Note: Descriptions are shown in the official language in which they were submitted.
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SUSTAINABLE COMPOSITIONS FOR AUTOMATIC DISHWASHING
DETERGENTS AND SUSTAINABLE PACKAGING FOR THE
COMPOSITIONS
TECHNICAL FIELD
The present invention relates generally to automatic dishwashing (ADW)
compositions and
packaging for ADW compositions and, more specifically, to ADW compositions and
packaging,
whereby the ADW compositions themselves and/or the packaging for the ADW
compositions
comprise sustainable materials made from bio-derived materials.
BACKGROUND
Automatic dishwashing detergents typically comprise a number of organic
ingredients such as
surfactants, builders, polymers, and adjuncts. As used here, "organic
ingredients" refers to
ingredients containing chemical compositions having carbon atoms. In typical
commercial
detergents, the carbon atoms of these organic ingredients trace their origin
to a petroleum
product.
In view of current global drives to decrease reliance on petroleum sources,
owing at least in part
both to decreasing supplies of petroleum and also to increased recognition of
global warming
caused from carbon dioxide emissions during petroleum capture and refining,
there is a constant
need for developing products whose organic ingredients are derived from
sources other than
petroleum. Technology for producing organic molecules from natural or so-
called bio-derived
sources continues to improve with regard to providing organic chemicals having
carbon atoms, of
which a substantial portion, or even all, of the carbon atoms in the chemicals
are bio-derived.
Thus, there remains a need for consumer products such as automatic dishwashing
detergents,
including the packaging used for the detergents, that are effective and also
advantageously are
bio-derived.
SUMMARY
To address the foregoing needs, embodiments disclosed herein are directed to
automatic
dishwashing compositions comprising at least one bio-derived ingredient. In
preferred
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embodiments, the automatic dishwashing compositions are composed entirely of
bio-derived
ingredients.
Further embodiments disclosed herein are directed to packaging materials for
automatic
dishwashing compositions, for example, unit-dose pouches and outer secondary
packaging, for
which at least one of the unit-dose pouch and the secondary packaging is
formed from a bio-
derived material. Preferably, all of the packaging materials for the automatic
dishwashing
compositions are bio-derived.
Still further embodiments disclosed herein are directed to consumer products
comprising a bio-
derived automatic dishwashing composition packaged in bio-derived packaging
materials.
These and other features, aspects, and advantages of the present invention
will become better
understood with reference to the following description and appended claims.
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
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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.
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.
As used herein, the term "petroleum derived" means a product derived from or
synthesized from
petroleum or a petrochemical feedstock.
"Biologically produced" means organic compounds produced by one or more
species or strains
of living organisms, including particularly strains of bacteria, yeast, fungus
and other microbes.
"Bio-produced" and biologically produced are used synonymously herein. Such
organic
compounds are composed of carbon from atmospheric carbon dioxide converted to
sugars and
starches by green plants.
"Fermentation" as used refers to the process of metabolizing simple sugars
into other organic
compounds. As used herein fermentation specifically refers to the metabolism
of plant derived
sugars, such sugar are composed of carbon of atmospheric origin.
_
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"Carbon of atmospheric origin" as used herein refers to carbon atoms from
carbon dioxide
molecules that have recently, in the last few decades, been free in the
earth's atmosphere. Such
carbons in mass are identifiable by the present of particular radioisotopes as
described herein.
"Green carbon", "atmospheric carbon", "environmentally friendly carbon", "life-
cycle carbon",
"non-fossil fuel based carbon", "non-petroleum based carbon", "carbon of
atmospheric origin",
and "biobased carbon" are used synonymously herein.
"Carbon of fossil origin" as used herein refers to carbon of petrochemical
origin. Such carbon
has not been exposed to UV rays as atmospheric carbon has, therefore masses of
carbon of fossil
origin has few radioisotopes in their population. Carbon of fossil origin is
identifiable by means
described herein. "Fossil fuel carbon", "fossil carbon", "polluting carbon",
"petrochemical
carbon", "petro-carbon" and carbon of fossil origin are used synonymously
herein.
"Naturally occurring" as used herein refers to substances that are derived
from a renewable
source and/or are produced by a biologically-based process.
"Fatty acid" as used herein refers to carboxylic acids that are often have
long aliphatic tails,
however, carboxylic acids of carbon length 1 to 40 are specifically included
in this definition for
the purpose of describing the present invention. "Fatty acid esters" as used
herein are esters,
which are composed of such, defined fatty acids.
As used herein, "sustainable" refers to a material having an improvement of
greater than 10% in
some aspect of its Life Cycle Assessment or Life Cycle Inventory, when
compared to the
relevant virgin petroleum-based plastic material that would otherwise have
been used to
manufacture the article.
As used herein, "Life Cycle Assessment" (LCA) or "Life Cycle Inventory" (LCI)
refers to the
investigation and evaluation of the environmental impacts of a given product
or service caused or
necessitated by its existence. The LCA or LCI can involve a "cradle-to-grave"
analysis, which
refers to the full Life Cycle Assessment or Life Cycle Inventory from
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
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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".
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 "C
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
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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 14C that
exists in the atmosphere becomes part of all life forms, and their biological
products. Because
these renewably based organic molecules that biodegrade to CO2 do not
contribute to global
warming as there is no net increase of carbon emitted to the atmosphere. In
contrast, fossil fuel
based carbon does not have the signature radiocarbon ratio of atmospheric
carbon dioxide.
Assessment of the renewably based carbon in a material can be performed
through standard test
methods. Using radiocarbon and isotope ratio mass spectrometry analysis, the
biobased content
of materials can be determined. ASTM International, formally known as the
American Society
for Testing and Materials, has established a standard method for assessing the
biobased content
of materials. The ASTM method is designated ASTM-D6866.
The application of ASTM-D6866 to derive a "biobased content" is built on the
same concepts as
radiocarbon dating, but without use of age equations. The analysis is
performed by deriving a
ratio of the amount of radiocarbon (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 modem 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
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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.
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.
Automatic dishwashing detergent composition
Embodiments disclosed herein are directed to automatic dishwashing (ADW)
compositions
comprising bio-derived ingredients. The ADW compositions comprise one or more
detergent
active components selected from surfactants, builders, enzymes, bleaches,
bleach activators,
bleach catalysts, polymers, dying aids and metal care agents. At least one of
the one or more
detergent active components is a bio-derived compound. Preferably, at least
two, at least three,
at least four, or even all of components of the ADW compositions are bio-
derived compounds.
More preferably, at least the primary active ingredients of the ADW
compositions all are bio-
derived. Also preferably, the ADW compositions exhibit pMC values, as defined
and determined
above, of at least 50%, at least 60%, at least 70%, at least 80%, at least
90%, at least 95%, at least
99%, or even 100%.
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In preferred embodiments, the ADW compositions are composed entirely of
ecologically
responsible ingredients, particularly bio-derived ingredients. The ADW
compositions of the
present invention may include bio-derived nonionic surfactants, most
preferably the bio-derived
fatty alcohol ethoxylates and/or bio-derived alkyl polyglycoside surfactants ;
optionally bio-
derived anionic surfactant components, preferably bio-derived alkyl ether
sulfates, bio-derived
alkyl sulfate, bio-derived alpha-sulfonated fatty acid esters, and/or bio-
derived fatty acid soaps; ;
optionally, a bio-derived "natural essence" such as an essential oil, natural
tree, plant, fruit, nut or
seed extract, or other purified synthetic organic material to boost
performance and enzyme
stability, and in many instances to also provide fragrance; optionally, a
builder, most preferably
carbonate, bicarbonate, and/or citrate; optionally a bio-derived soil
dispersant/anti-redeposition
Surfactant
Surfactants suitable for use herein may include bio-derived surfactants and,
optionally, non-bio-
derived surfactants. The bio-derived surfactants may include bio-derived
anionic surfactants,
bio-derived nonionic surfactants, bio-derived cationic surfactants, or
combinations thereof.
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 ADW 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 ADW composition, either or both portions may be
biobased. Bio-derived
surfactants containing biologically derived carbon may include, without
limitation, glycosides of
fatty acids and alcohols, polyether glycosidic ionophores, macrocyclic
glycosides, carotenoid
glycosides, isoprenoid glycosides, fatty acid amide glycosides and analogues
and derivatives
thereof, glycosides of aromatic metabolites, alkaloid glycosides,
hemiterpenoid glycosides,
monoterpenoid glycosides, phospholipids, lysophospholipids, ceramides,
gangliosides,
sphingolipids, fatty acid amides, alkylpolyglucosides, polyol alkyl
ethoxylates, anhydrohexitol
alkyl ethoxylates, and combinations of any thereof.
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The hydrophilic portions of bio-derived surfactants in the ADW compositions
include, without
limitation, a polyol alkyl ethoxylate containing biobased carbon (bioderived
polyol alkyl
ethoxylate). The polyol portions of polyol alkyl ethoxylates may be
biologically derived polyols
from biological or botanical sources. Biobased polyols suitable as a starting
material for polyols
suitable for use in polyol alkyl ethoxylates include, but are not limited to,
anhydrohexitols,
saccharides, such as monosaccharides including but not limited to dioses, such
as
glycolaldehyde; trioses, such as glyceraldehyde and dihydroxyacetone;
tetroses, such as erythrose
and threose; aldo-pentoses such as arabinose, lyxose, ribose, deoxyribose,
xylose; keto-pentoses,
such as ribulose and xylulose; aldo-hexoses such as allose, altrose,
galactose, glucose (dextrose),
gulose, idose, mannose, talose; keto-hexoses, such as fructose, psicose,
sorbose, tagatose;
heptoses, such as mannoheptulose and sedoheptulose; octoses, such as octolose
and 2-keto-3-
deoxy-manno-octonate; and nonoses, such as sialose; disaccharides including
but not limited to
sucrose (table sugar, cane sugar, saccharose, or beet sugar), lactose (milk
sugar), maltose,
trehalose cellobiose; oligosaccharides, such as raffinose (melitose),
stachycose, and verbascose,
sorbitol, glycerol, sorbitan, isosorbide; polyglycerols; hexoses; pentoses;
polyols; hydrogenated
sugars; hydroxymethylfurfural; refined sugars; crude sugars; products of the
breakdown of
cellulose; products of the breakdown of hemicellulose; products of the
breakdown of lignin; plant
fiber hydrolyzates; fermented plant fiber hydrolyzates; carbohydrate
hydrogenolyzates; and
combinations of any of these.
The bio-derived polyol feedstock may be a side product or co-product from the
synthesis of
biodiesel or the saponification of vegetable oils and/or animal fats (i e ,
triacylglycerols), such as
glycerol. According to further embodiments, the polyol portion of polyol alkyl
ethoxylate
containing biobased carbon may be derived from polyol feedstocks obtained as
mixed polyols
from hydrolyzed natural (biobased) fibers. Natural fibers may be hydrolyzed
(producing a
hydrolyzate) to provide bioderived polyol feedstock comprising plant fiber
hydrolyzate, such as
mixtures of polyols. Fibers suitable for this purpose include, without
limitation, corn fiber from
corn wet mills, dry corn gluten feed which may contain corn fiber from wet
mills, wet corn
gluten feed from wet corn mills, distiller dry grains solubles (DDGS) and
Distiller's Grain
Solubles (DGS) from dry corn mills, canola hulls, rapeseed hulls, peanut
shells, soybean hulls,
cottonseed hulls, cocoa hulls, barley hulls, oat hulls, wheat straw, corn
stover, rice hulls, starch
streams from wheat processing, fiber streams from corn mesa plants, edible
bean molasses,
edible bean fiber, and mixtures of any of these. Plant fiber hydrolyzates,
such as hydrolyzed corn
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fiber, may be enriched in bio-derived polyol compositions suitable for use as
a feedstock in the
hydrogenation reaction described herein, including, but not limited to,
arabinose, xylose, sucrose,
maltose, isomaltose, fructose, mannose, galactose, glucose, and mixtures of
any of these.
The bio-derived surfactants may be derived from a polyol feedstock obtained
from biobased
fibers which have been hydrolyzed and subjected to fermentation. The
fermentation of plant
fiber hydrolyzates may provide new biobased polyol feedstocks, or may alter
the amounts of
residues of polysaccharides or polyols obtained from hydrolyzed fibers. After
fermentation, a
fermentation broth may be obtained and residues of polysaccharides or polyols
can be recovered
and/or concentrated from the fermentation broth to provide a biobased polyol
feedstock suitable
for use as a starting material for polyols suitable for use in polyol alkyl
ethoxylates, as described
herein.
According to certain embodiments, the bio-derived surfactant may be prepared
from bio-derived
propylene glycol or bio-derived ethylene glycol, such as through reaction with
one or more bio-
derived substances such as bio-derived methanol, bio-derived 2-propanol, bio-
derived glycerol,
bio-derived lactic acid, bio-derived glyceric acid, bio-derived sodium
lactate, and/or bio-derived
sodium glycerate. Reaction products or intermediates during preparation of the
bio-derived
surfactants may include butanediols (BDO) such as bio-derived 1,2-butanediol,
bio-derived 1,3-
butanediol, bio-derived 1,4-butanediol, bio-derived 2,3-butanediol and bio-
derived 2,4-
Pentanediol (2,4-PeD0).
Bio-derived 6-carbon sugars (hexoses), such as mannose, can be converted to
mannitol, which
can be converted to mannitan, which can be converted to isomannide for use in
polyol alkyl
ethoxylates. In certain embodiments, biobased surfactants may contain portions
derived from
hydrogenolysis of biobased polyol feed stocks, such as a carbohydrate having
been subjected to
hydrogenolysis, where the carbonyl group (aldehyde or ketone) of the
carbohydrate has been
reduced to a primary or secondary hydroxyl group to provide a carbohydrate
hydrogenolyzate.
The anhydrohexitol portion of anhydrohexitol alkyl ethoxylates may be derived
from sorbitan
Sorbitan (IUPAC name (3S)-2-(1,2-Dihydroxyethyl)tetrahydrofuran-3,4-diol) may
comprise a
mixture of chemical compounds derived from the dehydration of sorbitol. The
sorbitan mixture
can vary, but may include, without limitation: 1,4-anhydrosorbitol; 1,5-
anhydrosorbitol; and
1,4,3,6-dianhydrosorbitol. Sorbitan is used in the production of surfactants
such as polysorbates.
As a further example, a nonionic sorbitan fatty acid ethoxylate may be
employed.
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The alkyl portion of polyol alkyl ethoxylates may be derived from bio-derived
fatty acids or
biobased or bio-derived fatty alcohols. Bio-derived carboxylic acids may
include, without
limitation, animal or vegetable fatty acids selected from the group consisting
of butyric acid,
caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic
acid, stearic acid,
arachic acid, behenic acid, lignoceric acid, hexacosanoic acid, octacosanoic
acid, triacontanoic
acid and n-dotriacontanoic acid; fatty acids having an odd number of carbon
atoms, such as
propionic acid, n-valeric acid, enanthic acid, pelargonic acid, henadecanoic
acid, tridecanoic acid,
pentadecanoic acid, heptadecanoic acid, nonadecanoic acid, heneicosanoic acid,
tricosanoic acid,
pentacosanoic acid, and heptacosanoic acid; branched fatty acids such as
isobutyric acid,
isocaproic acid, isocaprylic acid, isocaprilic acid, isolauric acid, 11-
methyldodecanoic acid,
isomyristic acid, 13-methyl- tetradecanoic acid, isopalmitic acid, 15-methyl-
hexadecanoic acid,
isostearic acid, 17-methyloctadecanoic acid, isoarachic acid, 19-methyl-
eicosanoic acid, a-ethyl-
hexanoic acid, a-hexyldecanoic acid, a-heptylundecanoic acid, 2-
decyltetradecanoic acid, 2-
undecyltetradecanoic acid, 2-decylpentadecanoic acid, 2-undecylpentadecanoic
acid, 6-methyl-
octanoic acid, 8-methyl-decanoic acid, 10-methyl-dodecanoic acid, 12-methyl-
tetradecanoic acid,
14-methyl-hexadecanoic acid, 16-methyl-octadecanoic acid, 18-methyl-eicosanoic
acid, 20-
methyl-docosanoic acid, 22-methyl-tetracosanoic acid, 24-methyl-hexacosanoic,
26-
methyloctacosanoic acid; unsaturated fatty acids, such as 4-decenoic acid,
caproleic acid, 4-
dodecenoic acid, 5-dodecenoic acid, lauroleic acid, 4-tetradecenoic acid, 5-
tetradecenoic acid, 9-
tetradecenoic acid, palmitoleic acid, 6-octadecenoic acid, oleic acid, 9-
octadecenoic acid, 11-
octadecenoic acid, 9-eicosenoic acid, cis-11-eicosenoic acid, cetoleic acid,
13-docosenoic acid,
15-tetracosenoic acid, 17-hexacosenoic acid, 6,9,12,15- hexadecatetraenoic
acid, linoleic acid,
linolenic acid, gamma linolenic acid, a-eleostearic acid, gadoleic acid, a-
eleostearic acid, punicic
acid, 6,9,12,15-octadecatetraenoic acid, parinaric acid, 5,8,1 1 ,14-
eicosatetraenoic acid, erucic
acid, 5,8,11,14,17-eicosapentaenoic acid (EPA), 7,10,13,16,19-docosapentaenoic
acid,
4,7,10,13,16,19-docosahexaenoic acid (DHA); hydroxylated fatty acids, such as
a-hydroxylauric
acid, a-hydroxymyristic acid, a-hydroxypalmitic acid, a-hydroxystearic acid,
co-hydroxylauric
acid, a-hydroxyarachic acid, 9-hydroxy-12-octadecenoic acid, ricinoleic acid,
a-hydroxybehenic
acid, 9-hydroxy-trans-10,12-octadecadienic acid, kamolenic acid, ipurolic
acid, 9,10-
dihydroxystearic acid, 12-hydroxystearic acid, the corresponding alcohol of
any thereof,
derivatives of any thereof, and combinations of any thereof. These fatty acids
may be reduced to
their corresponding fatty alcohols.
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The alkyl portion of the polyol alkyl ethoxylate may comprise a bio-derived
fatty acid alkyl
portion, such as from the group consisting of animal oil, vegetable oil,
biodiesel, triacylglycerols,
diacylglycerols, monoacylglycerols, fatty acids, fatty alcohols, branched
dicarboxylic acids,
dicarboxylic acid ethers, phospholipids, soapstock, deodorizer distillate,
acid oil, polymerized oil,
heat-bodied oil, blown oil, derivatives of any thereof; and combinations of
any thereof. Fatty
acids may comprise a mixture of bio-derived fatty acids, such as from the
group consisting of
animal fat, beef tallow, biodiesel, borneo tallow, butterfat, camelina oil,
candlefish oil, canola oil,
castor oil, ceramides, cocoa butter, cocoa butter substitutes, coconut oil,
cod-liver oil, coriander
oil, corn oil, cottonseed oil, diacylglycerols, flax oil, float grease from
wastewater treatment
facilities, hazelnut oil, hempseed oil, herring oil, illipe fat, jatropha oil,
kokum butter, lanolin,
lard, linseed oil, mango kernel oil, marine oils, meadowfoam oil, menhaden
oil, milk fat,
monoacylglycerols, mowrah fat, mustard oil, mutton tallow, neat's foot oil,
olive oil, orange
roughy oil, palm oil, palm kernel oil, palm kernel olein, palm kernel stearin,
palm olein, palm
stearin, peanut oil, phospholipids, phulwara butter, pile herd oil, pork lard,
rapeseed oil, rice bran
oil, safflower oil, sal fat, sardine oil, sasanqua oil, shea fat, shea butter,
soybean oil,
sphingolipids, sunflower seed oil, tall oil, tallow, tsubaki oil, tung oil,
triacylglycerols, triolein,
used cooking oil, vegetable oil, whale oil, white grease, yellow grease, and
derivatives,
conjugated derivatives, genetically-modified derivatives, and mixtures of any
thereof.
The alkyl portion of the polyol alkyl ethoxylate may comprise a bio-derived
branched
dicarboxylic acid. Bio-derived branched dicarboxylic acids may be obtained by
subjecting fatty
acid-containing compositions containing one or more double bonds to cross-
linking, such as by
industrial processes including but not limited to heat bodying, oxidation,
polymerization, and
blowing. For example, soybean oil may be cross-linked by blowing, wherein
polymerization is
carried out by bubbling air through a triacylglycerol oil while heating to
temperatures of about
110 C. Typical oils include but are not limited to, drying oils, such as
linseed oil, and semi-
drying oils, such as soybean oil.
Carbon¨carbon and ether cross-linkages are formed between fatty acids of fatty
acid-containing
compositions during the blowing process of a fatty acid-containing composition
containing
unsaturated fatty acid. Double bonds in the cross-linked molecule may be cis
or trans double
bonds, or may become single bonds in the blowing process. The carbon¨carbon
and ether
linkages formed as a result of the blowing process polymerize a portion of the
monounsaturated
fatty acids, such as oleic acid, and/or a portion of the polyunsaturated fatty
acids, such as linoleic
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acid and linolenic acid, cross-linking the fatty acid-containing compositions.
In the case of
triacylglycerol oils, dimers or polymers of fatty acid alkyl chains linked to
glycerol molecules are
formed. The heat- bodying of fatty acid-containing compositions also forms
cross linkages but
tends to form more carbon-carbon linkages and fewer ether linkages.
When one or more of the resulting cross-linked fatty acids is joined to one or
more alcohols
through an ester bond, the ester bonds can be broken to form cross-linked
acids having two
carboxylic acid groups. For example, hydrolysis of the ester bonds of a cross-
linked
triacylglycerol oil results in breaking the ester bonds holding each of the
three fatty acids to the
glycerol backbone of the triacylglycerol units, while cross-linkages between
the fatty acids
remain intact. Hydrolysis can be carried out with heat and pressure, and under
conditions which
minimize the isomerization of remaining cis double bonds to trans double
bonds, for example as
described in US Patent No. 7,126,019 issued Oct. 24, 2006. Hydrolysis of the
ester bonds of the
cross-linked triacylglycerols yields a mixture of dicarboxylic acids and cross-
linked dicarboxylic
ethers. Selection of suitable starting fatty acid-containing compositions and
cross-linking
reaction designs will allow a portion of double bonds to remain in the cross-
linked fatty acids
The dicarboxylic acids and dicarboxylic ethers are biobased and can be reacted
to form ABA
type bio-derived surfactants, wherein the polar anhydrohexitol and ethoxylate
chains are
represented by A and the nonpolar cross-linked alkyl chain are represented by
B. Because the
melting points of branched-chain fatty acids are lower than the straight-chain
counterparts, these
branched B fatty acid chains of the surfactant molecules should crystallize at
lower temperatures
than the non-cross- linked counterparts. Bio-derived dicarboxylic acids or bio-
derived cross-
linked dicarboxylic ethers can be used to form AB type bio-derived
surfactants. Blends of bio-
derived AB and ABA surfactants may be synthesized from bio-derived
dicarboxylic acids,bio-
derived cross-linked dicarboxylic ethers, mixtures of bio-derived dicarboxylic
acids and bio-
derived unsaturated fatty acids, or mixtures of any thereof.
An ABA type surfactant comprises at least one polyol, at least one ethoxylate
group, and at least
one dicarboxylic acid derived from cross-linked fatty acids. A bio-derived ABA
type surfactant
may comprise at least two polyols, at least two ethoxylate groups, and at
least one cross-linked
dicarboxylic acid derived from polymerized fatty acids. A bio-derived ABA type
surfactant may
comprise at least two polyols, at least two ethoxylate groups, and at least
one cross-linked
dicarboxylic acid ether derived from polymerized fatty acids.
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In some embodiments, a bio-derived surfactant is an polyol alkyl ethoxylate
containing
biologically derived carbon.
