CA2762589A1

CA2762589A1 - Sustainable containers and dispensers for consumer compositions, sustainable consumer products comprising sustainable consumer compositions in sustainable containers, and methods thereof

Info

Publication number: CA2762589A1
Application number: CA 2762589
Authority: CA
Inventors: Jeffrey Donald Painter
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 2011-12-20
Filing date: 2011-12-20
Publication date: 2013-06-20

Abstract

Sustainable consumer products may include a sustainable container optionally having a delivery device. The sustainable containers include or are made from bio-derived polymers. The containers and delivery devices include, for example, bottles and dispensers such as spray applicators and pump applicators. The sustainable consumer product may include a consumer composition contained in the sustainable container. Further consumer products may include sustainable compositions that are contained within a sustainable container.
The sustainable compositions may contain one or more bio-derived ingredients including, but not limited to, bio-derived surfactants, bio-derived solvents, bio-derived chelants, bio-derived polymers, and bio-derived thickeners.

Description

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SUSTAINABLE CONTAINERS AND DISPENSERS FOR CONSUMER
COMPOSITIONS, SUSTAINABLE CONSUMER PRODUCTS COMPRISING
SUSTAINABLE CONSUMER COMPOSITIONS IN SUSTAINABLE
CONTAINERS, AND METHODS THEREOF
TECHNICAL FIELD
The present specification relates generally to sustainable consumer products and, more specifically, to sustainable containers and dispersers for consumer products, to sustainable consumer products contained in a sustainable container or dispenser and a treatment composition, and to sustainable consumer products including a sustainable composition contained within a sustainable container or dispenser.
BACKGROUND
Consumer products for fabric-care and home-care represent a multi-billion dollar worldwide industry. Typically, these consumer products include a liquid-based composition within a packaging. The packaging may include a storage container, a delivery device such as a nozzle, and/or secondary packaging that may include a label. Each of these components requires consumable resources and energy. A large portion of the consumable resources are derived at least in part from petroleum, which, in view of increased global consciousness of needs for sustainable products, is rather concerning.
For example, plastic packaging uses nearly 40% of all polymers, a substantial share of which is used for consumer products, such as personal care packages (e.g., shampoo, conditioner, and soap bottles) and household packages (e.g., for laundry detergent and cleaning compositions). Most of the materials used to produce polymers for plastic packaging applications, such as polyethylene, polyethylene terephthalate, and polypropylene, are derived from monomers (e.g., ethylene, propylene, terephthalic acid, ethylene glycol), which are obtained from non-renewable, fossil-based resources, such as petroleum, natural gas, and coal. Thus, the price and availability of the petroleum, natural gas, and coal feedstock ultimately have a significant impact on the price of polymers used for plastic packaging materials. As the worldwide price of petroleum, natural gas, and/or coal escalates, so does the price of plastic packaging materials. Furthermore, many consumers display an aversion to purchasing products that are derived from petrochemicals. In some instances, consumers are hesitant to purchase products made from limited non-renewable resources (e.g., petroleum, natural gas and coal).

Other consumers may have adverse perceptions about products derived from petrochemicals as being "unnatural" or not environmentally friendly.
In response, producers of plastic packages have begun to use polymers derived from renewable resources to produce parts of their packages. For example, polyethylene terephthalate (PET) that is about 30% renewable (i.e., 30% of the monomers used to form PET, such as ethylene glycol, are derived from renewable resources) has been used for the formation of soft drink bottles. Further, polylactic acid (PLA) derived from corn has been used for plastic packaging purposes. Although containers made from PLA are biodegradable and environmentally friendly, they are currently unfit for long-term preservation because of their sensitivity to heat, shock, and moisture. Packages derived from PLA also tend to shrivel up, shrink, and often break down when exposed to household chemicals, such as bleach and alcohol ethoxylate (iwhen the PLA is in direct contact with the product. Parts of food packaging and containers used to hold personal care products have also been formed from polyethylene derived from a renewable resource.
Although the current plastic packaging in the art can be partially composed of polymers derived from renewable materials, this current packaging contains at least one component (e.g., container, closure, label) that includes at least some virgin petroleum-based material, such as polyethylene, polyethylene terephthalate, or polypropylene. None of the current plastic packaging is substantially free of virgin petroleum-based compounds, 100%
sustainable, and 100% recyclable, while having a shelf life of at least two years.
Current plastic packaging also can face difficulties during recycling. In the first few steps of a typical recycling procedure, a commonly used flotation process is used to separate polymers in a mixture based on density. Polymers that are denser than water, such as polyethylene terephthalate, sink to the bottom of a solution, while polymers that are less dense than water, such as polyethylene and polypropylene, rise to the top of the solution.
Contamination issues frequently occur during recycling because current plastic packaging that is highly filled or that is composed of some renewable materials often contains dense materials that sink during the flotation process and contaminate the polyethylene terephthalate stream (e.g., polylactic acid, highly filled high density polyethylene, or highly filled polypropylene). The polyethylene terephthalate stream is very sensitive to contamination, while the polyethylene stream is typically more robust.
The packaging materials for consumer products are but one global concern. The compositions packaged within the packaging Materials represent another. The consumer compositions typically comprise a number of organic ingredients such as plastics, fibers, surfactants, builders, polymers, and adjuncts. As used here, "organic ingredients" refers to ingredients containing chemical compositions having carbon atoms. In typical commercial products such as these, the carbon atoms of these organic ingredients trace their origin to a petroleum product. There is a constant need for developing products whose organic ingredients are derived from sources other than petroleum. Technology for producing organic molecules from natural or so-called bio-derived sources continues to improve with regard to providing organic chemicals having carbon atoms, of which a substantial portion, or even all, of the carbon atoms in the chemicals are bio-derived.
Accordingly, it would be desirable to provide plastic packaging that is substantially free of virgin petroleum-based compounds, 100% sustainable, 100% recyclable, has a long-lasting shelf life, and that can minimize or eliminate contamination during recycling.
It would be desirable also to deliver fabric-care and home-care compositions in such sustainable packaging.
Ultimately, it would be desirable to provide fabric-care and home-care compositions that themselves are derived from bio-based, non-petroleum resources, within the sustainable packaging materials.
SUMMARY
Embodiments disclosed herein address the foregoing needs by providing sustainable articles, such as packaging materials and containers, for use with consumer compositions, and sustainable consumer compositions that are packaged in sustainable packaging materials to result in a fully-sustainable, eco-friendly consumer product.
Embodiments directed toward a first aspect disclosed herein relate to sustainable plastic containers and delivery devices made from bio-derived polymers. The plastic containers and delivery devices include, for example, bottles and dispensers such as spray applicators and pump applicators.
Embodiments directed toward a second aspect disclosed herein relate to liquid treatment compositions packaged in the plastic containers according to the first aspect.
Embodiments directed toward a third aspect disclosed herein relate to consumer products including sustainable liquid treatment compositions packaged within the plastic containers of the first aspect. The sustainable liquid treatment compositions may contain bio-derived ingredients including, but not limited to, bio-derived surfactants, bio-derived solvents, bio-derived chelants, bio-derived polymers, and bio-derived thickeners.
These and other features, aspects; and advantages of the present invention will become better understood with reference to the following description and appended claims.

DETAILED DESCRIPTION
Features and advantages of the invention will now be described with occasional reference to specific embodiments. However, the invention may be embodied in different forms and should not be construed as limited to the embodiments set forth herein.
Rather, these embodiments are provided so that this disclosure will be thorough and complete and will fully convey the scope of the invention to those skilled in the art.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the invention belongs. The terminology used in the description herein is for describing particular embodiments only and is not intended to be limiting. As used in the specification and appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
DEFINITIONS AND BIO-DERIVED CONTENT ASSESSMENT METHODS
As used herein, the term "bio-derived" means derived from or synthesized by a renewable biological feedstock, such as, for example, an agricultural, forestry, plant, bacterial, or animal feedstock. The renewable biological feedstocks may include biological feedstocks used in their naturaly-occurring state (i.e., as they are found in nature without human intervention), and also biological feedstocks that are produced with some degree of human intervention such as through genetic engineering, for example. Thus, "bio-derived compounds" typically are compounds obtained from a plant, animal, or microbe, and then modified via chemical reaction.
Modification of the compounds can include esterification of fatty acids (e.g., ethoxylation, methoxylation, propoxylation, etc.), transesterification of an oil (e.g., reaction of an alcohol with a glyceride to form esters of the fatty acid portions of the glycerides), etc.
Hydrogenation or other steps may also be considered.
As used herein, the term "biobased" means a product that is composed, in whole or in significant part, of biological products or renewable agricultural materials (including plant, animal and marine materials) or forestry materials. "Bio-based", and "bio-sourced";
"biologically derived"; "bio-derived"; "naturally-derived" and simply any compound or composition having the prefix "bio-" are used synonymously herein.
As used herein, the term "petroleum derived" means a product derived from or synthesized from petroleum or a petrochemical feedstock.

"Biologically produced" means organic compounds produced by one or more species or strains of living organisms, including particularly strains of bacteria, yeast, fungus and other microbes. "Bio-produced" and biologically produced are used synonymously herein. Such organic compounds are composed of carbon from atmospheric carbon dioxide converted to 5 sugars and starches by green plants.
"Fermentation" as used refers to the process of metabolizing simple sugars into other organic compounds. As used herein fermentation specifically refers to the metabolism of plant derived sugars, such sugar are composed of carbon of atmospheric origin.
"Carbon of atmospheric origin" as used herein refers to carbon atoms from carbon dioxide molecules that have recently, in the last few decades, been free in the earth's atmosphere.
Such carbons in mass are identifiable by the present of particular radioisotopes as described herein. "Green carbon", "atmospheric carbon", "environmentally friendly carbon", "life-cycle carbon", "non-fossil fuel based carbon", "non-petroleum based carbon", "carbon of atmospheric origin", and "biobased carbon" are used synonymously herein.
"Carbon of fossil origin" as used herein refers to carbon of petrochemical origin. Such carbon has not been exposed to UV rays as atmospheric carbon has, therefore masses of carbon of fossil origin has few radioisotopes in their population. Carbon of fossil origin is identifiable by means described herein. "Fossil fuel carbon", "fossil carbon", "polluting carbon", "petrochemical carbon", "petro-carbon" and carbon of fossil origin are used synonymously herein.
"Naturally occurring" as used herein refers to substances that are derived from a renewable source and/or are produced by a biologically-based process.
"Fatty acid" as used herein refers to carboxylic acids that are often have long aliphatic tails, however, carboxylic acids of carbon length 1 to 40 are specifically included in this definition for the purpose of describing the present invention. "Fatty acid esters" as used herein are esters, which are composed of such, defined fatty acids.
As used herein, "sustainable" refers to a material having an improvement of greater than 10% in some aspect of its Life Cycle Assessment or Life Cycle Inventory, when compared to the relevant virgin petroleum-based plastic material that would otherwise have been used to manufacture the article.
As used herein, "Life Cycle Assessment" (LCA) or "Life Cycle Inventory" (LCI) refers to the investigation and evaluation of the environmental impacts of a given product or service caused or necessitated by its 'existence. The LCA or LCI can involve a "cradle-to-grave"
analysis, which refers to the full Life Cycle Assessment or Life Cycle Inventory from manufacture ("cradle") to use phase and disposal phase ("grave"). For example, high density polyethylene (HDPE) containers can be recycled into HDPE resin pellets, and then used to form containers, films, or injection molded articles, for example, saving a significant amount of fossil-fuel energy. At the end of its life, the polyethylene can be disposed of by incineration, for example. All inputs and outputs are considered for all the phases of the life cycle.
As used herein, "End of Life" (EoL) scenario refers to the disposal phase of the LCA or LC1. For example, polyethylene can be recycled, incinerated for energy (e.g., 1 kilogram of polyethylene produces as much energy as 1 kilogram of diesel oil), chemically transformed to other products, and recovered mechanically. Alternatively, LCA or LCI can involve a "cradle-to-gate" analysis, which refers to an assessment of a partial product life cycle from manufacture ("cradle") to the factory gate (i.e., before it is transported to the customer) as a pellet. Sometimes this second type is also termed "cradle-to-cradle".
Various methods have been developed for determining biobased content. These methods typically require the measurement of variations in isotopic abundance between biobased products and petroleum derived products, for example, by liquid scintillation counting, accelerator mass spectrometry, or high precision isotope ratio mass spectrometry. Isotopic ratios of the isotopes of carbon, such as the 13C/12C carbon isotopic ratio or the 4C/12C carbon isotopic ratio, can be determined using analytical methods, such as isotope ratio mass spectrometry, with a high degree of precision. Studies have shown that isotopic fractionation due to physiological processes, such as, for example, CO2 transport within plants during photosynthesis, leads to specific isotopic ratios in natural or bioderived compounds. Petroleum and petroleum derived products have a different 13C/12C carbon isotopic ratio due to different chemical processes and isotopic fractionation during the generation of petroleum. In addition, radioactive decay of the unstable 14C carbon radioisotope leads to different isotope ratios in biobased products compared to petroleum products. Biobased content of a product may be verified by ASTM
International Radioisotope Standard Method D 6866. ASTM International Radioisotope Standard Method D
6866 determines biobased content of a material based on the amount of biobased carbon in the material or product as a percent of the weight (mass) of the total organic carbon in the material or product. Both bioderived and biobased products will have a carbon isotope ratio characteristic of a biologically derived composition.
A small amount of the carbon dioxide in the atmosphere is radioactive. This 14C carbon dioxide is created when nitrogen is struck by a neutron, causing the nitrogen to lose a proton and form carbon of molecular weight 14 that is immediately oxidized to carbon dioxide. This radioactive isotope represents a small but measurable fraction of atmospheric carbon.

