CA2762583A1 - Sustainable compositions for automatic dishwashing detergents and sustainable packaging for the compositions - Google Patents

Abstract

Automatic dishwashing compositions comprise at least one bio-derived ingredient. In preferred embodiments, the automatic dishwashing compositions are composed entirely of bio-derived ingredients. Packaging materials are provided for the automatic dishwashing compositions, for example, unit-dose pouches and outer secondary packaging, of 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. Consumer products comprise a bio-derived automatic dishwashing composition packaged in bio-derived packaging materials.

Description

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 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 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.
_ "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 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 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 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%.

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.

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 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.

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, 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.

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 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.

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.

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 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 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;

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.

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:

R3¨CH--C¨OR4 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 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 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 -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 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, 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 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 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.

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 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.

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.

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.

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 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.

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 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 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 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 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:

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 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 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., 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."

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 (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.

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.

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.

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.

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 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' 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 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%, 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):

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):

H2C=- (11) X

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):

(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-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 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 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.

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 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.

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-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 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;

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 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 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 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.

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 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 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 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.

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.

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.

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 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--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 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.

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 (Applicants case number CM2396F). Preferably, the perfume ingredients comprise or consist of natural or bio-derived substances.
In the perfume art, some auxiliary materials having no odor, or a low odor, are used, e.g., as solvents, diluents, extenders or fixatives. Non-limiting examples of these materials are ethyl alcohol, carbitol, diethylene glycol, dipropylene glycol, diethyl phthalate, triethyl citrate, isopropyl myristate, and benzyl benzoate, any or all of which may be bio-derived substances.
These materials are used for, e.g., solubilizing or diluting some solid or viscous perfume ingredients to, e.g., improve handling and/or formulating. These materials are useful in the blooming perfume compositions, but are not counted in the calculation of the limits for the definition/formulation of the blooming perfume compositions of the present invention.
It can be desirable to use blooming and delayed blooming perfume ingredients and even other ingredients, preferably in small amounts, in the blooming perfume compositions of the present invention, that have low odor detection threshold values. The odor detection threshold of an odorous material is the lowest vapor concentration of that material which can be detected. The odor detection threshold and some odor detection threshold values are discussed in, e.g., "Standardized Human Olfactory Thresholds", M. Devos et al, IRL Press at Oxford University Press, 1990, and "Compilation of Odor and Taste Threshold Values Data", F. A.
Fazzalari, editor, ASTM Data Series DS 48A, American Society for Testing and Materials, 1978, both of 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 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.

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 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 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, 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 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.

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 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.

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 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.

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.
_ _ 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 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.

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.

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.

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 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 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 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 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 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 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-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.

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 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.

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.

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 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 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.

Claims (3)

1. An automatic dishwashing composition comprising at least one bio-derived ingredient.

2. A packaging material comprising a unit-dose pouch and a secondary packaging, wherein at least one of the unit-dose pouch and the secondary packaging is formed from a bio-derived material.

3. A product comprising an automatic dishwashing composition disposed in a packaging material, wherein at least one of the automatic dishwashing composition and the packaging material is formed from a bio-derived material.