Bio-derived surfactants described herein may be synthesized, for example,
using a glycerol
feedstock. The glycerol feedstock may include a diluent, such as water, or a
non-aqueous
solvent. Non-aqueous solvents that may be used include, but are not limited
to, methanol,
ethanol, ethylene glycol, propylene glycol, n-propanol and iso-propanol,
preferably bio-derived
methanol, bio-derived ethanol, bio-derived ethylene glycol, bio-derived
propylene glycol, bio-
derived n-propanol and bio-derived iso-propanol. Glycerol feed stocks are
commercially
available, or can be obtained as a byproduct of commercial biodiesel
production. The bio-
derived polyol feedstock may be a side product or co-product from the
synthesis of bio-diesel or
the saponification of vegetable oils and/or animal fats (i.e.,
triacylglycerols). For instance, the
glycerol feedstocks may be obtained through fats and oils processing or
generated as a byproduct
in the manufacture of soaps. The feedstock may be provided, for example, as
glycerol byproduct
of primary alcohol alcoholysis of a bio-derived glyceride, such as a bio-
derived mono-, di- or tri
glyceride. These bio-derived glycerides may be obtained from refining edible
and non-edible
plant feedstocks including without limitation butterfat, cocoa butter, cocoa
butter substitutes,
illipe fat, kokum butter, milk fat, mowrah fat, phulwara butter, sal fat, shea
fat, borneo tallow,
lard, lanolin, beef tallow, mutton tallow, tallow, animal fat, canola oil,
castor oil, coconut oil,
coriander oil, corn oil, cottonseed oil, hazelnut oil, hempseed oil, jatropha
oil, linseed oil, mango
kernel oil, meadowfoam oil, mustard oil, neat's foot oil, olive oil, palm oil,
palm kernel oil,
peanut oil, rapeseed oil, rice bran oil, safflower oil, sasanqua oil, shea
butter, soybean oil,
sunflower seed oil, tall oil, tsubaki oil, tung oil, vegetable oils, marine
oils, menhaden oil,
candlefish oil, cod-liver oil, orange roughy oil, pile herd oil, sardine oil,
whale oils, herring oils,
triglyceride, diglyceride, monoglyceride, triolein palm olein, palm stearin,
palm kernel olein,
palm kernel stearin, triglycerides of medium chain fatty acids, and
derivatives, conjugated
derivatives, genetically-modified derivatives and mixtures of any thereof.
Glycerol feedstocks are known to those of ordinary skill in the art and can be
used either in pure
or crude form. The purity of United States Pharmacopeia grade glycerol is
greater than 99%.
However, the purity of the glycerol having utility in the present invention
may be between 10%
and 99% by weight. The glycerol also may contain other constituents such as
water,
triglycerides, free fatty acids, soap stock, salt, and unsaponifiable matter.
In some examples, the
glycerol feedstocks may comprise from 20% to 80% by weight of bio-derived
glycerol.
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The bio-derived surfactants also may be derived from natural lipids, such as
vegetable oils and
naturally occurring fatty acids or their naturally occurring derivatives such
as mono-, di-, or
triglycerides or phospholipids. The bio-derived surfactants may be obtained,
for example, from
natural oils such as soybean and castor oils, wherein the bio-derived
surfactants are obtained by
processes that typically include esterification of the oils to add alkoxy
groups such as methoxy,
ethoxy, or propoxy groups. In one version, the bio-derived surfactants are
obtained by reactions
that include hydrolysis, esterification of the liberated fatty acids with
methanol, and then
hydrogenation to create a bio-derived fatty acid alcohol. Bio-derived datty
alcohols can be
prepared from natural fatty acids with a variety of other technologies. In any
case, the alcohols
may then be further modified by reaction with ethylene oxide, such as bio-
derived ethylene
oxide, to add a plurality of ethoxy groups, forming a polyethoxy ether.
Polyoxy ethers with
relatively high HLB values can be formed from fatty alcohols via reaction with
other known
reactants as well to form, for example, bio-derived surfactants with multiple
propoxy groups,
butoxy groups, etc. In other cases, transesterification of a bio-derived fatty
acid ester with a
variety of bio-derived linear chain or other alcohols may be involved,
followed by conversion of
the ester to an alcohol. In some embodiments, the bio-derived surfactants have
aliphatic chains
with relatively high carbon numbers, such as 14 or more carbons, 16 or more
carbons, or 18 or
more carbons. For example, the carbon number may be from 16 to 18.
The bio-derived surfactant may comprise a bio-derived ethoxylated fatty acid
or a bio-derived
fatty alcohol, wherein the fatty acid or alcohol has a carbon number of
sixteen or greater and at
least 5 ethoxy groups, specifically at least 10 ethoxy groups, and more
specifically at least 20
ethoxy groups, such as between 5 and 80 ethoxy groups, or between 10 and 60
ethoxy groups, or
between 15 and 55 ethoxy groups. Such bio-derived surfactants may be obtained
by
esterification or epoxidation of soybean oil or castor oil, or of fatty
alcohols obtained from either
of these.
More generally, but by way of example only, the bio-derived surfactants may be
derived from
any of the following lipids: soybean oil, castor oil, cottonseed oil, linseed
oil, canola oil,
safflower oil, sunflower oil, peanut oil, olive oil, sesame oil, coconut oil,
walnut oil or other nut
oils, flax oil, neem oil, meadowfoam oil, other seed oils, fish oils, animal
fats, and the like.
Exemplary fatty acids include omega-3 fatty acids such as alpha-linolenic
acid, stearidonic acid,
eicosapentaenoic acid, docosahexaenoic acid, and so forth; omega-6 fatty acids
such as linoleic
acid, gamma-linolenic acid, dihomo-gamma-linolenic acid, arachidonic acid,
calendic acid, and
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the like; omega-9 fatty acids such as oleic acid, erucic acid, elaidic acid,
and the like; saturated
fatty acids such as myristic acid, palmitic acid, stearic acid,
dihydroxystearic acid, arachidic acid
(eicosanoic acid), behenic acid (docosanoic acid), lignoceric acid; and other
fatty acids including
various conjugated linoleic acids; and omega-5 fatty acids such as myristoleic
acid, malvalic
acid, sterculic acid. Natural waxes or the fatty acids therefrom may also be
used, particularly
ester waxes such as straight chain ester waxes; examples include jojoba oil,
carnauba wax,
beeswax, candellia wax, and the like. Fatty alcohols can be obtained from any
of these fatty
acids by any known method, including catalytic conversion, esterification plus
hydrogenation,
etc.
The bio-derived surfactants may be obtained from two or more vegetable oil
sources, such as
from mixtures of any two or more of the vegetable oils mentioned herein.
Alternatively, two or
more vegetable oils may be reconstituted to form a reconstituted oil according
to known methods
such as those described in U.S. Pat. No. 6,258,965, "Reconstituted Meadowfoam
Oil," issued
July 10, 2001 to A.J. O'Lenick, Jr., and U.S. Pat. No. 6,013,818,
"Reconstituted Meadowfoam
Oil," issued Jan. 11 , 2001 to A.J. O'Lenick, Jr. The O'Lenick patents
describe processes in
which one or more oils of natural origin are transesterified under conditions
of high temperature
in the presence of a catalyst to make a "reconstituted product" having an
altered alkyl distribution
and consequently altered chemical and physical properties. While bio-derived
surfactants
obtained from natural lipids are useful, it is recognized that identical
materials obtained from
synthetic raw materials can be created and, in some embodiments, may be
suitable for use in the
ADW compositions described herein.
Bio-derived surfactants also may be obtained, in whole or in significant part,
from bioorganic
substances directly obtainable from algae (from direct extraction for
example), and/or through
standard synthetic organic transformations starting from bioorganic molecules
that are in turn
obtainable from algae. Some of the more practical starting materials directly
obtainable from
algae include lipids and polysaccharides, which are useful bio-derived
feedstocks for bio-derived
surfactants. High yield, lipid-rich algae can be grown in water-ponds in
temperature and
environmentally controlled greenhouses and bioreactors. Through autotrophic
and/or
heterotrophic processes, the lipid oil can be extracted through known
mechanical, chemical, and
biological techniques. Through algae strain selection, and technologies to
influence the algae
metabolic pathways, algae is also capable of producing high percentages of
starch and cellulose
via autotrophic and heterotrophic routes, giving additional feedstocks for
specialty chemicals
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such as bio-derived for use in consumer products. In particular,
hydrogenolysis, hydrolysis,
amidation, esterification, ethoxylation and transesterification processes from
algal lipid starting
materials, along with the hydrolysis, enzymolysis, and/or fermentation of
algal polysaccharides
are available routes to the production of the bio-derived surfactants. Also
the direct production
of glucose, cellulose, and sucrose as metabolites from living cyanobacteria
give useful bioorganic
ingredients and bio-feedstock for bio-derived surfactants.
Algae that may be used to produce bioorganic substances that are directly
incorporable into bio-
derived surfactants, or which are useful as precursors to bio-derived
surfactants include, but are
not limited to, Chlorophyta (green algae), Charophyta (Stoneworts and
Brittleworts),
Euglenophyta (Euglenoids), Chrysophyta (golden-brown and yellow-green algae
and diatoms),
Phaeophyta (brown algae), Rhodophyta (red algae), Cyanophyta (blue-green
algae, same as blue-
green bacteria or cyanobacteria), and the Pyrrhophyta (dinoflagellates). Most
algae are
photoautotrophs, and most dried algae mass, wet algae colonies, or algae
metabolites will provide
some levels of lipid, saccharidic substances including polysaccharides and
sulfated materials
(cellulose, hemicellulose, pectin, alginic acid, carrageenan, agarose,
porphyran, fucelleran,
funoran, starch, simple sugars, and the like), glycoproteins, and a variety of
photosynthetic
pigments (chlorophyll, astaxanthin, etc).
For algal lipid feedstock, some species of algae and diatom algae that may
produce commercially
significant levels of lipids include, but are not limited to; Actinastnim;
Actinochloris; Anabaena;
Ankistrodesnnis; Apatococcus; Asterarcys; Auzenochlorella; Bacilliarophy;
Botrydiopsis;
Botiyococciis; Bracteacoccus; Biimilleriopsis; Chaetophorcr, Chant ransia;
Charachtm;
Chlamydomonas', Chlorella; Chlorideilcr, Chlorobotrys; Chlorococcum;
Chlorokybns;
Chloroliimula; Chlormonas; Chlorophyceae; Chlorosarcinopsis; Chlorotetraedron;
Chloricystis;
Coccomyxa; Coelasirella; Coelastropsis; Coelastrum; Coenochloris;
Coleochlomys; Cosmarivm;
Crucigenia; Crucigeniella; Desmodesmus; Diadesmis; Dictyococciis;
Dictyosphaenum;
Dipfosphaera; Dunaliella; Ellipsoidion; Ena/lax; Ettlia; Euglena; Fortiea;
Geminella; Gonium;
Graesiella; Haematococcus; Heterococcus; Interfilum; Isochrysis;
Kentrosphaera; Keratococcus;
Klebsormidium; Koliella; Lagerheimia; Lobosphaera; Macrochloris;
Microthamnion; Monodus;
Monoraphidium; Mougeotia; Muriel Ia; Mychonastes; Myrmecia; Nannochlolis;
Nannochloropsis; Nautococcus; navicular, Navioua; Neochloris; Neodesmus;
Neospongiococcum; Nephrochlamys; Oocyst is; Oonephris; Orthotrichum;
Pediastrum;
Phaeodactylum; Pithophora; Pleurastrum; Pleurochrysis; Porphyridium; Possonia;
Prasiolopsis;
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Protosiphon; Prymnesium, Pseudollipsoidion; Pseudendoclonium;
Pseudocharaciopsis;
Pseudococcomyxa; Pseudoendoclonium; Raphidocelis; Raphidonema; Rhexinema;
Rhopalocystis; Scenedesmus; Schroederiella; Scotiella; Scotiellopsis;
Selenastrum,
Sphaerocystis; Spirogyra; Spirulina; Spongiochloris; Stichococcus;
Stigeoclonium; Synechoccus;
Tetradesmus; Tetrahedron; Tetraselmis; Tetrastrum; Tribonema; Vischeria;
Willea; Xanthonema;
and Zygnema.
From these and other algae and diatom algae may be obtained lipid (or "algal
fat") high in C14
through C22 triglycerides including saturated and unsaturated fatty acid
chains. Other lipid and
oil producing algae include blue algae, green algae, blue-green algae, and
golden-brown algae,
often collectively referred to as micro-algae. This lipid constitution is
similar to fresh water fish
oils. Brown algae and red algae produce longer chain triglycerides, for
example with carbon
chains greater than 24-carbons.
The algae-derived lipid oils (triglycerides), starch, and cellulose may be
converted to algae-
derived surfactants through established chemical synthetic routes, such as:
(1) Algae ¨0 Lipid Triglycerides --0 Surfactants;
(2) Algae Starch or Cellulose ¨0. Sugar Surfactants;
(3) Algae ¨0 Starch or Cellulose ¨0 Surfactants; and, combinations of the
intermediates and end
molecules obtainable from these basic routes, (e.g., a sugar from route 2
combined with a fatty
acid from route Ito produce an alkylpolyglycoside surfactant).
Examples of bio-derived surfactants having carbon chains traceable back to
algae may include,
but are not limited to, alkyl glycosides and alkyl polyglycosides, fatty
alcohol ethoxylates, fatty
acid soaps, fatty acid amides and alkanolamides, fatty amines and ethoxylated
amines, quaternary
ammonium compounds (cationic surfactants), fatty acid esters and ethoxylated
esters, alpha-
sulfonated fatty acid esters, fatty acid phosphates, glyceryl esters,
glucamides, polyglycerol
esters, lecithins, lignin sulfonates, proteins and protein derivatives,
saponins, sorbitol and
sorbitan esters, sucroglycerides, sucrose esters, alkyl sulfates and alcohol
ether sulfates.
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Some bioorganic materials, such as alkylglycoside, lignin, saponins,
glycolipids (such as
ascarosides, simplexides, plakopolyprenosides, and the like), etc. may or may
not be found in
algae species currently known to date; however, some of these materials are
known to be plant
derived and may eventually be sourced from alga species that are currently
undiscovered or not
Anionic Surfactants¨In view of the above-mentioned sources and production
methods for
obtaining bio-derived surfactants generally, bio-derived anionic surfactants
useful in the present
ADW composition are preferably selected from the group consisting of, bio-
derived linear
The anionic surfactant may include alkyl ester sulfonates. These are desirable
because they can
Preferred alkyl ester sulfonate surfactant comprise alkyl ester sulfonate
surfactants of the
structural formula:
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0
R3¨CH--C¨OR4
S03/14
where R3 is a C8 -C20 hydrocarbyl, preferably an alkyl, or combination
thereof, R4 is a C1¨C6
hydrocarbyl, preferably an alkyl, or combination thereof, and M is a soluble
salt-forming cation.
Suitable salts include metal salts such as sodium, potassium, and lithium
salts, and substituted or
unsubstituted ammonium salts, such as methyl-, dimethyl, -trimethyl, and
quaternary ammonium
cations, e.g. tetramethyl-ammonium and dimethyl piperdinium, and cations
derived from
alkanolamines, e.g. monoethanol-amine, diethanolamine, and triethanolamine.
Preferably, R3 is
Cio¨C16alkyl, and R4 is methyl, ethyl, or isopropyl. Especially preferred are
the methyl ester
sulfonates wherein R3 is C14¨C16 alkyl.
Bio-derived alkyl sulfate surfactants are another type of bio-derived anionic
surfactant of
importance for use herein. In addition to providing excellent overall cleaning
ability when used
in combination with polyhydroxy fatty acid amides (see below), including good
grease/oil
cleaning over a wide range of temperatures, wash concentrations, and wash
times, dissolution of
alkyl sulfates can be obtained, as well as improved formulability in 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 C1o¨C20alkyl 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.
Bio-derived alpha-sulfonated alkyl esters may be include linear esters of
C6¨C22 carboxylic acids
sulfonated with gaseous S03. Alpha, (or a-, used interchangeably herein),
pertains to the first
position on the carbon chain adjacent to the carboxylate carbon, as per
standard organic
chemistry nomenclature. The alpha-sulfonated alkyl esters may be pure alkyl
ester or a blend of
(1) a mono-salt of an alpha-sulfonated alkyl ester of a fatty acid having from
8 to 20 carbon
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atoms where the alkyl portion forming the ester is straight alkyl chain of 1
to 6 carbon atoms; and
(2) a di-salt of an alpha-sulfonated fatty acid, the ratio of mono-salt to di-
salt being at least 2:1.
The alpha-sulfonated alkyl esters useful herein are typically prepared by
sulfonating an alkyl
ester of a fatty acid with a sulfonating agent such as S03. As an example, the
bio-derived fatty
acid esters are readily available by transesterification of algae lipids, or
alternatively by
esterification of the fatty acids obtained by hydrolysis of the algae lipids.
When prepared by
sulfonation of fatty acid esters, the alpha-sulfonated alkyl esters normally
contain a minor
amount, (typically less than 33% by weight), of the di-salt of the alpha-
sulfonated fatty acid
which results from saponification of the ester. Preferred alpha-sulfonated
alkyl esters contain
less than about 10% by weight of the di-salt of the corresponding alpha-
sulfonated fatty acid.
The alpha-sulfonated fatty acid ester surfactants that may be incorporated
into the ADW
compositions may comprise alkyl ester sulfonate surfactants of the structural
formula
R3¨CH(S03M)¨0O2R4, where R3 is a C8¨C20 algae-sourced carbon chain, R4 is a
straight or
branched chain C1¨C6 alkyl group, and M is a cation that forms a water-soluble
salt with the alkyl
ester sulfonate, including sodium, potassium, magnesium, and ammonium cations.
Preferably,
R3 is C10¨C16 fatty alkyl, and R4 is ethyl, in turn indirectly derived from
algal polysaccharides
(transesterification of the algae-lipid with ethanol obtained through algae
cellulose fermentation).
Other anionic surfactants that may be included in the ADW compositions herein
include bio-
derived alkyl sulfates, also known as alcohol sulfates. These bio-derived
surfactants have the
general formula R¨O¨SO3Na, where R is a hydrocarbyl having from about 10 to 18
carbon
atoms, and these materials may also be denoted as sulfuric monoesters of
C10¨C18 alcohols,
examples being sodium decyl sulfate, sodium palmityl alkyl sulfate, sodium
myristyl alkyl
sulfate, sodium dodecyl sulfate, sodium tallow alkyl sulfate, sodium coconut
alkyl sulfate, and
mixtures of these surfactants, or of C10--C20 oxo alcohols, and those
monoesters of secondary
alcohols of this chain length. The alkyl sulfates are readily obtainable by
sulfonation of the bio-
derived fatty alcohols described above, which can be directly synthesized
through hydrogenolysis
of algae lipids, or less directly through transesterification of algae lipids
and hydrogenation of the
intermediate fatty acid esters.
Fatty alkylamidopropyl betaines may be present in the ADW compositions and
represent an
important class of mild detergents. For example, cocamidopropyl betaine, with
or without
sodium laureth sulfate as co-surfactant, is the surfactant system of choice
for most shampoo and
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bodywash compositions. The synthesis of betaines is well known and is
described in U.S. Patent
No. 5,354,906 (Weitemeyer, et al.) incorporated herein in its entirety by
reference. The
amidoamine intermediates described by Weitemeyer as obtainable from coconut
fatty acid are
just as easily be obtainable from a fatty acid blend derived from hydrolysis
or hydrogenolysis of
algal lipids. Alternatively, algae lipids may be directly amidated using bio-
derived 1,3-
propanediamine to give fatty amidoamines that then may be converted to
alkylamidopropyl
betaines using the methods described in the '906 patent.
The bio-derived anionic surfactants may include alkyl alkoxylated sulfate
surfactants. These
surfactants are water-soluble salts or acids typically of the formula
RO(A),,S03M, where R is an
unsubstituted C10¨C24 alkyl or hydroxyalkyl group having a Cio¨C24 alkyl
component, preferably
a C12¨C20 alkyl or hydroxyalkyl, more preferably C12¨C18 alkyl or
hydroxyalkyl; A is an ethoxy
or propoxy unit; m is greater than zero, typically between about 0.5 and about
6, more preferably
between about 0.5 and about 3; and M is H or a cation which can be, for
example, a metal cation
(e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or
substituted-
ammonium cation. Alkyl ethoxylated sulfates as well as alkyl propoxylated
sulfates are
contemplated herein. Specific examples of substituted ammonium cations include
methyl-,
dimethyl-, trimethyl-ammonium and quaternary ammonium cations, such as
tetramethyl-
ammonium, dimethyl piperidinium and cations derived from alkanolamines, e.g.
monoethanolamine, diethanolamine, and triethanolamine, and mixtures thereof.
Exemplary
surfactants include C12¨C18 alkyl polyethoxylate (1.0) sulfate, C12¨C18
allcylpolyethoxylate (2.25)
sulfate, C12¨C18 alkyl polyethoxylate (3.0) sulfate, and C12¨C18 alkyl
polyethoxylate (4.0) sulfate
where M is selected from sodium and potassium. Surfactants for use herein can
be made from
natural or synthetic alcohol feedstocks. Chain lengths represent average
hydrocarbon
distributions, including branching.
Preferred anionic surfactants for use in the ADW composition include the alkyl
ether sulfates,
also known as alcohol ether sulfates. Alcohol ether sulfates are the sulfuric
monoesters of the
straight chain or branched alcohol ethoxylates and have the general formula
R¨(OCH2CH2)x¨O¨S03M, where R preferably comprises C7--C21 alcohol ethoxylated
with from
about 0.5 mol to about 9 mol of ethylene oxide (i.e., x=0.5 to 9 EO), such as
C12¨C18 alcohols
containing from 0.5 to 9 EO, and where M is alkali metal or ammonium, alkyl
ammonium or
alkanol ammonium counterion. Preferred alkyl ether sulfates are C8¨C18 alcohol
ether sulfates
with a degree of ethoxylation of from about 0.5 to about 9 ethylene oxide
moieties and most
-
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preferred are the C12¨C15 alcohol ether sulfates with ethoxylation from about
4 to about 9
ethylene oxide moieties, with 7 ethylene oxide moieties being most preferred.
In another
embodiment, the C12-C15 alcohol ether sulfates with ethoxylation from about
0.5 to about 3
ethylene oxide moieties are preferred. In keeping with the spirit of only
using natural feedstock
for ingredients for the ADW composition, the fatty alcohol portion of the
surfactant is preferably
animal or vegetable derived, rather than petroleum derived. Therefore the
fatty alcohol portion
of the surfactant will comprise distributions of even number carbon chains,
e.g. C12, C14, C169 C189
and so forth. It is understood that when referring to alkyl ether sulfates,
these substances are
already salts (hence "sulfate" nomenclature), and most preferred and most
readily available are
the sodium alkyl ether sulfates (also referred to as NaAES, or simply FAES).
Commercially available alkyl ether sulfates include the CALFOAMe alcohol ether
sulfates from
Pilot Chemical, the EMALe, LEVENOL and LATEMAL products from Kao
Corporation, and
the POLYSTEP products from Stepan, most of these with fairly low EO content
(e.g., average 3
or 4-E0). Alternatively, the alkyl ether sulfates may be prepared by
sulfonation of alcohol
ethoxylates (i.e., nonionic surfactants) if the commercial alkyl ether sulfate
with the desired chain
lengths and EO content are not easily found, but perhaps where the nonionic
alcohol ethoxylate
starting material may be. For example, sodium lauryl ether sulfate ("sodium
laureth sulfate",
having about 2-3 ethylene oxide moieties) is very readily available
commercially and quite
common in shampoos and detergents. Depending on the degree of ethoxylation
desired, it may
be more practical to sulfonate a commercially available nonionic surfactant
such as Neodol 25-7
Primary Alcohol Ethoxylate (a C12-C15/7E0 nonionic from Shell) to obtain for
example the C12-
C15/7E0 alkyl ether sulfate that may have been more difficult to source
commercially. However,
the surfactants may include sodium lauryl sulfate-2E0, available as Calfoam
ES-302, from Pilot
Chemical. The preferred level of C12-C18/0.5-9E0 alkyl ether sulfate is from
about 1 wt% to
about 50wt%. To the extent that these commercially available surfactants may
not be bio-
derived, it will be understood that bio-derived surfactants having similar
structures and utility
may be used in the ADW composition, whether such bio-derived surfactants are
available now or
are made available in the future.