Atmospheric carbon dioxide is cycled by green plants to make organic molecules during the process known as photosynthesis. The cycle is completed when the green plants or other forms of life metabolize the organic molecules producing carbon dioxide which is released back to the atmosphere. Virtually all forms of life on Earth depend on this green-plant production of organic molecules to produce the chemical energy that facilitates growth and reproduction. Therefore, the "C that exists in the atmosphere becomes part of all life forms, and their biological products.
Because these renewably based organic molecules that biodegrade to CO2 do not contribute to global warming as there is no net increase of carbon emitted to the atmosphere. In contrast, fossil fuel based carbon does not have the signature radiocarbon ratio of atmospheric carbon dioxide.
Assessment of the renewably based carbon in a material can be performed through standard test methods. Using radiocarbon and isotope ratio mass spectrometry analysis, the biobased content of materials can be determined. ASTM International, formally known as the American Society for Testing and Materials, has established a standard method for assessing the biobased content of materials. The ASTM method is designated ASTM-D6866.
The application of ASTM-D6866 to derive a "biobased content" is built on the same concepts as radiocarbon dating, but without use of age equations. The analysis is performed by deriving a ratio of the amount of radiocarbon ("C) in an unknown sample to that of a modem reference standard. The ratio is reported as a percentage with the units "pMC"
(percent modern carbon, sometimes referred to as "RCI", the Renewable Carbon Index). If the material being analyzed is a mixture of present day radiocarbon and fossil carbon (containing no radiocarbon), then the pMC value obtained correlates directly to the amount of Biomass material present in the sample.
The modern reference standard used in radiocarbon dating is a NIST (National Institute of Standards and Technology) standard with a known radiocarbon content equivalent approximately to the year AD 1950. The year AD 1950 was chosen because it represented a time prior to thermo-nuclear weapons testing that introduced large amounts of excess radiocarbon into the atmosphere with each explosion (termed "bomb carbon"). The AD 1950 reference thus is defined as 100 pMC.
"Bomb carbon" in the atmosphere reached almost twice normal levels in 1963 at the peak of testing and prior to the treaty halting the testing. Distribution of bomb carbon within the atmosphere has been approximated since its appearance, showing values that are greater than 100 pMC for plants and animals living since AD 1950. Bomb carbon has gradually decreased over time, with the value in the year 2011 being near 107.5 pMC. This means that a fresh biomass material such as corn could give a radiocarbon signature near 107.5 pMC.
Combining fossil carbon with present day carbon into a material will result in a dilution of the present day pMC content. By presuming 107.5 pMC represents present day biomass materials and 0 pMC represents petroleum derivatives, the measured pMC value for that material will reflect the proportions of the two component types. A material derived 100% from present day soybeans would give a radiocarbon signature near 107.5 pMC. If that material was diluted with 50% petroleum derivatives, it would give a radiocarbon signature near 54 pMC.
A biomass content result is derived by assigning 100% equal to 107.5 pMC and 0% equal to 0 pMC. In this regard, a sample measuring 99 pMC will give an equivalent biobased content result of 93%.
Compositions comprising bio-based materials also may be assessed according to a "percent natural" standard, as disclosed in U.S. Pat. Appl. Pub. No.
2010/0311179. In contrast to pMC (RCI), which is understood to refer to the amount of bio-derived carbon in active ingredients, the percent natural standard is a measure of the percentage of natural (e.g., non-petroleum) materials in a composition, assuming that water in the composition is 100% natural.
SUSTAINABLE ARTICLES AND BIO-DERIVED MATERIALS FOR THE SUSTAINABLE ARTICLES
According to some embodiments, sustainable consumer products are provided that comprise a sustainable article such as, for example, a sustainable container, a sustainable dispenser, and/or sustainable packaging materials. The sustainable article contains one or more bio-derived materials and, in some embodiments, is formed entirely from one or more bio-derived materials.
The sustainable article is advantageous because it has the same look and feel as similar articles made from virgin petroleum-based sources, similar performance characteristics as the articles made from virgin petroleum-based sources (e.g., similar drop and top load), and can be disposed of in the same way (e.g., by recycling the article), yet the sustainable article has improved sustainability over articles derived from virgin petroleum-based sources.
The sustainable article is also advantageous because any virgin polymer used in the manufacture of the article is derived from a renewable resource. As used herein, a "renewable resource" is one that is produced by a natural process at a rate comparable to its rate of consumption (e.g., within a 100 year time frame). The resource can be replenished naturally, or via agricultural techniques. Nonlimiting examples of renewable resources include plants (e.g., sugar cane, beets, corn, potatoes, citrus fruit, woody plants, lignocellulosics, hemicellulosics, cellulosic waste), animals, fish, bacteria, fungi, and forestry products.
These resources can be naturally occurring, hybrids, or genetically engineered organisms. Natural resources such as crude oil, coal, natural gas, and peat, which take longer than 100 years to form, are not considered renewable resources. Because at least part of the sustainable article is derived from a renewable resource, which can sequester carbon dioxide, use of the article can reduce global warming potential and fossil fuel consumption. For example, some LCA or LCI
studies on the resin from which the article is derived have shown that about one ton of polyethylene made from virgin petroleum-based sources results in the emission of up to about 2.5 tons of carbon dioxide to the environment. Because sugar cane, for example, takes up carbon dioxide during growth, one ton of polyethylene made from sugar cane removes up to about 2.5 tons of carbon dioxide from the environment. Thus, use of about one ton of polyethylene from a renewable resource, such as sugar cane, results in a decrease of up to about 5 tons of environmental carbon dioxide versus using one ton of polyethylene derived from petroleum-based resources.
Nonlimiting examples of renewable polymers include polymers produced directly from organisms, such as polyhydroxyalkanoates (e.g., poly(beta-hydroxyalkanoate), poly(3-hydroxybutyrate-co-3-hydroxyvalerate, NODAXTm), and bacterial cellulose;
polymers extracted from plants and biomass, such as polysaccharides and derivatives thereof (e.g., gums, cellulose, cellulose esters, chitin, chitosan, starch, chemically modified starch), proteins (e.g., zein, whey, gluten, collagen), lipids, lignins, and natural rubber; and current polymers derived from naturally sourced monomers and derivatives, such as bio-derived polyethylene, bio-polypropylene, bio-derived polytrimethylene terephthalate, bio-derived polylactic acid, bio-derived NYLON 11, bio-derived alkyd resins, bio-derived succinic acid-based polyesters, and bio-derived polyethylene terephthalate.
The sustainable article is further advantageous because its properties can be tuned by varying the amount of bio-material, recycled material, and regrind material used to form the container, closure, label, or mixture thereof, or by the introduction of fillers. For example, increasing the amount of bio-material at the expense of recycled material (when comparing like for like, e.g., homopolymer versus copolymer), tends to increase the stress crack resistance, increase the impact resistance, decrease opaqueness, and increase surface gloss. Increasing the amount of specific types of recycled and/or regrind material can improve some properties. For example, recycled material containing an elastomeric content will increase impact resistance, and reduce the cost of the article, depending on the exact grade. In contrast, recycled material that does not contain elastomeric content will often slightly decrease impact resistance. Further, because recycled material is often already colored, use of recycled materials over virgin materials often results in cost savings on colorant masterbatches, particularly if the color of the recycled material is similar to the intended color of the article.
The ability to tune the composition of the sustainable article allows the incorporation of 5 polymers that are either less or more dense than water, to result in an overall composition that has a density below that of water, such as when the article is not composed of polyethylene terephthalate. Therefore, the sustainable article is easier to recycle in typical recycling streams than current plastic packaging materials that appear to be at least partly sustainable (e.g., those that include polylactic acid as part of the packaging), because issues concerning the 10 contamination of polyethylene terephthalate streams during the flotation separation process can be avoided.
Even further, the sustainable article is advantageous because it can act as a one to one replacement for similar articles containing polymers that are wholly or partially derived from virgin petroleum-based materials, and can be produced using existing manufacturing equipment, reactor conditions, and qualification parameters. Its use results in a reduction of the environmental footprint, and in less consumption of non-renewable resources.
The reduction of the environmental footprint occurs because the rate of replenishment of the resources used to produce article's raw construction material is equal to or greater than its rate of consumption;
because the use of a renewable derived material often results in a reduction in greenhouse gases due to the sequestering of atmospheric carbon dioxide, or because the raw construction material is recycled (consumer or industrial) or reground within the plant, to reduce the amount of virgin plastic used and the amount of used plastic that is wasted, e.g., in a landfill. Further, the sustainable article does not lead to the destruction of critical ecosystems, or the loss of habitat for endangered species.
Embodiments disclosed herein relate to a sustainable article that has a shelf life of at least two years, is 100% recyclable, and is substantially free of virgin petroleum-based materials (i.e., less than 10 wt.%, preferably less than 5 wt.%, more preferably less than 3 wt.% of virgin petroleum-based materials, based on the total weight of the article). As used herein, "virgin petroleum-based" refers to materials that are derived from a petroleum source, such as oil, natural gas, or coal, and that have not been recycled, either industrially or through the consumer waste stream.
The sustainable article includes a container, a closure, and a label, with each of the = components derived from renewable materials, recycled materials, regrind materials, or a mixture thereof. Optionally, the sustainable article may further include a sustainable dispenser such as a trigger sprayer or a pump, for example. The container includes at least 90 wt.%, preferably at least 95 wt.%, more preferably at least 97 wt.%, for example, about 100 wt.%
of bio-polymer, recycled polymer, regrind polymer, or a mixture thereof. The closure includes at least 90 wt.%, preferably at least 95 wt.%, more preferably at least 97 wt.%, for example, about 100 wt.% of bio-polymer, recycled polymer, regrind polymer, or a mixture thereof. The label includes at least 90 wt.%, preferably at least 95 wt.%, more preferably at least 97 wt.%, for example, about 100 wt.% of bio-polymer, recycled polymer, regrind polymer, or a mixture thereof.
The optional dispenser, when present, includes at least 90 wt.%, preferably at least 95 wt.%, more preferably at least 97 wt.%, for example, about 100 wt.% of bio-polymer, recycled polymer, regrind polymer, or a mixture thereof. In some embodiments, the sustainable article may be a component of a sustainable consumer product that comprises the sustainable article and at least one of a sustainable composition and/or sustainable packaging, both of which are described in greater detail below. The sustainable packaging may comprise a secondary packaging and, optionally, a tertiary packaging, both described below, and each layer of packaging may optionally be labeled with one or more sustainable labels, which sustainable tables may be printed with indicia using sustainable or bio-derived inks.
Examples of renewable materials include bio-polyethylene, bio-polyethylene terephthalate, and bio-polypropylene. As used herein and unless otherwise noted, "polyethylene"
encompasses high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and ultra low density polyethylene (ULDPE). As used herein and unless otherwise noted, "polypropylene" encompasses homopolymer polypropylene, random copolymer polypropylene, and block copolymer polypropylene.
As used herein, "recycled" materials encompass post-consumer recycled (PCR) materials, post-industrial recycled (PIR) materials, and a mixture thereof. In some embodiments, the container and/or closure are composed of recycled high density polyethylene, recycled polyethylene terephthalate, recycled polypropylene, recycled LLDPE, or recycled LDPE, preferably recycled high density polyethylene, recycled polyethylene terephthalate, or recycled polypropylene, more preferably recycled high density polyethylene or recycled polyethylene terephthalate. In some embodiments, the labels are composed of recycled high density polyethylene, polypropylene, or polyethylene terephthalate from containers.
As used herein, "regrind" material is thermoplastic waste material, such as sprues, runners, excess parison material, and reject parts from injection and blow molding and extrusion operations, which has been reclaimed by shredding or granulating.

In some preferred embodiments, the sustainable article may contain one or more bio-derived polymers or plastics selected from the group consisting of bio-derived polyethylene, bio-derived high-density polyethylene, bio-derived polypropylene, bio-derived polyethylene terephthalate, and mixtures thereof. In the following sections, these bio-derived materials and exemplary methods for attaining them are described.
Bio-Derived Polyethylene and Bio-Derived High Density Polyethylene In one aspect, the sustainable article includes bio-polyethylene and/or bio-high density polyethylene. Bio-polyethylene may be produced from the polymerization of bio-ethylene, which is formed from the dehydration of bio-ethanol. Bio-ethanol can be derived from, for example, (i) the fermentation of sugar from sugar cane, sugar beet, or sorghum; (ii) the saccharification of starch from maize, wheat, or manioc; and (iii) the hydrolysis of cellulosic materials. U.S. Patent Application Publication No. 2005/0272134, incorporated herein by reference, describes the fermentation of sugars to form alcohols and acids.
Suitable sugars used to form ethanol include monosaccharides, disaccharides, trisaccharides, and oligosaccharides. Sugars, such as sucrose, glucose, fructose, and maltose, are readily produced from renewable resources, such as sugar cane and sugar beets.
As previously described, sugars also can be derived (e.g., via enzymatic cleavage) from other agricultural products (i.e., renewable resources resulting from the cultivation of land or the husbandry of animals). For example, glucose can be prepared on a commercial scale by enzymatic hydrolysis of corn starch. Other common agricultural crops that can be used as the base starch for conversion into glucose include wheat, buckwheat, arracaha, potato, barley, kudzu, cassava, sorghum, sweet potato, yam, arrowroot, sago, and other like starchy fruit, seeds, or tubers. The sugars produced by these renewable resources (e.g., corn starch from corn) can be used to produce alcohols, such as propanol, ethanol, and methanol. For example, corn starch can be enzymatically hydrolyzed to yield glucose and/or other sugars. The resultant sugars can be converted into ethanol by fermentation.
Monofunctional alcohols, such as ethanol and propanol can also be produced from fatty acids, fats (e.g., animal fat), and oils (e.g., monoglycerides, diglycerides, triglycerides, and mixtures thereof). These fatty acids, fats, and oils can be derived from renewable resources, such as animals or plants. "Fatty acid" refers to a straight chain monocarboxylic acid having a chain length of 12 to 30 carbon atoms. "Monoglycerides," "diglycerides," and "triglycerides" refer to containing multiple mono-, di- and tri- esters, respectively, of (i) glycerol and (ii) the same or mixed fatty acids unsaturated double bonds. Nonlimiting examples of fatty acids include oleic acid, myristoleic acid, palmitoleic acid, sapienic acid, linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid, and docosahexaenoic acid. Nonlimiting examples of monoglyeerides include monoglycerides of any of the fatty acids described herein. Nonlimiting examples of diglycerides include diglycerides of any of the fatty acids described herein.
Nonlimiting examples of the triglycerides include triglycerides of any of the fatty acids described herein, such as, for example, tall oil, corn oil, soybean oil, sunflower oil, safflower oil, linseed oil, perilla oil, cotton seed oil, tung oil, peanut oil, oiticica oil, hempseed oil, marine oil (e.g.
alkali-refined fish oil), dehydrated castor oil, and mixtures thereof.
Alcohols can be produced from fatty acids through reduction of the fatty acids by any method known in the art. Alcohols can be produced from fats and oils by first hydrolyzing the fats and oils to produce glycerol and fatty acids, and then subsequently reducing the fatty acids.
In a preferred embodiment, the bio-ethylene is produced from sugar cane. The life cycle stages of ethylene production from sugar cane include (i) sugar cane farming, (ii) fermentation of sugar cane to form bio-ethanol, and (iii) dehydration of bio-ethanol to form ethylene.
Specifically, sugar cane is washed and transported to mills where sugar cane juice is extracted, leaving filter cake, which is used as fertilizer, and bagasse (residual woody fiber of the cane obtained after crushing). The bagasse is burned to generate steam and the electricity used to power the sugar cane mills, thereby reducing the use of petroleum-derived fuels. The sugar cane juice is fermented using yeast to form a solution of ethanol and water. The ethanol is distilled from the water to yield about 95% pure bio-ethanol. The bio-ethanol is subjected to catalytic dehydration (e.g., with an alumina catalyst) to produce ethylene, which is subsequently polymerized to form polyethylene.
Advantageously, a Life Cycle Assessment & Inventory of ethylene produced from sugar cane shows favorable benefits in some aspects over ethylene produced from petroleum feedstock for global warming potential, abiotic depletion, and fossil fuel consumption.
For example, some studies have shown that about one ton of polyethylene made from virgin petroleum-based sources results in the emission of up to about 2.5 tons of carbon dioxide to the environment, as previously described. Thus, use of up to about one ton of polyethylene from a renewable resource, such as sugar cane, results in a decrease of up to about 5 tons of environmental carbon dioxide versus using one ton of polyethylene derived from petroleum-based resources.
BRASKEM has demonstrated the production of high density polyethylene (HDPE) and linear, low density polyethylene (LLDPE) from sugar cane using a Hostalen/Basell technology for the I IDPE production and a Spherilene/Basell technology for the LLDPE
production. These catalysts allow (in some cases), superior processability of the bio-polyethylene and results in products with superior consistency to incumbent resins made by other processes.
Bio-Derived Polypropylene In yet another aspect, the sustainable article may include bio-polypropylene.
Bio-polypropylene may be produced from the polymerization of propylene formed from the dehydration of propanol. Renewable resources used to derive propanol are as previously described. Propanol also can be derived from bio-ethylene. In this pathway, bio-ethylene is converted into propionaldehyde by hydroformylation using carbon monoxide and hydrogen in the presence of a catalyst, such as cobalt octacarbonyl or a rhodium complex.
Hydrogenation of the propionaldehyde in the presence of a catalyst, such as sodium borohydride and lithium aluminum hydride, yields propan-l-ol, which can be dehydrated in an acid catalyzed reaction to yield propylene, as described in U.S. Patent Application Publication No.
2007/0219521, incorporated herein by reference.
Bio-Derived Polyethylene Terephthalate In another aspect, the sustainable article may include bio-polyethylene terephthalate.
Bio-polyethylene terephthalate may be produced from the polymerization of bio-ethylene glycol with bio-terephthalic acid. Bio-ethylene glycol can be derived from renewable resources via a number of suitable routes, such as, for example, those described in WO
2009/155086 and U.S.
Patent No. 4,536,584, each incorporated herein by reference. Bio-terephthalic acid can be derived from renewable alcohols through renewable p-xylene, as described in International Patent Application Publication No. WO 2009/079213, which is incorporated herein by reference.
In some embodiments, a renewable alcohol (e.g,. isobutanol) is dehydrated over an acidic catalyst in a reactor to form isobutylene. The isobutylene is recovered and reacted under the appropriate high heat and pressure conditions in a second reactor containing a catalyst known to aromatize aliphatic hydrocarbons to form renewable p-xylene.
In another embodiment, the renewable alcohol, e.g. isobutanol, is dehydrated and dimerized over an acid catalyst. The resulting diisobutylene is recovered and reacted in a second reactor to form renewable p-xylene.
In yet another embodiment, a renewable alcohol, e.g. isobutanol, containing up to 15 wt.% water is dehydrated, or dehydrated and oligomerized, and the resulting oligomers are aromatized to form renewable p-xylene.

In yet another embodiment, the dehydration of the renewable alcohol and the aromatization of the resulting alkene occurs in a single reactor using a single catalyst, to form a mixture of renewable aromatic compounds. The resulting renewable aromatic compounds are purified, e.g. by distillation or crystallization, to obtain pure streams of individual renewable 5 aromatic products. The pure xylenes from these reactions are oxidized to their corresponding phthalic acids and phthalate esters.
Renewable phthalic acid or phthalate esters can be produced by oxidizing p-xylene over a transition metal catalyst (see, e.g., Ind. Eng. Chem. Res., 39:3958-3997 (2000)), optionally in the presence of one or more alcohols.

As described above, the sustainable article may comprise a sustainable container, a sustainable dispenser, or both, either of which may function as sustainable packaging for a sustainable consumer product. In some embodiments, the sustainable article comprises a sustainable container such as a bottle and a sustainable dispenser configured as a trigger sprayer, 15 a pump sprayer, a dosing cap, or a press tab, for example. However, it should be understood that the sustainable article may take a variety of other forms suitable for storing, shipping, delivering, and dispensing any of the consumer products described herein.
In some embodiments, the sustainable article may further comprise a closure and/or a label, either of which may comprise or be made from one or more bio-derived materials. In further embodiments, the sustainable article may further comprise a consumer composition, as described in detail below. In still further embodiments, the consumer composition is a sustainable composition, as described below.
The consumer composition and/or the sustainable composition may be deliverable with or without a sustainable dispenser, if present, by a natural, bio-derived, or sustainable propellant packaged with the consumer composition or sustainable composition. In some embodiments, the sustainable article may comprise a sustainable container and/or a sustainable dispenser that is packaged in a sustainable packaging material. Sustainable packaging materials are described in greater detail below and may include, for example, secondary packaging and tertiary packaging.
The any or all layers of sustainable packaging present in the sustainable article optionally may be labelled with one or more sustainable labels as described herein, which labeled optionally may contain indicia printed with sustainable or bio-derived inks.

