheet. Use of the
preferred lower levels, especially of additives that improve adherence of soil
to the sheet,
provides surprisingly good cleaning, dust suppression in the air, preferred
consumer impressions,
especially tactile impressions, and, in addition, the additive can provide a
means for
incorporating and attaching perfumes, pest control ingredients,
antimicrobials, including
fungicides, and a host of other beneficial ingredients, especially those that
are soluble, or
dispersible, in the additive. These benefits are by way of example only. Low
levels of additives
are especially desirable where the additive can have adverse effects on the
substrate, the
packaging, and/or the surfaces that are treated. Preferably, these ingredients
are bio-derived or
are attained from natural sources of carbon.
In general, as consistent with or in addition to any of the embodiments
described above, the
cleaning sheet according to the present invention may be made according to
commonly assigned
US patents 6,305,046; 6,484,346; 6,561,354; 6,645,604; 6,651,290; 6,777,064;
6,790,794;
6,797,357; 6,936,330; D409,343; D423,742; D489,537; D498,930; D499,887;
D501,609;
D511,251 and/or D615,378. The entireties of each of these documents are
incorporated by
reference herein.
Cleaning Implements
The cleaning sheet according to the present invention may be used with a stick-
type cleaning
implement. The cleaning implement may comprise a plastic head for holding the
cleaning sheet
and an elongate handle aiticulably connected thereto. The handle may comprise
a metal or
plastic tube or solid rod. Some or all of these components may be formed of,
or may comprise
bio-derived plastics.
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The head may have a downwardly facing surface, to which the cleaning sheet may
be attached.
The downwardly facing service may be generally flat, or slightly convex. The
head may further
have an upwardly facing surface. The upwardly facing surface may have a
universal joint to
facilitate connection of the elongate handle to the head.
The upwardly facing surface may further comprise a mechanism, such as
resilient grippers, for
removably attaching the cleaning sheet to the implement. Alternatively, a hook
and loop system
may be used to attach the cleaning sheet to the head. If grippers are used
with the cleaning
implement, the grippers may be made according to commonly assigned US patents
6,305,046;
6,484,346; 6,651,290 and/or D487,173. The grippers may be formed of a bio-
derived material
such as a bio-derived plastic or rubber.
If desired, the cleaning implement may have an axially rotatable beater bar
and/or vacuum type
suction to assist in removal of debris from the target surface. Debris removed
from the target
surface may be collected in a dust bin. The dust bin may be mounted within the
head, or,
alternatively, on the elongate handle. The beater, the dust bin, or both, may
be formed from or
may comprise one or more bio-derived materials.
A suitable stick-type cleaning implement may be made according to commonly
assigned US
patents Des. 391,715; D409,343; D423,742; D481,184; D484,287; D484,287 and/or
D588,770.
A suitable vacuum type cleaning implement may be made according to the
teachings of US
patents 7,137,169, D484,287 S, D615,260 S and D615,378 S.
Cleaning Pad Refills
Cleaning pads and cleaning sheets described above, preferably comprising bio-
derived fibers,
may be packaged in bio-derived packaging, for example, as refills for the
above-described
cleaning implement. The cleaning sheet refills according to the present
invention may comprise
a nonwoven. The nonwoven may be synthetic and/or have cellulosic fibers
therein. The
synthetic fibers may comprise carded, staple, wet laid, air laid and/or
spunbond fibers.
The cleaning sheet may comprise layers, to provide for absorption and storage
of cleaning fluid
deposited on the target surface. If desired, the cleaning sheet may comprise
absorbent gelling
materials, described above, to increase the absorbent capacity of the cleaning
sheet. The
absorbent gelling materials may be distributed within the cleaning sheet in
such a manner to
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avoid rapid absorbency and absorb fluids slowly, to provide for the most
effective use of the
cleaning sheet. Preferably, all or a portion of the absorbent gelling
materials are bio-derived.
As with the cleaning sheets described according to various embodiments above,
the cleaning
sheets provided as refills may comprise plural layers disposed in a laminate.