As noted above, anionic surfactants that may find use in the ADW compositions
include the
alpha-sulfonated alkyl esters of C12-C16 fatty acids. The alpha- sulfonated
alkyl esters may be
pure alkyl ester or a blend of (1) a mono-salt of an alpha- sulfonated alkyl
ester of a fatty acid
having from 8 to 20 carbon atoms where the alkyl portion forming the ester is
straight or
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branched chain alkyl of 1 to 6 carbon atoms; and (2) a di-salt of an alpha-
sulfonated fatty acid,
the ratio of mono-salt to di-salt being at least about 2:1. The alpha-
sulfonated alkyl esters useful
herein are typically prepared by sulfonating an alkyl ester of a fatty acid
with a sulfonating agent
such as S03. When prepared in this manner, the alpha-sulfonated alkyl esters
normally contain a
minor amount, (typically less than 33% by weight), of the di-salt of the alpha-
sulfonated fatty
acid which results from saponification of the ester. Preferred alpha-
sulfonated alkyl esters
contain less than about 10% by weight of the di-salt of the corresponding
alpha-sulfonated fatty
acid.
The alpha-sulfonated alkyl esters, i.e., alkyl ester sulfonate surfactants,
include linear esters of
C8¨C20 carboxylic acids that are sulfonated with gaseous SO3 as described in
the "The Journal of
American Oil Chemists Society," 52 (1975), pp. 323-329. Suitable starting
materials preferably
include natural fatty substances as derived from tallow, palm oil, etc.,
rather than petroleum
derived materials. The preferred alkyl ester sulfonate surfactants may
comprise alkyl ester
sulfonate surfactants of the structural formula R3¨CH(S03M)¨0O2R4, where R3 is
a C8¨C20
hydrocarbon chain preferably naturally derived, R4 is a straight or branched
chain C1¨C6 alkyl
group, and M is a cation that forms a water soluble salt with the alkyl ester
sulfonate, including
sodium, potassium, magnesium, and ammonium cations. Preferably, R3 is C10¨C16
fatty alkyl,
and R4 is methyl or ethyl. Most preferred are alpha-sulfonated methyl or ethyl
esters of a
distribution of fatty acids having an average of from 12 to 16 carbon atoms.
For example, the
alpha-sulfonated esters; Alpha-Step BBS-45, Alpha-Step MC-48, and Alpha-
Step PC-48, all
available from the Stepan Co. of Northfield, Ill., may be suitable in the ADW
composition.
However, the methyl esters are derived from methanol sources. Thus, the ethyl
esters, which are
currently not commercially available, would be the most preferred alpha-
sulfonated fatty acid
esters. When used in the present ADW compositions, the alpha-sulfonated alkyl
ester is
preferably incorporated at from about 3% to about 15% by weight actives.
The ADW compositions may also include bio-derived fatty acid soaps as an
anionic surfactant
ingredient. The fatty acids that may be represented by the general formula
R¨COOH, where R
represents a linear or branched alkyl or alkenyl group having between about 8
and 24 carbons. It
is understood that within the ADW compositions, the free fatty acid form (the
carboxylic acid)
will be converted to the carboxylate salt in-situ (that is, to the fatty acid
soap), by the excess
alkalinity present in the composition from added alkaline builder. As used
herein, "soap" means
salts of fatty acids. Thus, after mixing and obtaining the compositions of the
present invention,
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the fatty acids will be present in the composition as R¨COOM, where R
represents a linear or
branched alkyl or alkenyl group having between about 8 and 24 carbons and M
represents an
alkali metal such as sodium or potassium.
The fatty acid soap, which is often a desirable component having suds-reducing
effect in the
dishwasher, is preferably comprised of higher fatty acid soaps. The fatty
acids that are added
directly into the ADW compositions may be derived from natural fats and oils,
such as those
from animal fats and greases and/or from vegetable and seed oils, for example,
tallow,
hydrogenated tallow, whale oil, fish oil, grease, lard, coconut oil, palm oil,
palm kernel oil, olive
oil, peanut oil, corn oil, sesame oil, rice bran oil, cottonseed oil, babassu
oil, soybean oil, castor
oil, and mixtures thereof Although fatty acids can be synthetically prepared,
for example, by the
oxidation of petroleum, or by hydrogenation of carbon monoxide by the Fischer-
Tropsch
process, the naturally obtainable fats and oils are preferred. The fatty acids
of particular use in
the ADW compositions are linear or branched and contain from about 8 to about
24 carbon
atoms, preferably from about 10 to about 20 carbon atoms and most preferably
from about 14 to
about 18 carbon atoms. Preferred fatty acids include coconut, tallow or
hydrogenated tallow
fatty acids, and most preferred is to use entirely coconut fatty acid.
Preferred salts of the fatty
acids are alkali metal salts, such as sodium and potassium or mixtures thereof
and, as mentioned
above, preferably the soaps generated in-situ by neutralization of the fatty
acids with excess
alkali from the silicate. Other useful soaps are ammonium and alkanol ammonium
salts of fatty
acids, with the understanding that these soaps would necessarily be added to
the compositions as
the preformed ammonium or alkanol ammonium salts and not neutralized in-situ
within the
added alkaline builders of the present invention. The bio-derived fatty acids
that may be
included in the present compositions will preferably be chosen to have
desirable detergency and
suds-reducing effect. Fatty acid soaps may be incorporated in the ADW
compositions of the
present invention at from about 1% to about 10% by weight of the ADW
composition.
The ADW compositions may also include alkyl sulfate as the sole anionic
surfactant component,
or in combination with one of more other anionic surfactants mentioned above.
Fatty alkyl
sulfates have the general formula R-S03M, where R preferably comprises a C7-
C21 fatty alkyl
chain, and where M is alkali metal or ammonium, alkyl ammonium or alkanol
ammonium
counterion. Preferred alkyl sulfates for use in the present invention are C8--
C18 fatty alkyl sulfate.
Most preferred is to incorporate sodium lauryl sulfate, such as Standapol WAQ-
LC marketed by
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Cognis, and to have from about 1% to about 10% by actives weight basis in the
ADWcomposition.
Other Anionic Surfactants¨Other anionic surfactants useful for detersive
purposes can also be
included in the ADW compositions. These can include salts (including, for
example, sodium,
potassium, ammonium, and substituted ammonium salts such as mono-, di- and
triethanolamine
salts) of soap, C9-C20 linear alkylbenzenesulfonates, C8¨C22 primary or
secondary
alkanesulfonates, C8¨C24olefinsulfonates, sulfonated polycarboxylic acids
prepared by
sulfonation of the pyrolyzed product of alkaline earth metal citrates, e.g.,
as described in British
patent specification No. 1,082,179, alkyl glycerol sulfonates, fatty acyl
glycerol sulfonates, fatty
oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin
sulfonates, alkyl
phosphates, isothionates such as the acyl isothionates, N-acyl taurates, fatty
acid amides of
methyl tauride, alkyl succinatnates and sulfosuccinates, monoesters of
sulfosuccinate (especially
saturated and unsaturated C12¨C18 monoesters) diesters of sulfosuccinate
(especially saturated
and unsaturated C6¨C14 diesters), N-acyl sarcosinates, sulfates of
alkylpolysaccharides such as
the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being
described below),
branched primary alkyl sulfates, alkyl polyethoxy carboxylates such as those
of the formula
RO(CH2CH20)kCH2COOM+ , where R is a C8¨C22 alkyl, k is an integer from 0 to
10, and M is a
soluble salt-forming cation, and fatty acids esterified with isethionic acid
and neutralized with
sodium hydroxide. Resin acids and hydrogenated resin acids are also suitable,
such as rosin,
hydrogenated rosin, and resin acids and hydrogenated resin acids present in or
derived from tall
oil. Further examples are given in "Surface Active Agents and Detergents"
(Vol. I and II by
Schwartz, Perry and Berch). A variety of such surfactants are also generally
disclosed in U.S.
Pat. No. 3,929,678, issued Dec. 30, 1975 to Laughlin, et al. at Column 23,
line 58 through
Column 29, line 23. Preferably, the other anionic surfactants are bio-derived.
Specific examples of bio-derived anionic surfactants suitable herein include
Caflon 2L28U by
Univar, a sodium lauryl ether sulfate from bio-derived C12¨C14 alcohols; Akypo
LF 1 and Akypo
LF 2 by Kao, low-foaming bio-derived anionic surfactants from palm kernal oil
and comprising
capryleth carboxylic acids; and Akypo RLM bio-derived surfactants by Kao,
laureth carboxylic
acids from bio-derived C12¨C14 alcohols.
Secondary Surfactants¨Secondary detersive surfactants can be selected from the
group
consisting of nonionics, cationics, ampholytics, zwitterionics, and mixtures
thereof. By selecting
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the type and amount of detersive surfactant, along with other adjunct
ingredients disclosed
herein, the present ADW compositions can be formulated to be used in the
context of
dishwashing. The particular surfactants used can therefore vary widely
depending upon the
particular end-use envisioned. Suitable secondary surfactants are described
below.
Nonionic Detergent Surfactants¨Suitable nonionic detergent surfactants are
generally disclosed
in U.S. Pat. No. 3,929,678, Laughlin et al., issued Dec. 30, 1975, at column
13, line 14 through
column 16, line 6, incorporated herein by reference. Exemplary, non-limiting
classes of useful
nonionic surfactants include: alkyl dialkyl amine oxide, alkyl ethoxylate,
alkanoyl glucose amide,
the so-called narrow peaked alkyl ethoxylates, C 6-C 12alkyl phenol
alkoxylates (especially
ethoxylates and mixed ethoxy/propoxy) and mixtures thereof. In the present ADW
compositions,
preferably the nonionic surfactants are bio-derived.
The nonionic surfactants for use herein may include, for example, the
polyethylene,
polypropylene, and polybutylene oxide condensates of alkyl phenols. In
general, the
polyethylene oxide condensates are preferred. These compounds include the
condensation
products of alkyl phenols having an alkyl group containing from about 6 to
about 12 carbon
atoms in either a straight-chain or branched-chain configuration with the
allcylene oxide. In a
preferred embodiment, the ethylene oxide is present in an amount equal to from
about 5 to about
moles of ethylene oxide per mole of alkyl phenol. Commercially available
nonionic
surfactants of this type include Igepal CO-630, marketed by the GAF
Corporation; and Triton
20 X-45, X-114, X-100, and X-102, all marketed by the Rohm & Haas Company.
These
compounds are commonly referred to as alkyl phenol alkoxylates, (e.g., alkyl
phenol
ethoxylates).
Specific examples of bio-derived nonionic surfactants suitable herein include
Ecosurf SA
surfactants by Dow, alcohol ethoxylates made from bio-derived modified seed
oils; Amidet N by
25 Kao, a bio-derived amine surfactant made from polyethylene glycol and
rapeseed oil; Levenol by
Kao, glycereth cocoate surfactants made from bio-derived glycerine of
vegetable origin; Emanon
XLf by Kao, comprising vegetable-derived glycereth caprylate; Caflon SP20 by
Kao/Univar,
vegetable-derived sorbitan laurate; Caflon SP60 by Kao/Univar, vegetable-
derived sorbitan
stearate; Kaopan SP-010, vegetable-derived sorbitan oleate; Kaopan TX and
Caflon TW
surfactants, vegetable-derived polyethylene glycol¨sorbitan surfactants; and
Caflon LF, Triton
BG, and Triton CG by Univar/Dow, all vegetable-derived alkyl polyglucoside
surfactants.
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The nonionic surfactants for use herein further may include, for example, the
condensation
products of bio-derived aliphatic alcohols with from about 1 to about 25 moles
of bio-derived
ethylene oxide. The alkyl chain of the aliphatic alcohol can either be
straight or branched,
primary or secondary, and generally contains from about 8 to about 22 carbon
atoms.
Particularly preferred are the condensation products of alcohols having an
alkyl group containing
from about 10 to about 20 carbon atoms with from about 2 to about 18 moles of
ethylene oxide
per mole of alcohol. Examples of commercially available nonionic surfactants
of this type
include Tergitol 15-S-9 (the condensation product of C11¨C15 linear secondary
alcohol with 9
moles ethylene oxide), Tergitol 24-L-6 NMW (the condensation product of
C12¨C14 primary
alcohol with 6 moles ethylene oxide with a narrow molecular weight
distribution), both marketed
by Union Carbide Corporation; Neodol 45-9 (the condensation product of
C14¨C15 linear
alcohol with 9 moles of ethylene oxide), Neodol 23-6.5 (the condensation
product of C12¨C13
linear alcohol with 6.5 moles of ethylene oxide), Neodol 45-7 (the
condensation product of
C14¨C15 linear alcohol with 7 moles of ethylene oxide), Neodol 45-4 (the
condensation product
of C14¨C15 linear alcohol with 4 moles of ethylene oxide), marketed by Shell
Chemical
Company, and Kyro EOB (the condensation product of C13¨C15 alcohol with 9
moles ethylene
oxide), marketed by The Procter & Gamble Company. Other commercially available
nonionic
surfactants include Dobanol 91-80 marketed by Shell Chemical Co. and Genapol
UD-080
marketed by Hoechst. This category of nonionic surfactant is referred to
generally as "alkyl
ethoxylates." Preferably, the alkyl ethoxylates are bio-derived and may be
obtained according to
the methods described herein.
The nonionic surfactants for use herein may include, for example the
condensation products of
bio-derived ethylene oxide with a hydrophobic base formed by the condensation
of bio-derived
propylene oxide with bio-derived propylene glycol. The hydrophobic portion of
these
compounds preferably has a molecular weight of from about 1500 to about 1800
and exhibits
water insolubility. The addition of polyoxyethylene moieties to this
hydrophobic portion tends to
increase the water solubility of the molecule as a whole, and the liquid
character of the product is
retained up to the point where the polyoxyethylene content is about 50% of the
total weight of
the condensation product, which corresponds to condensation with up to about
40 moles of bio-
derived ethylene oxide. Examples of compounds of this type include certain of
the
commercially-available Pluronic surfactants, marketed by BASF.
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The ADW compositions may also include bio-derived amide type nonionic
surfactants, for
example alkanolamides that are condensates of algae-derived fatty acids with
alkanolamines such
as bio-derived monoethanolamine (MEA), bio-derived diethanolamine (DEA) and
bio-derived
monoisopropanolamine (MIPA), that have previously found widespread use in
cosmetic,
personal care, household and industrial formulations. Useful alkanolamides
include bio-derived
ethanolamides and/or bio-derived isopropanolamides such as monoethanolamides,
diethanolamides and isopropanolamides in which the fatty acid acyl radical
typically contains
from 8 to 18 carbon atoms. Especially satisfactory alkanolamides have been
mono- and
diethanolamides such as those derived from mixed fatty acids or special
fractions containing, for
instance, predominately C12 to C14 fatty acids. For example, bio-derived fatty
acids may be
obtained from algae lipids through a number of routes, and these may be
amidated with the
required alkanolamine. Alternatively, and more directly, the nonionic
alkanolamides may be
obtained by direct amidation of the algae lipid (e.g., the crude algae fat).
Additional classes of bio-derived nonionic surfactants that may be used in the
ADW
compositions herein include bio-derived ethoxylated fatty acid alkyl esters,
preferably having 1
to 4 carbon atoms in the alkyl chain, especially bio-derived fatty acid ethyl
esters. An algae-
sourced fatty acid ester may be ethoxylated, for example, with bio-derived
ethylene oxide, such
as ethylene oxide obtained from algae-sourced ethanol. Additionally,
ethoxylated fatty amines
may be obtained by ethoxylation of fatty amines, wherein these starting
materials are obtained
from bio-derived ethanol and algae lipid, respectively.
Further examples of suitable nonionic surfactants are alcohol ethoxylates
containing linear
radicals from alcohols of natural origin having 12 to 18 carbon atoms, e.g.,
from coconut, palm,
tallow fatty or oleyl alcohol and on average from 4 EO to about 12 EO per mole
of alcohol. Also
useful as a nonionic surfactant is the C12¨C14 alcohol ethoxylate-7E0, and the
C12¨C14 alcohol
ethoxylate-12E0 incorporated in the composition at from about 1 wt% to about
10 wt%.
Preferred nonionic surfactants for use in this invention include for example,
Neodol 45-7,
Neodol 25-9, or Neodol 25-12 from Shell Chemical Company and most preferred
are
Surfonic L24-7, which is a C12- C14 alcohol ethoxylate-7E0, and Surfonic L24-
12, which is a
C12¨C14 alcohol ethoxylate-12E0, both available from Huntsman. Combinations of
more than
one alcohol ethoxylate surfactant may also be desired in the ADW composition
to maximize
cleaning performance.
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The nonionic surfactants for use herein further may include, for example, the
condensation
products of bio-derived ethylene oxide with the product resulting from the
reaction of bio-
derived propylene oxide and bio-derived ethylenediamine. The hydrophobic
moiety of these
products consists of the reaction product of bio-derived ethylenediamine and
excess bio-derived
propylene oxide, and generally has a molecular weight of from about 2500 to
about 3000. This
hydrophobic moiety is condensed with bio-derived ethylene oxide to the extent
that the
condensation product contains from about 40% to about 80% by weight of bio-
derived
polyoxyethylene and has a molecular weight of from about 5,000 to about
11,000. Examples of
this type of nonionic surfactant include bio-derived analogs of the
commercially available
Tetronic compounds, marketed by BASF.
Fatty alcohol ethoxylates may be obtained additionally through synthetic
organic transformations
starting from algae bioorganic materials. Algae-derived examples may include
alcohol
ethoxylates containing linear radicals from bio-derived alcohols having 14 to
24 carbon atoms,
e.g., from the hydrogenation of fatty acids and/or fatty acid esters that are
in turn derived from
algal lipids through hydrolysis or transesterification, respectively. Fatty
alcohols may also be
obtained by direct high-pressure hydrogenation of the algae lipid mass and
separation of the fatty
alcohols from the propane diol. The ethoxylation or the propoxylation
(preferably on average
from 4 to about 12 EO, PO, or EO/PO per mole of alcohol) does not necessarily
have to come
from bio-sources, although that would be preferred. So for example, a fatty
alcohol with carbon
chain directly from algae sources may be conventionally ethoxylated with
ethylene oxide
obtained from petroleum sources (cracked ethylene and oxygen). In this way, a
preferred
detergent surfactant such as C14¨C16 alcohol ethoxylate-7E0 would at least
have about 50% of
the carbon (the C14¨C16 chain) obtained from algae, and about 50% of the
carbon from petroleum
sources (the 7E0, or 14-carbons from the 7-moles of ethylene oxide). More
preferred is to
incorporate bio-derived ethylene oxide as the building blocks for the
ethoxylate (E0) chains of
these nonionic surfactants to create molecules having all of the carbon bio-
derived. In known
processes, bio-derived ethanol may be dehydrated to ethylene, which may in
turn be oxidized to
ethylene oxide with oxygen. Additionally, once fatty alcohols are obtained
from algae lipids, the
alcohols may be reacted in a Guerbet Reaction ("Guerbetization") to produce
the branched
"Guerbet Alcohols", which then may be ethoxylated to give bio- derived
branched chain alcohol
ethoxylate surfactants.
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Semi-polar nonionic surfactants are a special category of nonionic surfactants
that include water-
soluble amine oxides containing one alkyl moiety of from about 10 to about 18
carbon atoms and
2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl
groups
containing from about 1 to about 3 carbon atoms; water-soluble phosphine
oxides containing one
alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected
from the group
consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to
about 3 carbon
atoms; and water-soluble sulfoxides containing one alkyl moiety of from about
10 to about 18
carbon atoms and a moiety selected from the group consisting of alkyl and
hydroxyalkyl moieties
of from about 1 to about 3 carbon atoms.
Semi-polar nonionic detergent surfactants include the amine oxide surfactants
having the formula
0.\
R3(0R4)x N(R5)2
where R3 is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures thereof
containing from
about 8 to about 22 carbon atoms; R4 is an alkylene or hydroxyallcylene group
containing from
about 2 to about 3 carbon atoms or mixtures thereof; x is from 0 to about 3;
and each R5 is an
alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms or
a polyethylene
oxide group containing from about 1 to about 3 ethylene oxide groups. The R5
groupscan be
attached to each other, e.g., through an oxygen or nitrogen atom, to form a
ring structure.
Preferably, a substantial portion or, more preferably, all of the carbon atoms
in these groups are
bio-derived.
The amine oxide surfactants in particular include C10¨C18 alkyl dimethyl amine
oxides and C8--
C12 alkoxy ethyl dihydroxy ethyl amine oxides. Specfic examples of bio-derived
amine oxide
surfactants suitable herein include ChemoxideTM SO Surfactant by Lubrizol, a
soy-based amine
oxide, and Genaminox CHE by Clariant.
The nonionic surfactants for use herein further may include, for example, bio-
derived analogs of
alkylpolysaccharides disclosed in U.S. Pat. No. 4,565,647, Llenado, issued
Jan. 21, 1986, having
a hydrophobic group containing from about 6 to about 30 carbon atoms,
preferably from about 10
to about 16 carbon atoms and a polysaccharide, e.g., a polyglycoside,
hydrophilic group
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containing from about 1.3 to about 10, preferably from about 1.3 to about 3,
most preferably
from about 1.3 to about 2.7 saccharide units. Any reducing saccharide
containing 5 or 6 carbon
atoms can be used, e.g., glucose, galactose and galactosyl moieties can be
substituted for the
glucosyl moieties. (Optionally the hydrophobic group is attached at the 2-, 3-
, 4-, etc. positions
thus giving a glucose or galactose as opposed to a glucoside or galactoside.)
The intersaccharide
bonds can be, e.g., between the one position of the additional saccharide
units and the 2-, 3-, 4-,
and/or 6- positions on the preceding saccharide units. The sacchrides may be
bio-derived, such
as from algae or from another renewable resource.
Optionally, and less desirably, there can be a polyalkylene-oxide chain
joining the hydrophobic
moiety and the polysaccharide moiety. The preferred alkyleneoxide is ethylene
oxide, such as
bio-derived ethylene oxide. Typical hydrophobic groups include alkyl groups,
either saturated or
unsaturated, branched or unbranched containing from about 8 to about 18,
preferably from about
10 to about 16, carbon atoms. Preferably, the alkyl group is a straight chain
saturated alkyl
group. The alkyl group can contain up to about 3 hydroxy groups and/or the
polyalkyleneoxide
chain can contain up to about 10, preferably less than 5, alkyleneoxide
moieties. Suitable alkyl
polysaccharides are octyl, nonyl, decyl, undecyldodecyl, tridecyl, tetradecyl,
pentadecyl,
hexadecyl, heptadecyl, and octadecyl, di-, tri-, tetra-, penta-, and
hexaglucosides, galactosides,
lactosides, glucoses, fructosides, fructoses and/or galactoses. Suitable
mixtures include coconut
alkyl, di-, tri-, tetra-, and pentaglucosides and tallow alkyl tetra-, penta-,
and hexa-glucosides.
Preferably, these groups are obtained from natural sources so as to produce
bio-derived
surfactants.