Sustainable Containers Composition of Sustainable Containers In some embodiments, the sustainable article may comprise a container, such as a bottle, suitable for containing a consumer composition, in particular a liquid composition. In further embodiments, the container may be an aerosol container suitable for containing a liquid or solid product and a propellant such as a compressed gas. The container comprises or is made from one or more bio-derived materials. Preferably, the bio-derived materials selected for the container all are chemically and physically compatible with any composition intended to be contained therein.
As used here, "chemically and physically compatible" means that the consumer composition does not react with, substantially soften or harden, dissolve, or cause deleterious effects such as crazing within the container that is the sustainable article. The container may have any desired shape or size and may include ornamental features being indicative of a consumer composition contained therein or intended only to provide pleasing aesthetic value to a consumer product.
Several embodiments of the bio-derived materials content of such containers will now be described. It should be understood that these embodiments are meant to be exemplary, not limiting.
In some embodiments, the container may be composed of at least 10 wt.%, preferably at least 25 wt.%, more preferably at least 50 wt.%, even more preferably about 75 wt.%, for example, at least 90 wt.% or 100 wt.% of high density polyethylene (HDPE), based on the total weight of the container, which has a biobased content of at least 95%, preferably at least 97%, more preferably at least 99%, for example about 100%. The container may further include a polymer selected from the group consisting of post-consumer recycled polyethylene (PCR-PE), post-industrial recycled polyethylene (PIR-PE), regrind polyethylene, and a mixture thereof. The recycled polyethylene is optionally present in an amount of up to about 90 wt.%, preferably up to about 50 wt.%, more preferably up to about 25 wt. %, based on the total weight of the container.
The regrind polyethylene is optionally present in an amount of up to about 75 wt.%, preferably up to about 50 wt.%, more preferably up to about 40 wt. %, based on the total weight of the container.The container may include, for example, about 50 wt.% of bio-HDPE, about 25 wt.%
of PCR-PE, and about 25 wt.% of regrind PE; or, if recycled PE is not available, about 65 wt.%
of bio-HDPE and about 35 wt.% of regrind PE. The container has a density of less than 1 g/mL
to aid separation during the floatation process of recycling, as previously described.
In further embodiments, the container may be composed of at least 10 wt.%, preferably at least 25 wt.%, more preferably at least 50 wt.%, even more preferably at least 75 wt.%, for example, at least 90 wt.% or about 100 wt.% of polyethylene terephthalate (PET). In embodiments when the container includes PET with a biobased content of at least 90%, the container further includes a polymer selected from the group consisting of post-consumer recycled polyethylene terephthalate (PCR-PET), post-industrial recycled polyethylene terephthalate (PIR-PET), regrind polyethylene terephthalate, and a mixture thereof. The recycled PET is optionally present in an amount of up to about 90 wt.%, preferably up to about 50 wt.%, more preferably up to about 25 wt. cY0, based on the total weight of the container. The regrind PET is optionally present in an amount of up to about 75 wt.%, preferably up to about 50 wt.%, more preferably up to about 40 wt. %, based on the total weight of the container. The container can include, for example, about 30 wt.% bio-PET and about 70 wt.% of PCR-PET.
The containers according to these embodiments may have densities of greater than 1 g/mL.
Without intent to be limited by theory, it is believed that poly(ethylene terephthalate) (PET) aerosol-type containers or bottles may be less desirable in certain instances. For example, it is believed that limonene and other perfume raw materials, as well hydrocarbon propellants and other formula ingredients, can diffuse into PET and lower its crazing initiation stress. As a result, these chemicals can cause crazing of PET in the neck and shoulder regions of the aerosol bottle where the tensile stresses, due to the presence of the pressurized propellant, exceed the crazing initiation stress. This crazing of PET can progress into cracking and cause integrity problems in the aerosol bottles. In still further embodiments, the container may be composed of at least 10 wt.%, preferably at least 25 wt.%, more preferably at least 50 wt.%, even more preferably at least 75 wt.%, for example, at least 90 wt.% or about 100 wt.%.
of polypropylene (PP), based on the total weight of the container, which has a biobased content of at least 90%, preferably at least 93%, more preferably at least 95%, for example, about 100%. The container further may include a polymer selected from the group consisting of post-consumer recycled polypropylene (PCR-PP), post-industrial recycled polypropylene (PIR-PP), regrind polypropylene, and a mixture thereof. The recycled polypropylene is optionally present in an amount of up to about 90 wt.%, preferably up to about 50 wt.%, more preferably up to about 25 wt. %, based on the total weight of the container. The regrind polypropylene is optionally present in an amount of up to about 75 wt.%, preferably up to about 50 wt.%, more preferably up to about 40 wt. %, based on the total weight of the container. The containers of these embodiments may have a density of less than 1 g/mL to aid separation during the floatation process of typical recycling systems, as previously described. For example, the container can include about 50 wt.% of bio-PP, about 25 wt.% of PCR-PP, and about 25 wt.% of regrind PP;
or, if recycled PP is not available, about 60 wt.% of bio-PP and about 40 wt.%
of regrind PP.

The sustainable container useful herein may have a hollow body for holding a consumer composition, and is typically a bottle or canister formed of bio-derived plastic, glass, and/or metal, preferably a bio-derived polymer or resin such as bio-derived polyethylene, bio-derived polypropylene, bio-derived polyethylene terephthalate, bio-derived polycarbonate, bio-derived polystyrene, bio-derived ethyl vinyl alcohol, bio-derived polyvinyl alcohol, bio-derived thermoplastic elastomer, and combinations thereof, although other materials known in the art may also be used. Such containers will typically hold from about 100 mL to about 2 L of liquid, preferably from about 150 mL to about 1.2 L of liquid, and more preferably from about 200 mL
to about 1 L of liquid, and are well known for holding liquid consumer products.
Characterization of Sustainable Containers Preferably, each bio-derived component and each non-bio-derived component of the sustainable article has a shelf life of at least two years. The density of the container can be determined using ASTM D792.
A container with a shelf life of at least two years can be characterized by at least one the following expedients: its water vapor transmission rate (WVTR), environmental stress cracking (ESC), and column crush.
Water vapor transmission rate is the steady state rate at which water vapor permeates through a film at specified conditions of temperature and relative humidity, and can be determined using ASTM 1249-06. A container that is composed of HDPE has a WVTR
of less than 0.3 grams per 100 square inches per 1 day (g/100 in2/day), preferably less than 0.2 g/100 in2/day, more preferably less than 0.1 g/100 in2/day, at about 38 C and about 90% relative humidity. A container that is composed of PP has a WVTR of less than 0.6 g/100 in2/day, preferably less than 0.4 g/100 in2/day, more preferably less than 0.2 g/100 in2/day, at about 38 C
and about 90% relative humidity. A container that is composed of PET has a WVTR of less than 2.5 g/100 in2/day, preferably less than 1.25 g/100 in2/day, more preferably less than 0.625 g/100 in2/day, at about 38 C and about 90% relative humidity.
Environmental Stress Cracking (ESC) is the premature initiation of cracking and embrittlement of a plastic due to the simultaneous action of stress, strain, and contact with specific chemical environments. One method of determining ESC is by using ASTM
D-2561. A
container of the invention can survive a 4.5 kilogram load under 60 C for 15 days, preferably for 30 days, when subjected to ASTM D-2561.
Alternatively, the ESC can be determined according to the following procedure.
A
container to be tested is filled with liquid to a target fill level and, optionally, a closure is fitted on the container. If the closure is a screw type closure, it is tightened to a specified torque. The test container is conditioned for four hours under 50 C 1.5 C. The screw-type container closures are then re-torqued to the original specified torque level and leaking samples are eliminated. At its conditioning temperature, the container is placed in an upright position and a 4.5 to 5.0 kilogram weight is placed on top of it. The container is inspected every day for thirty days for evidence of stress cracking or signs of leakage that may indicate stress cracking. A
container of the invention can survive a 4.5 to 5.0 kilogram load for about thirty days, during which the first fifteen days are the most critical.
The Column Crush test provides information about the mechanical crushing properties (e.g., crushing yield load, deflection at crushing yield load, crushing load at failure, apparent crushing stiffness) of blown thermoplastic containers. When an empty, uncapped, air vented container of the invention is subjected to the ASTM D-2659 Column Crush test using a velocity of 50 mm/min, the compression strength peak force (at a deflection of no more than about 5 mm), is no less than SON, preferably no less than 100 N, more preferably no less than 230 N.
Also, when the container of the invention is tested filled with water at a temperature between 28 C and 42 C and subjected to the ASTM D-2659 Column Crush test using a velocity of 12.5 mm/min, the compression strength peak force (at a deflection of no more than about 5 mm), is no less than 150 N, preferably no less than 250 N, more preferably no less than 300 N. The Column Crush tests are performed in a room held at room temperature.
Additionally or alternatively, the raw construction material comprising HDPE, PET, or PP; and polymer, as described above, used to produce the container of the invention preferably has a heat distortion temperature or Vicat softening point as specified below, and/or can survive an applied stress according to the full notch creep test, as specified below.
Heat distortion temperature (HDT) is the temperature at which a test material deflects a specified amount when loaded in 3-point bending at a specified maximum outer fiber stress. The heat distortion temperature can be determined using the standard procedure outlined in ISO 75, where method A uses an outer fiber stress of 1.80 MPa, and method B uses an outer fiber stress of 0.45 MPa. The raw construction material of a HDPE container of the invention has a HDT of at least 40 C, preferably at least 45 C, more preferably at least 50 C, according to method A
and at least 73 C, preferably at least 80 C, more preferably at least 90 C, according to method B. The raw construction material of a PET container of the invention has a HDT
of at least 61.1 C, preferably at least 63 C, more preferably at least 65 C according to method A, and at least 66.2 C, preferably at least 68 C, more preferably at least 70 C, according to method B. The raw construction material of a PP container of the invention has a HDT of at least 57 C, preferably at least 65 C, more preferably at least 70 C, according to method A and at least 75 C, preferably at least 90 C, more preferably at least 100 C, according to method B.
Vicat softening point is the determination of the softening point for materials that have no definite melting point, but can still be measured for those materials that do have melting point. It 5 is taken as the temperature at which the material is penetrated to a depth of 1 millimeter by a flat-ended needle with a one square millimeter circular or square cross-section.
The Vicat softening point can be determined using the standard procedure outlined in ISO 306, where a load of 10 N
and a heating rate of 50 C per hour is used for test method A50, and a load of 50 N and a heating rate of 50 C per hour is used for test method B50. The raw construction material of a HDPE
10 container of the invention has a Vicat softening temperature of at least 112 C, preferably at least 125 C, more preferably at least 130 C, according to test method A50 and at least 75 C, preferably at least 77 C, more preferably at least 80 C, according to test method B50. The raw construction material of a PET container of the invention has a Vicat softening temperature of at least 79 C, preferably at least 85 C, more preferably at least 90 C, according to test method 15 A50 and at least 75 C, preferably at least 77 C, more preferably at least 80 C, according to test method B50. The raw construction material of a PP container of the invention has a Vicat softening temperature of at least 125 C, preferably at least 154 C, more preferably at least 175 C, according to test method A50 and at least 75 C, preferably at least 85 C, more preferably at least 95 C, according to test method B50.

20 The Full Notch Creep Test (FNCT) is an accelerated test used to assess the resistance of a polymer to slow crack growth in a chosen environment. When subjected to the FNCT described in ISO 16770, the raw construction material of a HDPE or a PP container of the invention can survive at least 4 hours, preferably at least 18 hours, more preferably at least 50 hours, even more preferably about 100 hours at an applied stress of about 4A MPa, at room temperature.
Methods for Forming Sustainable Containers The containers can be produced using blow molding, for example. Blow molding is a manufacturing process by which hollow plastic parts are formed from thermoplastic materials.
The blow molding process begins with melting down thermoplastic and forming it into a parison or preform. The parison is a tube-like piece of plastic with a hole in one end through which compressed air can pass. Pressurized gas, usually air, is used to expand the parison or the hot preform and press it against a mold cavity. The pressure is held until the plastic cools. After the plastic has cooled and hardened the mold opens up and the part is ejected.

There are three main types of blow molding: extrusion blow molding, injection blow molding, and injection stretch blow molding. In extrusion blow molding, a molten tube of plastic is extruded into a mold cavity and inflated with compressed air. One end of the cylinder is pinched closed. After the plastic part has cooled, it is removed from the mold. Extrusion blow molding can be used to produce the HDPE and PP containers of the invention.
These containers can be single layer or multilayer.
Injection blow molding (IBM) involves three steps: injection, blowing and ejection.
First, molten polymer is fed into a manifold where it is injected through nozzles into a hollow, heated preform mold. The preform mold forms the external shape of the resulting container and is clamped around a mandrel (the core rod) which forms the internal shape of the preform. The preform consists of a fully formed bottle/jar neck with a thick tube of polymer attached, which will form the body. The preform mold opens and the core rod is rotated and clamped into the hollow, chilled blow mold. The core rod opens and allows compressed air into the preform, which inflates it to the finished article shape. After a cooling period the blow mold opens and the core rod is rotated to the ejection position. The finished article is stripped off the core rod and leak-tested. Injection blow molding, as well as the other blow molding methods described herein, is useful for the formation of article components that have embedded biodegradable polymer. Injection blow molding can be used to produce containers that include blends of biodegradable polymers.
Injection stretch blow molding (ISBM) is a method for producing a plastic container from a preform or parison that is stretched in both the hoop direction and the axial direction when the preform is blown into its desired container shape. In the ISBM process, a plastic is first molded into a "preform" using the injection molding process. These preforms are produced with the necks of the containers, including threads. The preforms are packaged, and after cooling, fed into a reheat stretch blow molding machine. The preforms are heated above their glass transition temperature, then blown using high pressure air into containers using metal blow molds.
Typically, the preform is stretched with a core rod as part of the process.
Injection stretch blow molding can be used to produce the bio-HDPE, bio-PET, and bio-PP containers of the invention.
Sustainable Closures Compositions of Sustainable Closures In some embodiments, the sustainable containers described above may comprise a closure that closes the container to seal in any consumer composition contained in the container. In some embodiments the closure may be configured as a threaded cap, a snap-on cap, a snap-shut cap with a hinged portion connected to a cap body, an interlocking track that may be sealed by a user's fingers or with a zipper-type mechanism, and the like. The closure may be used in conjunction with the container according to any suitable means such as by threads on the closure that engage mating threads on the container, suitable sealing mechanisms, child-proof mechanisms known in the art, simple snap-on mechanisms, and the like.
In some embodiments, the closure is composed of a polymer selected from the group consisting of polypropylene that has a biobased content of at least 90%, preferably at least 93%, more preferably at least 95%, for example, about 100%; post-consumer recycled polypropylene (PCR-PP); post-industrial recycled polypropylene (PIR-PP); and a mixture thereof. In some embodiments, the closure is composed of a polymer selected from the group consisting of linear low density polyethylene (LLDPE) that has a biobased content of at least 90%, preferably at least 93%, more preferably at least 95%, for example, about 100%; post-consumer recycled LLDPE;
post-industrial recycled LLDPE; high density polyethylene (HDPE) that has a biobased content of at least 90%, preferably at least 93%, more preferably at least 95%, for example, about 100%;
post-consumer recycled polyethylene (PCR-PE); post-industrial recycled polyethylene (PIR-PE);
and a mixture thereof.
For example, the closure can be composed of (i) a polymer selected from the group consisting of bio-linear low density polyethylene (LLDPE), as described above;
post-consumer recycled LLDPE; post-industrial recycled LLDPE, and a mixture thereof; or (ii) a polymer selected from the group consisting of bio-high density polyethylene (HDPE), as described above;
post-consumer recycled HDPE; post-industrial recycled polyethylene HDPE; low density polyethylene (LDPE) that has a biobased content of at least 90%, preferably at least 93%, more preferably at least 95%, for example, about 100%; post-consumer recycled LDPE;
post-industrial recycled LDPE; and a mixture thereof.
The closure in these embodiments may have a density of less than 1 g/mL to aid separation during the floatation process of recycling, as previously described. For example, the closure can include a mixture of bio-polypropylene and recycled polypropylene;
recycled polypropylene without bio-polypropylene; or bio-polypropylene without recycled polypropylene.
Characterization of Sustainable Closures Each component of the sustainable article has a shelf life of at least two years. The density of the closure can be determined using ASTM D792.

A closure with a shelf life of at least two years can be characterized by at least one of the following expedients: its hinge life, if the closure design include a hinge, stress crack resistance, drop impact resistance, change in modulus with immersion in water, and Vicat softening point.
Hinge life is the ability of a hinge to sustain multiple openings by a person or a machine. If the hinge life of the closure is tested manually, the closure of the invention can sustain at least 150, preferably at least 200, more preferably at least 300 openings by the person at room temperature.
If the hinge life of the closure is tested by machine, it can sustain at least 1500, preferably at least 1700, more preferably at least 2000 openings by the machine at room temperature. In some of these embodiments, the closure is comprised of polypropylene. After each test, the hinge region is inspected for breakages. When the closure of the invention is placed in a cold environment (e.g., less than 5 C), it shows no breakages.
Stress crack resistance of the closure can be determined by the ESC methods previously described. For example, a closure of the invention can survive a 4.5 kilogram load at about 50 C
for about fifteen days, preferably for about thirty days. Alternatively, under ASTM D-5419, a closure of the invention can withstand cracking at immersion stress crack resistance (ISCR) and exhibit no de-coloration for about 15 days, preferably for about 30 days.
Drop impact resistance is the ability of a closure to survive a fall. To determine drop impact resistance, a container that is free from damage and constructed as intended is filled with tap water to nominal fill capacity and left uncapped for 24 hours at 23 2 C
to achieve normalized temperature. The container is capped and dropped from a specified height. A
closure of the invention, when assembled on a container that is filled with water, can survive a side panel or horizontal drop and an upside-down drop from a height of about 1.2 m. A closure of the invention, when assembled on a container that is filled with water, can survive a vertical bottom drop from a height of about 1.5 m.
Additionally or alternatively, the raw construction material comprising the PP, LLDPE, HDPE, and LDPE closure, as described above, used to produce the closure of the invention preferably has a change in modulus with immersion in water or Vicat softening point as specified below.
Change in modulus with immersion in water is tested with ASTM D-638, which measures the modulus of plastics. The modulus is compared before and after immersion in product for two weeks at room temperature and at 45 C. The raw construction material comprising the closure of the invention exhibits negligible change in modulus when it is immersed in water, with less than 1% reduction in modulus.