The lowest, or
downwardly facing outer layer, may comprise apertures to allow for absorption
of cleaning
solution therethrough and to promote the scrubbing of the target surface.
Intermediate layers
may provide for storage of the liquids, and may comprise the absorbent gelling
materials. The
cleaning sheet may have an absorbent capacity of at least 10, 15, or 20 grams
of cleaning solution
per gram of dry cleaning sheet, as set forth in commonly assigned US Patent
6,716,805. Here,
some or all layers of the laminate may be formed from or may comprise bio-
derived materials.
Likewise, the cleaning composition may comprise or consist of one or more
chemical
compounds, for which all or a substantial portion of the carbon atoms therein
are naturally-based
or bio-derived.
The top, or upwardly facing outer layer, may be liquid impervious in order to
minimize loss of
absorbed fluids. The top layer may further provide for releasable attachment
of the cleaning
sheet to a cleaning implement. The top layer may be made of a polyolefinic
film, such as LDPE,
preferably a bio-derived polyolefinic film or bio-derived LDPE.
Wet Cleaning Implement
The cleaning sheets and refills according to the present invention may be used
with a cleaning
implement. The cleaning implement may comprise a plastic head for holding the
cleaning sheet
and an elongate handle articulably connected thereto. The handle may comprise
a metal or
plastic tube or solid rod.
The head may have a downwardly facing surface, to which the sheet may be
attached. The
downwardly facing service may be generally flat, or slightly convex. The head
may further have
an upwardly facing surface. The upwardly facing surface may have a universal
joint to facilitate
connection of the elongate handle to the head. The components of the head may
comprise or
consist of one or more bio-derived materials such as bio-derived plastics.
A hook and loop system may be used to attach the cleaning sheet directly to
the bottom of the
head. Alternatively, the upwardly facing surface may further comprise a
mechanism, such as
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resilient grippers, for removably attaching the cleaning sheet to the
implement. If grippers are
used with the cleaning implement, the grippers may be made according to
commonly assigned
US patents 6,305,046; 6,484,346; 6,651,290 and/or D487,173. The grippers may
be formed of or
may comprise a bio-derived plastic or a bio-derived rubber.
The cleaning implement may further comprise a reservoir for storage of
cleaning solution. The
reservoir may be replaced when the cleaning solution is depleted and/or
refilled as desired. The
reservoir may be disposed on the head or the handle of the cleaning implement.
The neck of the
reservoir may be offset per commonly assigned US patent 6,390,335. The
cleaning solution
contained therein may be made according to the teachings of commonly assigned
US patent
6,814,088. The reservoir may be formed from or may comprise one or more bio-
derived
materials.
The cleaning implement may further comprise a pump for dispensing cleaning
solution from the
reservoir onto the target surface, such as a floor. The pump may be battery
powered or operated
by line voltage. Alternatively, the cleaning solution may be dispensed by
gravity flow. The
cleaning solution may be sprayed through one or more nozzles to provide for
distribution of the
cleaning solution onto the target surface in an efficacious pattern.
If a replaceable reservoir is utilized, the replaceable reservoir may be
inverted to provide for
gravity flow of the cleaning solution. Or the cleaning solution may be pumped
to the dispensing
nozzles. The reservoir may be a bottle, and may made of plastic, such as a
polyolefin, preferably
a bio-derived polyolefin. The cleaning implement may have a needle to receive
the cleaning
solution from the bottle. The bottle may have a needle piercable membrane,
complementary to
the needle, and which is resealed to prevent undesired dripping of the
cleaning solution during
insertion and removal of the replaceable reservoir.
A suitable reservoir and fitment therefor may be made according to the
teachings of commonly
assigned US Patents 6,386,392, 7,172,099; D388,705; D484,804; D485,178. A
suitable cleaning
implement may be made according to the teachings of commonly assigned US
Patents 5,888,006;
5,960,508; 5,988,920; 6,045,622; 6,101,661; 6,142,750; 6,579,023; 6,601,261;
6,722,806;
6,766,552; D477,701 and/or D487,174.
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=
Dry Dusters
The cleaning pads described above may be used with a dry duster implement. As
noted above,
the cleaning article according to the present invention may comprise a
nonwoven sheet having
tow fibers joined thereto. The cleaning article may have a longitudinal axis.