The nonionic surfactants for use herein further may include, for example
alkylpolyglycosides
having the formula:
R20(CõH2õ0)t (glycosypx
where R2 is selected from the group consisting of alkyl, alkyl-phenyl,
hydroxyallyl,
hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain
from about 10 to
about 18, preferably from about 12 to about 14, carbon atoms; n is 2 or 3,
preferably 2; t is from
0 to about 10, preferably 0; and x is from about 1.3 to about 10, preferably
from about 1.3 to
about 3, most preferably from about 1.3 to about 2.7. The glycosyl is
preferably derived from
glucose. Preferably, the alkylpolyglycosides are bio-derived.
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To prepare these compounds, a bio-derived alcohol or bio-derived
alkylpolyethoxy alcohol is
formed first and then reacted with glucose, such as bio-derived glucose, to
form the glucoside
(attachment at the 1-position). The additional glycosyl units can then be
attached between their
1-position and the preceding glycosyl units 2-, 3-, 4- and/or 6-position,
preferably predominantly
the 2-position.
Thus, alkyl polyglycosides (APGs), also called alkyl polyglucosides if the
saccharide moiety is
glucose, are naturally derived, nonionic surfactants. The alkyl polyglycosides
also may fatty
ester derivatives of saccharides or polysaccharides that are formed when a
carbohydrate is
reacted under acidic condition with a bio-derived fatty alcohol through
condensation
polymerization. The APGs are typically derived from corn-based carbohydrates
and fatty
alcohols from natural oils in animals, coconuts and palm kernels. Such methods
for preparing
APGs are well known in the art. For example, U.S. Pat. No. 5,003,057 to
McCurry, et al.,
incorporated herein, describes methods for making APGs, along with their
chemical properties.
The alkyl polyglycosides that are preferred contain a hydrophilic group
derived from bio-derived
carbohydrates and are composed of one or more bio-derived anhydroglucose
units. Each of the
bio-derived glucose units can have two ether oxygen atoms and three hydroxyl
groups, along
with a terminal hydroxyl group, which together impart water solubility to the
glycoside. 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 ADW 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-0-121, 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 ADW composition. For the APGs used in the ADW compositions, x preferably
has a value
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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
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
The ADW compositions of have the advantage of having less adverse impact on
the environment
than conventional detergent compositions. Bio-derived alkyl polyglycosides
used in the present
Most preferably, the ADW compositions comprise low foaming nonionic
surfactants (LFNIs),
Preferred LFNIs include bio-derived nonionic alkoxylated surfactants,
especially ethoxylates
obtained from bio-derived primary alcohols, and blends thereof with more
sophisticated
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suppressing or defoaming action, especially in relation to common food soil
ingredients such as
egg.
In a preferred embodiment, the LFNI is a bio-derived ethoxylated surfactant
obtained from the
reaction of a bio-derived monohydroxy alcohol or alkylphenol containing from
about 8 to about
20 carbon atoms, excluding cyclic carbon atoms, with from about 6 to about 15
moles of bio-
derived ethylene oxide per mole of alcohol or alkyl phenol on an average
basis.
A particularly preferred LFNI is obtained from a bio-derived straight chain
fatty alcohol
containing from about 16 to about 20 carbon atoms (C16¨C20 alcohol),
preferably a C18 alcohol,
condensed with an average of from about 6 to about 15 moles, preferably from
about 7 to about
12 moles, and most preferably from about 7 to about 9 moles of bio-derived
ethylene oxide per
mole of alcohol. Preferably the ethoxylated nonionic surfactant so derived has
a narrow
ethoxylate distribution relative to the average.
The LFNI can optionally contain bio-derived propylene oxide in an amount up to
about 15% by
weight. Bio-derived analogs of certain of the block polymer surfactant
compounds designated
PLURONICO and TETRONIC by the BASF-Wyandotte Corp., Wyandotte, Mich., are
suitable
in ADW compositions herein. Highly preferred gel ADW detergents herein,
wherein the LFNI is
present, make use of bio-derived ethoxylated monohydroxy alcohol or bio-
derived alkyl phenol
and additionally comprise a bio-derived polyoxyethylene, bio-derived
polyoxypropylene block
polymeric compound; the bio-derived ethoxylated monohydroxy alcohol or alkyl
phenol fraction
of the LFNI comprising from about 20% to about 80%, preferably from about 30%
to about 70%,
of the total LFNI.
LFNIs which may also be used include a C18 alcohol polyethoxylate, having a
degree of
ethoxylation of about 8, commercially available SLF18 from Olin Corp.
Another low foaming nonionic surfactant is an esterified alkyl alkoxylated
surfactant having the
following general formula:
R3 f.1
RO-(CH2CH0)/(CH2CH20),n(CH2d1-10)õ -C -R`
where R is a branched or unbranched alkyl radical having 8 to 16 carbon atoms,
preferably from
10 to 16 and more preferably from 12 to 15; R3 and RI independently of one
another, are
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hydrogen or a branched or unbranched alkyl radical having 1 to 5 carbon atoms;
preferably R3
and RI are hydrogen; R2 is an unbranched alkyl radical having 5 to 17 carbon
atoms; preferably
from 6 to 14 carbon atoms; / and n independently of one another, are a number
from 1 to 5; and
m is a number from 13 to 35.
US2008/0167215, paragraphs [0036] to [0042], incorporated herein by reference.
Some alkyl glycosides and polyglycosides occur in nature, e.g. in
cyanobacteria such as
Anabaena cylindrica, Anamaeba torulosa and Cyanospira rippkae, where they may
take part in
cell protection. However, synthetic alkyl polyglycosides that may be used in
the ADW
When carbohydrate molecules react with fatty alcohol compounds, alkyl
polyglycoside
molecules are formed having single or multiple anhydroglucose units, which are
termed
monoglycosides and polyglycosides, respectively. The final alkyl polyglycoside
product
typically has a distribution of glucose units (i.e., degree of
polymerization).
tri-, etc. saccharides) of hexose or pentose, and a fatty aliphatic group
having 6 to 20 carbon
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atoms. Exemplary saccharides from which G can be derived are glucose,
fructose, mannose,
galactose, talose, gulose, allose, aitrose, idose, arabinose, xylose, lyxose
and ribose. Because of
the ready availability of glucose from algae, polyglycosides having glucose
substituents may be
obtained from algae. The glucose may be obtained as a metabolite from certain
cyanobacteria or
may be obtained by cellulolysis (chemically or enzymatically) of algal
cellulose. The fatty alkyl
group is preferably saturated, although unsaturated fatty chains may be used.
Generally,
commercially available polyglycosides have C8 to C16 alkyl chains and an
average degree of
polymerization of from 1.4 to 1.6, and these may be readily synthesized from
algae-derived
intermediates rather than crop-based substances.
Polyhydroxy Fatty Acid Amide Surfactant¨The ADW compositions may also contain
an
effective amount of polyhydroxy fatty acid amide surfactant. By "effective
amount" is meant
that the formulator of the composition can select an amount of polyhydroxy
fatty acid amide to
be incorporated into the compositions that will improve the cleaning
performance of the
detergent composition. In general, for conventional levels, the incorporation
of about 1%, by
weight, polyhydroxy fatty acid amide will enhance cleaning performance.
The ADW compositions herein may comprise about 1% weight basis, polyhydroxy
fatty acid
amide surfactant, preferably from about 3% to about 30%, of the polyhydroxy
fatty acid amide.
The polyhydroxy fatty acid amide surfactant component comprises compounds of
the structural
formula:
0 RI
11 I
R2¨C-14--Z
where: 12' is H, C1¨C4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, or a
mixture thereof,
preferably C1 -C4 alkyl, more preferably C1 or C2 alkyl, most preferably C1
alkyl (i.e., methyl);
and R2 is a C5¨C31 hydrocarbyl, preferably straight-chain C7¨C19 alkyl or
alkenyl, more
preferably straight chain C9¨C17 alkyl or alkenyl, most preferably straight
chain C11¨C15 alkyl or
alkenyl, or mixtures thereof; and Z is a polyhydroxyhydrocarbyl having a
linear hydrocarbyl
chain with at least 3 hydroxyls directly connected to the chain, or an
alkoxylated derivative
(preferably ethoxylated or propoxylated) thereof. Z preferably will be derived
from a reducing
sugar in a reductive amination reaction; more preferably Z will be a glycityl.
Suitable reducing
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sugars include glucose, fructose, maltose, lactose, galactose, mannose, and
xylose. As raw
materials, high dextrose corn syrup, high fructose corn syrup, and high
maltose corn syrup can be
utilized as well as the individual sugars listed above. These corn syrups may
yield a mix of sugar
components for Z. It should be understood that it is by no means intended to
exclude other
suitable raw materials. Z preferably will be selected from the group
consisting of
¨CH2¨(CHOH)n¨CH2OH; ¨CH(CH2OH)¨(CHOH)n; ¨CH2OH,
¨CH2¨(CHOH)2(CHOR')(CHOH) ¨CH2OH, and alkoxylated derivatives thereof, where n
is an
integer from 3 to 5, inclusive, and R' is H or a cyclic or aliphatic
monosaccharide. Most
preferred are glycityls wherein n is 4, particularly ¨CH2¨(CHOH)4CH2OH. RI can
be, for
example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-2-hydroxyethyl,
or N-
2-hydroxypropyl. R2¨CO¨N< can be, for example, cocamide, stearamide, oleamide,
lauramide,
myristamide, capricamide, palmitamide, tallowamide, etc. Z can be 1-
deoxyglucityl,
2-deoxyfructityl, 1-deoxymaltityl, 1-deoxylactityl, 1-deoxygalactityl, 1-
deoxymannityl,
1-deoxymaltotriotityl, etc.
Methods for making polyhydroxy fatty acid amides are known in the art. In
general, they can be
made by reacting an alkyl amine with a reducing sugar in a reductive anation
reaction to form a
corresponding N-alkyl polyhydroxyarine, and then reacting the N-alkyl
polyhydroxyamine with a
fatty aliphatic ester or triglyceride in a condensation/amidation step to form
the N-alkyl, N-
polyhydroxy fatty acid amide product. Processes for making compositions
containing
polyhydroxy fatty acid amides are disclosed, for example, in G.B. Patent
Specification 809,060,
published Feb. 18, 1959, by Thomas Hedley & Co., Ltd.; U.S. Pat. No.
2,965,576, issued Dec.
20, 1960 to E. R. Wilson; and U.S. Pat. No. 2,703,798, Anthony M. Schwartz,
issued Mar. 8,
1955; and U.S. Pat. No. 1,985,424, issued Dec. 25, 1934 to Piggott, each of
which is incorporated
herein by reference.
Fatty acid surfactants are also derivable from algae sources. For example, the
fatty acid
surfactants that may be used here have general formula R¨0O2M, where R
represents an algae-
derived linear alkyl (saturated or unsaturated) group having between about 8
and 24 carbons and
M represents an alkali metal such as sodium or potassium or ammonium or alkyl-
or diallcyl- or
trialkyl-ammonium or alkanolammonium cation. The fatty acids of particular use
in the ADW
compositions include carbon chains of from about 8 to about 24 carbon atoms,
preferably from
about 10 to about 20 carbon atoms and most preferably from about 14 to about
18 carbon atoms.
Preferred fatty acids should have similar structure to the animal derived
tallow or hydrogenated
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tallow fatty acids and their preferred salts (soaps) are alkali metal salts,
such as sodium and
potassium or mixtures thereof. That being said, hydrolysis of algae lipids
will produce a mixture
of unsaturated fatty acids and glycerol and the unsaturated fatty acids may in
turn be
hydrogenated as necessary to arrive at more saturated fats. Well known are
purification
processes such as distillation to arrive at particular fatty acid
distribution. So for example, crude
algae triglyceride may be transesterified with methanol and the resulting
fatty acid methyl esters
mixture may be fractionally distilled. The resulting methyl ester distillate
"cuts" may then be
hydrolyzed to yield fatty acids with narrower carbon chain distributions.
Cationic Surfactants-Cationic detersive surfactants can also be included in
ADW compositions
of the present invention. Cationic surfactants include the ammonium
surfactants such as
alkyldimethylammonium halogenides, and those surfactants having the formula:
[R2(0R3)3,][R4(0R3)3]2R5N+X-
where R2 is an alkyl or alkyl benzyl group having from about 8 to about 18
carbon atoms in the
alkyl chain; each R3 is selected from the group consisting of -CH2CH2-, -
CH2CH(CH3)
-CH2CH(CH2OH) -CH2CH2CH2-, and mixtures thereof; each R4 is selected from the
group
consisting of C1-C4 alkyl, CI-Ca hydroxyalkyl, benzyl, ring structures formed
by joining the two
R4 groups, -CH2CHOHCHOHCOR6CHOH-CH 20H wherein R6 is any hexose or hexose
polymer having a molecular weight less than about 1000, and hydrogen when y is
not 0; R5 is
the same as R4 or is an alkyl chain wherein the total number of carbon atoms
of R2 plus le is not
more than about 18; each y is from 0 to about 10 and the sum of the y values
is from 0 to about
15; and X is any compatible anion. Preferably at least 50%, more preferably
all of the carbon
atoms in the cationic surfactants are bio-derived.
Other cationic surfactants useful herein are also described in U.S. Pat. No.
4,228,044, Cambre,
issued Oct. 14, 1980, incorporated herein by reference.
Other Surfactants¨In addition to the above-mentioned surfactants, ampholytic
surfactants can
be incorporated into the ADW compositions hereof. These surfactants can be
broadly described
as aliphatic derivatives of secondary or tertiary amines, or aliphatic
derivatives of heterocyclic
secondary and tertiary amines in which the aliphatic radical can be straight
chain or branched.
One of the aliphatic substituents contains at least about 8 carbon atoms,
typically from about 8 to
about 18 carbon atoms, and at least one contains an anionic water-solubilizing
group, e.g.,
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carboxy, sulfonate, sulfate. See U.S. Pat. No. 3,929,678 to Laughlin et al.,
issued Dec. 30, 1975
at column 19, lines 18-35 for examples of ampholytic surfactants. Preferred
amphoteric include
C12-C18 betaines and sulfobetaines ("sultaines"), C 10-C 18 amine oxides, and
mixtures thereof.
The ampholytic surfactants preferably contain carbon atoms that are bio-
derived.
Zwitterionic surfactants can also be incorporated into the ADW 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.
The bio-derived surfactants described above may be formed from a naturally
occurring lipid by
any known method such as by esterification, Fischer esterification,
epoxidation, etc. Prior to the
formation of a bio-derived surfactant, bio-derived fatty acids may be
liberated from natural lipids
by, for example, triglyceride hydrolysis, which separates the fatty acids from
glycerol. The fatty
acids may then be reacted to yield the bio-derived surfactants, including
fatty alcohol ethoxylates
or other high HLB-value surfactants derived from fatty alcohols. In one
version, a reaction is
performed of fatty acids is with an alcohol or an epoxide. Exemplary alcohols
include methanol,
ethanol, propanol, and other primary or secondary alkyl alcohols.
In ethoxylation, bio-derived ethylene oxide is added to bio-derived fatty
acids or fatty alcohols,
typically in the presence of potassium hydroxide, resulting in the addition of
multiple ethoxy
groups to the molecule. To obtain a bio-derived surfactant with a relatively
high HLB value that
is the product of a natural lipid, ethoxylation is a useful technique because
a chain of hydrophilic
ethoxy groups can be readily added to the molecule. Thus, the bio-derived
surfactants are
preferably obtained through a simple operation or small number of operations
from the natural
raw materials themselves, such as via hydrolysis and esterification (e.g.,
ethoxylation) or via
esterification alone. A hydrogenation step may also be included prior to or
after esterification
(e.g, in the formation of alcohols, hydrogenation may follow methylation of a
fatty acid). Bio-
derived surfactants may be produced from any known method of ethoxylating
triglycerides such
as vegetable oils, including the methods discussed in U.S. Pat. No. 6,268,517,
"Method for
Producing Surfactant Compositions."
12174-DW CA 02762583 204111-12-20
For example, if the bio-derived surfactant is an ethoxylated mono-, di-, or
triglyceride, it may be
prepared by the condensation of bio-derived ethylene oxide with a mono-, di-,
or triglyceride.
The reaction may be performed using from 5 to 70 moles, 10 to 50 moles, or 20
to 50 moles of
preferably bio-derived ethylene oxide per mole of mono-, di-, or triglyceride.
The resulting
condensation product may have a melting point of at least 15 C, at least 25
C, or at least 30 C.
As discussed by Ernst W. Flick in Industrial Surfactants, 2nd ed., p. 230,
ethoxylated fatty acids
and polyethylene glycol fatty acid esters are nonionic mono and diesters of
various fatty acids,
typically prepared by the condensation or addition of ethylene oxide to a
fatty acid at the site of
the active hydrogen or by esterification of the fatty acid with polyethylene
glycol. The chemical
structure of the monoester product is generally R¨00¨(0¨CH2CH2)õ-0H where R¨CO
represents the hydrophobic base and n denotes the mole ratio of oxyethylene to
the base. The
diester product has a chemical structure of R¨00¨(0¨CH2CH2)n¨O¨CO¨R.
U.S. Pat. No. 6,300,508, "Thickened Aqueous Surfactant Solutions," issued Oct.
9, 2001 to
Raths, Milstein, and Seipel, herein incorporated by reference to the extent it
is compatible
herewith, describes a method for the production of fatty acid esters of an
ethylene-propylene
glycol of the formula RICOO(E0)),(P0)y(E0),F1 where RICO is a linear
aliphatic, saturated or
unsaturated acyl group, or a combination thereof, having from about 6 to about
22 carbon atoms
(though a more specific range of 14 to 22 or 16 to 22 carbon atoms may be
considered), EO is
¨CH2CH2¨, and PO is ¨CH2CH(CH3)0¨ or ¨CH2CH2CH20¨ or a combination thereof.
The
method of U.S. Pat. No. 6,300,508 comprises reacting a fatty acid having from
about 6 to about
22 carbon atoms with an alkylene oxide selected from the group consisting of
propylene oxide,
ethylene oxide or a combination thereof, in the presence of an alkanolamine.
For some
embodiments of the present invention, the use of additional moles of alkylene
oxide reactants
relative to the recommendations of U.S. Pat. No. 6,300,508 may be considered
to increase the
degree of ethoxylation or propoxylaytion and thereby increase HLB. Preferably,
each of the
reactants in these processes is bio-derived.
U.S. Pat. No. 6,221 ,919, "Utilization of Ethoxylated Fatty Acid Esters as
Self-Emulsifiable
Compounds," issued April 24, 2001, to G. Trouve, herein incorporated by
reference to the extent
that it is noncontradictory herewith, discloses methods of producing
ethoxylated fatty acid esters
that may have one or more of the following three formulas:
(A) RI¨00¨ (0¨CH2¨CH2)k-0R2
(B) R3-03¨ (0¨CH2¨CH2)10R40¨ (CH2¨CH2-0)m¨CO¨R5
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(C) R6-00- (0-CH2-CH2).--0-R7-CHRIL-R9-0- (CH2-CH2-0)q-CO-R10
where R" is -0-((0-CH2-CH2)õ-CO-R8; RI 5R35 R55 -6,
K R8 and RI each represent a linear or
branched, saturated or unsaturated hydrocarbon chain having from 5 to 30
carbon atoms,
preferably from 14 to 30 carbon atoms; and R2, R4, R7 and R9 each represent a
linear or branched,
saturated or unsaturated hydrocarbon chain having from 1 to 5 carbon atoms. US
6,221 ,919
teaches that the values of k, l+m, and n+p+q should be adapted to give HLB
values between
about 4 and about 10, preferably neighboring 5, although higher HLB values are
within the scope
of the present invention, so elevated values of k, l+m, and n+p+q may be
useful.
Example 2 described by U.S. 6,221,919 is specifically incorporated herein by
reference, for it
describes ethoxylation of rapeseed oil via a process that may be useful for a
variety of other
vegetable oils. Ethoxylation is most easily performed by direct condensation
reactions with
ethylene oxide with fatty acids or fats themselves. Ethoxylation can also be
carried out on fatty
acid methyl esters if the appropriate catalysts are used, as described by I.
Hama, T. Okamoto and
H. Nakamura of Lion Corporation, Tokyo, Japan, in "Preparation and Properties
of Ethoxylated
Fatty Methyl Ester Nonionics," Journal of the American Oil Chemists' Society,
Vol. 72, No. 7,
July, 1995, pp. 781-784. Their method directly inserts EO into fatty methyl
esters (RCOOCH3)
to give [RCO(OCH2CH2)õOCH3] using a solid catalyst modified by metal cations.
Ethoxylates
of fatty methyl esters obtained by this method were homogeneous monoesters and
had good
properties as nonionic surfactants.
Fischer esterification involves forming an ester by refluxing a carboxylic
acid and an alcohol in
the presence of an acid catalyst. Typical catalysts for a Fischer
esterification include sulfuric
acid, tosic acid, and lewis acids such as scandium(111) triflate or
dicyclohexylcarbodiimide.
Vegetable oils, after basic purification, can be processed to produce
methylated or ethylated seed
oils, commonly referred by the abbreviations MS0 and ESO, respectively, which
typically have a
single moiety added, unlike epoxidation reactions which can add numerous
groups. MSOs and
ESOs are created by hydrolysis of the glycerol molecule from the fatty acids,
and the acids are
then esterified with methanol or ethanol. Such compounds can be used as bio-
derived surfactants
in the ADW composition, but when higher HLB values are desired, additional
hydrophilic groups
should be added.
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Examples of commercially available compositions comprising bio-derived
surfactants that may
be used within the ADW compositions described herein include, without
limitation, the
following:
SC-1000TM, a surface washing agent marketed by GemTek Products (Phoenix, AZ).
SC-
l000Tm is part of GemTek's SAFE CARE product series, that are said to contain
alcohols, fatty
acids, esters, waxes, saponifiers, chelators, enzymes and other fractions from
soy, corn, palm
kernel, peanut, walnut, safflower, sunflower, Canola, and cotton seed.
SoyFastTM Manufacturer's Base marketed by Soy Technologies (Nicholasville,
Kentucky) as a
soy-based biodegradable all-purpose cleaner, and related soy-based products
such as SoyFastTM
Cleaner and SoyGreenTM Solvents. Manufacturer's Base, according to its MSDS,
comprises two
bio-derived surfactants, ethoxylated castor oil (average degree of
ethoxylation said to be about
30) and soybean oil methyl ester (formed by reaction of soybean oil with
methanol, resulting in
hydrolysis of the triglyceride to yield methylated fatty acids and glycerol).
It also comprises
pentanedioic acid, dimethyl ester; butanedioic acid, dimethyl ester;
hexanedioic acid, dimethyl
ester; and polyoxyethylene tridecyl ester.
Soy-Dex Plus marketed by Helena Chemical Co. (Memphis, Tennessee), said to be
a proprietary
blend of vegetable oil, polyol fatty acid ester, polyethoxylated esters
thereof, and ethoxylated
allcylaryl phosphate ester.
Esterified vegetable oils, for example from Cognis Corp. (Monheim, Germany),
including
AGNIQUE SBO-10 Ethoxylated Soybean Oil, POE 10; AGNIQUE SBO-30 Ethoxylated
Soybean Oil POE 30; AGNIQUE SBO-42 (Trylox 5919-C) Ethoxylated Soybean Oil,
POE 42;
AGNIQUE SBO- 60 Ethoxylated Soybean Oil POE 60; AGNIQUE CSO-44 (Mergital EL
44)
Ethoxylated Castor Oil, POE (polyoxyethylene) 44; AGNIQUE CSO-60H (Eumulgin
HRE 60)
Hydrogenated Ethoxylated Castor Oil, POE 60; AGNIQUE CSO-200 (Etilon R 200)
Ethoxylated
Castor Oil, POE 200; AGNIQUE RS0-0303 (Eumulgin CO 3522) Alkoxylated Rapeseed
Oil,
POE 3, POP (polyoxypropylene) 3; AGNIQUE RSO-2203 (Eumulgin CO 3526)
Alkoxylated
Rapeseed Oil, POE 3, POP 22; AGNIQUE RSO-30 (Eumulgin CO 3373) Ethoxylated
Rapeseed
Oil, POE 30. Also, Ethoxolated Soybean Oil, marketed by Adjuvants Unlimited of
Memphis,
TN, as AU970 could be used.