The raw construction material comprising the closure of the invention exhibits a Vicat softening point of at least 75 C, preferably at least 125 C, according to test method A50 of ISO
306, as previously described. For example, the raw construction material comprising the closure of the invention can exhibit a Vicat softening point of about 75 C to about 175 C, preferably about 125 C to about 154 C. The closure of the invention exhibits a Vicat softening point of at least 50 C to about 95 C, preferably about 75 C to about 85 C, according to test method B50 of ISO 306, as previously described.
Methods for Closures The closures described above can be formed using injection molding. Injection molding is a manufacturing process for producing parts from thermoplastic materials, thermosetting plastic materials, or a mixture thereof. During injection molding, polymeric material is fed into a barrel, mixed, formed into a melt, and forced into a three-dimensional mold cavity where it solidifies into the configuration of the moldcavity via cooling, heating, and/or chemical reaction.
Injection molding can be used to make single layer closures or multilayer closures.
Sustainable Trigger Sprayer-Type Dispensers In some embodiments, the sustainable article may comprise a spray-type dispenser that may be used in conjunction with the sustainable container according to one or more embodiments described above. For example, compositions for reducing malodor impression may be placed into a spray dispenser to be distributed onto the fabric. Said spray dispenser may be any of the manually activated means for producing a spray of liquid droplets as is known in the art, e.g.
trigger-type, pump-type, non-aerosol self-pressurized, and aerosol-type spray means. The spray dispenser herein does not include those that will substantially foam a clear, aqueous composition.
It may be preferred that at least 80%, more preferably, at least 90% of the droplets have a particle size of larger than 30 um.
The spray dispenser can be an aerosol dispenser. Said aerosol dispenser comprises a container which can be constructed of any of the conventional materials employed in fabricating aerosol containers. The dispenser must be capable of withstanding internal pressure in the range of from about 20 to about 110 p.s.i.g., more preferably from about 20 to about 70 p.s.i.g. The one important requirement concerning the dispenser is that it be provided with a valve member which will permit the clear, aqueous odor absorbing composition contained in the dispenser to be dispensed in the form of a spray of very fine, or finely divided, particles or droplets. The valve member may comprise or be made from a bio-derived plastic such as bio-derived polyethylene or bbe polyethylene terephthalate, for example.
The aerosol dispenser may utilize a pressurized sealed sustainable container from which a composition may be dispensed through a special actuator/valve assembly under pressure. The 5 aerosol dispenser may be pressurized by incorporating therein a gaseous component generally known as a propellant. Common aerosol propellants, e.g., gaseous hydrocarbons such as isobutane, and mixed halogenated hydrocarbons, are not preferred but, if present, may comprise or consist of bio-derived hydrocarbons to increase sustainability of the consumer product as a whole. Halogenated hydrocarbon propellants such as chlorofluoro hydrocarbons have been 10 alleged to contribute to environmental problems. Hydrocarbon propellants can form complexes with the cyclodextrin molecules thereby reducing the availability of uncomplexed cyclodextrin molecules for odor absorption. Preferred propellants are compressed air, nitrogen, inert gases, carbon dioxide, etc. A more complete description of commercially available aerosol-spray dispensers appears in U.S. Pat. No. 3,436,772, Stebbins, issued Apr. 8, 1969;
and U.S. Pat. No.
15 3,600,325, Kaufman et al., issued Aug. 17, 1971; both of said references are incorporated herein by reference. Because nitrogen and many inert gases do not contain carbon atoms, they may be regarded as "natural" according to the definitions provided herein, even if they are not bio-derived. As such, natural propellants such as nitrogen and inert gases that do not contain carbon are particularly preferred.
20 Preferably the spray dispenser can be a self-pressurized non-aerosol container having a convoluted liner and an elastomeric sleeve, either or both of which may be formed from bio-derived materials. Said self-pressurized dispenser comprises a liner/sleeve assembly containing a thin, flexible radially expandable convoluted plastic liner of from about 0.010 to about 0.020 inch thick, inside an essentially cylindrical elastomeric sleeve. The liner/sleeve is capable of holding a 25 substantial quantity of odor-absorbing fluid product and of causing said product to be dispensed.
A more complete description of self-pressurized spray dispensers can be found in U.S. Pat. No.
5,111,971, Winer, issued May 12, 1992, and U.S. Pat. No. 5,232,126, Winer, issued Aug. 3, 1993; both of said references are herein incorporated by reference. Another type of aerosol spray dispenser is one wherein a barrier separates the odor absorbing composition from the propellant (preferably compressed air or nitrogen), as disclosed in U.S. Pat. No.
4,260,110, issued Apr. 7, 1981, and incorporated herein by reference. Such a dispenser is available from EP Spray Systems, East Hanover, N.J.
In some embodiments, the sustainable article may comprise a spray-type dispenser that may be used in conjunction with the sustainable container according to one or more embodiments described above. Suitable spray-type dispensers may include aerosols as well as manually-operated foam trigger-type dispensers according to the design and operation principles of those sold by Specialty Packaging Products, Inc. or Continental Sprayers, Inc., for example. These types of dispensers are disclosed, for example, in U.S. Pat. No. 4,701,311 to Dunnining et al. and U.S. Pat. No. 4,646,973 and U.S. Pat. No. 4,538,745, both to Focarracci.
Particularly preferred to be used herein are spray-type dispensers having the design and operation principals of devices such as T 8500 commercially available from Continental Spray International or commercially available from Canyon, Northern Ireland. In such a spray-type dispenser the liquid composition is divided in fine liquid droplets resulting in a spray that is directed onto the surface to be treated. Indeed, in such a spray-type dispenser the composition contained in the body of said dispenser is directed through the spray-type dispenser head via energy communicated to a pumping mechanism by the user as said user activates said pumping mechanism.
More particularly, in said spray-type dispenser head the composition is forced against an obstacle, e.g.
a grid or a cone or the like, thereby providing shocks to help atomize the liquid composition, i.e.
to help the formation of liquid droplets.
Most preferably, the spray dispenser is a manually activated trigger-spray dispenser.
Such a trigger-spray dispenser comprises a container and a trigger, both of which can be constructed of any of the conventional material employed in fabricating trigger-spray dispensers, including, but not limited to: polyethylene; polypropylene; polyacetal;
polycarbonate;
polyethyleneterephthalate; polyvinyl chloride; polystyrene; blends of polyethylene, vinyl acetate, and rubber elastomer. If these materials are used, most preferably all or a portion thereof are bio-derived materials such as bio-derived polyethylene; bio-derived polypropylene;
bio-derived polyacetal; bio-derived polycarbonate; bio-derived polyethyleneterephthalate;
bio-derived polyvinyl chloride; bio-derived polystyrene; blends of bio-derived polyethylene, bio-derived vinyl acetate, and bio-derived rubber elastomer; combinations thereof, and mixtures thereof.
Other materials can include stainless steel and glass. A preferred container is made of clear, e.g.
polyethylene terephthalate.
The trigger-spray dispenser does not incorporate a propellant gas into the composition contained therein, and preferably it does not include those that will foam the odor-absorbing composition. The trigger-spray dispenser herein is typically one which acts upon a discrete amount of the composition itself, typically by means of a piston or a collapsing bellows that displaces the composition through a nozzle to create a spray of thin liquid.
Such a trigger-spray dispenser typically comprises a pump chamber having either a piston or bellows which is movable through a limited stroke response to the trigger for varying the volume of said pump chamber. This pump chamber or bellows chamber collects and holds the product for dispensing.
The trigger spray dispenser typically has an outlet check valve for blocking communication and flow of fluid through the nozzle and is responsive to the pressure inside the chamber. For the piston type trigger sprayers, as the trigger is compressed, it acts on the fluid in the chamber and the spring, increasing the pressure on the fluid. For the bellows spray dispenser, as the bellows is compressed, the pressure increases on the fluid. The increase in fluid pressure in either trigger spray dispenser acts to open the top outlet check valve. The top valve allows the product to be forced through the swirl chamber and out the nozzle to form a discharge pattern. An adjustable nozzle cap can be used to vary the pattern of the fluid dispensed.
For the piston spray dispenser, as the trigger is released, the spring acts on the piston to return it to its original position. For the bellows spray dispenser, the bellows acts as the spring to return to its original position. This action causes a vacuum in the chamber.
The responding fluid acts to close the outlet valve while opening the inlet valve drawing product up to the chamber from the reservoir.
A more complete disclosure of commercially available dispensing devices appears in U.S.
Pat. No. 4,082,223, Nozawa, issued Apr. 4, 1978; U.S. Pat. No. 4,161,288, McKinney, issued Jul.
17, 1985; U.S. Pat. No. 4,434,917, Saito etal., issued Mar. 6, 1984; and U.S.
Pat. No. 4,819,835, Tasaki, issued Apr. 11, 1989; U.S. Pat. No. 5,303,867, Peterson, issued Apr.
19, 1994; all of said references are incorporated herein by reference.
Thus, in general, trigger-operated spray-type dispensers may comprise a neck adapted to fit on the sustainable container, for example by a thread fitting; a straw having a first end that reaches into a liquid contained in the sustainable container and a second end in fluidic communciation with a compression chamber; a trigger; a nozzle; and mechanical components that compress and deliver a liquid composition from the compression chamber and through the nozzle in a suitable spray pattern. In specific non-limiting embodiments, any or all of the straw, the compression chamber, the trigger, the nozzle, and/or the mechanical components may comprise or be formed from one or more bio-derived materials. In further non-limiting embodiments any or all of these components may comprise or be made from the same materials or combinations of materials of the sustainable containers or the sustainable closures described above. For example, the components of the spray-type dispenser may comprise or be made from bio-derived polyethylene, bio-derived high-density polyethylene, bio-derived polypropylene, bio-derived polyethylene terephthalic acid, combinations thereof, and mixtures thereof.

Sustainable Pump-Type Dispensers In some embodiments, the sustainable article may comprise a pump-type dispenser that may be used in conjunction with the sustainable container according to one or more embodiments described above. In this sense, the pump-type dispenser may be a non-aerosol, manually activated, pump-spray dispenser. Such a pump-spray dispenser may comprise a sustainable container, as described above, and a pump mechanism that securely screws or snaps onto the container. The container comprises a vessel for containing the particular composition to be dispensed.
The pump mechanism may comprise a pump chamber of substantially fixed volume, having an opening at the inner end thereof. Within the pump chamber is located a pump stem having a piston on the end thereof disposed for reciprocal motion in the pump chamber. The pump stem has a passageway there through with a dispensing outlet at the outer end of the passageway and an axial inlet port located inwardly thereof.
The container and the pump mechanism may be constructed of any conventional material employed in fabricating pump-spray dispensers, including, but not limited to:
polyethylene;
polypropylene; polyethyleneterephthalate; blends of polyethylene, vinyl acetate, and rubber elastomer. A preferred container is made of clear, e.g., polyethylene terephthalate. Other materials can include stainless steel. A more complete disclosure of commercially available dispensing devices appears in: U.S. Pat. No. 4,895,279, Schultz, issued Jan.
23, 1990; U.S. Pat.
No. 4,735,347, Schultz et al., issued Apr. 5, 1988; and U.S. Pat. No.
4,274,560, Carter, issued Jun. 23, 1981; all of said references are herein incorporated by reference.
Most preferably, the pump-spray dispensers comprise or are formed from bio-derived materials such as: bio-derived polyethylene; bio-derived polypropylene; bio-derived polyethyleneterephthalate; blends of bio-derived polyethylene, bio-derived vinyl acetate, and bio-derived rubber elastomer; combinations thereof; and mixtures thereof.
A broad array of designs for trigger sprayers or finger pump sprayers are suitable for use with the compositions of this invention. Suitable designs include those available from suppliers such as Calmar, Inc., City of Industry, Calif.; CSI (Continental Sprayers, Inc.), St. Peters, Mo.;
Berry Plastics Corp., Evansville, Ind.--a distributor of Gualag sprayers; or Seaquest Dispensing, Cary, Ill., preferably made with components comprising bio-derived materials.
The preferred trigger sprayers are the blue inserted Guala sprayer, available from Berry Plastics Corp., or the Calmar TS800-1A sprayers, available from Calmar Inc., because of the fine uniform spray characteristics, spray volume, and pattern size. Any suitable bottle or container can be used with the trigger sprayer, the preferred bottle is a 17 fl-oz.
bottle (about 500 ml) of good ergonomics similar in shape to the Cinch bottle. It can be made of any materials such as high density polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyethylene terephthalate, glass, or any other material that forms bottles. Preferably, it is made of high density polyethylene or clear polyethylene terephthalate. Most preferably, the container is a sustainable container such as those described above.
For smaller four fl-oz. size (about 118 ml), a finger pump can be used with canister or cylindrical bottle. The preferred pump for this application is the cylindrical Euromist II , from Seaquest Dispensing.
The pump-type dispenser may further comprise a foam-generating dispenser for generating a foam. When activated, the foam-generating dispenser generates foam and concurrently dispenses the foamed composition from the container. The foam-generating dispenser may be formed as either integral with, or separate from the container. If formed separately, the foam-generating dispenser may attach to the container via methods known in the art such as by employing a transition piece, corresponding threaded male and female members, pressurized and non-pressurized seals, locking and snap-on parts, and/or other methods known in the art. Preferably, the foam-generating dispenser is attached to the container via a transition piece and/or with corresponding threaded male and female members which allow easy refilling.
The foam-generating dispenser may generate a foam via any method, such as a chemical reaction, an enzymatic reaction, and/or a mechanical action. However, a mechanical action is preferred herein, and typically involves a mechanism which imparts a gas, such as air, nitrogen, carbon dioxide, etc., directly into the dishwashing composition in a turbulent manner as it dispenses, so as to physically form the foam. Preferably, the foam-generating dispenser includes a gas imparting mechanism to form the foam, such as, for example, a propellant or liquefied gas, a pressurized gas, an aerosol gas, an air injection piston, foam-generating aperture, an impinging surface, a mesh or net, a pump, and/or a sprayer, more preferably, an air injection piston, a pump, an impinging surface, a mesh or net, and/or a sprayer which injects or imparts air from the atmosphere into the dishwashing composition.
The foam-generating dispenser also typically includes an activator, preferably a manual activator such as, for example, a trigger, a pressure-activated pumping mechanism, a button, and/or a slider, more preferably a trigger and/or a pressure-activated pumping mechanism which can be activated with a single finger. It is highly preferred that the activator be designed such that a consumer may easily activate it when their. hands are wet and/or slippery. Such an activator should allow the user to easily and conveniently control both the speed of dispensing and the volume dispensed. For certain applications, such as in industry or in public facilities, other activators may be useful, such as an electronic activator, a computer-controlled activator, an electric eye or an infrared detection activator, a manual lever-assist activator, etc. It may be preferably that any or all of the components of the foam-generating dispenser be formed from a 5 bio-derived material such as bio-PE, bio-HDPE, bio-PP, or bio-PET, for example.
Sustainable Labels The sustainable article, particularly any of the sustainable containers, the sustainable closures, the sustainable trigger spray dispensers, and the trigger pump dispensers described above, may be labeled with a suitable sustainable label that may contain printed indicia.
10 In non-limiting embodiments, the label may be composed of a substrate that includes a polymer selected from the group consisting of polyethylene that has a biobased content of at least 90%, preferably at least 93%, more preferably at least 95%, for example, about 100%; post-consumer recycled polyethylene (PCR-PE); post-industrial recycled polyethylene (PIR-PE);
paper; and a mixture thereof. The polyethylene can include LDPE, LLDPE, or HDPE. In 15 alternative embodiments, the substrate includes a polymer selected from the group consisting of polyethylene terephthalate that has a biobased content of at least 90%, preferably at least 93%, more preferably at least 95%, for example, about 100%; post-consumer recycled polyethylene terephthalate (PCR-PET); post-industrial recycled polyethylene terephthalate (PIR-PET); paper;
and a mixture thereof In other alternative embodiments, the substrate includes a polymer 20 selected from the group consisting of polypropylene that has a biobased content of at least 90%, preferably at least 93%, more preferably at least 95%, for example, about 100%; post-consumer recycled polypropylene (PCR-PP); post-industrial recycled polypropylene (PIR-PP); paper; and a mixture thereof.
In further embodiments, the label may be composed of a substrate that includes a polymer 25 selected from the group consisting of polyethylene terephthalate that has a biobased content of at least 90%, preferably at least 93%, more preferably at least 95%, for example, about 100%; post-consumer recycled polyethylene terephthalate (PET); post-industrial recycled PET; regrind PET;
paper, or a mixture thereof. In some alternative embodiments, the label is composed of a substrate that includes a polymer selected from the group consisting of polyethylene that has a 30 biobased content of at least 90%, preferably at least 93%, more preferably at least 95%, for example, about 100%; post-consumer recycled polyethylene (PCR-PE); post-industrial recycled polyethylene (PIR-PE); paper; and a mixture thereof. In other alternative embodiments, the substrate includes a polymer selected from the group consisting of polypropylene that has a biobased content of at least 90%, preferably at least 93%, more preferably at least 95%, for example, about 100%; post-consumer recycled polypropylene (PCR-PP); post-industrial recycled polypropylene (P1R-PP); paper; and a mixture thereof.
In still further embodiments, the label may be composed of a substrate that includes a polymer selected from the group consisting of polyethylene that has a biobased content of at least 90%, preferably at least 93%, more preferably at least 95%, for example about 100%; post-consumer recycled polyethylene (PCR-PE); post-industrial recycled polyethylene (PIR-PE);
paper; and a mixture thereof. In alternative embodiments, the label is composed of a substrate that includes a polymer selected from the group consisting of polypropylene that has a biobased content of at least 90%, preferably at least 93%, more preferably at least 95%, for example, about 100%; post-consumer recycled polypropylene (PCR-PP), post-industrial recycled polypropylene (PIR-PP); regrind polypropylene; paper; and a mixture thereof. In other alternative embodiments, the substrate includes a polymer selected from the group consisting of polyethylene terephthalate that has a biobased content of at least 90%, preferably at least 93%, more preferably at least 95%, for example, about 100%; post-consumer recycled polyethylene terephthalate (PCR-PET); post-industrial recycled polyethylene terephthalate (PIR-PET); paper; and a mixture thereof.
The label may further include printed indicia made from an ink. The ink can be solvent-based or water-based. In some embodiments, the ink is derived from a renewable resource, such as soy, a plant, or a mixture thereof. The ink can be cured using heat or ultraviolet radiation (UV). In some preferred embodiments, the ink is cured by UV, which results in a reduction of curing time and energy output. Nonlimiting examples of inks include ECO-SURE!TM from Gans Ink & Supply Co. and the solvent-based VUTEk and BioVuTM inks from EFI, which are derived completely from renewable resources (e.g., corn).
The label can be fixed to the sustainable container using adhesive. In some preferred embodiments, the adhesive is a renewable adhesive, such as BioTAK by Berkshire Labels, which is fully biodegradable and compostable, conforms to European standard EN
13432, and is approved by the FDA, a shrink sleeve, or by melting the label onto the container during manufacturing. Alternatively, the label can be molded directly into the plastic of the container.
The label can optionally comprise layers. For example, a metallization effect results when a layer composed of ink/metallization is flanked by outer layers composed of polyethylene in a trilayer label.
When the label is composed of polyethylene or polypropylene, it may have a density of less than 1 g/mL to aid separation during the floatation process of recycling, as previously described. When the label is composed of polyethylene terephthalate it has a density of greater than 1 g/mL.
Characterization of Labels Each component of the sustainable article has a shelf life of at least two years. The density of the label can be determined using ASTM D792.
A label with a shelf life of at least two years can be characterized by at least one of the following expedients: its chemical resistance, product resistance, shrinkage, friction test, and rub test. The chemical resistance of the label is determined by the Soak Squeeze Test, which assesses the label adhesion to the container, the label de-lamination resistance, and the label product or water resistance during a simulated shower or bath use. The results of the test are determined by the performance of the label after submerging containers filled with a diluted soap solution in a 38 C diluted soap solution bath (i.e., 5 grams per liter) for one hour and squeezing the container 10, 50, and 100 times. The labels of the invention exhibit no change (e.g., creases in the label, blisters, bubbles, flaking ink, changes in printing ink colors) after the multiple squeezes.
Product resistance is the ability of a label to resist its intended product.
To test product compatibility, product is dropped on the printed side of label at about 20 to 24 C. After about 24 hours, the product is wiped off the label surface using a soft paper tissue, and the label is examined for traces of ink bleed, surface discoloration, and foil blocking.
The labels of the invention exhibit no change in each of the examined parameters.
Shrinkage is the loss of label size. The labels of the invention exhibit less than 0.2%, preferably less than 0.1%, shrinkage 24 hours after their manufacture.
The friction test measures the level of friction of label surfaces to determine the slip of the product on a packing line's conveyors. In this test, a label is wrapped around a 200 g steel block and dragged at least 15 mm across a rubber mat at a rate of 150 mm/min. The labels of the invention remain unchanged when subjected to the friction test.
The rub test ensures that label artwork does not rub off or scratch during manufacture or use. In this test, a label is folded with printed side in and placed between the thumb and forefinger. The label is lightly rolled back and forth between the finger for ten cycles. The label of the invention remains unchanged after the rub test.