The tow fibers may
be joined to the nonwoven sheet in a generally transverse direction and
particularly in a direction
normal the longitudinal axis, to provide a laminate structure of two laminae.
At least a portion of
the tow fibers may comprise or consist of one or more bio-derived materials.
If desired, the cleaning article may comprise additional laminae. For example,
the tow fibers
may be disposed intermediate two nonwoven sheets. Plural laminae of tow fibers
may be
disposed intermediate the nonwoven sheets and/or outboard thereof. Optionally,
one or more of
the nonwoven sheets may be cut to provide comprise strips. The strips may be
generally normal
to the longitudinal axis. Some or all of the laminae may comprise or consist
of bio-derived
materials.
The tow fibers and/or nonwoven sheets may comprise an additive to assist in
removal of dust and
other debris from the target surface. The additive may comprise wax, such as
microcrystalline
wax, oil, adhesive and combinations thereof. Natural oils and waxes may be
used. The cleaning
article may be made according to US Patent 6,813,801. Preferably, if present,
the additive
comprises or consists of one or more bio-derived materials, as described
above.
The laminae of the cleaning article may be joined together using adhesive,
thermal bonding,
ultrasonic welding, etc. If desired, the bonding lines may be generally
parallel to the longitudinal
axis and may be continuous, or discontinuous as desired. Three longitudinally
parallel bonding
lines may be utilized to define two sleeves.
The two sleeves may accept one or more complementary fork tines of a handle.
The fork tines
may be removably inserted into the sleeves of the cleaning article to provide
for improved
ergonomics. The handle may be plastic and made according to the teachings of
US patents
7,219,386; 7,293,317 and/or 7,383,602. Individual components constituting the
handle, the
housing handle, the support member, the pivot connection, and the locking
mechanism are all
made of synthetic resin, such as ABS, vinyl chloride, PE (polyethylene), PP
(polypropylene) and
PET (polyethylene terephthalate), except for the coil spring. Preferably the
synthetic resin is bio-
derived, such as bio-derived polyethylene, bio-derived polypropylene, or bio-
derived PET. In
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one embodiment, recycled forms of these materials may be used, e.g., recycled
PET (or "rPET").
In yet another embodiment, combinations of bio-derived and recycled materials
are used. In yet
another embodiment, a least a port of the material contaions rPET.
Bio-derived resins are known and may be formed from a biomass, such as
terpenes and
terpenoids, and mixtures thereof, that are converted to bio-based terephthalic
acid (TPA) and bio-
based di-methyl terephthalate (DMT). In particular, both a- and 13-pinene, the
main component
of turpentine oil, and limonene, the main component of lemon essential oil,
possess a six-member
hydrocarbon ring. These terpenes are an available biomass source, and may be
transformed into
six member ring aromatic compounds such as para-cymene, which is then
converted to bio-based
terephthalic acid (bio-TPA) and bio-based di-methyl terephthalate (bio-DMT).
The bio-TPA and
bio-DMT may be subsequently polymerized to form bio-based polyesters, such as
bio-based
poly(ethylene terephthalate) (bio-PET), bio-based poly(trimethylene
terephthalate) (bio-PTT),
and bio-based poly(butylene terephthalate) (bio-PBT). A biomass is also
converted to bio-based
cyclohexane di-methanol and polymerized with bio-based terephthalic acid or
bio-based di-
methyl terephthalate (bio-DMT) to produce bio-based poly(cyclohexylene
dimethyl
terephthalate) (bio-PCT). These bio-derived materials may be prepared from bio-
derived sources
as described in detail in Berti, et al., U.S. Pat. App!. Pub. No.
2010/0168371, entitled "Bio-Based
Terephthalate Polymers."
Bio-polyethylene is 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. As used here, "polyethylene" encompasses
high density
polyethylene (HDPE), low density polyethylene (LDPE), linear low density
polyethylene
(LLDPE), and ultra low density polyethylene (ULDPE).