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TOXIMUL ethoxylated castor oils from Stepan Chemical (Northfield, Illinois),
including
TOXIMUL 8240 (POE-36), TOXIMUL 8241 (POE- 30), and TOXIMUL 8242 (POE-40).
Genapol surfactants by Hoechst Chemical, such as Genapol OXD-080, a fatty
alcohol polyglycol
ether.
Ethoxylated castor oil is available as Shree Chem-Co 35 from Shree Vallabh
Chemicals (Gujarat,
India). In Shree Chem-Co 35, the hydrophobic constituents comprise about 83%
of the total
mixture, the main component being glycerol polyethylene glycol ricinoleate.
Other hydrophobic
constituents include fatty acid esters of polyethylene glycol along with some
unchanged castor
oil. The hydrophilic part (17%) consists of polyethylene glycols and glycerol
ethoxylates. In a
related compound, Shree Chem-Co 40, approximately 75% of the components of the
mixture are
hydrophobic. These comprise mainly fatty acid esters of glycerol polyethylene
glycol and fatty
acid esters of polyethylene glycol. The hydrophilic portion consists of
polyethylene glycols and
glycerol ethoxylates.
Ethoxylated castor oil and hydrogenated castor oil products marketed by Global
Seven Corp.
(Franklin, NJ). These products, marketed as emulsifiers, solubilizers, and
conditioners, include
HETOXIDE C-200, a PEG-200 castor oil compound having an HLB of 18.1; HETOXIDE
C-81,
a PEG-81 castor oil compound said to have an HLB of 15.9; HETOXIDE C-40, a PEG-
40 castor
oil compound having an HLB of 13.0; HETOXIDE C-30, a PEG-30 castor oil
compound having
an HLB of 11.8; HETOXIDE C25, a PEG-25 castor oil compound having an HLB of
10.8;
HETOXIDE C-16, a PEG-16 castor oil compound having an HLB of 8.6; and HETOXIDE
C-5, a
PEG-5 castor oil compound having an HLB of 4Ø
In an example embodiment, the bio-derived surfactants of the present ADW
compositions
comprise surfactants obtained by esterification of vegetable lipids. In a
particular embodiment,
the lipids are selected from soybean oil and castor oil. These may also be
derived from single cell
organisms, such as bacteria, algae, yeast, and fungi. The major unsaturated
fatty acids in soybean
oil triglycerides are 7% linolenic acid (C-18:3); 51% linoleic acid (C-18:2);
and 23% oleic acid
(C-18:1). Castor oil is a triglyceride in which about 85% to 95% of the fatty
acids are ricinoleic
acid (C18:1-0H), about 2% to 6% are oleic acid (C-18:1), about 1% to 5% is
linoleic acid (C-
18:2), with there being about 0.3% to 1% each of linolenic acid (C18:3),
stearic acid (C18:0),
palmitic acid (C16:0), and dihydroxystearic acid, with small amounts of some
other acids.
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Additional steps, such as hydrogenation and dehydrogenation may be
contemplated. In one
embodiment, the bio-derived compound comprises an ester of a fatty acid,
wherein the fatty acid
has not been chemically modified apart from the formation of an ester bond to
join the fatty acid
to a hydrophilic moiety. Alternatively, a bio-derived surfactant may be the
ethoxylated product
of a naturally occurring fatty acid or lipid.
Other bio-derived or natural surfactants may be included in the ADW
composition, such as the
rhamnolipids and rhamnolipid derivatives marketed by Jeneil Biosurfactant
Company (Saukville,
Wisconsin), such as JBR425 (CAS Number: 147858-26-2) as well as those
described in U.S. Pat.
No. 5,455,232, "Pharmaceutical Preparation Based in Rhamnolipid," issued Oct.
3, 1995 to Piljac
and Piljac, or in U.S. Pat. No. 7,129,218, "Use of Rhamnolipids in Wound
Healing, Treatment
and Prevention of Gum Disease and Periodontal Regeneration," issued Oct. 31,
2006 to Stipcevic
et at. Lipopeptide biosurfactants such as those produced by Bacillus species
may also be
included. Natural plant oils may be provided in the form of oil cakes that can
be used.
Builder
Builders for use in the ADW compositions include non-phosphate builders. If
present, builders
are used in a level of from 5% to 60%, preferably from 10% to 50% by weight of
the ADW
composition. In another embodiment, the builders are present in an amount of
up to 50%, more
preferably up to 45%, even more preferably up to 40%, and especially up to 35%
by weight of
the composition. The compositions of the present invention are preferably
phosphate free or
essentially free, and most preferably comprise carbon atoms that are bio-
derived.
One example of a builder is an aminocarboxylic builder. Preferably the
aminocarboxylic builder
is an aminopolycarboxylic builder, more preferably a glycine-N,N-diacetic acid
or derivative of
general formula MO0C-CHR-N(CH2COOM)2, where R is a C1_12 alkyl and M is alkali
metal.
Aminocarboxylic builders may include MGDA (methyl-glycine-diacetic acid), GLDA
(glutamic-
N,N-diacetic acid), iminodisuccinic acid (IDS), carboxymethyl inulin and salts
and derivatives
thereof. MGDA (salts and derivatives thereof) is especially preferred
according to the invention,
with the tri-sodium salt thereof being preferred and a sodium/potassium salt
being specially
preferred for the low hygroscopicity and fast dissolution properties of the
resulting particle.
Preferably, the aminocarboxylic acid builders are obtained from bio-derived
sources of carbon.
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Other suitable aminocarboxylic builders include; for example, aspartic acid-N-
monoacetic acid
(ASMA), aspartic acid-/V,N-diacetic acid (ASDA), aspartic acid-N-monopropionic
acid (ASMP) ,
iminodisuccinic acid (IDA), N-(2-sulfomethyl) aspartic acid (SMAS), N-(2-
sulfoethyl) aspartic
acid (SEAS), N-(2-sulfomethyl) glutamic acid (SMGL), N-(2-sulfoethyl) glutamic
acid (SEGL),
thereof.
In addition to the aminocarboxylic builders in the particle of the invention,
the composition can
comprise carbonate and/or citrate.
Other non-phosphate builders include homopolymers and copolymers of
polycarboxylic acids
and their partially or completely neutralized salts, monomeric polycarboxylic
acids and
Suitable polycarboxylic acids are acyclic, alicyclic, heterocyclic and
aromatic carboxylic acids,
in which case they contain at least two carboxyl groups which are in each case
separated from
Polymer
A polymer, if present, is used in any suitable amount from about 0.1% to about
50%, preferably
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In one example, sulfonated/carboxylated polymers are particularly suitable for
the ADW
composition of the invention.
Preferred ADW compositions may contain a dispersant polymer typically in the
range from 0 to
about 25%, preferably from about 0.5% to about 20%, more preferably from about
1% to about
7% by weight of the ADW composition.
One dispersant polymer suitable for use in the present composition includes an
ethoxylated
cationic diamine comprising the formula (III):
(CEI2CII2017 X
(CH2CR20),, ¨X (CII2CH201, ¨X
(III)
where X of formula (III) is a nonionic group selected from the group
consisting of H, C1-C4 alkyl
or hydroxyallcyl ester or ether groups, and mixtures thereof; n is at least
about 6; and a is from 0
to 4 (e. g. ethylene, propylene, hexamethylene). For preferred ethoxylated
cationic diamines, n
of formula (III) is at least about 12 with a typical range of from about 12 to
about 42. See U.S.
Pat. No. 4,659,802 for further information regarding the ethoxylated cationic
diamines. The
alkylene oxide components in all regards are preferably obtained from bio-
derived ethylene
oxide.
Further suitable dispersant polymers suitable for use herein are illustrated
by formula (IV):
CTONa
COONa COON'
0
S 03Na
(IV)
Formula IV is an Acrylic acid (AA), maleic acid (MA) and sodium 3-allyloxy-2-
hydroxy-1 -
propanesulfonate (HAPS) copolymer, preferably comprising about 45 wt% of the
polymer of
AA, about 45 wt % of the polymer of MA and about 10 wt% of the polymer HAPS.
Molecular
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weight may be from about 8000 to about 15000. In one embodiment, dispersant
polymers of
formula (IV) have a molecular weight of about 8000 to about 8500. In another
embodiment
dispersant polymers of formula (IV) have a molecular weight of about 12500 to
about 13300.
Salts of formula (IV) may be selected from any water soluble salt such as
sodium or potassium
salt.
Further suitable dispersant polymers suitable for use herein are illustrated
by the film-forming
polymers. Suitable for use as dispersants herein are co-polymers synthesized
from bio-derived
acrylic acid, bio-derived maleic acid and bio-derived methacrylic acid. Such
polymers may be
bio-derived analogs of commercial products such as ACUSOL 480N supplied by
Rohm &
Haas and polymers containing both carboxylate and sulfonate monomers, such as
ALCOSPERSE polymers (supplied by Alco). In one embodiment an ALCOSPERSE
polymer sold under the trade name ALCOSPERSE 725, is a co-polymer of Styrene
and Acrylic
Acid.
In certain embodiments, a dispersant polymer may be present in an amount in
the range from
about 0.01% to about 25%, or from about 0.1% to about 20%, and alternatively,
from about 0.1%
to about 7% by weight of the ADW composition.
Further suitable dispersant polymers include polyacrylic phosphono end group
polymers or
acrylic-maleic phosphono end group copolymers according to the general formula
H2P03¨
(CH2¨CHCOOH),,¨(CHCOOH-CHCOOH)m--where n is an integer greater than 0, m is an
integer of 0 (for polyacrylic polymers) or greater (for acrylic¨maleic
copolymers) and n and m
are integers independently selected to give a molecular weight of the polymer
of between 500
and 200,000, preferably of between 500 and 100,000, and more preferably
between 1,000 and
50,000. For polyacrylates, m is zero. Suitable polyacrylic phosphono end group
polymers or
acrylic-maleic phosphono end group copolymers for use herein are available
from Rohm &Haas
under the tradenames ACUSOLO E 420 or 470 or 425. In one embodiment Acusol
425N is
used. Acusol 425N is an acrylic-maleic (ratio 80/20) phosphono end group
copolymers and is
available from Rohm &Haas.
Particularly preferred dispersant polymers are low molecular weight modified
polyacrylate
copolymers, most preferably obtained from bio-derived sources of carbon. Such
copolymers
contain as monomer units: (a) from about 90% to about 10%, preferably from
about 80% to
about 20% by weight bio-derived acrylic acid or its salts and (b) from about
10% to about 90%,
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preferably from about 20% to about 80% by weight of a substituted bio-derived
acrylic monomer
or its salt and having the general formula ¨[(C(R2)C(R1)(C(0)0R3)]¨where the
incomplete
valencies inside the square braces are hydrogen and at least one of the
substituents RI, R2 or R3,
preferably RI or R2, is a C1 to C4 alkyl or hydroxyalkyl group, RI or R2 canbe
a hydrogen; and R3
can be a hydrogen or alkali metal salt. Most preferred is a substituted
acrylic monomer wherein
RI is methyl, R2 is hydrogen and R3 is sodium.
The low molecular-weight polyacrylate dispersant polymer preferably has a
molecular weight of
less than about 15,000, preferably from about 500 to about 10,000, most
preferably from about
1,000 to about 5,000. The most preferred polyacrylate copolymer for use herein
has a molecular
weight of 3500 and is the fully neutralized form of the polymer comprising
about 70% by weight
bio-derived acrylic acid and about 30% by weight bio-derived methacrylic acid.
Suitable sulfonated/carboxylated polymers described herein may have a weight
average
molecular weight of less than or equal to about 100,000 Da, or less than or
equal to about 75,000
Da, or less than or equal to about 50,000 Da, or from about 3,000 Da to about
50,000 Da,
preferably from about 5,000 Da to about 45,000 Da.
The sulfonated/carboxylated polymers may comprise (a) at least one structural
unit derived from
at least one carboxylic acid monomer having the general formula (I):
R1 R3
R2 R4
where RI to R4 are independently hydrogen, methyl, carboxylic acid group or
¨CH2COOH and
wherein the carboxylic acid groups can be neutralized; (b) optionally, one or
more structural
units derived from at least one nonionic monomer having the general formula
(II):
R5
H2C=- (11)
X
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where R5 is hydrogen, CI to C6 alkyl, or C1 to C6 hydroxyalkyl, and X is
either aromatic (with R5
being hydrogen or methyl when X is aromatic) or X is of the general formula
(III):
C=--0
(III)
I
where R6 is (independently of R5) hydrogen, CI to C6 alkyl, or CI to C6
hydroxyalkyl, and Y is 0
or N; and at least one structural unit derived from at least one sulfonic acid
monomer having the
general formula (IV):
R7
(A)t
(IV)
(3)t
S03- M+
where R7 is a group comprising at least one sp2 bond, A is 0, N, P, S, or an
amido or ester
linkage; B is a monocyclic or polycyclic aromatic group or an aliphatic group;
each t is
independently 0 or 1; and M is a cation. In one aspect, R7 is a C2 to C6
alkene. In another
aspect, R7 is ethene, butene or propene.
Preferred carboxylic acid monomers include one or more of the following: bio-
derived acrylic
acid, bio-derived maleic acid, bio-derived itaconic acid, bio-derived
methacrylic acid, or
ethoxylate esters of bio-derived acrylic acids, acrylic and methacrylic acids
being more preferred.
Preferred sulfonated monomers include one or more of the following: bio-
derived sodium (meth)
allyl sulfonate, bio-derived vinyl sulfonate, bio-derived sodium phenyl (meth)
allyl ether
sulfonate, or bio-derived 2-acrylamido-methyl propane sulfonic acid ("AMPS"),
or bio-derived
sodium 3-allyloxy-2-hydroxy-1-propanesulfonate ("HAPS"). Preferred non-ionic
monomers
include one or more of the following: bio-derived methyl (meth) acrylate, bio-
derived ethyl
(meth) acrylate, bio-derived t-butyl (meth) acrylate, bio-derived methyl
(meth) acrylamide, bio-
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derived ethyl (meth) acrylamide, bio-derived t-butyl (meth) acrylamide, bio-
derived styrene, or
bio-derived a-methyl styrene. Preferably, the polymer comprises the following
levels of
monomers: from about 40% to about 90%, preferably from about 60% to about 90%
by weight of
the polymer of one or more bio-derived carboxylic acid monomer; from about 5%
to about 50%,
The polymers for use in the ADW 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
Other suitable intermediate compounds derived from renewable resources include
monofunctional alcohols such as methanol or ethanol and polyfunctional
alcohols such as
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
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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 ADW
compositions. An
intermediate compound may be capable of producing more than one secondary
intermediate
compound. Similarly, a specific intermediate compound may be derived from a
number of
different precursors, depending upon the reaction pathways used.
Particularly desirable intermediates include bio-derived (meth)acrylic acids
and their esters and
salts; and olefins. In particular embodiments, the intermediate compound may
be bio-derived
acrylic acid, bio-derived ethylene, or bio-derived propylene.
For example, acrylic acid is a monomeric compound that may be derived from
renewable
resources via a number of suitable routes. Examples of such routes are
provided below.
Acrylic and methacrylic monomers represent a large portion of the monomers
that are used to
produce the acrylic polymers. For example, both bio-derived 3-hydroxypropionic
acid and bio-
derived 2-hydroxyisobutyric acids are available via bio-transformation
pathways, see for
example, Biotechnology Journal, volume 1, pages 756-769, 2006 and Applied
Microbiological
Biotechnology, volume 66, pages 131-142, 2004. These bio-derived acids can be
dehydrated to
form bio-derived acrylic acid and bio-derived methacrylic acid.
The bio-derived acrylic acid and bio-derived acrylic acid monomers, and
derivatives thereof, can
be used to form numerous bio-derived methacrylic acid, bio-derived alkyl
acrylate and bio-
derived alkyl methacrylate esters as well as bio-derived acrylamides, bio-
derived
methacrylamides, bio-derived acrylonitrile and bio-derived methacrylonitrile.
Bio-derived
acrylate and bio-derived methacrylate esters can be produced, via
esterification reactions with
bio-derived alcohols. By incorporating an excess of bio-derived diols into the
esterification
reaction, hydroxy functional bio-derived acrylate and bio-derived methacrylate
esters can be
formed. Using at least two equivalents excess of the bio-derived acrylic acid
and bio-derived
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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 ADW 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.
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.
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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
ADW compositions that all of the carbon atoms of the monomers used to form the
polymer
components to be bio-derived.
As an example route to obtaining bio-derived acrylic acid, glycerol starting
material may be
derived from a renewable resource (e.g., via hydrolysis of soybean oil and
other triglyceride oils)
and converted into acrylic acid according to a two-step process. In a first
step, the glycerol may
be dehydrated to yield acrolein. A particularly suitable conversion process
involves subjecting
glycerol in a gaseous state to an acidic solid catalyst such as H3PO4 on an
aluminum oxide carrier
(which is often referred to as solid phosphoric acid) to yield acrolein.
Specifics relating to
dehydration of glycerol to yield acrolein are disclosed, for instance, in U.S.
Patent Nos.
2,042,224 and 5,387,720. In a second step, the acrolein is oxidized to form
acrylic acid. A
particularly suitable process involves a gas phase interaction of acrolein and
oxygen in the
presence of a metal oxide catalyst. A molybdenum and vanadium oxide catalyst
may be used.
Specifics relating to oxidation of acrolein to yield acrylic acid are
disclosed, for instance, in U.S.
Patent No. 4,092,354.
Alternatively, glucose derived from a renewable resource (e.g., via enzmatic
hydrolysis of corn
starch) may be converted into acrylic acid via a two step process with lactic
acid as an
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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
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.
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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
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), allyl alcohol
(2-propen-1-ol), and
1,3-propanediol, having a 100% biobased carbon isotope ratio. For example,
bioderived glycerol
may be dehydrated to give acrolein (2-propenal). The acrolein may be oxidized
to afford acrylic
acid (2-propenoic acid). Alternatively, acrolein may be reduced to give ally'
alcohol (2-propen-
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1-01). 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. App!. Pub. No. 2007/0213247. Moreover, ADW compositions
herein may
comprise bio-derived 1,3-propanediol prepared as disclosed in U.S. Pat. Appl.
Pub. No.
2007/0213247.
Alternatively, bio-derived acrylic acid or acrylate esters may be synthesized
from bio-derived
lactic acid or lactate esters. Biobased lactic acid derivatives may be bio-
synthesized, for
example, by fermentation of a carbohydrate material. Conversion of lactic acid
and lactate esters
into acrylic acid and acrylate esters, respectively, may be accomplished by
dehydration of the
alcohol group of the lactate moiety. Suitable methods for the conversion of
lactic acid and
lactate esters, for example, lactic acid/lactate esters from the fermentation
of carbohydrate
material in the presence of ammonia, into an acrylate ester or acrylic acid
are disclosed in U.S.
Pat. Nos. 5,071,754 and 5,252,473, the disclosures of which are incorporated
by reference herein
in their entirety.
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 ADW 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
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hydrolysis (saponification) or by a catalytic de-esterification. Suitable
triglycerides for use in the
formation of bio-derived glycerol include, but are not limited to, corn oil,
soybean oil, canola oil,
vegetable oil, safflower oil, sunflower oil, nasturtium seed oil, mustard seed
oil, olive oil, sesame
oil, peanut oil, cottonseed oil, rice bran oil, babassu nut oil, castor oil,
palm oil, palm kernel oil,
rapeseed oil, low erucic acid rapeseed oil, lupin oil, jatropha oil, coconut
oil, flaxseed oil,
evening primrose oil, jojoba oil, tallow, beef tallow, butter, chicken fat,
lard, dairy butterfat, shea
butter, biodiesel, used frying oil, oil miscella, used cooking oil, yellow
trap grease, hydrogenated
oils, derivatives of these oils, fractions of these oils, conjugated
derivatives of these oils, and
mixtures of any thereof.
Suitable bioderived olefins include, but are not limited to monoacrylates,
diacrylates, and allyl
esters.
Alternatively, bio-derived glycerol may be produced as a co-product of
biodiesel production.
Glycerol produced by these methods will have a carbon isotope ratio consistent
with a 100% bio-
derived product and will provide a renewable source of acrolein and acrylic
acid that may be
used as a feedstock for the bio-derived monomers and polymers for use in the
ADW
compositions. Non-limiting examples of methods and processes for producing
biodiesel may be
found in U.S. Pat. No. 5,354,878; U.S. Patent Application Publication Nos.
20050245405A1;
2007-0181504; and 20070158270A1; Provisional Patent Application Ser. No.
60/851,575, the
disclosures of which are incorporated in their entirety by reference herein.
The monomers and polymers, as set forth herein, may have up to 100% biobased
carbon isotope
ratio as determined by ASTM Method D 6866. The monomers and polymers may be
differentiated from, for example, similar monomers and polymers comprising
petroleum derived
components by comparison of the carbon isotope ratios, for example, the
14C/12C or the 13C/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;
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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,
isomaft, 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
ADW compositions.
Other embodiments of bio-derived diols suitable for producing diacrylate
esters having 100%
biobased carbon may be produced from fatty acids, such as, for example,
unsaturated fatty acids.
For example, hydroformylation of unsaturated fatty acids and their derivatives
to produce fatty
acid derivatives having a hydroxymethylene group is described in U.S. Pat. No.
3,210,325 to De
Witt et al., the disclosure of which is incorporated in its entirety by
reference herein. Reduction
of the carbonyl of the fatty acid derivative, for example, by hydrogenation,
produces a biobased
diol suitable for esterification or transesterification with acrylic acid or
an acrylate ester, as
produced herein, to form a biobased diacrylate monomer.
Additionally, bio-derived diols suitable for producing diacrylate esters
having 100% bio-derived
carbon may be produced by epoxidation of at least one of the double bonds of
an unsaturated
fatty acid/ester or unsaturated fatty alcohol. One non-limiting example of the
epoxidation
procedure is described by Rao et al., Journal of the American Oil Chemists'
Society, (1968),
45(5), 408, the disclosure of which is incorporated in its entirety by
reference herein. The
epoxidation may be followed by reduction, for example, by hydrogenation, to
open the epoxide
to the alcohol, which may also include reduction of the carbonyl of the fatty
acid/ester to the
alcohol. Any biobased diol may then be esterified or transesterified with
acrylic acid or an
acrylate ester, as produced herein, to form a diacrylate monomer having 100%
biobased carbon.
Still further, diols suitable for producing diacrylate esters having 100%
biobased carbon may be
produced by reduction of a,o)-dicarboxylic acids. As used herein, the term
a,o)-dicarboxylic
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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, am-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,w-dicarboxylic acids from biobased sources, such as,
for example,
maleic acid, fumaric acid, oxalic acid, malonic acid, adipic acid, succinic
acid, and glutaric acid,
adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid may
also be used in the
ADW compositions. According to certain embodiments, the am-dicarboxylic acid
may be an
unsaturated a,w-dicarboxylic acid or a saturated a,w-dicarboxylic acid.
Reduction of the
carbonyls of the a,w-dicarboxylic acids provides a biobased diol which may
then be esterified or
transesterified with acrylic acid or an acrylate ester, as produced herein, to
form a biobased
diacrylate monomer.