Methods for Labels The labels of the invention can be formed using film extrusion. In film extrusion, thermoplastic material is melted and formed into a continuous profile. In some embodiments, multilayer films are coextruded. Film extrusion and coextrusion can be performed by any method known to one skilled in the art.
Consumer Compositions The sustainable container may be used in any suitable manner such as to deliver to a consumer, to contain, or to dispense for application, a consumer product that may be beneficial for fabric care, personal care, or home care. The type of consumer products suitable for use herein are limited generally only by the compatibility of the compositions with the materials from which the sustainable container is made. Without intent to be bound by theory, it is believed that compatibility issues with bio-derived materials will be substantially identical to those encountered with petroleum-derived counterparts. As such, it should be clear to the person of ordinary skill how to most appropriately select materials for the sustainable container, in view of what is already known about petroleum-derived containers.
The consumer products typically are liquids but may also be solids, semi-solids, creams, gels, compressed gases, or combinations thereof. In several embodiments, compositions that may be contained in the sustainable containers include, but are not limited to, liquid laundry detergents, liquid fabric softeners, laundry stain removers, dryer sheets, toothpastes, mouthwashes, hand dishwashing compositions, automatic dishwashing compositions, fabric freshening compositions, air freshening compositions including those used in energized devices (e.g., plug-in air fresheners and battery-powered air fresheners) and those used in passive air-freshening systems (e.g., air freshening systems activated by gravity, actuated by a timer, or intended for use over a moving air source such as found over a vent opening in a vehicle cabin such as the passenger compartment of a car), odor control compositions, shaving creams, shampoos, hair conditioners, hair colorants, deodorants, antiperspirants, personal beauty products, cosmetics, dental products, feminine hygiene products, colognes, hand soaps, bath soaps, hair-styling products, skin-care compositions, body washes, body sprays, hard-surface cleaning compositions, glass cleaning compositions, toilet cleaning compositions, and carpet cleaning compositions. In preferred embodiments, the consumer products suited for the sustainable containers described herein are hard-surface cleaners appropriate for cleaning household hard surfaces such as glass, ceramic tile, wood, stainless steel, natural and synthetic countertops, stone surfaces, granite, baseboards, floors, and kitchen appliances. In some embodiments, the hard-surface cleaners may comprise one or more surfactants compatible with the bio-derived material of the sustainable container. In some embodiments, the hard-surface cleaners may further comprise one or more odor-reducing agents and/or antibactierial agents.
Exemplary Embodiments of Sustainable Articles The container of the sustainable articles described above, preferably when composed of polypropylene, can further include an impact modifier in an amount of about 2 wt.% to about 20 wt.%, preferably about 5 wt.% to about 10 wt.%. The impact modifier typically includes LDPE
in an amount of about 5 wt.% to about 10 wt.%, an olefinic elastomer in an amount of about 5 wt.% to about 15 wt.%, a styrenic elastomer in an amount of about 2 wt.% to about 10 wt.%, or a mixture thereof Examples of impact modifiers include Dow AFFINITYTm (i.e., polyolefin plastomer), Exxon Mobil VISTAMAXXTm (i.e., polypropylene based elastomer), and KRATON from GLS (i.e., styrenic based block-copolymer/elastomer), any of which can vary in the level of saturation of the olefinic portion. The impact modifier can be derived wholly or partly from oil, wholly or partially from a renewable resource, or wholly or partially from recycled material.
The closure of the sustainable article in any of the aspects can optionally include up to 70 wt.%, preferably up to about 30 wt.%, more preferably up to about 40 wt.%, even more preferably up to about 50 wt.%. of regrind polypropylene, regrind polyethylene, or a mixture thereof, based on the total weight of the closure. In some embodiments, the amount of regrind polymer can be about 5 wt.% to about 75 wt.%, preferably about 25 wt.% to about 50 wt.%, based on the total weight of the closure. The incorporation of regrind material in the closure decreases the cost of the resulting article and prevents material waste within plants, further improving sustainability of the plant.
Additionally or alternatively, the closure of the sustainable article in any of the aspects can optionally include elastomer derived from a recycled material, for example, from diaper scrap, which contains an amount of elastomer. The presence of elastomer in the closure improves, for example, the stress crack resistance, and drop impact resistance, of the closure.
Elastomer can be present in the closure in an amount of about 0.1 wt.% to about 60 wt.%, preferably about 0.1 wt.% to about 40 wt.%, more preferably about 0.1 wt.% to about 20 wt.%, depending on the exact performance needs. The elastomer also can be derived wholly or partly from oil, wholly or partially from a renewable resource, or wholly or partially from recycled material.
At least one of the container, closure, or label of the sustainable article in aspects where the container, closure, and label are not composed of polyethylene terephthalate, can optionally 5 include less than 70 wt.% of a biodegradable polymer, based on the total weight of the container, closure, or label, as long as the resulting container, closure, or label has a density of less than 1 g/mL. The biodegradable polymer can be embedded into the polymer matrix of the renewable, recycled, or regrind material (e.g., by physical blending) to prevent the biodegradable polymer from being exposed to the surface of the article component, preventing it from biodegrading 10 and/or deteriorating. Nonlimiting examples of biodegradable polymers include aliphatic polyesters, such as polylactic acid (PLA), polyglycolic acid (PGA), polybutylene succinate (PBS), and copolymers thereof; aliphatic-aromatic polyesters such as ECOFLEX
from BASF
(i.e., an aliphatic-aromatic copolyester based on terephthalic acid, adipic acid, and 1,4-butanediol), BIOMAX from DuPont (i.e., an aromatic copolyester with a high terephthalic acid 15 content); polyhydroxyalkanoate (PHA), and copolymers thereof;
thermoplastic starch (TPS) materials; cellulosics; and a mixture thereof. In some embodiments, the biodegradable polymer further includes an inorganic salt, such as calcium carbonate calcium sulfate, talcs, clays (e.g., nanoclays), aluminum hydroxide, CaSiO3, glass fibers, crystalline silicas (e.g., quartz, novacite, crystallobite), magnesium hydroxide, mica, sodium sulfate, lithopone, magnesium carbonate, 20 iron oxide, or a mixture thereof.
At least one of the container, closure, or label of the sustainable article in any of the aspects can optionally include a colorant masterbatch. As used herein, a "colorant masterbatch"
refers to a mixture in which pigments are dispersed at high concentration in a carrier material.
The colorant masterbatch is used to impart color to the final product. In some embodiments, the 25 carrier is a biobased plastic or a petroleum-based plastic, while in alternative embodiments, the carrier is a biobased oil or a petroleum-based oil. The colorant masterbatch can be derived wholly or partly from a petroleum resource, wholly or partly from a renewable resource, or wholly or partly from a recycled resource. Nonlimiting examples of the carrier include bio-derived or oil derived polyethylene (e.g,. LLDPE, LDPE, HDPE), bio-derived oil (e.g., olive oil, 30 rapeseed oil, peanut oil), petroleum-derived oil, recycled oil, bio-derived or petroleum derived polyethylene terephthalate, polypropylene, and a mixture thereof. The pigment of the carrier, which can be derived from either a renewable resource or a non-renewable resource, can include, for example, an inorganic pigment, an organic pigment, a polymeric resin, or a mixture thereof.
Nonlimiting examples of pigments include titanium dioxide (e.g., rutile, anatase), copper phthalocyanine, antimony oxide, zinc oxide, calcium carbonate, fumed silica, phthalocyamine (e.g., phthalocyamine blue), ultramarine blue, cobalt blue, monoazo pigments, diazo pigments, acid dye, base dye, quinacridone, and a mixture thereof. In some embodiments, the colorant masterbatch can further include one or more additives, which can either be derived from a renewable resource or a non-renewable resource. Nonlimiting examples of additives include slip agents, UV absorbers, nucleating agents, UV stabilizers, heat stabilizers, clarifying agents, fillers, brighteners, process aids, perfumes, flavors, and a mixture thereof.
In some embodiments, color can be imparted to the container, closure, or label of the sustainable article in any of the aspects by using direct compounding (i.e., in-line compounding).
In these embodiments, a twin screw compounder is placed at the beginning of the injection molding, blow molding, or film line and additives, such as pigments, are blended into the resin just before article formation.
At least one of the container or closure of the sustainable article in any of the aspects can further include about I wt.% to about 50 wt.%, preferably about 3 wt.% to about 30 wt.%, more preferably about 5 wt.% to about 15 wt.% of a filler, based on the total weight of the container, closure, or label. Nonlimiting examples of fillers include starches, renewable fibers (e.g., hemp, flax, coconut, wood, paper, bamboo, grass), inorganic materials (e.g., calcium carbonate, mica, talc), gases (e.g., high pressure gas), foaming agents, microspheres, biodegradable polymers (e.g., PLA, PHA, TPS), a renewable, but non-biodegradable polymer (e.g., particles of cellulose acetate, polyaminde-11, alkyd resin), and mixtures thereof.
One or more of the container, closure, and label of the sustainable article in any of the aforementioned aspects can exhibit a single layer or multiple layers. When a component of the sustainable article exhibits multiple layers, the component can include 2, 3, 4, 5, 6, 7, 8, 9, or 10 layers. Preferably, the multilayer is a bilayer, trilayer, quadruple layer, or a quintuple layer. In some embodiments, the multilayer is a bilayer that has a weight ratio of outer layer to inner layer of about 99:1 to about 1:99, preferably about 10:90 to about 30:70, for example, about 20:80. In some embodiments, the multilayer is a trilayer that has a weight ratio of outer layer to middle layer to inner layer of about 1:98:1 to about 30:40:30, for example, about 5:90:5, 10:80:10 or 20:60:20. In some embodiments when a component of the article has at least three layers, recycled material, one or more biodegradable polymers (e.g., PLA, PHA, TPS, cellulose), or a mixture thereof comprises a middle layer. The middle layer composed of recycled material, biodegradable polymer, or a mixture thereof can further include an inorganic salt, such as calciUm carbonate calcium sulfate, talcs, clays (e.g., nanoclays), aluminum hydroxide, CaSiO3, glass fibers, crystalline silicas (e.g., quartz, novacite, crystallobite), magnesium hydroxide, mica, sodium sulfate, lithopone, magnesium carbonate, iron oxide, or a mixture thereof. A multilayer component with recycled material or biodegradable polymer as the middle layer can be achieved, for example, by injection techniques (e.g., co-injection), a stretch blow process, or an extrusion blow molding process, as described herein. In some embodiments, a multilayer component of the sustainable article includes a barrier layer to gases (e.g., oxygen, nitrogen, carbon dioxide, helium). The barrier layer can be biobased or petroleum-based, and composed of, for example, ethyl vinyl alcohol copolymer (EVOH).
SUSTAINABLE COMPOSITIONS
The sustainable consumer product may comprise a sustainable composition contained within a sustainable container according to any of the embodiments described above. The sustainable composition may be any consumer product that may be beneficial for fabric care, personal care, or home care, provided that the consumer product comprises or consists of one or more bio-derived ingredients. The type of consumer products suitable for use herein are limited generally only by the compatibility of the compositions with the materials from which the sustainable container is made. Without intent to be bound by theory, it is believed that compatibility issues with bio-derived sustainable compositions and bio-derived materials will be substantially identical to those encountered with petroleum-derived counterparts. As such, it should be clear to the person of ordinary skill how to most appropriately select materials for the bio-derived sustainable composition in the sustainable container, in view of what is already known about petroleum-derived containers and petroleum-derived compositions.
The sustainable consumer compositions typically are liquids but may also be solids, semi-solids, creams, gels, compressed gases, or combinations thereof. In several embodiments, compositions that may be contained in the sustainable containers include, but are not limited to, liquid laundry detergents, liquid fabric softeners, laundry stain removers, dryer sheets, toothpastes, mouthwashes, hand dishwashing compositions, automatic dishwashing compositions, fabric freshening compositions, odor control compositions, air fresheners, shaving creams, shampoos, hair conditioners, hair colorants, deodorants, antiperspirants, personal beauty products, cosmetics, dental products, feminine hygiene products, colognes, hand soaps, bath soaps, hair-styling products, skin-care compositions, body washes, body sprays, hard-surface cleaning compositions, glass cleaning compositions, toilet cleaning compositions, and carpet cleaning compositions. In preferred embodiments, the consumer products suited for the sustainable containers described herein are hard-surface cleaners appropriate for cleaning household hard surfaces such as glass, ceramic tile, wood, stainless steel, natural and synthetic countertops, stone surfaces, granite, baseboards, floors, and kitchen appliances. In some embodiments, the hard-surface cleaners may comprise one or more surfactants compatible with the bio-derived material of the sustainable container. In some embodiments, the hard-surface cleaners may further comprise one or more odor-reducing agents and/or antibactierial agents.
In exemplary embodiments, the sustainable composition comprises at least one bio-derived ingredient selected from the group consisting of sustainable bio-derived low-residue surfactants, sustainable bio-derived solvents, sustainable bio-derived polymers, sustainable bio-derived thickening agents, sustainable bio-derived fragrances and/or natural essences, sustainable bio-derived odor-control agents; optional additional sustainable bio-derived surfactants; bio-derived adjuncts; bio-derived builders; and/or enzymes.
Sustainable Low-Residue Surfactant The sustainable compositions will normally have one of the preferred surfactants present, such as alkylpolysaccharides or nonionic surfactants, including alkyl ethoxylates. The surfactants may be petroluem-derived, bio-derived, or part petroleum-derived and part bio-derived. In a preferred embodiment, the composition according to the present invention comprises a low-residue surfactant or a mixture thereof.
By "low-residue surfactant" it is meant herein any surfactant that mitigates the appearance of either streaks or films upon evaporation of the aqueous compositions comprising said surfactant. A low residue surfactant-containing composition may be identified using either gloss-meter readings or expert visual grade readings. The conditions for the determination of what constitutes a low-residue surfactant are one of the following: (a) less than 1.5% gloss loss on black shiny porcelain tiles, preferably on black shiny Extracompa porcelain tiles used in this invention; or (b) lack of significant filming and/streaking as judged by one skilled in the art. One of the important advantages of the low residue surfactant is that it requires less polymeric biguanide compound for gloss enhancement, relative to non-low residue surfactants. This can be important in light of cost considerations, potential stickiness issues delivered by higher concentrations of the polymeric biguanide, and/or concerns over the ability to completely strip a more concentrated polymeric biguanide film.
As identified within this invention there are three classes of low-residue surfactants:
selected non-ionic surfactants, and zwitterionic surfactants and amphoteric surfactants and mixtures thereof. One class of low residue surfactants is the group of non-ionic surfactants that include a head group consisting of one or more sugar moieties. Examples include alkyl polyglycosides, especially poly alkyl glucosides, and sucrose esters. The chain length of these non-ionic surfactants is preferably about C6 to about C18, more preferably from about C8 to about C16. The hydrophilic component of these surfactants may comprise one or more sugar moieties liked by glycosidic linkages. In a preferred embodiment, the average number of sugar moieties per surfactant chain length is from about 1 to about 3, more preferably from about 1.1 to about 2.2.
The most preferred non-ionic low residue surfactants are the alkylpolysaccharides that are disclosed in U.S. Patents: U.S. Pat. No. 5,776,872, Cleansing compositions, issued Jul. 7, 1998, to Giret, Michel Joseph; Langlois, Anne; and Duke, Roland Philip; U.S. Pat.
No. 5,883,059, Three in one ultra mild lathering antibacterial liquid personal cleansing composition, issued Mar.
16, 1999, to Furman, Christopher Allen; Giret, Michel Joseph; and Dunbar, James Charles; etc.;
U.S. Pat. No. 5,883,062, Manual dishwashing compositions, issued Mar. 16, 1999, to Addison, Michael Crombie; Foley, Peter Robert; and Allsebrook, Andrew Micheal; and U.S.
Pat. No.
5,906,973, issued May 25, 1999, Process for cleaning vertical or inclined hard surfaces, by Ouzounis, Dimitrios and Nierhaus, Wolfgang.
The low-residue surfactants for use herein further may include, for example alkylpolyglycosides having the formula:
R20(CõH2O)t (glycosyl),x where R2 is selected from the group consisting of alkyl, alkyl-phenyl, hydroxyallyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from about 10 to about 18, preferably from about 12 to about 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 to about 10, preferably 0; and x is from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7. The glycosyl is preferably derived from glucose. Preferably, the alkylpolyglycosides are bio-derived.
To prepare these compounds, a bio-derived alcohol or bio-derived alkylpolyethoxy alcohol is formed first and then reacted with glucose, such as bio-derived glucose, to form the glucoside (attachment at the 1-position). The additional glycosyl units can then be attached between their 1-position and the preceding glycosyl units 2-, 3-, 4- and/or 6-position, preferably predominantly the 2-position.
Thus, alkyl polyglycosides (APGs), also called alkyl polyglucosides if the saccharide moiety is glucose, are naturally derived, nonionic surfactants. The alkyl polyglycosides also may fatty ester derivatives of saccharides or polysaccharides that are formed when a carbohydrate is reacted under acidic condition with a bio-derived fatty alcohol through condensation polymerization. The APGs are typically derived from corn-based carbohydrates and fatty alcohols from natural oils in animals, coconuts and palm kernels. Such methods for preparing APGs are well known in the art. For example, U.S. Pat. No. 5,003,057 to McCurry, et al., 5 incorporated herein, describes methods for making APGs, along with their chemical properties.
The alkyl polyglycosides that are preferred contain a hydrophilic group derived from bio-derived carbohydrates and are composed of one or more bio-derived anhydroglucose units. Each of the bio-derived glucose units can have two ether oxygen atoms and three hydroxyl groups, along with a terminal hydroxyl group, which together impart water solubility to the glycoside.
10 The presence of the alkyl carbon chain leads to the hydrophobic tail to the molecule. When carbohydrate molecules react with fatty alcohol compounds, alkyl polyglycoside molecules are formed having single or multiple anhydroglucose units, which are termed monoglycosides and polyglycosides, respectively. The final alkyl polyglycoside product typically has a distribution of varying concentration of glucose units (or degree of polymerization).
15 The APGs for use in the sustainable composition preferably comprise saccharide or polysaccharide groups (i.e., mono-, di-, tri-, etc. saccharides) of hexose or pentose, and a fatty aliphatic group having 6 to 20 carbon atoms. Preferred alkyl polyglycosides are represented by the general formula, Gx¨O¨RI, where G is a moiety derived from reducing saccharide containing 5 or 6 carbon atoms, e.g., pentose or hexose; RI is fatty alkyl group containing 6 to 20 carbon 20 atoms; and x is the degree of polymerization of the polyglycoside, representing the number of monosaccharide repeating units in the polyglycoside. Generally, x is an integer on the basis of individual molecules, but because there are statistical variations in the manufacturing process for APGs, x may be a noninteger on an average basis when referred to APG used as an ingredient for the sustainable composition. For the APGs used in the sustainable compositions, x preferably 25 has a value of less than 2.5, and more preferably is between 1 and 2.
Exemplary bio-derived saccharides from which G can be derived are glucose, fructose, mannose, galactose, talose, gulose, allose, altrose, idose, arabinose, xylose, lyxose and ribose. Because of the ready availability of glucose, glucose is preferred in polyglycosides. The fatty alkyl group is preferably saturated, although unsaturated fatty chains may be used. Generally, the commercially available 30 polyglycosides have C8 to C16 alkyl chains and an average degree of polymerization of from 1.4 to 1.6.
Commercially available alkyl polyglycoside can be obtained as concentrated aqueous solutions ranging from 50 wt.% to 70wt% actives and are available from Cognis.
Most preferred for use in the present compositions are APGs with an average degree of polymerization of from 1.4 to 1.7 and the chain lengths of the aliphatic groups, preferably bio-derived aliphatic groups are between C8 and C16. For example, one preferred APG for use herein has chain length of Cg and C10 (ratio of 45:55) and a degree of polymerization of 1.7.
The sustainable compositions of have the advantage of having less adverse impact on the environment than conventional sustainable compositions. Bio-derived alkyl polyglycosides used in the present invention exhibit low oral and dermal toxicity and irritation on mammalian tissues.
These bio-derived alkyl polyglycosides are also biodegradable in both anaerobic and aerobic conditions and they exhibit low toxicity to plants, thus improving the environmental compatibility of the rinse aid of the present invention. Because of the carbohydrate property and the excellent water solubility characteristics, alkyl polyglycosides are compatible in high caustic and builder formulations. The sustainable compositions may include a sufficient amount of alkyl polyglycoside surfactant in an amount that provides a desired level of cleaning, that being from about 0.01% and about 10% by weight alkyl polyglycoside surfactant. Most preferred is to include an amount between about 0.5% and about 5% by weight actives.
Some alkyl glycosides and polyglycosides occur in nature, e.g. in cyanobacteria such as Anabaena cylindrica, Anamaeba torulosa and Cyanospira rippkae, where they may take part in cell protection. However, synthetic alkyl polyglycosides that may be used in the sustainable compositions may be practically conceived as fatty ester derivatives of saccharides or polysaccharides that are formed when a carbohydrate is reacted under acidic conditions with a fatty alcohol through condensation polymerization. The APGs may be derived from corn-based carbohydrates and fatty alcohols from natural oils found in animals, coconuts and palm kernels.
However, these surfactants alternatively may be constructed with algae-derived bioorganics. As described above, glucose may be directly obtained from algae, or alternately the sugars used to synthesize APG surfactants may be derived from cellulose or other algal polysaccharides. The fatty alcohols may be obtained by hydrolysis or transesterification of algae lipids followed by hydrogenation of the intermediate fatty acids or fatty acid esters. Such methods for deriving APGs from vegetative sources are well known in the art and may be extrapolated to algae-sourced, rather than crop-sourced, bioorganic substances. The alkyl polyglycosides that are preferred for use in the sustainable composition contain a hydrophilic group derived from carbohydrates and are composed of one or more anhydroglucose units. Each of the glucose units may have two ether oxygen atoms and three hydroxyl groups, along with a terminal hydroxyl group, which together impart water solubility to the glycoside. The presence of the alkyl carbon chain leads to the hydrophobic tail of the molecule.