Bio-polypropylene is 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
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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-polyethylene terephthalate is 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 one embodiment, a PLA polymer is used. Lactic acid polymers and lactide
polymers suitable
for use herein include, but are not limited to, those polylactic acid-based
olymers and polylactide-
based polymers that are generally referred to in the industry as "PLA."
Therefore, the terms
"pollactic acid," "polylactide," and "PLA" are used interchangeably to include
homopolymers
and copolymers of lactic acid and lactide based on polymer characterization of
the polymers
being formed from a specific monomer or the polymers being comprised of the
smallest
repeating monomer unites. See e.g., US 6,770,356 B2 at col. 16, 1. 59¨ col.
18, 1. 53. See also
US 2002/0143116 Al at paragraphs 32-42.
In another embodiment, a polyethylene ("PE"), or a PE/PLGA blend is used.
Alternatively a
thermoplastic starch ("TPS") is used. Examples of TPS include PLANTIC brand of
products
(e.g., EG501, GP100, HF301, WR700, WR702) from Plantic Technologies Limited.
In a further
embodiment, a PE/TPS blend is used.
Additional suitable bio-derived materials for use in the fiber-containing
cleaning sheets described
herein include the materials disclosed in U.S. App. Pub. No. 2011/0120902,
incorporated herein
by reference in its entirety.
Cleaning Compositions
The cleaning pads described above, used alone or in combination with the above-
described
cleaning implements, may comprise, be packaged with, or be used in combination
with one or
more cleaning compositions. The one or more cleaning compositions may comprise
one or more
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solvents, one or more chelants, one or more thickeners, one or more
surfactants, one or more
odor-reducing additives, one or more fragrances, or combinations thereof. In
preferred
embodiments, the cleaning compositions comprise at least one bio-derived
surfactant. In some
embodiments the cleaning compositions may further comprise one or more non-bio-
derived
surfactants in addition to the at least one bio-derived surfactant, one or
more bio-derived
solvents, one or more bio-derived chelants, one or more bio-derived
thickeners, one or more bio-
derived polymers, one or more bio-derived odor-reducing additives, one or more
bio-derived
fragrances, or combinations thereof. Preferably, the cleaning compositions
comprise a number of
carbon-containing compounds, wherein at least 1% by weight, at least 10% by
weight, at least
25% by weight, at least 50% by weight, at least 75% by weight, at least 90% by
weight, at least
95% by weight, at least 99% by weight, or 100% by weight of the carbon atoms,
based on the
total weight of the carbon atoms, are bio-derived.
Surfactant
Surfactants suitable for use in the cleaning compositions 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. Preferably, the bio-derived surfactants
include at least one
bio-derived low-foaming non-ionic surfactant. 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 cleaning
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 cleaning composition, either or both portions may be
biobased or bio-
derived. 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
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When the polymer is not present in the cleaning compositions herein, the
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 particularly 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
about 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 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,
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12176-AF 42
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.
The surfactants for use herein further may include, for example
allcylpolyglycosides having the
formula:
R20(C.H2õ0)t (glycosyl),
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 xis 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
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
Thus, alkyl polyglycosides (APGs), also called alkyl polyglucosides if the
saccharide moiety is
glucose, are naturally derived, nonionic surfactants. The alkyl polyglycosides
also may be fatty
ester derivatives of saccharides or polysaccharides that are formed when a
carbohydrate is
reacted under acidic condition with a bio-derived fatty alcohol through
condensation
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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. 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).
The APGs for use in the cleaning 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 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 cleaning composition. For the APGs used in the cleaning compositions, x
preferably 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
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 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
C8 and C10 (ratio
of 45:55) and a degree of polymerization of 1.7.
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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 ADW
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
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¨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 cleaning compositions
herein.
Zwitterionic surfactants can also be incorporated into the cleaning
compositions. These
surfactants can be broadly described as derivatives of secondary and tertiary
amines, derivatives
of heterocyclic secondary and tertiary amines, or derivatives of 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 "Miranole", 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.