Still further, bioderived diacrylamide derivatives may serve as monomers for
the polymerization
reactions described herein. For example, according to certain embodiments, the
diol component
in the formation of the diacrylate esters described herein, may be chemically
converted to a bio-
derived diamine, for example, by a double Mitsunobu-type reaction. Non-
limiting examples of
resulting biobased diamines may include, for example, bis-amino isosorbide,
2,5-
bisaminomethyltetrahydrofuran, 2,5-bisaminomethylfuran. Alternatively,
naturally occurring
bioderived diamines, such as, for example, 1,4-diaminobutane, 1,5-
diaminopentane, or other
alkyldiamines or diamine containing alkaloid derivatives, may be replace the
diol reactant in the
reaction with the bioderived acrylate derivative to form a diacryl amide
compound. Further, it is
also contemplated that bioderived amino alcohols may replace the diol
component in the
formation of the biobased monomers. According to these embodiments, the
bioderived amino
alcohols may be reacted with the bioderived acrylic acid or bioderived
acrylate esters to form a
bioderived monomer possessing both an acrylate ester and an acrylamide
functionality.
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 ADW
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
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involving a metal carbene acting as a catalyst to metathesize alkene monomers
or co-monomers
into a polyunsaturated polymer through a metallocyclobutane intermediate.
Thus, a polymer
comprising a product from an olefin metathesis polymerization reaction of a
bioderived olefin
and a diacrylate ester of a bioderived diol may be used, wherein the
diacrylate ester is produced
by reacting a bioderived diol with at least two equivalents of bio-derived
acrylic acid or an
acrylate ester derived from a bioderived glycerol. The olefin metathesis
polymerization reaction
may be catalyzed by an olefin metathesis catalyst, such as a metal carbene
catalyst, for example,
metal carbenes of molybdenum or ruthenium. Commercially available olefin
metathesis catalysts
suitable for use in the polymerization reactions of the present disclosure
include, but are not
limited to, the "Schrock catalyst" (i.e., [Mo(=CHMe2Ph)(=N¨Ar)(0CMe(CF3)2)21),
the "1st
generation Grubb's catalyst" (i.e., [Ru(=CHPh)C12(PCy3)21), and the "2nd
generation Grubb's
catalyst" (i.e, [Ru(=CHPh)C12PCy3(N,IT-diary1-2-imidazolidinyl)l) (Me=methyl,
Ph=phenyl,
Ar=aryl, and Cy=cyclohexyl). Other olefin metathesis catalysts that may be
suitable include
those catalysts set forth in U.S. Pat. 7,034,096 to Choi et al. at column 12,
line 27 to column 19,
line 2, the disclosure of which is incorporated in its entirety by reference
herein. It should be
noted that the polymers and polymerization process described in the present
disclosure are not
limited to a particular olefin metathesis catalyst(s) and that any olefin
metathesis catalyst, either
currently available or designed in the future, may be suitable for use in
various embodiments of
the present disclosure.
Additionally, the bio-derived olefin component of the metathesis
polymerization may be a
bioderived cyclic olefin, wherein the metathesis polymerization reaction is a
ring opening
metathesis polymerization ("ROMP") reaction. As used herein, the term "ring
opening
metathesis polymerization reaction" includes olefin metathesis polymerization
reactions wherein
at least one of the monomer alkene units comprises a cyclic olefin. Thus, the
ROMP reaction
may react a bioderived diacryl derivative with a bioderived cyclic olefin to
produce a polymer
that is up to 100% biobased as determined by ASTM Method D 6866. Bio-derived
cyclic olefins
may be prepared, for example, from palmitoleic acid, oleic acid, erucic acid,
linoleic acid,
linolenic acid, arachidonic acid, eicosapentaenoic acid, docosahexaenoic acid,
and other
unsaturated fatty acids.
Further processes for producing bio-derived acrylic acid, acrylic acid esters,
and acrylate
polymers are disclosed in WO 2011/002284; US 7,928,148; US 2009/0018300; EP
1710227, and
Xu et al, "Advances in the Research and Development of Acrylic Acid Production
from
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Biomass," Chinese J. Chem. Eng., vol. 14, pp. 419-427 (2006), all of which are
incorporated
herein in their entirety.
In example embodiments of the ADW compositions comprising a carboxylic acid
polymer, the
carboxylic acid is preferably bio-derived (meth)acrylic acid. Sulfonic acids,
when present in the
ADW compositions, preferably are derived from a monomer selected from: bio-
derived 2-
acrylamido methyl-l-propanesulfonic acid, bio-derived 3-allyloxy-2-hydroxy-1-
propanesulfonic
acid ("HAPS"), bio-derived 2-methacrylamido-2-methyl-1-propanesulfonic acid,
bio-derived 3-
methacrylamido-2-hydroxypropanesulfonic acid, bio-derived allylsulfonic acid,
bio-derived
methallylsulfonic acid, bio-derived allyloxybenzenesulfonic acid, bio-derived
methallyloxybenzensulfonic acid, bio-derived 2-hydroxy-3-(2-
propenyloxy)propanesulfonic acid,
bio-derived 2-methy1-2-propene-1-sulfonic acid, bio-derived styrene sulfonic
acid, bio-derived
vinylsulfonic acid, bio-derived 3-sulfopropyl acrylate, bio-derived 3-
sulfopropyl methacrylate,
bio-derived sulfomethylacrylamide, bio-derived sulfomethylmethacrylamide, and
water soluble
salts thereof. The unsaturated sulfonic acid monomer is most preferably 2-
acrylamido-2-
propanesulfonic acid (AMPS).
In the polymers, all or some of the carboxylic or sulfonic acid groups can be
present in
neutralized form, i.e. the acidic hydrogen atom of the carboxylic and/or
sulfonic acid group in
some or all acid groups can be replaced with metal ions, preferably alkali
metal ions and in
particular with sodium ions. Preferably, at least 50%, at least 60%, at least
70%, at least 80%, at
least 90%, at least 95%, at least 99%, or 100% of the carbon atoms in the
polymers are bio-
derived.
Thickening Agent
The ADW compositions may comprise a thickener system. A particularly preferred
thickener for
use in the compositions herein comprises xanthan gum or similar material and a
co-thickener
such as an associative polymer or water soluble silicates. The thickener
system may constitute
from about 0.1% to about 15% by weight of the composition.
Suitable thickening agents are viscoelastic, thixotropic thickening agents.
The viscoelastic,
thixotropic thickening agent in the compositions of the present invention is
from about 0.1% to
about 10%, preferably from about 0.25% to about 8%, most preferably from about
0.5% to about
5%, by weight of the detergent composition. Preferably, the thickening agents
are bio-derived.
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Suitable thickeners which can be used in this composition include natural
gums, such as xanthan
gum, locust bean gum, guar gum, and the like. In one embodiment, xanthan gums
are utilized.
Xanthan gums are biopolysaccharides and suitable xanthan gums include, without
limitation,
products sold by Kelco Corporation under the trade names KELTROL , such as
KETROL RD
and KELTROL CG-SFT and KELZAN as well as products sold by Rhodia under the
trade
names RHODIPOL , RHODIGEL and RHODICARE , such as RHODICARE T.
The ADW detergent composition may comprise water-soluble silicates. Water-
soluble silicates
herein are any silicates which are soluble to the extent that they do not
adversely affect
spotting/filming characteristics of the ADW composition. Aluminosilicate
builders can be used
in the present compositions though are not preferred for automatic dishwashing
detergents.
The soluble silicate is typically used in an amount of about 0.4% to about
4.0% by weight; more
preferably is present in an amount of about 0.75% to about 3% by weight and
most preferably
present in an amount of about 1% to about 2% by weight, based on the total
weight of the
composition.
The associative thickener is typically an addition polymer of three
components: (1) an alpha-
beta-monoethylenically unsaturated monocarboxylic acid or dicarboxylic acid of
from 3 to 8
carbon atoms such as bio-derived acrylic acid or bio-derived methacrylic acid
to provide water
solubility; (2) a monoethylenically unsaturated copolymerizable monomer
lacking surfactant
capacity such as bio-derived methyl acrylate or bio-derived ethyl acrylate to
obtain the desired
polymer backbone and body characteristics; and (3) a monomer possessing
surfactant capacity
which provides the pseudo plastic properties to the polymer and is the
reaction product of a
monoethylenically unsaturated monomer with a nonionic surfactant compound
wherein the
monomer is copolymerizable with the foregoing monomers such as the reaction
product of bio-
derived methacrylic acid with a monohydric nonionic surfactant to obtain a
monomer such as
CH3(CH2)15--17(OCH2CH2)e0OCC(CH3)=CH2, where "e" has an average value of about
10 or 20.
Optionally, up to about 2.0% of a polyethylenically unsaturated monomer sloth
as bio-derived
ethylene glycol diacrylate or dimethacrylate or divinylbenzene can be included
if a higher
molecular weight polymer is desired.
Additional associative thickeners include bio-derived maleic anhydride
copolymers reacted with
nonionic surfactants such as bio-derived ethoxylated C12-C14 primary alcohol,
similar to the
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compounds available under the tradename Surfonic L Series from Texaco Chemical
Co. and the
tradename Gantrez AN-119 from ISP.
The associative thickeners may include C10¨C22 alkyl groups in an alkali-
soluble acrylic
emulsion polymer such as those available under the trademark "Acusol " from
Rohm & Haas
Co. of Philadelphia, Pa. The most preferred associative thickeners are Acusol
820 ("820") and
1206A ("1206A"). Acusol 820 is a 30.0% active emulsion polymer of 40.0%
methacrylic acid,
50% ethyl acrylate and 10.0% stearyl oxypoly ethyl methacrylic emulsion
polymer having
approximately 20 moles of ethylene oxide. Acusol 1206A is a 30% active
emulsion polymer
with 44% methacrylic acid, 50% ethyl acrylate and 6% stearyl methacrylate
polymer having
about 10 moles of ethylene oxide. These polymers are described in U.S. Pat.
No. 4,351,754 to
Dupre. Most preferably, the associative thickeners are provided as 100% bio-
derived analogs of
these commercially available products.
The associative thickener is typically used in an amount of about 0.01% to
about 1.0% by weight;
more preferably is present in an amount of about 0.05% to about 0.5% by weight
and most
preferably present in an amount of about 0.1% to about 0.3% by weight, based
on the total
weight of the ADW composition.
In addition to the xanthan gum thickener, other thickeners may be utilized.
Suitable are various
carboxyvinyl polymers, homopolymers and copolymers are commercially available
from B. F.
Goodrich Company, New York, N.Y., under the trade name CARBOPOL . These
polymers are
also known as carbomers or polyacrylic acids. Carboxyvinyl polymers useful in
formulations of
the present invention include CARBOPOL 910 having a molecular weight of about
750,000,
CARBOPOL 941 having a molecular weight of about 1,250,000, and CARBOPOL 934
and
940 having molecular weights of about 3,000,000 and 4,000,000, respectively.
More preferred
are the series of CARBOPOL which use ethyl acetate and cyclohexane in the
manufacturing
process, for example, CARBOPOL 981, 2984, 980, and 1382. Analogous compounds
may be
produced from bio-derived carbon sources and may be used in the ADW
compositions in
preferred embodiments.
Further suitable additional thickeners include polycarboxylate polymers of the
invention are non-
linear, water-dispersible, polyacrylic acid cross-linked with a polyalkenyl
polyether and having a
molecular weight of at lease 750,000, preferably from about 750,000 to about
4,000,000, all
preferably bio-derived. Suitable examples of these polycarboxylate polymers
include are
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SOKALAN PHC-25 , a polyacrylic acid available from BASF Corporation and the
POLYGEL
series available from 3-V Chemical Corporation. Mixtures of polycarboxylate
polymers may
also be used.
Semi-synthetic thickeners such as the cellulosic type thickeners: hydroxyethyl
and
hydroxymethyl cellulose (ETHOCEL and METHOCEL available from Dow Chemical)
can
also be used. Preferably the semi-synthetic thickeners are obtained from bio-
derived sources of
carbon. Mixtures of inorganic clays (e.g., aluminum silicate, bentonite, fumed
silica) are also
suitable for use as a thickener herein. The preferred clay thickening agent
can be either naturally
occurring or synthetic. An example of a suitable synthetic clay is disclosed
in the U.S. Pat. No.
3,843,598. Naturally occurring clays further include some smectite and
attapulgite clays as
disclosed in U.S. Pat. No. 4,824, 590.
Other suitable organic polymer for use herein includes a polymer comprising an
acrylic acid
backbone and alkoxylated side chains, the polymer having a molecular weight of
from about
2,000 to about 20,000, and said polymer having from about 20 wt% to about 50
wt% of an
alkylene oxide, preferably a bio-derived alkylene oxide. The polymer should
have a molecular
weight of from about 2,000 to about 20,000, or from about 3,000 to about
15,000, or from about
5,000 to about 13,000. The alkylene oxide (AO) component of the polymer is
generally
propylene oxide (PO) or ethylene oxide (E0), preferably bio-derived EO and/or
bio-derived PO,
and generally comprises from about 20 wt% to about 50 wt%, or from about 30
wt% to about
45 wt%, or from about 30 wt% to about 40 wt% of the polymer. The alkoxylated
side chains of
the water soluble polymers may comprise from about 10 to about 55 AO units, or
from about 20
to about 50 AO units, or from about 25 to 50 AO units. The polymers,
preferably water soluble,
may be configured as random, block, graft, or other known configurations.
Methods for forming
alkoxylated acrylic acid polymers are disclosed in U.S. Patent No. 3,880,765.
Further methods for producing bio-based glycol compositions as synthetic
feedstocks for bio-
derived monomers and bio-derived polymers are disclosed in WO 2008/057220,
incorporated
herein by reference.
Polyvalent Metal Compounds
The ADW composition may comprise a polyvalent metal compound. Any suitable
polyvalent
metal compound may be used in any suitable amount or form. Suitable polyvalent
metal
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compounds include, but are not limited to: polyvalent metal salts, oxides,
hydroxides, and
mixtures thereof. Suitable polyvalent metals include, but are not limited to:
Groups IIA, IIIA,
IVA, VA, VA, VIIA, JIB, IIIB, IVB, VB and VIII of the Periodic Table of the
Elements. For
example, suitable polyvalent metals may include Al, Mg, Co, Ti, Zr, V, Nb, Mn,
Fe, Ni, Cd, Sn,
Sb, Bi, and Zn. These polyvalent metals may be used in any suitable oxidation
state. Suitable
oxidation states are those that are stable in the ADW detergent compositions
described herein.
Any suitable polyvalent metal salt may be used in any suitable amount or form.
Suitable salts
include but are not limited to: organic salts, inorganic salts, and mixtures
thereof. For example,
suitable polyvalent metal may include: water-soluble metal salts, slightly
water-soluble metal
salts, water-insoluble metal salts, slightly water-insoluble metal salts, and
mixtures thereof.
Suitable water-soluble aluminum salts may include, but are not limited to:
aluminum acetate,
aluminum ammonium sulfate, aluminum chlorate, aluminum chloride, aluminum
chlorohydrate,
aluminum diformate, aluminum fluoride, aluminum formoacetate, aluminum
lactate, aluminum
nitrate, aluminum potassium sulfate, aluminum sodium sulfate, aluminum
sulfate, aluminum
tartrate, aluminum triformate, and mixtures thereof. Suitable water-insoluble
aluminum salts may
include, but are not limited to: aluminum silicates, aluminum salts of fatty
acids (e.g., aluminum
stearate and aluminum laurate), aluminum metaphosphate, aluminum monostearate,
aluminum
oleate, aluminum oxylate, aluminum oxides and hydroxides (e.g., activated
alumina and
aluminum hydroxide gel), aluminum palmitate, aluminum phosphate, aluminum
resinate,
aluminum salicylate, aluminum stearate, and mixtures thereof.
Suitable water-soluble magnesium salts may include, but are not limited to:
magnesium acetate,
magnesium acetylacetonate, magnesium ammonium phosphate, magnesium benzoate,
magnesium biophosphate, magnesium borate, magnesium borocitrate, magnesium
bromate,
magnesium bromide, magnesium calcium chloride, magnesium chlorate, magnesium
chloride,
magnesium citrate, magnesium fluosilicate, magnesium formate, magnesium
gluconate,
magnesium glycerophosphate, magnesium lauryl sulfate, magnesium nitrate,
magnesium
phosphate monobasic, magnesium salicylate, magnesium stannate, magnesium
stannide,
magnesium sulfate, magnesium sulfite, and mixtures thereof. Suitable water-
insoluble
magnesium salts may include, but are not limited to: magnesium aluminate,
magnesium fluoride,
magnesium oleate, magnesium perborate, magnesium phosphate dibasic, magnesium
phosphate
tribasic, magnesium pyrophosphate, magnesium silicate, magnesium trisilicate,
magnesium
sulfide, magnesium tripolyphosphate, and mixtures thereof.
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Suitable water-soluble zinc salts may include, but are not limited to: zinc
acetate, zinc benzoate,
zinc borate, zinc bromate, zinc bromide, zinc chlorate, zinc chloride, zinc
ethysulfate, zinc
fluorosilicate, zinc formate, zinc gluconate, zinc hydrosulfite, zinc lactate,
zinc linoleate, zinc
malate, zinc nitrate, zinc perborate, zinc salicylate, zinc sulfate, zinc
sulfamate, zinc tartrate, and
mixtures thereof. Suitable water-insoluble zinc salts may include, but are not
limited to: zinc
bacitracin, zinc carbonate, zinc basic carbonate or basic zinc carbonate,
hydrozincite, zinc
laurate, zinc phosphate, zinc tripolyphosphate, sodium zinc tripolyphosphate,
zinc silicate, zinc
stearate, zinc sulfide, zinc sulfite, and mixtures thereof.
Any suitable polyvalent metal oxide and/or hydroxide may be used in any
suitable amount or
form. Suitable polyvalent metal oxides may include, but are not limited to:
aluminum oxide,
magnesium oxide, and zinc oxide. Suitable polyvalent metal hydroxides may
include, but are not
limited to: aluminum hydroxide, magnesium hydroxide, and zinc hydroxide.
In certain non-limiting embodiments, polyvalent metal compounds may be used in
their water-
insoluble form. The presence of the polyvalent metal compounds in an
essentially insoluble but
dispersed form may inhibit the growth of large precipitates from within ADW
detergent product
and/or wash liquor solution. Not to be bound by theory, it is believed that
because the water-
insoluble polyvalent metal compound is in a form in product that is
essentially insoluble, the
amount of precipitate, which will form in the wash liquor of the dishwashing
process, is greatly
reduced. Although the insoluble polyvalent metal compound will dissolve only
to a limited
extent in the wash liquor, the dissolved metal ions are in sufficient
concentration to impart the
desired glasscare benefit to treated dishware. Hence, the chemical reaction of
dissolved species
that produce precipitants in the dishwashing process is controlled. Thus, use
of water-insoluble
polyvalent metal compounds allows for control of the release of reactive metal
species in the
wash liquor, as well as, the control of unwanted precipitants.
In certain non-limiting embodiments, the amount of polyvalent metal compound
may be
provided in a range of from about 0.01% to about 60%, from about 0.02% to
about 50%, from
about 0.05% to about 40%, from about 0.05% to about 30%, from about 0.05% to
about 20%,
from about 0.05% to about 10%, and alternatively, from about 0.1% to about 5%,
by weight, of
the ADW composition.
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Enzyme
Enzymes may be included in the ADW compositions. One such enzyme includes a
protease.
Suitable proteases include metalloproteases and serine proteases, including
neutral or alkaline
microbial serine proteases, such as subtilisins (EC 3.4.21.62). Suitable
proteases include those of
animal, vegetable or microbial origin. Another enzyme for use herein includes
alpha-amylases,
including those of bacterial or fungal origin. Chemically or genetically
modified mutants
(variants) are included. Additional enzymes suitable for use in the ADW
composition can
comprise one or more enzymes selected from the group comprising
hemicellulases, cellulases,
cellobiose dehydrogenases, peroxidases, proteases, xylanases, lipases,
phospholipases, esterases,
cutinases, pectinases, mannanases, pectate lyases, keratinases, reductases,
oxidases,
phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases,
pentosanases, malanases,
13-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase,
amylases, and mixtures
thereof.
Drying aids
Preferred drying aids for use herein include polyesters, especially anionic
polyesters formed from
monomers of terephthalic acid, 5-sulfoisophthalic acid, alkyl diols or
polyalkylene glycols, and,
polyalkyleneglycol monoalkylethers. Suitable polyesters to use as drying aids
are disclosed in
WO 2008/110816. Other suitable drying aids include specific polycarbonate-,
polyurethane-
and/or polyurea-polyorganosiloxane compounds or precursor compounds thereof of
the reactive
cyclic carbonate and urea type, as described in WO 2008/119834. Preferably,
the polymeric
drying aids are obtained from bio-derived monomers.
Improved drying can also be achieved by a process involving the delivery of
surfactant and an
anionic polymer as proposed in WO 2009/033830 or by combining a specific non-
ionic
surfactant in combination with a sulfonated polymer as proposed in WO
2009/033972.
Preferably, at least some, more preferably all of such surfactants used as
drying aids are bio-
derived.
Preferably the composition of the invention comprises from 0.1% to 10%, more
preferably from
0.5% to 5% and especially from 1% to 4% by weight of the composition of a
drying aid.
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Natural Essence
In addition to bio-derived anionic and nonionic surfactant components, the
automatic
dishwashing compositions of the present invention include a bio-derived
"natural essence". As
used herein, "natural essence" is intended to include a broader class of
natural products
comprising natural oils extracted from plants and trees and their fruits, nuts
and seeds, (for
example by steam or liquid extraction of ground-up plant/tree material),
natural products that
may be purified by distillation, (i.e., purified single organic molecules or
close boiling point
"cuts" of organic materials such as terpenes and the like), and synthetic
organic materials that are
the synthetic versions of naturally occurring materials (e.g., either
identical to the natural
material, or the optical isomer, or the racemic mixture). Synthetic versions
of naturally occurring
materials preferably are synthesized from bio-derived carbon sources. An
example of the
synthetic essence is D,L-limonene that is synthetically prepared and is a good
and eco-friendly
substitute for natural orange oil (mostly D-limonene) when citrus is
expensive, for example,
because of crop freezes.
Thus, it should be understood that "natural essence" incorporates a wide range
of pure organic
materials either natural or synthetic versions thereof, mixtures of these
previously purified
individual materials or distillate cuts of materials, and complex natural
mixtures directly
extracted from plant/tree materials through infusion, steam extraction, etc.
Also, it should be
understood that these natural essence ingredients may double as fragrance
materials for the ADW
composition, and in fact many natural extracts, oils, essences, infusions and
such are very
fragrant materials. However, for use in the present ADW 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 ADW 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
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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, 13-phenyl ethyl
alcohol, cis-3-
hexenol, terpineol and like alcohols; anethole, musk xylol, isoeugenol, methyl
eugenol and like
phenols; a-amylcinnamic 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 13-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, allyl
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-
-
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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, isobomyl
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 ADW
composition and may help to impart an overall fragrance perception as well to
the composition
including but not limited to, fruity, musk, floral, herbaceous (including
mint), and woody, or
perceptions that are in-between (fruity-floral for example). Typically these
essence or essential
oil mixtures may be compounded by mixing a variety of these active extract or
synthetic
materials along with various solvents to adjust cost, viscosity, flammability,
ease of handling, etc.
Since many natural extract ingredients are compounded into fragrances, the
essential oils,
infusions, distillates, etc. that are considered "natural essences" are also
available from the
fragrance companies such as International Flavors & Fragrances, Givaudan,
Symrise, Firmenich,
Robertet, and many others. The natural essences are preferably incorporated at
a level of from
about 0.1% to about 5% as the 100% neat substance or mixture of substances. It
is important to
note that these levels tend to be greater than those levels used for scenting
a product with a
perfume.