When carbohydrate molecules react with fatty alcohol compounds, alkyl polyglycoside molecules are formed having single or multiple anhydroglucose units, which are termed monoglycosides and polyglycosides, respectively. The final alkyl polyglycoside product typically has a distribution of glucose units (i.e., degree of polymerization).
As noted above, the APGs may comprise saccharide or polysaccharide groups (i.e., mono-, di-, tri-, etc. saccharides) of hexose or pentose, and a fatty aliphatic group having 6 to 20 carbon atoms. Exemplary saccharides from which G can be derived are glucose, fructose, mannose, galactose, talose, gulose, allose, aitrose, idose, arabinose, xylose, lyxose and ribose.
Because of the ready availability of glucose from algae, polyglycosides having glucose substituents may be obtained from algae. The glucose may be obtained as a metabolite from certain cyanobacteria or may be obtained by cellulolysis (chemically or enzymatically) of algal cellulose. The fatty alkyl group is preferably saturated, although unsaturated fatty chains may be used. Generally, commercially available polyglycosides have C8 to C16 alkyl chains and an average degree of polymerization of from 1.4 to 1.6, and these may be readily synthesized from algae-derived intermediates rather than crop-based substances.
Bio-derived alkyl sulfate surfactants are another type of bio-derived anionic surfactant of importance for use herein. In addition to providing excellent overall cleaning ability when used in combination with polyhydroxy fatty acid amides (see below), including good grease/oil cleaning over a wide range of temperatures, wash concentrations, and wash times, dissolution of alkyl sulfates can be obtained, as well as improved formulability in sustainable compositions are water soluble salts or acids of the formula ¨ROSO3M, where R preferably is a hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C10¨C20 alkyl component, more preferably a C12¨C18 alkyl or hydroxyalkyl, and M is H or a cation, e.g., an alkali or alkaline (Group IA or Group 1IA) metal cation (e.g., sodium, potassium, lithium, magnesium, calcium), substituted or unsubstituted ammonium cations such as methyl-, dimethyl-, and trimethyl ammonium and quaternary ammonium cations, e.g., tetramethyl-ammonium and dimethyl piperdinium, and cations derived from alkanolamines such as ethanolamine, diethanolamine, triethanolamine, and mixtures thereof, and the like. Typically, alkyl chains of C12¨C16 are preferred. For example, sodium octyl sulfate, preferably in which the octyl chains thereof are partially or wholly bio-derived, may be a preferred surfactant for use in the sustainable compositions herein.
Zwitterionic surfactants can also be incorporated into the sustainable compositions as low-residue surfactants. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds.
See U.S. Pat.
No. 3,929,678 to Laughlin et al., issued Dec. 30, 1975 at column 19, line 38 through column 22, line 48 for examples of zwitterionic surfactants. Ampholytic and zwitterionic surfactants are generally used in combination with one or more anionic and/or nonionic surfactants and most preferably are formed from bio-derived carbon atoms obtained from natural sources.
Other suitable, amphoteric surfactants being either cationic or anionic depending upon the pH of the system are represented by surfactants such as dodecylbeta-alanine, N-alkyltaurines such as the one prepared by reacting dodecylamine with sodium isethionate according to the teaching of U.S. Pat. No. 2,658,072, N-higher alkylaspartic acids such as those produced according to the teaching of U.S. Pat. No. 2,438,091, and the products sold under the trade name "Miranolg", and described in U.S. Pat. No. 2,528,378, said patents being incorporated herein by reference.
Low-residue surfactants contribute to the filming/streaking performance (i.e., low or substantially no streaks- and/or film-formation) of the compositions according to the present invention.
Low-residue surfactants can be present in the compositions of this invention at levels from about 0.01% to about 15%, preferably of from about 0.01% to about 10%, and more preferably of from about 0.03% to about 0.75% by weight of the total composition. At actual product use levels, following recommended product dilution, if any, the low-residue surfactants are typically present at levels from about 0.01% to about 1.5%, more preferably from about 0.01% to about 10%, and more preferably of from about 0.03% to about 0.75% by weight of the total composition. Importantly, the Applicant has found that the use of a low residue surfactant in combination with a conventional surfactant (i.e., non-low residue) can mitigate filming and/or streaking issues relative to similar compositions that only use the conventional surfactant.
Solvents The sustainable compositions can optionally contain limited amounts of organic solvents.
Preferably, the organic solvents are bio-derived solved such as bio-derived ethanol, bio-derived sorbitol, bio-derived glycerol, bio-derived propylene glycol, bio-derived glycerol, bio-derived 1,3-propanediol, and mixtures thereof. These solvents may be less than 10% of the composition;
preferably less than 5% of the composition. It is preferred that the sustainable compositions described herein be non-flammable, and/or have relatively high flash points, and/or have relatively low amounts of volatile organic compounds (VOCs) meeting, exceeding, or preferably substantially exceeding environmental guidelines recommended or established by law or other guideline in the jurisdictions in which the sustainable compositions may be used. The incorporation of these solvents in sustainable compositions is useful for controlling aesthetic factors of the undiluted products, such as viscosity, and/or for controlling the stability of Alternatively, the sustainable compositions may also be substantially devoid of solvents and may include solvent-free surfactants such as Berol CLF by AkzoNobel. The sustainable Bio-derived solvents can be produced from renewable resources, even if not directly available from the renewable resource. In cases where the bio-solvent is not directly available from the renewable resource, the component that can be derived from the renewable resource may need to undergo one or more chemical reactions and/or purification steps to form the desired bio-derived solvent. For example, two or more chemical components, at least one of which is derived from bio-derived sources, may be used to produce the desired bio-derived solvent. As an 5 example, the esterification of bio-derived acetic acid with bio-derived butanol, can form bio-derived butyl acetate. Preferably, any bio-derived solvent present in the sustainable composition derives greater than 50%, grater than 75%, greater than 90%, or even 100% of its carbon from renewable resources.
The renewably resourcing of solvents is an area of the chemical industry that has a large 10 potential for displacing petroleum-derived solvents. Commonly used solvents include alcohols, esters, ketones, ethers and hydrocarbons. Many of these materials are not available as pure compounds from bio-mass sources, but the reaction of two or more compounds available via bio-transformation processes can result in useful solvents. Classes of bio-derived solvents include alcohols, esters, ketones and aldehydes, ethers, alkanes, aromatics, 15 Bio-derived alcohols that can be produced via renewable resources include mono-, di-, tri- and higher alcohols having one or more carbon atoms. For example, bio-derived methanol, bio-derived ethanol, isomers of bio-derived propanol, isomers of bio-derived butanol, isomers of bio-derived pentanol, isomers of bio-derived hexanol, bio-derived cyclopentanol, bio-derived ethylene glycol, bio-derived 1,3-propanediol, bio-derived 1,2-propanediol, bio-derived 1,4-20 butane diol, bio-derived 2-methyl-1,4-butanediol, bio-derived 1,4-pentanediol, bio-derived 1,5-pentanediol, bio-derived glycerol, bio-derived isobomyl alcohol, and others.
Bio-derived methanol, bio-derived ethanol and bio-derived butanol can be formed by well-known fermentation process. Other alcohols can be produced as well, see for example, US 4,536,584.
Ester-based solvents can be produced from the reaction of a bio-derived carboxylic acid 25 and a bio-derived alcohol. Suitable acids that can be produced via renewable resources include, for example, formic acid, acetic acid, propionic acid, butyric acid, lactic acid, malonic acid, and adipic acid. See US 5,874,263; WO 95/07996; Biotechnology Letters Vol. 1 1 (3), pages 189-194, 1989; and Green Chemistry 2008, DOI: 10.1039/b802076k. Bio-derived esters can be formed from a bio-derived acid and a bio-derived alcohol via the well-known esterification 30 industrial process of these generic components. For example, bio-derived acetic acid can be reacted under esterification reaction conditions with bio-derived butanol to form bio-derived butyl acetate. Bio-derived butyl acetate can be used in the synthesis of polyacrylates and as a reducer. As an additional example, bio-derived tert-butyl acetate can be produced using indium catalysts, see Journal of Molecular Catalysis, volume 235, page 150-153, 2005.