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¨ 12176-AF 45
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 cleaning 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. The incorporation of these
solvents in cleaning
compositions is useful for controlling aesthetic factors of the undiluted
products, such as
viscosity, and/or for controlling the stability of important adjuncts such as
enzymes, and/or for
controlling the stability of the undiluted formulations at temperatures
significantly above or
below ambient temperature. It is believed that these solvents have no
significant effect on the
cleaning performance of the formulations. The compositions preferably contain
solvents from
natural sources rather than solvents from synthetic petrochemical sources,
such as glycol ethers,
hydrocarbons, and polyalkylene glycols. Water insoluble solvents such as
terpenoids, terpenoid
derivatives, terpenes, terpenes derivatives, or limonene can be mixed with a
water-soluble
solvent when employed. Methanol and propylene glycol may be incidental
components in the
cleaning compositions.
Alternatively, the cleaning compositions may also be substantially devoid of
solvents and may
include solvent-free surfactants such as Berol CLF by AlczoNobel. The cleaning
compositions
may be free of other organic solvents (or only trace amounts of less than 0.5%
or 0.1%) other
than the ones already enumerated above. The compositions may comprise the
following bio-
derived alkanols: bio-derived n-propanol, bio-derived isopropanol, bio-derived
butanol, bio-
derived pentanol, and bio-derived hexanol, and isomers thereof. The
compositions may comprise
one or more of the following diols: bio-derived methylene glycol, bio-derived
ethylene glycol,
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12176-AF
and bio-derived butylene glycols. The compositions comprise bio-derived
alkylene glycol ethers
which include, but are not limited to, bio-derived ethylene glycol monopropyl
ether, bio-derived
ethylene glycol monobutyl ether, bio-derived ethylene glycol monohexyl ether,
bio-derived
diethylene glycol monopropyl ether, bio-derived diethylene glycol monobutyl
ether, bio-derived
diethylene glycol monohexyl ether, bio-derived propylene glycol methyl ether,
bio-derived
propylene glycol ethyl ether, bio-derived propylene glycol n-propyl ether, bio-
derived propylene
glycol monobutyl ether, bio-derived propylene glycol t-butyl ether, bio-
derived di- or tri-
polypropylene glycol methyl or ethyl or propyl or butyl ether, acetate and
propionate esters of
glycol ethers. The compositions may comprise bio-derived short-chain esters
which include, but
are not limited to, bio-derived glycol acetate, and cyclic or linear volatile
methylsiloxanes. The
compositions may comprise bio-derived alkyl glycol ethers, bio-derived alcohol
alkoxylates, bio-
derived alkyl monoglycerolether sulfate, or bio-derived alkyl ether sulfates.
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 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 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 cleaning
composition derives greater
than 50%, grater than 75%, greater than 90%, or even 100% of its carbon from
renewable
resources.
The renewable resourcing of solvents is an area of the chemical industry that
has a large 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, and aromatics.
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-
_
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12176-AF 47
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-
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 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
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.
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 cleaning 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
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12176-AF 48
=
ethylene. Bio-derived low molecular-weight polyethers, especially bio-derived
alkyl capped-
polyethers, may be used as solvents in the cleaning 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 about 0.25%, and, at least about
0.5%, preferably at least
about 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 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
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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 cleaning
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 about 5,
preferably less than about 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 P-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.
Hydrophilic Polymer
In some of the embodiments of the invention, a polymeric material that
improves the
hydrophilicity of the surface being treated is desirable. 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
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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 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]n¨CH(C6115)--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
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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
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, 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,
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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 about 200
cp, preferably less
than about 100 cp, more preferably less than about 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 about 0.5%,
preferably from about
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 cleaning 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.
=
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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., 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.
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 cleaning
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
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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 cleaning 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-
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.
. _
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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 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
cleaning compositions that all of the carbon atoms of the monomers used to
form the polymer
components to be bio-derived.
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= 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 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
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= 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
propionaldehyde 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-scalants
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
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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.
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), ally! 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-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
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, cleaning
compositions herein
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
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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.