Fragrances
The ADW 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 ADW 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 ADW
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
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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 ADW compositions may further comprise a perfume. In a particularly
preferred
embodiment the ADW compositions comprise different perfumes such that the user
will gain a
different olfactory experience, for example, when the ADW compositions are
contained within
different types of dosing devices such as pouches.
The ADW 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.P.) and its
octanol/water partition
coefficient (P). As used in this context, "boiling point" refers to boiling
point measured under
normal standard pressure of 760 mmHg. The boiling points of many perfume
ingredients, at
standard 760 mm Hg are given in, e.g., "Perfume and Flavor Chemicals (Aroma
Chemicals),"
Steffen Arctander, published by the author, 1969, incorporated herein by
reference.
The octanol/water partition coefficient of a perfume ingredient is the ratio
between its
equilibrium concentrations in octanol and in water. The partition coefficients
of the preferred
perfume ingredients may be more conveniently given in the form of their
logarithm to the base
10, logP. The logP values of many perfume ingredients have been reported; for
example, the
Pomona92 database, available from Daylight Chemical Information Systems, Inc.
(Daylight
CIS), Irvine, Calif., contains many, along with citations to the original
literature. However, the
logP values are most conveniently calculated by the "CLOGP" program, also
available from
Daylight CIS. This program also lists experimental logP values when they are
available in the
Pomona92 database. The "calculated logP" (ClogP) is determined by the fragment
approach of
Hansch and Leo (cf., A. Leo, in Comprehensive Medicinal Chemistry, Vol. 4, C.
Hansch, P. G.
Sammens, J. B. Taylor and C. A. Ramsden, Eds., p. 295, Pergamon Press, 1990,
incorporated
herein by reference). The fragment approach is based on the chemical structure
of each perfume
ingredient, and takes into account the numbers and types of atoms, the atom
connectivity, and
chemical bonding. The ClogP values, which are the most reliable and widely
used estimates for
this physicochemical property, are preferably used instead of the experimental
logP values in the
selection of perfume ingredients which are useful in ADW compositions.
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The perfume, if present in the ADW 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 ADW 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
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 ADW 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 ADW
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
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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
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 ADW 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 ADW
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
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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.
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.
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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
known as D1MEB, 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
ADW 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
etal., 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 ADW composition.
Generally, only a portion (not all) of the fragrance materials mixed with the
cyclodextrin will be
encapsulated by the cyclodextrin and form part of the cyclodextrin/perfume
complex; the
remaining fragrance materials will be free of the cyclodextrin and when the
cyclodextrin/perfume
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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 cyclodextirns and fragrance
materials will come into
the presence of each other in the composition, and a portion of each will
combine to form the
desired fragrance materials/cyclodextrin complex.
In general, perfume/cyclodextrin complexes have a molar ratio of perfume
compound to
cyclodextrin of 1:1. However, the molar ratio can be either higher or lower,
depending on the
size of the perfume compound and the identity of the cyclodextrin compound.
For example, the
the molar ratio of fragrance materials to cyclodextrin may be from 4:1 to 1:4,
preferably from
1.5:1 to 1:2, more preferably from 1:1 to 1:1.5. The molar ratio can be
determined easily by
forming a saturated solution of the cyclodextrin and adding the perfume to
form the complex. In
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.
Natural Thickener
The ADW 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
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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,
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 ADW 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 ADW 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.
Adjuncts
The ADW compositions optionally contain one or more of the following adjuncts:
enzymes such
as protease, amylase, mannanase, and lipase, stain and soil repellants,
lubricants, odor control
agents, perfumes, builders, fragrances and fragrance release agents, reducing
agents such as
sodium sulfite, and bleaching agents. Other adjuncts include, but are not
limited to, acids, pH
adjusting agents, electrolytes, dyes and/or colorants, solubilizing materials,
stabilizers,
thickeners, defoamers, hydrotropes, cloud point modifiers, preservatives, and
other polymers.
Electrolytes, when used, include, calcium, sodium and potassium chloride.
Preferably the
adjuncts are bio-derived. Optional pH adjusting agents include inorganic acids
and bases such as
sodium hydroxide, and organic agents such as monoethanolamine, diethanolamine,
and
triethanolamine, preferably bio-derived. Thickeners, when used, include, but
are not limited to,
polyacrylic acid, xanthan gum, calcium carbonate, aluminum oxide, alginates,
guar gum, methyl,
ethyl, clays, and/or propyl hydroxycelluloses, preferably bio-derived.
Defoamers, when used,
include, but are not limited to, silicones, aminosilicones, silicone blends,
and/or
silicone/hydrocarbon blends, all preferably bio-derived. Bleaching agents,
when used, include,
but are not limited to, peracids, hypohalite sources, hydrogen peroxide,
and/or sources of
hydrogen peroxide. In a preferred embodiment, the ADW composition includes a
builder such as
ethylenediamine disuccinate. In a suitable embodiment the compositions contain
an effective
amount of one or more of the following bio-derived enzymes: protease, lipase,
amylase,
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cellulase, and mixtures thereof. Suitable enzymes are available from
manufacturers including,
but not limited to, Novozymese and Genencor .
Any suitable adjunct ingredient in any suitable amount may be used in the ADW
detergent
composition. Suitable adjunct ingredients as described herein may be
substantially sodium ion-
free. Suitable adjunct ingredients may include, but are not limited to: co-
surfactants; suds
suppressors; builders; enzymes; bleaching systems; dispersant polymers;
carrier media;
thickeners and mixtures thereof.
Other suitable adjunct ingredients may include, but are not limited to: enzyme
stabilizers, such as
calcium ion, boric acid, bio-derived propylene glycol, bio-derived short-chain
carboxylic acids,
boronic acids, and mixtures thereof; chelating agents, such as, alkali metal
bio-derived ethane 1-
hydroxy diphosphonates (HEDP), bio-derived alkylene poly (alkylene
phosphonate), as well as,
amino phosphonate compounds, including amino aminotri(methylene phosphonic
acid) (ATMP),
bio-derived nitrilo trimethylene phosphonates (NTP), bio-derived ethylene
diamine tetra
methylene phosphonates, and bio-derived diethylene triamine penta methylene
phosphonates
(DTPMP); alkalinity sources; water softening agents; secondary solubility
modifiers; soil release
polymers; hydrotropes; binders; antibacterial actives, such as bio-derived
citric acid, bio-derived
benzoic acid, bio-derived benzophenone, bio-derived thymol, bio-derived
eugenol, bio-derived
menthol, bio-derived geraniol, bio-derived vertenone, bio-derived eucalyptol,
bio-derived
pinocarvone, bio-derived cedrol, bio-derived anethol, bio-derived carvacrol,
bio-derived
hinokitiol, bio-derived berberine, bio-derived ferulic acid, bio-derived
cinnamic acid, bio-derived
methyl salicylic acid, bio-derived methyl salicylate, bio-derived terpineol,
bio-derived limonene,
and halide-containing compounds; detergent fillers, such as potassium sulfate;
abrasives, such as,
quartz, pumice, pumicite, titanium dioxide, silica sand, 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
bio-derived dyes, bio-derived colorants, bio-derived pigments, bio-derived
speckles, bio-derived
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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.
Silicates
Preferred silicates are sodium silicates such as sodium disilicate, sodium
metasilicate and
crystalline phyllosilicates. Silicates, if present in the ADW composition, are
at a level of from
about 1% to about 20%, preferably from about 5% to about 15% by weight of the
ADW
composition.
Bleach
Inorganic and organic bleaches are suitable cleaning actives for use in the
ADW compositions.
Inorganic bleaches include perhydrate salts such as perborate, percarbonate,
perphosphate,
persulfate and persilicate salts. The inorganic perhydrate salts are normally
the alkali metal salts.
The inorganic perhydrate salt may be included as the crystalline solid without
additional
protection. Alternatively, the salt can be coated.
Alkali metal percarbonates, particularly sodium percarbonate are preferred
perhydrates for use in
the ADW compositions. The percarbonate is most preferably incorporated into
the products in a
coated form which provides in-product stability.
Potassium peroxymonopersulfate is another inorganic perhydrate salt of utility
herein.
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Typical organic bleaches are organic peroxyacids including diacyl and
tetraacylperoxides,
especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid, and
diperoxyhexadecanedioc acid. Dibenzoyl peroxide is a preferred organic
peroxyacid herein.
Mono- and diperazelaic acid, mono- and diperbrassylic acid, and
naphthaloylaminoperoxicaproic
acid are also suitable herein. Preferably, the organic portions of the
bleaches contain bio-derived
carbon obtained from natural sources.
Further typical organic bleaches include the peroxy acids, particular examples
being the
alkylperoxy acids and the arylperoxy acids. Preferred representatives are (a)
bio-derived
peroxybenzoic acid and its ring-substituted derivatives, such as bio-derived
alkylperoxybenzoic
acids, but also bio-derived peroxy-a-naphthoic acid and bio-derived magnesium
monoperphthalate, (b) the aliphatic or substituted aliphatic peroxy acids,
such as bio-derived
peroxylaufic acid, bio-derived peroxystearic acid, bio-derived e-
phthalimidoperoxycaproic acid,
bio-derived phthaloiminoperoxyhexanoic acid (PAP), bio-derived o-
carboxybenzamidoperoxycaproic acid, bio-derived N-nonenylamidoperadipic acid
and bio-
derived N-nonenylamidopersuccinates, and (c) bio-derived aliphatic and bio-
derived araliphatic
peroxydicarboxylic acids, such as bio-derived 1,12-diperoxycarboxylic acid,
bio-derived 1,9-
diperoxyazelaic acid, bio-derived diperoxysebacic acid, bio-derived
diperoxybrassylic acid, the
bio-derived diperoxyphthalic acids, bio-derived 2-decyldiperoxybutane-1,4-
dioic acid, bio-
derived N,N-terephthaloyldi(6-aminopercaproic acid).
Any suitable oxygen bleach may be used herein. Suitable oxygen bleaches can be
any
convenient conventional oxygen bleach, including hydrogen peroxide. For
example, perborate,
e.g., sodium perborate (any hydrate, e.g. mono- or tetra-hydrate), potassium
perborate, sodium
percarbonate, potassium percarbonate, sodium peroxyhydrate, potassium
peroxyhydrate, sodium
pyrophosphate peroxyhydrate, potassium pyrophosphate peroxyhydrate, sodium
peroxide,
potassium peroxide, or urea peroxyhydrate can be used herein. Organic peroxy
compounds can
also be used as oxygen bleaches. Examples of these are benzoyl peroxide and
the diacyl
peroxides. Mixtures of any convenient oxygen bleaching sources can also be
used.
Any suitable halogenated bleach may be used herein. Suitable halogenated
bleaches may include
chlorine bleaches. Suitable chlorine bleaches can be any convenient
conventional chlorine
bleach. Such compounds are often divided in to two categories namely,
inorganic chlorine
bleaches and organic chlorine bleaches. Examples of the former are sodium
hypochlorite,
calcium hypochlorite, potassium hypochlorite, magnesium hypochlorite and
chlorinated
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trisodium phosphate dodecahydrate. Examples of the latter are potassium
dichloroisocyanurate,
sodium dichloroisocyanurate, 1,3-dichloro-5,5-dimethlhydantoin, N-
chlorosulfamide, chloramine
1', dichloramine T, chloramine B, dichloramine T, N,N1-dichlorobenzoylene
urea, paratoluene
sulfondichoroamide, trichloromethylamine, N-chlorosuccinimide, N,N'-
dichloroazodicarbonamide, N-chloroacetyl urea, N,N'-dichlorobiuret and
chlorinated
dicyandamide.
Bleach activators
Bleach activators or precursors are organic compounds comprising at least one
acyl moiety and at
least one leaving group, typically having the structure RC(0)L, the function
of which is to
transfer an acyl group to the hydroperoxide anion HOO¨ which is formed by
hydrogen peroxide
under alkaline conditions. In this process the activator undergoes
perhydrolysis so as to form an
organic peracid (acyl hydroperoxide) that is a better oxidant than is hydrogen
peroxide itself.
Bleach activators enhance the bleaching action in the course of cleaning at
temperatures of 60 C
and below. Bleach activators suitable for use herein include compounds which,
under
perhydrolysis conditions, give aliphatic peroxoycarboxylic acids having from 1
to 14 carbon
atoms, preferably from 2 to 12 carbon atoms, and precursors of aromatic
peracids such as
optionally substituted perbenzoic acid can also be used. Suitable substances
bear 0-acyl and/or
N-acyl groups of the number of carbon atoms specified and/or optionally
substituted benzoyl
groups. Preference is given to polyacylated alkylenediatnines, in particular
tetraacetylethylenediamine (TAED) which is a peracetic acid precursor,
acylated triazine
derivatives, in particular 1,5-diacety1-2,4-dioxohexahydro-1,3,5-triazine
(DADHT), acylated
glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in
particular N-
nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-
nonanoyl- or
isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in
particular phthalic
anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene
glycol diacetate and 2,5-
diacetoxy-2,5-dihydrofuran and also triethylacetyl citrate (TEAC), and
pentaacetyl glucose
(PAG). Bleach activators useful herein also include precursors of cationically
charged
peroxyacids, sodium acetoxybenzene sulfonate, amide-substituted alkyl
peroxyacid precursors
(EP-A-0170386); benzoxazin peroxyacid precursors (EP 332294 and E 482807); and
acyl lactam
bleach activators as disclosed in U.S. 4,915,854; 4,412,934; 4,634,551;
4,634,551; and
4,966,723.
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Bleach activators if included in the compositions of the invention are in a
level of from about 0.1
to about 25%, preferably from about 0.5% to about 10% by weight of the total
composition.
Preferably, any or all of the bleach activators are bio-derived.
Bleach Catalyst
Compositions of the invention include embodiments which comprise a transition
metal
catalyst or "bleach catalyst". Such catalysts may be encapsulated or non-
encapsulated. The
bleach catalyst typically comprises a transition metal ion and a ligand,
preferably a
macropolycyclic ligand, more preferably a cross-bridged macropolycyclic
ligand. The transition
metal ion is preferably coordinated with the ligand.
Bleach catalysts preferred for use herein include Mn-Me TACN, as described in
EP 458
397 A; Co, Cu, Mn and Fe bispyridylamine and related complexes as described in
US 5,114,611;
and pentamine acetate cobalt (III) and related complexes as described in U.S.
4,810,410; U.S.
5,597,936, and U.S. 5,595,967. Further description of bleach catalysts
suitable for use herein can
be found in WO 99/06521, page 34, line 26 to page 40, line 16 and, in certain
highly preferred
embodiments, Mn complexes of cross-bridged macrocyclic donor ligands as
disclosed in U.S.
6,218,351. The bleach catalyst may be present in encapsulated form.
Simple transition metal salts lacking polydentate donor ligands can also be
useful as
bleach catalysts. For example, bleach catalysts can be manganese compounds
having varying
oxidation state and/or hydration degree, such as Mn(II)acetate tetrahydrate or
Mn(II) sulfate
monohydrate. It may be advantageous that this catalyst compound be mixed with
a water-
insoluble support matrix as described in W02010/133837A1 and WO 2010/139689A1.
A
preferred support matrix comprises organic polymer such as polyvinyl alcohol
(PVA).
Suitable bleach catalyst levels are from about 0.0001% to about 1%, more
typically from
about 0.001% to about 0.1% by weight of the total composition.
Metal care agents
Metal care agents may prevent or reduce the tarnishing, corrosion or oxidation
of metals,
including aluminum, stainless steel and non-ferrous metals, such as silver and
copper. Preferably
the composition of the invention comprises from 0.1% to 5%, more preferably
from 0.2% to 4%
and specially from 0.3% to 3% by weight of the composition of a metal care
agent, preferably the
metal care agent is a zinc salt.
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Solvent
The ADW 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 ADW
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 ADW compositions may also be substantially devoid of
solvents and may
include solvent-free surfactants such as Berol CLF by AkzoNobel. The ADW
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 be free of the following
alkanols: n-
propanol, isopropanol, butanol, pentanol, and hexanol, and isomers thereof.
The compositions
may be free of the following diols: methylene glycol, ethylene glycol, and
butylene glycols. The
compositions may be free of the following alkylene glycol ethers which
include, but are not
limited to, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether,
ethylene glycol
monohexyl ether, diethylene glycol monopropyl ether, diethylene glycol
monobutyl ether,
diethylene glycol monohexyl ether, propylene glycol methyl ether, propylene
glycol ethyl ether,
propylene glycol n-propyl ether, propylene glycol monobutyl ether, propylene
glycol t-butyl
ether, di- or tri-polypropylene glycol methyl or ethyl or propyl or butyl
ether, acetate and
propionate esters of glycol ethers. The compositions may be free of the
following short chain
esters which include, but are not limited to, glycol acetate, and cyclic or
linear volatile
methylsiloxanes. The composition may be free of alkyl glycol ethers, alcohol
alkoxylates, alkyl
monoglycerolether sulfate, or alkyl ether sulfates.
_ _
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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
resources.
The renewably 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-
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-
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-
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
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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 ADW compositions. See for
example, US
4,536,584.
Bio-derived ethers, including bio-derived polyethers, can be produced from
biomass or via the
condensation of bio-derived alcohols with bio-derived ketones and bio-derived
aldehydes
according to known ether forming reaction processes. Examples include, bio-
derived
diethoxymethane and bio-derived tetrahydrofuran. See for example, US
4,536,584. Other
methods to produce bio-derived polyethers can include the polymerization of
bio-derived
ethylene oxide. Bio-derived ethylene oxide can be produced from the
epoxidation of bio-derived
ethylene. Bio-derived low molecular-weight polyethers, especially bio-derived
alkyl capped-
polyethers, may be used as solvents in the ADW 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.
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Process of Manufacture
Any suitable conventional manufacturing process having any number of suitable
process steps
may be used to manufacture the ADW composition, disclosed herein, in any
suitable form as
described herein.
The ADW compositions described herein can also be suitably prepared and
packaged by any
suitable process chosen by the formulator, non-limiting examples of which may
be described in
U.S. Pat. No. 4,005,024 issued Jan. 25, 1977; U.S. Pat. No. 4,237,155 issued
Dec. 2, 1980; U.S.
Pat. No. 5,378,409 issued Jan. 3, 1995; U.S. Pat. No. 5,486,303 issued Jan.
23, 1996; U.S. Pat.
No. 5,489,392 issued Feb. 6, 1996; U.S. Pat. No. 5,516,448 issued May 14,
1996; U.S. Pat. No.
5,565,422 issued Oct. 15, 1996; U.S. Pat. No. 5,569,645 issued Oct. 29, 1996;
U.S. Pat. No.
5,574,005 issued Nov. 12, 1996; U.S. Pat. No. 5,599,400 issued Feb. 4, 1997;
U.S. Pat. No.
5,599,786 issued Feb. 4, 1997; U.S. Pat. No. 5,691,297 issued Nov. 11, 1997;
U.S. Pat. No.
5,698,505 issued Dec. 16, 1997; U.S. Pat. No. 5,703,034 issued Dec. 30, 1997;
U.S. Pat. No.
5,768,918 issued Jun. 23, 1998; U.S. Pat. No. 5,891,836 issued Apr. 6, 1999;
U.S. Pat. No.
5,952,278 issued Sep. 14, 1999; U.S. Pat. No. 5,952,278 issued Sep. 14, 1999;
U.S. Pat. No.
5,968,539 issued Oct. 19, 1999; U.S. Pat. No. 5,990,065 issued Nov. 23, 1999;
U.S. Pat. No.
6,069,122 issued May 30, 2000; U.S. Pat. No. 6,147,037 issued Nov. 14, 2000;
U.S. Pat. No.
6,156,710 issued Dec. 5, 2000; U.S. Pat. No. 6,162,778 issued Dec. 19, 2000;
U.S. Pat. No.
6,180,583 issued Jan. 30, 2001; U.S. Pat. No. 6,183,757 issued Feb. 6, 2001;
U.S. Pat. No.
6,190,675 issued Feb. 20, 2001; U.S. Pat. No. 6,204,234 issued Mar. 20, 2001;
U.S. Pat. No.
6,214,363 issued Apr. 10, 2001; U.S. Pat. No. 6,251,845 issued Jun. 26, 2001;
U.S. Pat. No.
6,274,539 issued Aug. 14, 2001; U.S. Pat. No. 6,281,181 issued Aug. 28, 2001;
U.S. Pat. No.
6,365,561 issued Apr. 2, 2002; U.S. Pat. No. 6,372,708 issued Apr. 16, 2002;
U.S. Pat. No.
6,444,629 issued Sep. 3, 2002; U.S. Pat. No. 6,451,333 issued Sep. 17, 2002;
U.S. Pat. No.
6,482,994 issued Nov. 19, 2002; U.S. Pat. No. 6,528,477 issued Mar. 4, 2003;
U.S. Pat. No.
6,559,116 issued May 6, 2003; U.S. Pat. No. 6,573,234 issued Jun. 3, 2003;
U.S. Pat. No.
6,589,926 issued Jul. 8, 2003; U.S. Pat. No. 6,627,590 issued Sep. 30, 2003;
U.S. Pat. No.
6,627,590 issued Sep. 30, 2003; U.S. Pat. No. 6,630,440 issued Oct. 7, 2003;
U.S. Pat. No.
6,645,925 issued Nov. 11, 2003; and U.S. Pat. No. 6,656,900 issued Dec. 2,
2003; U.S. patent
application Nos. 20030228998 to Dupont published Dec. 2003; US20010026792 to
Farrell et al.
published October 2001; 20010031714 to Gassenmeier et al. published October
2001;
20020004472 to Holderbaum et al. published January 2002; 20020004473 to Busch
et al.
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published January 2002; 20020013232 to Kinoshita et al. published January
2002; 20020013242
to Bailiely et al. published January 2002; 20020013243 to Brown published
March 2002;
20020028756 to Carter et al. published March 2002; 20020033004 to Edwards et
al. published
March 2002; 20020045559 to Forth et al. published April 2002; 20020055449 to
Porta et al.
published May 2002; 20020094942 to Danneels et al. published July 2002;
20020119903 to Lant
et al. published August 2002; 20020123443 to Bennie et al. published September
2002;
20020123444 to Fisher et al. published September 2002; 20020137648 to Sharma
et al. published
September 2002; 20020166779 to Etesse et al. published November 2002;
20020169092 to
Catlin et al. published November 2002; 20020169095 to Forth et al. November
2002;
20020198125 to Jones published December 2002; and U.S. Pat. No. 7,125,828.
Bio-derived Sustainable Packaging Materials
The ADW composition may be provided to the consumer in the form of a unit dose
pouch, and
many unit dose pouches may be packaged within a secondary packaging. Water-
soluble liquid-
encapsulated unit dose pouches are generally known in the art, and a suitable
for delivery of the
present ADW compositions. Examples of such unit dose pouches include capsules,
tablets,
multi-phase tablets, coated tablets, single-compartment water-soluble pouches,
multi-
compartment water-soluble pouches, and combinations thereof; and the ADW
composition may
be in at least one or more of the following forms: liquids, liquigels, gels,
foams, creams, and
pastes.
Unit Dose Pouches
The term "unit dose" herein refer to a dose of detergent product incorporating
one or more ADW
compositions and sufficient for a single wash cycle. Suitable unit dose forms
include capsules,
sachets and pouches which can have single or multiple compartments. Suitable
unit dose forms
for use herein include water-soluble, water-dispersible and water-permeable
capsules, sachets
and pouches. Preferred for use herein are water soluble pouches, based on
partially hydrolysed
polyvinyl alcohol as pouch material. ADW compositions incorporated therein can
be in liquid,
gel, paste or pouch form, but preferably composition in liquid gel or paste
form are substantially
anhydrous for reasons of pouch stability. Most preferably, the materials
composing the unit-dose
pouch are made from bio-derived sources of carbon.