Ketone-based and aldehyde-based solvents can be produced by the oxidation of many of the above listed bio-derived alcohols. Bio-derived acetone, bio-derived methyl ethyl ketone, bio-derived cyclopentanone, bio-derived cyclohexanone, bio-derived 2-pentanone, bio-derived 2,5-hexanedione, and the various isomers of 4 to 6 carbon bio-derived ketones are useful as solvents in many chemical reactions, such as, for example, free radical polymerization and also can also be used in the preparation of ingredients for sustainable compositions. See for example, US
4,536,584.
Bio-derived ethers, including bio-derived polyethers, can be produced from biomass or via the condensation of bio-derived alcohols with bio-derived ketones and bio-derived aldehydes according to known ether forming reaction processes. Examples include, bio-derived diethoxymethane and bio-derived tetrahydrofuran. See for example, US
4,536,584. Other methods to produce bio-derived polyethers can include the polymerization of bio-derived ethylene oxide. Bio-derived ethylene oxide can be produced from the epoxidation of bio-derived ethylene. Bio-derived low molecular-weight polyethers, especially bio-derived alkyl capped-polyethers, may be used as solvents in the sustainable compositions.
Alkane hydrocarbon solvents are commonly used in free radical polymerizations.
Bio-derived hydrocarbons having in the range of from 1 to 15 carbon atoms can be produced from bio-mass according to the procedures given in US 6,180,845 or Chemistry and Sustainable Chemistry, Volume 1, pages 417-424, 2008. Distillation or other purification procedures can provide pure fractions of bio-derived hydrocarbons, such as, for example, bio-derived hexane that can be used in, for example, free radical polymerization processes.
Aromatics, such as, toluene and xylene, are also commonly used in polymerization reactions. Using fast-pyrolosis techniques and certain zeolites, it is possible to produce bio-derived aromatics that can be used for polymerization. See, for example, Chemistry and Sustainable Chemistry, Volume 1, pages 397-400, 2008.
The compositions, optionally, can also contain one, or more, organic cleaning solvents at effective levels, typically no less than 0.25%, and, at least 0.5%, preferably at least 3.0%, and no more than about 7%, preferably no more than about 5%, by weight of the composition.
Preferably such solvents are bio-derived.
The surfactant, described below, provides cleaning and/or wetting even without an organic cleaning solvent present. However, the cleaning can normally be further improved by the use of the right organic cleaning solvent. By organic cleaning solvent, it is meant an agent which assists the surfactant to remove soils such as those commonly encountered in the bathroom. The organic cleaning solvent also can participate in the building of viscosity, if needed, and in increasing the stability of the composition. The compositions containing C8-16 alkyl polyglucosides, preferably bio-derived, and/or C8-14 alkylethoxylates, preferably bio-derived, also have lower sudsing when the solvent is present. Thus, the suds profile can be controlled in large part by simply controlling the level of hydrophobic solvent in the formulation.
The amount of organic cleaning solvent can vary depending on the amount of other ingredients present in the composition. The hydrophobic cleaning solvent is normally helpful in providing good cleaning, such as in floor cleaner applications. For cleaning in enclosed spaces, the solvent can cause the formation of undesirably small respirable droplets, so compositions/solutions for use in treating such spaces are desirably substantially free, more preferably completely free, of such solvents.
For purposes of soap scum and hard water stain removal, the sustainable compositions can be made acidic with a pH of from about 2 to about 5, more preferably about 3. Acidity is accomplished, at least in part, through the use of one or more organic acids that have a pKa of less than 5, preferably less than 4. Such organic acids also can assist in phase formation for thickening, if needed, as well as provide hard water stain removal properties.
It is found that organic acids are very efficient in promoting good hard water removal properties within the framework of the compositions of the present invention. Lower pH and use of one or more suitable acids is also found to be advantageous for disinfectancy benefits.
The organic acids may be bio-derived organic acids.
Examples of suitable mono-carboxylic acids include acetic acid, glycolic acid or f3-hydroxy propionic acid and the like. Examples of suitable polycarboxylic acids include citric acid, tartaric acid, succinic acid, glutaric acid, adipic acid, and mixtures thereof. Such acids are readily available in the trade. Examples of more preferred polycarboxylic acids, especially non-polymeric polycarboxylic acids, include citric acid (available from Aldrich Corporation, 1001 West Saint Paul Avenue, Milwaukee, Wis.), a mixture of succinic, glutaric and adipic acids available from DuPont (Wilmington, Del.) sold as "refined AGS di-basic acids", maleic acid (also available from Aldrich), and mixtures thereof. Citric acid is most preferred, particularly for applications requiring cleaning of soap scum. Glycolic acid and the mixture of adipic, glutaric and succinic acids provide greater benefits for hard water removal. The amount of organic acid in the compositions herein can be from about 0.01% to about 1%, more preferably from about 0.01% to about 0.5%, most preferably from about 0.025% to about 0.25% by weight of the composition. Most preferably all, or a portion of the acids, are bio-derived.
Suitable bio-derived acids, natural-based analogs of acids described above, are available and/or may be prepared as described above, for example.

Polymer The sustainable composition may comprise a polymer. The polymer, if present, is used in any suitable amount from about 0.1% to about 50%, preferably from 0.5% to about 20%, more preferably from 1% to 10% by weight of the sustainable composition.
In one example, sulfonated/carboxylated polymers are particularly suitable for the sustainable composition of the invention.
Preferred sustainable compositions may contain a dispersant polymer typically in the range from 0 to about 25%, preferably from about 0.5% to about 20%, more preferably from about 1% to about 7% by weight of the sustainable composition.
One dispersant polymer suitable for use in the present composition includes an ethoxylated cationic diamine comprising the formula (III):

X¨f-OCH2C112-t--N"¨CH2¨CH2¨(-CH2t7-N'¨ (C112CH20t X
(CH2CII29),,¨X (CH2CH20),¨X
(III) where X of formula (III) is a nonionic group selected from the group consisting of H, C1-C4 alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof n is at least 6;
and a is from 0 to 4 (e.
g. ethylene, propylene, hexamethylene). For preferred ethoxylated cationic diamines, n of formula (III) is at least 12 with a typical range of from about 12 to about 42. See U.S. Pat. No.
4,659,802 for further information regarding the ethoxylated cationic diamines.
The alkylene oxide components in all regards are preferably obtained from bio-derived ethylene oxide.
Further suitable dispersant polymers suitable for use herein are illustrated by formula (IV):
COONa COON4 COON(' OH
803Na (IV) Formula IV is an Acrylic acid (AA), maleic acid (MA) and sodium 3-allyloxy-2-hydroxy-I -propanesulfonate (HAPS) copolymer, preferably comprising about 45 wt% of the polymer of AA, about 45 wt % of the polymer of MA and about 10 wt% of the polymer HAPS.
Molecular weight may be from about 8000 to about 15000. In one embodiment, dispersant polymers of formula (IV) have a molecular weight of about 8000 to about 8500. In another embodiment dispersant polymers of formula (IV) have a molecular weight of about 12500 to about 13300.
Salts of formula (IV) may be selected from any water soluble salt such as sodium or potassium salt.
Further suitable dispersant polymers suitable for use herein are illustrated by the film-forming polymers. Suitable for use as dispersants herein are co-polymers synthesized from bio-derived acrylic acid, bio-derived maleic acid and bio-derived methacrylic acid. Such polymers may be bio-derived analogs of commercial products such as ACUSOL 480N
supplied by Rohm & Haas and polymers containing both carboxylate and sulfonate monomers, such as ALCOSPERSE polymers (supplied by Alco). In one embodiment an ALCOSPERSE
polymer sold under the trade name ALCOSPERSE 725, is a co-polymer of Styrene and Acrylic Acid.
In certain embodiments, a dispersant polymer may be present in an amount in the range from about 0.01% to about 25%, or from about 0.1% to about 20%, and alternatively, from about 0.1% to about 7% by weight of the sustainable composition.
Further suitable dispersant polymers include polyacrylic phosphono end group polymers or acrylic-maleic phosphono end group copolymers according to the general formula H2P03¨
(CH2¨CHCOOH)n¨(CHCOOH-CHCOOH)m¨where n is an integer greater than 0, m is an integer of 0 (for polyacrylic polymers) or greater (for acrylic¨maleic copolymers) and n and m are integers independently selected to give a molecular weight of the polymer of between 500 and 200,000, preferably of between 500 and 100,000, and more preferably between 1,000 and 50,000. For polyacrylates, m is zero. Suitable polyacrylic phosphono end group polymers or acrylic-maleic phosphono end group copolymers for use herein are available from Rohm &Haas under the tradenames ACUSOLO E 420 or 470 or 425. In one embodiment Acusol 425N is used. Acusol 425N is an acrylic-maleic (ratio 80/20) phosphono end group copolymers and is available from Rohm &Haas.
Particularly preferred dispersant polymers are low molecular weight modified polyacrylate copolymers, most preferably obtained from bio-derived sources of carbon. Such copolymers contain as monomer units: (a) from about 90% to about 10%, preferably from about 80% to about 20% by weight bio-derived acrylic acid or its salts and (b) from about 10% to about 90%, preferably from about 20% to about 80% by weight of a substituted bio-derived acrylic monomer or its salt and having the general formula ¨[(C(R2)C(RI)(C(0)0R3)]---where the incomplete valencies inside the square braces are hydrogen and at least one of the substituents RI, R2 or R3, preferably RI or R2, is a C1 to C4 alkyl or hydroxyalkyl group, RI or R2 canbe a The low molecular-weight polyacrylate dispersant polymer preferably has a molecular weight of less than 15,000, preferably from about 500 to about 10,000, most preferably from about 1,000 to about 5,000. The most preferred polyacrylate copolymer for use herein has a The sulfonated/carboxylated polymers may comprise (a) at least one structural unit derived from at least one carboxylic acid monomer having the general formula (I):

_______________________________________ C 2 R4 (I) R
where RI to R4 are independently hydrogen, methyl, carboxylic acid group or ¨CH2COOH and H2C ________________________________________ (II) X
where R5 is hydrogen, CI to C6 alkyl, or CI to C6 hydroxyalkyl, and X is either aromatic (with R5 being hydrogen or methyl when X is aromatic) or X is of the general formula (III):

C ¨0 (III) where R6 is (independently of R5) hydrogen, C1 to C6 alkyl, or C1 to C6 hydroxyalkyl, and Y is 0 or N; and at least one structural unit derived from at least one sulfonic acid monomer having the general formula (IV):

(A)1 (IV) (B)t SO3- M+
where R7 is a group comprising at least one sp2 bond, A is 0, N, P, S. or an amido or ester linkage; B is a monocyclic or polycyclic aromatic group or an aliphatic group;
each t is independently 0 or 1; and M+ is a cation. In one aspect, le is a C2 to C6 alkene. In another aspect, R7 is ethene, butene or propene.
Preferred carboxylic acid monomers include one or more of the following: bio-derived acrylic acid, bio-derived maleic acid, bio-derived itaconic acid, bio-derived methacrylic acid, or ethoxylate esters of bio-derived acrylic acids, acrylic and methacrylic acids being more preferred.
Preferred sulfonated monomers include one or more of the following: bio-derived sodium (meth) allyl sulfonate, bio-derived vinyl sulfonate, bio-derived sodium phenyl (meth) ally! ether sulfonate, or bio-derived 2-acrylamido-methyl propane sulfonic acid ("AMPS"), or bio-derived sodium 3-allyloxy-2-hydroxy-l-propanesulfonate ("HAPS"). Preferred non-ionic monomers include one or more of the following: bio-derived methyl (meth) acrylate, bio-derived ethyl (meth) acrylate, bio-derived t-butyl (meth) acrylate, bio-derived methyl (meth) acrylamide, bio-derived ethyl (meth) acrylamide, bio-derived t-butyl (meth) acrylamide, bio-derived styrene, or bio-derived a-methyl styrene. Preferably, the polymer comprises the following levels of monomers: from about 40% to about 90%, preferably from about 60% to about 90%
by weight of the polymer of one or more bio-derived carboxylic acid monomer; from about 5%
to about 50%, preferably from about 10% to about 40% by weight of the polymer of one or more sulfonic acid monomer; and optionally from about 1% to about 30%, preferably from about 2%
to about 20%

by weight of the polymer of one or more non-ionic monomer. An especially preferred polymer comprises about 70% to about 80% by weight of the polymer of at least one bio-derived carboxylic acid monomer and from about 20% to about 30% by weight of the polymer of at least one bio-derived sulfonic acid monomer.
The polymers for use in the sustainable compositions preferably are derived from a renewable resource via an indirect route involving one or more intermediate compounds.
Suitable intermediate compounds derived from renewable resources include sugars. Suitable sugars include monosaccharides, disaecharides, trisaccharides, and oligosaccharides. Sugars such as sucrose, glucose, fructose, maltose may be readily produced from renewable resources such as sugar cane and sugar beets. Sugars may also be derived (e.g., via enzymatic cleavage) from other agricultural products such as starch or cellulose. For example, glucose may be prepared on a commercial scale by enzymatic hydrolysis of corn starch. While corn is a renewable resource in North America, other common agricultural crops may be used as the base starch for conversion into glucose. Wheat, buckwheat, arracaha, potato, barley, kudzu, cassava, sorghum, sweet potato, yam, arrowroot, sago, and other like starchy fruit, seeds, or tubers are may also be used in the preparation of glucose.
Other suitable intermediate compounds derived from renewable resources include monofunctional alcohols such as methanol or ethanol and polyfunctional alcohols such as glycerol. Ethanol may be derived from many of the same renewable resources as glucose. For example, cornstarch may be enzymatically hydrolysized to yield glucose and/or other sugars.
The resultant sugars can be converted into ethanol by fermentation. As with glucose production, corn is an ideal renewable resource in North America; however, other crops may be substituted. Methanol may be produced from fermentation of biomass. Glycerol is commonly derived via hydrolysis of triglycerides present in natural fats or oils, which may be obtained from renewable resources such as animals or plants.
Other intermediate compounds derived from renewable resources include organic acids (e.g., citric acid, lactic acid, alginic acid, amino acids etc.), aldehydes (e.g., acetaldehyde), and esters (e.g., cetylpalmitate, methyl stearate, methyl oleate, etc.).
Additional intermediate compounds such as methane and carbon monoxide may also be derived from renewable resources by fermentation and/or oxidation processes.
Intermediate compounds derived from renewable resources may be converted into polymers (e.g., glycerol to polyglycerol) or they may be converted into other intermediate compounds in a reaction pathway which ultimately leads to a polymer useful in the sustainable compositions. An intermediate compound may be capable of producing more than one secondary intermediate compound. Similarly, a specific intermediate compound may be derived from a number of different precursors, depending upon the reaction pathways used.
Particularly desirable intermediates include bio-derived (meth)acrylic acids and their esters and salts; and olefins. In particular embodiments, the intermediate compound may be bio-derived acrylic acid, bio-derived ethylene, or bio-derived propylene.
For example, acrylic acid is a monomeric compound that may be derived from renewable resources via a number of suitable routes. Examples of such routes are provided below.
Acrylic and methacrylic monomers represent a large portion of the monomers that are used to produce the acrylic polymers. For example, both bio-derived 3-hydroxypropionic acid and bio-derived 2-hydroxyisobutyric acids are available via bio-transformation pathways, see for example, Biotechnology Journal, volume 1, pages 756-769, 2006 and Applied Microbiological Biotechnology, volume 66, pages 131-142, 2004. These bio-derived acids can be dehydrated to form bio-derived acrylic acid and bio-derived methacrylic acid.
The bio-derived acrylic acid and bio-derived acrylic acid monomers, and derivatives thereof, can be used to form numerous bio-derived methacrylic acid, bio-derived alkyl acrylate and bio-derived alkyl methacrylate esters as well as bio-derived acrylamides, bio-derived methacrylami des, bio-derived acrylonitrile and bio-derived methacrylonitrile.
Bio-derived acrylate and bio-derived methacrylate esters can be produced, via esterification reactions with bio-derived alcohols. By incorporating an excess of bio-derived diols into the esterification reaction, hydroxy functional bio-derived acrylate and bio-derived methacrylate esters can be formed. Using at least two equivalents excess of the bio-derived acrylic acid and bio-derived methacrylic acid with bio-derived diols, bio-derived diacrylates and bio-derived dimethacrylates can be formed. These types of monomers find widespread use in the acrylic polymers suitable for use in the sustainable compositions.
A representative sample of bio-derived alcohol, bio-derived acrylic acid, bio-derived acrylic acid, and derivatives thereof, includes, but is not limited to: bio-derived methanol, bio-derived methylacrylate, bio-derived methylmethacrylate, bio-derived ethanol, bio-derived ethyl acrylate, bio-derived ethylmethacrylate, bio-derived 1-propanol, bio-derived propyl acrylate, bio-derived propyl methacrylate, bio-derived 2-propanol, bio-derived isopropyl acrylate, bio-derived isopropyl methacrylate, bio-derived 1-butanol, bio-derived butyl acrylate, bio-derived butyl methacrylate, bio-derived 2-butanol, bio-derived isobutyl acrylate, bio-derived isobutyl methacrylate, bio-derived ethylene glycol, bio-derived 2-hydroxyethyl acrylate, bio-derived 2-hydroxyethyl methacrylate, bio-derived 1,2-propylene glycol, bio-derived 2-hydroxypropyl acrylate, bio-derived 2-hydroxypropyl methacrylate, bio-derived 1,3-propylene glycol, bio-derived 3-hydroxypropyl acrylate, bio-derived 3-hydroxypropyl methacrylate, bio-derived 1,4-butane diol, bio-derived 4-hydroxybutyl acrylate, bio-derived 4-hydroxybutyl methacrylate, bio-derived 1,2-butane diol, bio-derived 2-hydroxybutyl acrylate, bio-derived 2-hydroxybutyl methacrylate, bio-derived isobornyl alcohol, bio-derived isobornyl acrylate, and bio-derived isobornyl methacrylate.
Bio-epichlorhydrin is also available from bio-derived glycerol via the EPLCEROLTM
process developed by Solvay. Bio-derived epichlorohydrin allows the formation of bio-glycidyl acrylate and bio-glycidyl methacrylate monomers.
While bio-derived acrylic and bio-derived methacrylic esters monomers make up the majority of the monomers that are used to produce bio-derived acrylic polymers, other monomers can be copolymerized with these ester monomers to modify the properties of the polymer. These monomers can include, for example, bio-derived acrylamide, bio-derived methacrylamide, bio-derived acrylonitrile and bio-derived methacrylonitrile, bio-derived styrene and styrene derivatives, or combinations thereof are often used. Bio-acrylamides and bio-methacrylamides can be derived from the corresponding bio-derived acrylic acid and bio-derived methacrylic acid, for example, by the formation of bio-derived acid chlorides, followed by amination with ammonia or other primary and/or secondary amines.
Bio-derived acrylonitrile and bio-derived methacrylonitrile can be produced by the dehydration of bio-derived acrylamide and bio-derived methacrylamide using, for example, phosphorus pentoxide. Bio-derived styrene can be produced from phenylalanine by the deamination using phenylalanine ammonia lyase, which results in the formation of cinnamic acid. The formed cinnamic acid can then be decarboxylated using a variety of methods, including bio-synthetic pathways. See for example, The Chemical and Pharmaceuticals Bulletin, Volume 49(5), pages 639-641 , 2001. Another group of monomers that are important to the for formation of bio-derived polymers are the bio-derived monomers that produce polyesters. These bio-derived monomers include monoalcohols, diols, triols and higher polyols;
bio-derived monocarboxylic acids, bio-derived dicarboxylic acids, and bio-derived higher carboxylic acids;
as well as bio-derived hydroxy-functional carboxylic acids, for example, bio-derived 12-hydroxy stearic acid. There exist processes for many of these monomers to be produced from bio-mass sources, thereby providing a route to bio-derived monomers that can be used to form bio-derived polyesters. Bio-derived alcohols and some bio-derived acids have been discussed above. Bio-derived diacids are also available. References can be found to produce bio-derived adipic acid as well as other diacids; see for example, US 4,400,468 and US .4,965,201. It is preferable for the sustainable compositions that all of the carbon atoms of the monomers used to form the polymer components to be bio-derived.
As an example route to obtaining bio-derived acrylic acid, glycerol starting material may be derived from a renewable resource (e.g., via hydrolysis of soybean oil and other triglyceride 15 Alternatively, glucose derived from a renewable resource (e.g., via enzmatic hydrolysis of corn starch) may be converted into acrylic acid via a two step process with lactic acid as an intermediate product. In the first step, glucose may be biofermented to yield lactic acid. Any suitable microorganism capable of fermenting glucose to yield lactic acid may be used including members from the genus Lactobacillus such as Lactobacillus lactis as well as those identified in Another suitable reaction pathway for converting glucose into acrylic acid involves a two step process with 3-hydroxypropionic acid as an intermediate compound. In the first step, glucose may be biofermented to yield 3-hydroxypropionic acid. Microorganisms capable of production of the recombinant organism may be found in U.S. Patent No.
6,852,517. In the second step, the 3-hydroxypropionic acid may be dehydrated to produce acrylic acid.
Glucose derived from a renewable resource (e.g., via enzymatic hydrolysis of corn starch obtained from the renewable resource of corn) may be converted into acrylic acid by a multistep reaction pathway. Glucose may be fermented to yield ethanol, which itself may be obtained from bio-derived sources of carbon. Ethanol may be dehydrated to yield ethylene. At this point, ethylene may be polymerized to form polyethylene. However, ethylene may be converted into prop ionaldehyde by hydroformylation of ethylene using carbon monoxide and hydrogen in the presence of a catalyst such as cobalt octacarbonyl or a rhodium complex.
Propan-l-ol may be = formed by catalytic hydrogenation of propionaldehyde in the presence of a catalyst such as sodium borohydride and lithium aluminum hydride. Propan-l-ol may be dehydrated in an acid catalyzed reaction to yield propylene. At this point, propylene may be polymerized to form polypropylene. However, propylene may be converted into acrolein by catalytic vapor phase oxidation. Acrolein may then be catalytically oxidized to form acrylic acid in the presence of a molybdenum- vanadium catalyst.
While the above reaction pathways yield acrylic acid, a skilled artisan will appreciate that acrylic acid may be readily converted into an ester (e.g., methyl acrylate, ethyl acrylate, etc.) or salt. Thereby, the bio-derived acrylic acid becomes an intermediate in a pathway to bio-derived esters such as bio-derived methyl acrylate and bio-derived ethyl acrylate.
Scale formation is sometimes a problem, particularly in nil-phosphate formulation. Anti-sealants include polyacrylates and polymers based on acrylic acid combined with other moieties, preferably from bio-derived sources. Sulfonated varieties of these polymers are particular effective in nil phosphate formulation executions. Examples of anti-scalants include those described in US 5,783,540, column 15, line 20 through column 16, line 2; and EP 0 851 022 A2, page 12, lines 1-20. Commercially available examples may include Acusol series (e.g., Acusol 588) of polymers from Dow and sulfonated polymers from Nippon Shukobai.
Olefins such as ethylene and propylene may be derived from renewable resources. For example, methanol derived from fermentation of biomass may be converted to ethylene and/or propylene, which are both suitable monomeric compounds, as described in U.S.
Patent Nos.
4,296,266 and 4,083,889. Ethanol derived from fermentation of a renewable resource may be converted into monomeric compound of ethylene via dehydration as described in U.S. Patent No.
4,423,270. Similarly, propanol or isopropanol derived from a renewable resource can be dehydrated to yield the monomeric compound of Propylene as exemplified in U.S.
Patent No.