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 cleaning 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-esteriflcation. 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
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used as a feedstock for the bio-derived monomers and polymers for use in the
cleaning
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 14
C/I2C 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
cleaning 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
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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 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 am-dicarboxylic acids. As used herein, the term am-
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,a)-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
cleaning compositions. According to certain embodiments, the a,co-dicarboxylic
acid may be an
unsaturated a,co-dicarboxylic acid or a saturated am-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.
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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.
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 cleaning
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)2l), 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
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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
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.
Natural Thickener
The cleaning compositions can also comprise an auxiliary nonionic or anionic
polymeric
thickening component, especially cellulose thickening polymers, especially a
water-soluble or
water dispersible polymeric materials, having a molecular weight greater than
about 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
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,
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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 cleaning composition also may contain an anti-
redeposition polymer.
Examples of anti- redeposition polymers include, but are not limited to,
inulin, derivatized inulin,
guar and derivatized guar. Also suitable for use in the cleaning 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 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
preferably
from about 0.005% to about 0.025%, by weight of the composition.
Natural Essence
The cleaning 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
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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
cleaning composition, and in fact many natural extracts, oils, essences,
infusions and such are
very fragrant materials. However, for use in the present cleaning
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 cleaning 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, 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
oil, lemon oil, lemongrass oil, lime oil, lovage oil, mace oil, mandarin oil,
mimosa abs., myrrh
abs., mustard oil, narcissus abs., neroli bigarade oil, nutmeg oil, oakmoss
abs., olibanum res.,
onion oil, opoponax res., orange oil, orange flower oil, origanum, orris
concrete, pepper oil,
peppermint oil, peru balsam, petitgrain oil, pine needle oil, rose abs., rose
oil, rosemary oil, safe
officinalis oil, sandalwood oil, sage oil, spearmint oil, styrax oil, thyme
oil, tolu balsam, tonka
beans abs., tuberose abs., turpentine oil, vanilla beans abs., vetiver oil,
violet leaf abs., ylang
ylang oil and similar vegetable oils.
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, cis-3-
.
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hexenol, terpineol and like alcohols; anethole, musk xylol, isoeugenol, methyl
eugenol and like
phenols; a-amyleinnamic aldehyde, anisaldehyde, n-butyl aldehyde, cumin
aldehyde, cyclamen
aldehyde, decanal, isobutyl aldehyde, hexyl aldehyde, heptyl aldehyde, n-nonyl
aldehyde,
nonadienol, citral, citronellal, hydroxycitronellal, benzaldehyde, methyl
nonyl acetaldehyde,
cinnamic aldehyde, dodecanol, a-hyxylcinnamic aldehyde, undecenal,
heliotropin, vanillin, ethyl
vanillin and like aldehydes; methyl amyl ketone, methyl P-naphthyl ketone,
methyl nonyl ketone,
musk ketone, diacetyl, acetyl propionyl, acetyl butyryl, carvone, menthone,
camphor,
acetophenone, p-methyl acetophenone, ionone, methyl ionone and like ketones;
amyl
butyrolactone, diphenyl oxide, methyl phenyl glycidate, gamma.-nonyl lactone,
coumarin,
cineole, ethyl methyl phenyl glicydate and like lactones or oxides; methyl
formate, isopropyl
formate, linalyl formate, ethyl acetate, octyl acetate, methyl acetate, benzyl
acetate, cinnamyl
acetate, butyl propionate, isoamyl acetate, isopropyl isobutyrate, geranyl
isovalerate, ally!
capronate, butyl heptylate, octyl caprylate octyl, methyl heptynecarboxylate,
methine
octynecarboxylate, isoacyl caprylate, methyl laurate, ethyl myristate, methyl
myristate, ethyl
benzoate, benzyl benzoate, methylcarbinylphenyl acetate, isobutyl
phenylacetate, methyl
cinnamate, cinnamyl cinnamate, methyl salicylate, ethyl anisate, methyl
anthranilate, ethyl
pyruvate, ethyl a-butyl butylate, benzyl propionate, butyl acetate, butyl
butyrate, p-tert-
butylcyclohexyl acetate, cedryl acetate, citronellyl acetate, citronellyl
formate, p-cresyl acetate,
ethyl butyrate, ethyl caproate, ethyl cinnamate, ethyl phenylacetate, ethylene
brassylate, geranyl
acetate, geranyl formate, isoamyl salicylate, isoamyl isovalerate, isobornyl
acetate, linalyl
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 cleaning
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
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note that these levels tend to be greater than those levels used for scenting
a product with a
perfume.