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Unitized doses having multi-compartments can comprise at least one compartment
containing a
powder composition. This powder composition includes solid forms of one or
more of the ADW
compositions described herein and comprise ingredients described above, such
as builders,
alkalinity sources, bleaches, etc., any or all of which preferably are bio-
derived. Especially
useful are multi-compartment unit dose forms comprising different compartments
for solid
and/or for liquid compositions. In one embodiment, the unit dose is injection
molded. See e.g.,
US 2007/0157572 Al; US 2006/0207223 Al; US 2006/0016714 Al. The liquid
compositions
comprise liquid forms of the ADW compositions described herein and include
ingredients such
as non-ionic surfactants or the organic solvents described above, any or all
of which preferably
are bio-derived. Especially useful liquids for use in the case of multi-
compartment unit dose
forms comprising a powder compartment and a liquid compartment are liquids
with hygroscopic
and hydrophilic properties because they are capable to act as a moisture sink
and reduce moisture
pick-up by the powder compartment.
Examples of polymers, copolymers, or derivatives thereof suitable for use as
pouch material are
selected from polyvinyl alcohols, polyvinyl pyrrolidone, polyalkylene oxides,
acrylamide, acrylic
acid, cellulose, cellulose ethers, cellulose esters, cellulose amides,
polyvinyl acetates,
polycarboxylic acids and salts, polyaminoacids or peptides, polyamides,
polyacrylamide,
copolymers of maleic/acrylic acids, polysaccharides including starch and
gelatine, natural gums
such as xanthum and carragum. More preferred polymers are selected from
polyacrylates and
water-soluble acrylate copolymers, methylcellulose, carboxymethylcellulose
sodium, dextrin,
ethylcellulose, hydroxyethyl cellulose, hydroxypropyl methylcellulose,
maltodextrin,
polymethacrylates, and most preferably selected from polyvinyl alcohols,
polyvinyl alcohol
copolymers and hydroxypropyl methyl cellulose (HPMC), and combinations
thereof. Preferably,
the level of polymer in the pouch material, for example a PVA polymer, is at
least 60%.
Preferably the pouch material comprises at least 50%, at least 75%, at least
90%, at least 95%, at
least 99%, or even 100% polymers, copolymers, or derivatives thereof that are
obtained from
bio-derived sources of carbon.
The preferably bio-derived polymer can have any weight-average molecular
weight, preferably
from about 1000 to 1,000,000, more preferably from about 10,000 to 300,000 yet
more
preferably from about 20,000 to 150,000.
Mixtures of polymers, preferably all bio-derived polymers, can also be used as
the pouch
material. This can be beneficial to control the mechanical and/or dissolution
properties of the
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compartments or pouch, depending on the application thereof and the required
needs. Suitable
mixtures include for example mixtures wherein one polymer has a higher water-
solubility than
another polymer, and/or one polymer has a higher mechanical strength than
another polymer.
Also suitable are mixtures of polymers having different weight-average
molecular weights, for
example a mixture of bio-derived polyvinyl alcohol (PVA) or a copolymer
thereof of a weight-
average molecular weight of about 10,000-40,000, preferably around 20,000, and
of bio-derived
PVA or copolymer thereof, with a weight-average molecular weight of about
100,000 to
300,000, preferably around 150,000.
Also useful are polymer blend compositions, for example comprising
hydrolytically degradable
and water-soluble polymer blend such as bio-derived polylactide and bio-
derived polyvinyl
alcohol, achieved by the mixing of bio-derived polylactide and bio-derived
polyvinyl alcohol,
typically comprising 1% to 35% by weight bio-derived polylactide and
approximately from 65%
to 99% by weight bio-derived polyvinyl alcohol, if the material is to be water-
dispersible, or
water-soluble. It may be preferred that the PVA present in the film is from 60
to 98%
hydrolysed, preferably 80% to 90%, to improve the dissolution of the material.
Most preferred are films, which are water-soluble and stretchable films, as
described above.
Highly preferred water-soluble films are films which comprise bio-derived PVA
polymers and
that have similar properties to the film known under the trade reference
M8630, as sold by Chris-
Craft Industrial Products of Gary, Ind., US and also PT-75, as sold by Aicello
of Japan.
The water-soluble film herein may comprise other additive ingredients than the
polymer or
polymer material. For example, it may be beneficial to add plasticizers, for
example glycerol,
ethylene glycol, diethylene glycol, propylene glycol, sorbitol, and mixtures
thereof, or also
additional water or disintegrating aids. When present, the plasticizers
preferably are bio-derived,
such as bio-derived glycerol, bio-derived ethylene glycol, bio-derived
diethylene glycol, bio-
derived propylene glycol, bio-derived sorbitol, and mixtures thereof, for
example. It may be
useful that the pouch or water-soluble film itself comprises a detergent
additive to be delivered to
the wash water, for example organic polymeric soil release agents,
dispersants, dye transfer
inhibitors.
Preferably, the multi-compartment pouches formed according to any of the
processes described
herein comprise a plurality of compartments containing a powder composition
and a plurality of
compartments containing a liquid, gel, or paste composition. It will be
understood moreover that
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by the use of appropriate feed stations, it is possible to manufacture multi-
compartment pouches
incorporating a number of different or distinctive powder compositions and/or
different or
distinctive liquid, gel or paste compositions. This can be especially valuable
for manufacturing
unit dose forms displaying novel visual and/or other sensorial effects.
pouring, dissolving and dosing of a material to be delivered to a substrate.
For example, water
soluble pouches comprising water soluble film(s) are commonly used to package
household care
compositions (e.g., laundry detergent, dish detergent, or hard surface
cleaner) or personal care
compositions (e.g., soap or shampoo). A consumer can directly add the pouch to
a mixing
15 applications.
Water soluble pouches may comprise at least one sealed compartment containing
at least one
composition. It follows that water soluble pouches may comprise a single
compartment or
multiple compartments. In embodiments comprising multiple compartments, each
compartment
may contain identical and/or different compositions. Utilizing a pouch
comprising multiple
25 Company).
The compartments of multi-compartment pouches may be of the same or different
size(s) and/or
volume(s). The compartments of the present multi-compartment pouches can be
separate or
conjoined in any suitable manner. Moreover, the pouches and/or packets of the
present
disclosure may comprise one or more different films.
single compartment pouches may be made using vertical form filling, horizontal
form filling, or
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rotary drum filling techniques commonly known in the art. Such processes may
be either
continuous or intermittent. The film may be dampened, and/or heated to
increase the malleability
thereof. The method may instead or additionally involve the use of a vacuum to
draw the film
into a suitable mold.
It is preferred that the film used herein comprises material which is both
water-soluble and bio-
derived. Preferred bio-derived and water-soluble films are bio-derived
polymeric materials,
preferably bio-derived polymers which are formed into a film or sheet. The
material in the form
of a film can for example be obtained by casting, blow-molding, extrusion or
blow extrusion of
the polymer material, as known in the art. Preferred water-dispersible
material herein has a
dispersability of at least 50%, preferably at least 75% or even at least 95%,
as measured by the
method set out hereinafter using a glass-filter with a maximum pore size of 50
gm. More
preferably the material is water-soluble and has a solubility of at least 50%,
preferably at least
'75% or even at least 95%, as measured by the method set out hereinafter using
a glass-filter with
a maximum pore size of 50 microns, namely: Gravimetric method for determining
water-
solubility or water-dispersability of the material of the compartment and/or
pouch: 5 grams 0.1
gram of material is added in a 400-mL beaker, whereof the weight has been
determined, and 245
mL 1 mL of distilled water is added. This is stirred vigorously on magnetic
stirrer set at 600
rpm, for 30 minutes. Then, the mixture is filtered through a folded
qualitative sintered-glass
filter with the maximum pore sizes of 50 gm. The water is dried off from the
collected filtrate by
any conventional method, and the weight of the remaining polymer is determined
(which is the
dissolved or dispersed fraction). Then, the percentage solubility or
dispersability can be
calculated.
The bio-derived polymer can have any weight average molecular weight,
preferably from about
1000 to 1,000,000, or even from 10,000 to 300,000 or even from 15,000 to
200,000 or even from
20,000 to 150,000.
The unit-dose pouches may further comprise graphics or indicia printed
thereon, preferably with
bio-derived inks. The graphics or indicia may be any symbol or shape that can
be printed onto
the surface of a water soluble material. In some embodiments, the graphic or
indicia indicates
the origin of the unit dose product; the manufacturer of the unit dose
product; an advertising,
sponsorship or affiliation image; a trademark or brand name; a safety
indication; a product use or
function indication; a sporting image; a geographical indication; an industry
standard; preferred
orientation indication; an image linked to a perfume or fragrance; a charity
or charitable
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indication; an indication of seasonal, national, regional or religious
celebration, in particular
spring, summer, autumn, winter, Christmas, New Years; or any combination
thereof. Further
examples include random patterns of any type including lines, circles,
squares, stars, moons,
flowers, animals, snowflakes, leaves, feathers, sea shells and Easter eggs,
amongst other possible
designs.
Preferred methods for printing on the above-mentioned water soluble material
include but are not
limited to those described in US 5,666,785 and WO 06/124484. Printing is
usually done with
inks and dyes and used to impart patterns and colors onto a water-soluble
material. Any kind of
printing can be used, including rotogravure, lithography, flexography, porous
and screen printing,
inkjet printing, letterpress, tampography and combinations thereof. Preferred
for use herein is
flexography printing. Flexography is a printing technology which uses flexible
raised rubber or
photopolymer plates to carry the printing solution to a given substrate.
Secondary Packaging
The unit-dose pouches may be packaged within a secondary packaging such as a
display pack
comprising an outer package such as a see-through container, for example a
transparent or
translucent carton or bottle which contains a plurality of water-soluble
pouches or other unit
doses of detergent product in a multiplicity of visually or otherwise
sensorially distinctive
groups. By visually distinctive herein is meant that the groups can be
distinguished in terms of
shape, color, size, pattern, ornament, etc. Otherwise the groups are
distinctive in terms of
providing a unique sensorial signal such as smell, sound, feel, etc.
For example, the secondary packaging may comprise a see-through, preferably
transparent,
dishwashing detergent pack wherein the number of distinctive groups of pouches
or other unit
doses is at least 2, preferably at least 3, more preferably at least 4, and
especially at least 6, and
wherein the number of unit doses per pack is at least 10, preferably at least
16, and more
preferably at least 20. Preferably the unit doses are multi-compartment
pouches, each
compartment itself possibly being visually or otherwise distinctive from the
remainder of the
compartments in an individual pouch. In a preferred embodiment, groups of
pouches are
distinctive in terms of color. In the case of multi-compartment pouches at
least one group of
pouches has one compartment which is visually distinctive, for example in
terms of color, from
the corresponding compartment in one or more other groups of pouches.
Preferably in such
embodiments, all pouch groups have at least one 'common' compartment, i.e. the
appearance of
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which is the same from group to group. Preferably the visually distinctive
compartment contains
a liquid, gel or paste; the common compartment contains a powder or tablet.
The pouches can be arranged in any form in the pack, either randomly or
following an order, for
example suitable arrangements including layers wherein each pouch comprises at
least one
compartment of a different color to any of the compartments of the remainder
of the pouches on
the same layer. The pack can be made of plastic or any other suitable
material, provided the
material is strong enough to protect the pouches during transport. Preferably,
the plastic or other
suitable material comprises at least 50%, at least 75%, at least 90%, at least
95%, at least 99%, or
even 100% bio-derived material. This kind of pack is also very useful because
the user does not
need to open the pack to see how many pouches there are left, the different
colour pouches are
very easy to identify from the exterior. Alternatively, the pack can have non-
see-through outer
packaging, perhaps with indicia or artwork representing the visually-
distinctive contents of the
pack.
In another embodiment, distinctive groups of pouches may contain different
perfumes. The
perfumes can be color-associated perfumes, for example, yellow with lemon
smell, pink with
strawberry smell, blue with sea smell, etc. The processes described herein for
making multi-
compartment pouches can be adapted to form a plurality of pouches in a
multiplicity of
sensorially distinctive groups as described above, whereby each of a
multiplicity of
compartmental groups is filled with a corresponding sensorially-distinctive
composition. This
simplifies the manufacture of the display pack of the invention.
In further embodiments, when multiple unit dose products are stored in a
container or containers
through at least a portion of which the unit dose products contained therein
may be seen,
preferably as images on the printed material. Preferably the optional image is
linked
conceptually to graphic on the portions of the container through which the
unit dose products
may not be seen through. For example, the printed image may be of a lemon the
graphic on the
outside of the container may include images of lemons and/or a written
reference to the lemon or
citrus themes. This provides a strong and reinforced message to the consumer
about the benefits
of using the product.
The printed images preferably are formed with bio-derived inks. The inks can
be solvent-based
or water-based. In some embodiments, the ink is derived from a renewable
resource, such as soy,
a plant, or a mixture thereof The ink can be cured using heat or ultraviolet
radiation (UV). In
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some preferred embodiments, the ink is cured by UV, which results in a
reduction of curing time
and energy output. Nonlimiting examples of bio-derived inks include ECOSURE!TM
from Gans
Ink & Supply Co. and the solvent-based VUTEk and Bi0VuTM inks from EFI, all
of which are
derived completely from renewable resources (e.g., corn).
In further embodiment, when multiple unit dose products are stored in a
container or containers
through at least a portion of which the unit dose products within said
container may be seen,
preferably a plurality different multi-compartment pouches comprising the
printed images. In
one embodiment the shape of the portion of the container or "window" is in a
shape related to the
printed image.
The secondary packaging or containers preferably are made from bio-derived
and/or
biodegradable products such as from bio-derived paper or bio-derived plastic,
and from
biodegradable or bioplastic resins. Bioplastic resins may include bio-derived
polyhydroxyalkanoate (PHA), bio-derived poly 3-hydroxybutrate-co-3-
hydroxyhexanote
(PHBH), bio-derived polyhydroxybutyrate-co -valerate (PHBN), bio-derived poly-
3-
hydroxybutyrate (NAB), chemical synthetic polymer such as bio-derived
polybutylene succinate
(PBS), bio-derived polybutylene succinate adipate (PBSA), bio-derived
polybutylene succinate
carbonate, bio-derived polycaprolactone (PCL), bio-derived cellulose acetate
(PH), bio-derived
polylactic acid/chemical synthetic polymer such as bio-derived polylactic
polymer (PLA) or bio-
derived copoly-L-lactide (CPLA), and naturally occurring polymer, such as
starch modified
PVA+aliphatic polyester, or corn starch.
Polylactic acid (PLA) is a transparent bioplastic produced from corn, beet and
cane sugar. It not
only resembles conventional petrochemical mass plastics, such as polyethelene
(PE),
polyethylene terephthalate (PET or PETE), high density polyethylene (HDPE) and
polypropene
(PP) in its characteristics, but it can also be processed easily on standard
equipment that already
exists for the production of conventional plastics. PLA and PLA-blends
generally come in the
form of PA010-103 granulates with various properties and are used in the
plastic processing
industry for the production of foil, molds, cups, bottles and other packaging.
The bio-derived polymer poly-3-hydroxybutyrate (1311B) is polyester produced
by certain bacteria
processing glucose or starch. Its characteristics are similar to those of the
petro plastic
polypropylene. The South American sugar industry, for example, has decided to
expand PHB
production to an industrial scale. PHB is distinguished primarily by its
physical characteristics.
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It produces transparent film at a melting point higher than 130 C, and is
biodegradable without
residue.
Biodegradable resins may be made into products that are relatively rigid with
good transparency,
and thus use of these resins may be appropriate for rigid molded products,
such as the secondary
packaging described above.
The bio-derived plastic material may include a single, composite layer of
bioplastic resin mixed
with plasticizer. This material may be provided as a resin, which can be
formed into the desired
shape. Here, the plasticizer and resin cooperate to form a bio-derived plastic
material that may
be generally impermeable to fluids. The bioplastic resin may, for example, be
PLA, PHA, P1-113,
PHBH, PBS, PBSA, PCL, PH, CPLA or PVA. The plasticizer may be a silicone such
as, but not
limited to, polydimethyl siloxane with filler and auxiliary agents,
alkylsilicone resin with alkoxy
groups with filler and auxiliary agents and isooctyltrimethoxysilane or
silicone oxide, and
silicone dioxide. The bioplastic resin and silicone may be mixed to form a new
resin. This resin
may have been shown to have improved barrier properties, resulting in
permeability rates to less
than or equal to from 0.5 to 3 units for water vapor, oxygen from 75 to 1400
units, and carbon
dioxide from 200 to1800 units, measured; at g-mil/100 square inch per day for
water at 100%
RH, and cc-mill/100 sq inch day atm at 20 C and 0% RH for at 100% oxygen and
carbon
dioxide.
Additionally, bio-derived paper and bio-derived plastic resins (namely, for
example, PLA, PHA,
PHB, PHBH, PBS, PBSA, PCL, PH, CPLA and PVA) may be coated with ultraviolet
curable
acrylates, preferably bio-derived acrylates, to form a bio degradable
container. Some of these
ultraviolet curable acrylates are suitable for storing consumable materials
and are Food and Drug
Administration (FDA) approved, namely tripropylene glycol diacrylate,
trimethylolpropane
triacrylate, and bisphenol A diglycidal ether diacrylate. Other ultraviolet
cured materials might
not be FDA approved, but could still be used to coat a biodegradable
container.
Consumer Message
The unit-dose pouches, the secondary pacakging, or a combination thereof, may
further comprise
a related environmental message that communicates a related environmental
message to a
consumer. The related environmental message may convey the benefits or
advantages of the
ADW composition contained in the unit-dose pouch and/or secondary packaging,
particularly
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that the ADW composition, the packaging, or both, comprise or consist of a
polymer derived
from a renewable resource. The related environmental message may identify the
ADW
composition and its packaging as: being environmentally friendly or Earth
friendly; having
reduced petroleum (or oil) dependence or content; having reduced foreign
petroleum (or oil)
dependence or content; having reduced petrochemicals or having components that
are
petrochemical free; and/or being made from renewable resources or having
components made
from renewable resources. This communication is of importance to consumers
that may have an
aversion to petrochemical use (e.g., consumers concerned about depletion of
natural resources or
consumers who find petrochemical based products unnatural or not
environmentally friendly)
and to consumers that are environmentally conscious. Without such a
communication, the
benefit of the present invention maybe lost on some consumers.
The communication may be effected in a variety of communication forms.
Suitable
communication forms include store displays, posters, billboard, computer
programs, brochures,
package literature, shelf information, videos, advertisements, internet web
sites, pictograms,
iconography, or any other suitable form of communication. The information
could be available
at stores, on television, in a computer-accessible form, in advertisements, or
any other
appropriate venue. Ideally, multiple communication forms may be employed to
disseminate the
related environmental message.
The communication may be written, spoken, or delivered by way of one or more
pictures,
graphics, or icons. For example, a television or interne based-advertisement
may have narration,
a voice-over, or other audible conveyance of the related environmental
message. Likewise, the
related environmental message may be conveyed in a written form using any of
the suitable
communication forms listed above. It may be desirable to quantify the
reduction of
petrochemical usage of the ADW composition compared to other detergent
compositions that are
presently commercially available. The communication form may be one or more
icons, such as
those shown in FIGS. 3A-3F of WO 2007/109128, hereby incorporated by
reference. The one or
more icons may be used to convey the related environmental message of reduced
petrochemical
usage. Icons communicating the related environmental message of environmental
friendliness or
renewable resource may be used. The icons may be located on the unit-dose
pouch, on the
secondary packaging, or both. Preferably, the icons and any graphics on the
pouch or packaging
are printed with biodegradable and/or bio-derived inks.
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The related environmental message may also include a message of petrochemical
equivalence.
Because many renewable, naturally occurring, bio-derived, or non-petroleum
derived polymers
often are perceived to lack the performance characteristics that consumers
have come to expect
when used in absorbent articles, a message of petroleum equivalence may be
necessary to
educate consumers that the polymers derived from renewable resources, as
described above,
exhibit equivalent or better performance characteristics as compared to
petroleum derived
polymers. Thus, a suitable petrochemical equivalence message can include
comparison to an
ADW composition that does not have a polymer derived from a renewable
resource. For
example, a suitable combined message may be, "ADW Composition A with bio-
derived
ingredients is just as effective as ADW Composition B." This message conveys
both the related
environmental message and the message of petrochemical equivalence.
The dimensions and values disclosed herein are not to be understood as being
strictly limited to
the exact numerical values recited. Instead, unless otherwise specified, each
such dimension is
intended to mean both the recited value and a functionally equivalent range
surrounding that
value. For example, a dimension disclosed as "40 mm" is intended to mean
"about 40 mm".
Every document cited herein, including any cross referenced or related patent
or application, is
hereby incorporated herein by reference in its entirety unless expressly
excluded or otherwise
limited. The citation of any document is not an admission that it is prior art
with respect to any
invention disclosed or claimed herein or that it alone, or in any combination
with any other
reference or references, teaches, suggests or discloses any such invention.
Further, to the extent
that any meaning or definition of a term in this document conflicts with any
meaning or
definition of the same term in a document incorporated by reference, the
meaning or definition
assigned to that term in this document shall govern.
While particular embodiments of the present invention have been illustrated
and described, it
would be obvious to those skilled in the art that various other changes and
modifications can be
made without departing from the spirit and scope of the invention. It is
therefore intended to
cover in the appended claims all such changes and modifications that are
within the scope of this
invention.
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EXAMPLES
The compositions illustrated in the following Examples illustrate specific
embodiments of the
components of the ADW compositions as described above, but are not intended to
be limiting
thereof. Other modifications can be undertaken by the person of ordinary skill
without departing
from the spirit and scope of this invention.
The components illustrated in the following Examples are prepared by
conventional formulation
and mixing methods, examples of which are described above. All exemplified
amounts are listed
as weight percents and exclude minor materials such as diluents,
preservatives, adjuncts, and so
forth, unless otherwise specified.
The following examples of ADW detergent compositions are provided for purposes
of
illustration only, and as such are not intended to be limiting in any manner.
The examples
demonstrate liquid ADW detergent compositions which may be formed using the
premix
described herein.
Ingredients 1 2 3 4 5
Sodium carbonate 11.0 11.50 11.68 11.79
11.55
Sodium Sulfate 6.00
6.63
Sodium silicate 7.8 7.8 4.2 4.3
Zinc Carbonate AC 0.1 0.1 0.1
¨Alcypo LF 11 8 8 10
SLF182 10 8
Dispersant 7.00 6.25 6.15 6.78
6.20
polymer3
Sodium 1.1
hypochlorite
Sodium perborate 12.8 12.8 9.3
Bleach catalyst 0.05 0.02 0.003
0.01
Bio-derived 2.2 2.2 0.3 1.3
protease enzyme
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Bio-derived 1.7 1.7 0.9 0.2
Amylase enzyme
Bio-derived Balance Balance Balance Balance
Balance
adjuncts and water
Low-foaming bio-derived anionic surfactant from palm kernal oil and comprising
bio-
derived capryleth carboxylic acids
2 Low-foaming nonionic surfactant from bio-derived C18 alcohol
polyethoxylates having a
degree of ethoxylation of about 8, available from Olin Corp
3 Bio-derived terpolymer selected from either 60% bio-derived acrylic
acid/20% bio-
derived maleic acid/20% bio-derived ethyl acrylate, or 70% bio-derived acrylic
acid/10%
bio-derived maleic acid/20% bio-derived ethyl acrylate, or 45% bio-derived
acrylic
acid/45% bio-derived maleic acid/10% bio-derived HAPS.