Fragrances
The cleaning 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 cleaning 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 cleaning
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 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 cleaning compositions may further comprise a perfume. In a particularly
preferred
embodiment the cleaning compositions comprise different perfumes such that the
user will gain a
different olfactory experience, for example, when the cleaning compositions
are contained within
different types of dosing devices such as pouches.
The cleaning compositions may also comprise a blooming perfume. A blooming
perfume
composition is one which comprises blooming perfume ingredients. A blooming
perfume
ingredient may be characterized by its boiling point (B.F.) 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
_ .
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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 cleaning compositions.
The perfume, if present in the cleaning 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
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 cleaning composition, may be
characterized by a
boiling point of 250 C or less and ClogP of 3.0 or more. More preferably the
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
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the composition, more preferably at least 37.5% and most preferably greater
than 40% by weight
of the perfume composition.
More preferably the perfume, when present in the cleaning 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 cleaning composition may comprise at least one perfume ingredient selected
from either first
and/or second perfume ingredients which is present in an amount of at least 7%
by weight 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
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,
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.
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.,
"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
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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 salicylate,
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 cleaning 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 cleaning
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-fl-
cyclodextrin, commonly
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known as DIMEB, in which each glucose unit has 2 methyl groups with a degree
of substitution
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
cleaning 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 cleaning
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 cyclodextriniperfume
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
detergent 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.
_ _
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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
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 cleaning 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.
. .
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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
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
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.
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
compatible with the derivatised cyclodextrins.
Preferably, the aqueous cleaning solution of the present invention is 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 about 10 cm.
Preferably, the cyclodextrins used in the present invention are highly water-
soluble such 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,
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=
and ethylated cyclodextrins, wherein R is a methyl or an ethyl group; those
with hydroxyalkyl
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 carboxymethyl/quaternary
ammonium
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 about 10 g in 100
ml of water at room temperature, preferably at least about 20 g in 100 mL of
water, more
preferably at least about 25 g in 100 mL of water at room temperature. The
availability of
solubilized, 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 Ito about 18, preferably
from about 3 to
about 16. A known methylated beta-cyclodextrin is heptakis-2,6-di-O-methyl-p-
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
CA 02762593 2011-12-20
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=
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
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
15 Adjuncts
The cleaning 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
sodium hydroxide, and organic agents such as monoethanolamine, diethanolamine,
and
silicone/hydrocarbon blends, all preferably bio-derived. Bleaching agents,
when used, include,
-
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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, Novozymes 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 (allcylene
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, 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 about 500,000 (e.g. CARBOPOL 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
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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.
Other
The invention also comprises packages containing cleaning sheets, cleaning
implements, refills,
components, and/or cleaning compositions described herein, the packages being
in association
with information that will inform the consumer, by words and/or by pictures,
that use of the
sheets will provide cleaning benefits which include soil (e.g., dust, lint,
etc.) removal and/or
entrapment and this information can comprise the claim of superiority over
other cleaning
products. In a highly desirable variation, the package bears the information
that informs the
consumer that the use of the cleaning sheet provides reduced levels of dust
and other airborne
matter in the atmosphere. It is very important that the consumer be advised of
the potential to
use the sheets on non-traditional surfaces, including fabrics, pets, etc., to
ensure that the full
benefits of the sheets are realized. Accordingly, the use of packages in
association with
information that will inform the consumer, by words and/or by pictures, that
use of the
compositions will provide benefits such as improved cleaning, reduction of
particulate soil in the
air, etc. as discussed herein, is important. The information can include,
e.g., advertising in all of
the usual media, as well as statements and icons on the package, or the sheet
itself, to inform the
consumer. The printing of such information, as well as the printing of any and
all labels, may be
done with bio-derived inks. Likewise, the containers and packaging may
comprise or consist of
bio-derived or recycled materials.
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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".
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
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
_