5,475,183. Propanol is a major constituent of fusel oil, a by-product formed from certain amino acids when potatoes or grains are fermented to produce ethanol.
Charcoal derived from biomass can be used to create syngas (i.e., CO/H2) from which hydrocarbons such as ethane and propane can be prepared (Fischer-Tropsch Process). Ethane and propane can be dehydrogenated to yield the monomeric compounds of ethylene and propylene.
Acrylic acid having a 100% bio-derived carbon isotope ratio may be produced from bioderived glycerol, bio-derived lactic acid, and/or bio-derived lactate esters, as described in U.S.
Pat. Appl. Pub. No. 2009/0018300. In turn, the bioderived glycerol may be converted to other useful chemical feedstocks, such as, acrylic acid (2-propenoic acid), allyl alcohol (2-propen-1-ol), and 1,3-propanediol, having a 100% biobased carbon isotope ratio. For example, bioderived glycerol may be dehydrated to give acrolein (2-propenal). The acrolein may be oxidized to afford acrylic acid (2-propenoic acid). Alternatively, acrolein may be reduced to give ally' alcohol (2-propen-1-01). Suitable methods for the conversion of acrolein to allyl alcohol include, but are not limited to, reactions catalyzed by a silver indium catalyst as described by Lucas et al.
in Chemie Ingenieur Technik, 2005, 77, 110-113, the disclosure of which is incorporated by reference herein in its entirety. Further, acrolein may be converted to 1,3-propanediol. One suitable method for the conversion of acrolein to 1,3-propanediol includes hydration followed by hydrogenation as described in U.S. Pat. No. 5,171,898, the disclosure of which is incorporated by reference herein in its entirety. The industrial/chemical feedstocks produced from glycerol, via acrolein, as set forth herein, will have a carbon isotope ratio that can be identified as being derived from biomass (i.e., bio-derived). Bio-derived 1,3-propanediol may be prepared as disclosed in U.S. Pat. Appl. Pub. No. 2007/0213247. Moreover, sustainable compositions herein may comprise bio-derived 1,3-propanediol prepared as disclosed in U.S. Pat.
Appl. Pub. No.
2007/0213247.
Alternatively, bio-derived acrylic acid or acrylate esters may be synthesized from bio-derived lactic acid or lactate esters. Biobased lactic acid derivatives may be bio-synthesized, for example, by fermentation of a carbohydrate material. Conversion of lactic acid and lactate esters into acrylic acid and acrylate esters, respectively, may be accomplished by dehydration of the alcohol group of the lactate moiety. Suitable methods for the conversion of lactic acid and lactate esters, for example, lactic acid/lactate esters from the fermentation of carbohydrate material in the presence of ammonia, into an acrylate ester or acrylic acid are disclosed in U.S.
Pat. Nos. 5,071,754 and 5,252,473, the disclosures of which are incorporated by reference herein in their entirety.

The bio-derived monomers described herein may be used for the synthesis of polymers having up to a 100% bio-derived carbon isotope ratio. Thus, the bio-derived monomers may be used for the synthesis of polymers having from 1% to 99.9% bio-derived carbon.
The bio-derived polymers, then, are suited for use in the sustainable composition.
According to other embodiments, the bio-derived monomers may be used for the synthesis of polymers having from 50% to 99.9% biobased carbon. Thus, the glycerol and carbohydrate starting materials described herein will necessarily be derived from biological sources. For example, bio-derived glycerol containing 100% bio-derived carbon, as determined by ASTM Method D 6866, may be obtained from triglycerides (triacylglycerols) from biological sources, for example, a vegetable oil or an animal fat, by splitting the triglyceride into the corresponding fatty acids and glycerol.
Triglycerides may be converted into the corresponding fatty acids and glycerol by acidic hydrolysis, basic hydrolysis (saponification) or by a catalytic de-esterification. Suitable triglycerides for use in the formation of bio-derived glycerol include, but are not limited to, corn oil, soybean oil, canola oil, vegetable oil, safflower oil, sunflower oil, nasturtium seed oil, mustard seed oil, olive oil, sesame oil, peanut oil, cottonseed oil, rice bran oil, babassu nut oil, castor oil, palm oil, palm kernel oil, rapeseed oil, low erucic acid rapeseed oil, lupin oil, jatropha oil, coconut oil, flaxseed oil, evening primrose oil, jojoba oil, tallow, beef tallow, butter, chicken fat, lard, dairy butterfat, shea butter, biodiesel, used frying oil, oil miscella, used cooking oil, yellow trap grease, hydrogenated oils, derivatives of these oils, fractions of these oils, conjugated derivatives of these oils, and mixtures of any thereof.
Suitable bioderived olefins include, but are not limited to monoacrylates, diacrylates, and allyl esters.
Alternatively, bio-derived glycerol may be produced as a co-product of biodiesel production. Glycerol produced by these methods will have a carbon isotope ratio consistent with a 100% bio-derived product and will provide a renewable source of acrolein and acrylic acid that may be used as a feedstock for the bio-derived monomers and polymers for use in the sustainable compositions. Non-limiting examples of methods and processes for producing biodiesel may be found in U.S. Pat. No. 5,354,878; U.S. Patent Application Publication Nos.
20050245405A1;
2007-0181504; and 20070158270A1; Provisional Patent Application Ser. No.
60/851,575, the disclosures of which are incorporated in their entirety by reference herein.
The monomers and polymers, as set forth herein, may have up to 100% biobased carbon isotope ratio as determined by ASTM Method D 6866. The monomers and polymers may be differentiated from, for example, similar monomers and polymers comprising petroleum derived components by comparison of the carbon isotope ratios, for example, the 14C/12C or the 13C/'2C

carbon isotope ratios, of the materials. As described herein, isotopic ratios may be determined, for example, by liquid scintillation counting, accelerator mass spectrometry, or high precision isotopic ratio mass spectrometry.
Bio-derived acrylic acid (or acrylate esters), for example acrylic acid and esters synthesized by any of the embodiments described herein, may be esterified (or transesterified) with other bio-derived alcohols, diols, or polyols. Non-limiting suitable bio-derived alcohols and diols include, for example, methanol; ethanol; n-butanol, for example from an acetone/butanol fermentation; fusel oil alcohols (n-propanol, isobutyl alcohol, isoamyl alcohol, and/or furfural);
and alcohol and diol derivatives derived from carbohydrates or their derivatives.
Non-limiting examples of carbohydrate derived diols include hydroxymethylfurfuryl, 2,5-bis(hydroxymethyl)furan, 2,5-bis(hydroxymethyl)tetrahydrofuran, and isosorbide (dianhydrohexitol), isomannide, mannitol, xylitol, maltitol, maltitol syrup, lactitol, erythritol, isomalt, isoidide (the dianhydrohexitol of iditol), or ethoxylated or propoxylated derivatives of these.
Diacrylate esters may be produced from carbohydrate derived diols and may act as monomers or co-monomers having 100% bio-derived carbons, as determined by ASTM
Method D 6866, for the synthesis of polymers having up to 100% biobased carbon and being suitable for use in the sustainable compositions.
Other embodiments of bio-derived diols suitable for producing diacrylate esters having 100% biobased carbon may be produced from fatty acids, such as, for example, unsaturated fatty acids. For example, hydroformylation of unsaturated fatty acids and their derivatives to produce fatty acid derivatives having a hydroxymethylene group is described in U.S.
Pat. No. 3,210,325 to De Witt et al., the disclosure of which is incorporated in its entirety by reference herein.
Reduction of the carbonyl of the fatty acid derivative, for example, by hydrogenation, produces a biobased diol suitable for esterification or transesterification with acrylic acid or an acrylate ester, as produced herein, to form a biobased diacrylate monomer.
Additionally, bio-derived diols suitable for producing diacrylate esters having 100% bio-derived carbon may be produced by epoxidation of at least one of the double bonds of an unsaturated fatty acid/ester or unsaturated fatty alcohol. One non-limiting example of the epoxidation procedure is described by Rao et al., Journal of the American Oil Chemists' Society, (1968), 45(5), 408, the disclosure of which is incorporated in its entirety by reference herein.
The epoxidation may be followed by reduction, for example, by hydrogenation, to open the epoxide to the alcohol, which May also include reduction of the carbonyl of the fatty acid/ester to the alcohol. Any biobased diol may then be esterified or transesterified with acrylic acid or an acrylate ester, as produced herein, to form a diacrylate monomer having 100%
biobased carbon.
Still further, diols suitable for producing diacrylate esters having 100%
biobased carbon may be produced by reduction of cc,o)-dicarboxylic acids. As used herein, the term a,o)-5 dicarboxylic acid" includes organic molecules comprising a carbon chain of at least 1 carbon atom and two carboxylic acid functional groups, each of which is positioned at opposite ends of the carbon chain. For example, a,w-dicarboxylic acids may be produced by a fermentation process involving biobased fatty acids, such as, by a fermentation process as described in Craft, et al., Applied and Environmental Microbiology, (2003), 69(10), 5983-5991 and/or U.S. Pat. No.
10 6,569,670 to Anderson et al., the disclosures of which are incorporated in their entirety by reference herein. Other a,w-dicarboxylic acids from biobased sources, such as, for example, maleic acid, fumaric acid, oxalic acid, malonic acid, adipic acid, succinic acid, and glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid may also be used in the sustainable compositions. According to certain embodiments, the a,w-dicarboxylic acid may be 15 an unsaturated a,w-dicarboxylic acid or a saturated a,co-dicarboxylic acid. Reduction of the carbonyls of the a,co-dicarboxylic acids provides a biobased diol which may then be esterified or transesterified with acrylic acid or an acrylate ester, as produced herein, to form a biobased diacrylate monomer.
Still further, bioderived diacrylamide derivatives may serve as monomers for the 20 polymerization reactions described herein. For example, according to certain embodiments, the diol component in the formation of the diacrylate esters described herein, may be chemically converted to a bio-derived diamine, for example, by a double Mitsunobu-type reaction. Non-limiting examples of resulting biobased diamines may include, for example, his-amino isosorbide, 2,5-bisaminomethyltetrahydrofuran, 2,5-bisaminomethylfuran.
Alternatively, 25 naturally occurring bioderived diamines, such as, for example, 1,4-diaminobutane, 1,5-diaminopentane, or other alkyldiamines or diamine containing alkaloid derivatives, may be replace the diol reactant in the reaction with the bioderived acrylate derivative to form a diacryl amide compound. Further, it is also contemplated that bioderived amino alcohols may replace the diol component in the formation of the biobased monomers. According to these 30 embodiments, the bioderived amino alcohols may be reacted with the bioderived acrylic acid or bioderived acrylate esters to form a bioderived monomer possessing both an acrylate ester and an acrylamide functionality.
Bioderived diacryl derivatives, such as the diacrylate esters, diacrylamides, and acrylate/acrylamide monomers may serve as monomers or co-monomers in a polymerization reaction to produce a bio-derived polymer for inclusion in the sustainable compositions. For example, an olefin metathesis polymerization reaction may be used to produce the biobased polymer. As used herein, the term "metathesis polymerization" includes an olefin metathesis reaction involving a metal carbene acting as a catalyst to metathesize alkene monomers or co-monomers into a polyunsaturated polymer through a metallocyclobutane intermediate. Thus, a polymer comprising a product from an olefin metathesis polymerization reaction of a bioderived olefin and a diacrylate ester of a bioderived diol may be used, wherein the diacrylate ester is produced by reacting a bioderived diol with at least two equivalents of bio-derived acrylic acid or an acrylate ester derived from a bioderived glycerol. The olefin metathesis polymerization reaction may be catalyzed by an olefin metathesis catalyst, such as a metal carbene catalyst, for example, metal carbenes of molybdenum or ruthenium. Commercially available olefin metathesis catalysts suitable for use in the polymerization reactions of the present disclosure include, but are not limited to, the "Schrock catalyst" (i.e., [Mo(=CHMe2Ph)(=N¨
Ar)(0CMe(CF3)2)2]), the "1st generation Grubb's catalyst" (i.e., [Ru(=CHPh)C12(PCy3)2]), and the "2nd generation Grubb's catalyst" (i.e, [Ru(¨CHPh)C12PCy3(N,1\11-diary1-2-imidazolidiny1)]) (Me¨methyl, Ph¨phenyl, Ar=aryl, and Cy=cyclohexyl). Other olefin metathesis catalysts that may be suitable include those catalysts set forth in U.S. Pat. 7,034,096 to Choi et al. at column 12, line 27 to column 19, line 2, the disclosure of which is incorporated in its entirety by reference herein. It should be noted that the polymers and polymerization process described in the present disclosure are not limited to a particular olefin metathesis catalyst(s) and that any olefin metathesis catalyst, either currently available or designed in the future, may be suitable for use in various embodiments of the present disclosure.
Additionally, the bio-derived olefin component of the metathesis polymerization may be a bioderived cyclic olefin, wherein the metathesis polymerization reaction is a ring opening metathesis polymerization ("ROMP") reaction. As used herein, the term "ring opening metathesis polymerization reaction" includes olefin metathesis polymerization reactions wherein at least one of the monomer alkene units comprises a cyclic olefin. Thus, the ROMP reaction may react a bioderived diacryl derivative with a bioderived cyclic olefin to produce a polymer that is up to 100% biobased as determined by ASTM Method D 6866. Bio-derived cyclic olefins may be prepared, for example, from palmitoleic acid, oleic acid, erucic acid, linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid, docosahexaenoic acid, and other unsaturated fatty acids.
Further processes for producing bio-derived acrylic acid, acrylic acid esters, and acrylate polymers are disclosed in WO 2011/002284; US 7,928,148; US 2009/0018300; EP
1710227, and Xu et al, "Advances in the Research and Development of Acrylic Acid Production from Biomass," Chinese J. Chem. Eng., vol. 14, pp. 419-427 (2006), all of which are incorporated herein in their entirety.
In example embodiments of the sustainable compositions comprising a carboxylic acid polymer, the carboxylic acid is preferably bio-derived (meth)acrylic acid.
Sulfonic acids, when present in the sustainable compositions, preferably are derived from a monomer selected from:
bio-derived 2-acrylamido methyl-l-propanesulfonic acid, bio-derived 3-allyloxy-2-hydroxy-1-propanesulfonic acid ("HAPS"), bio-derived 2-methacrylamido-2-methyl-1-propanesulfonic acid, bio-derived 3-methacrylamido-2-hydroxypropanesulfonic acid, bio-derived allylsulfonic acid, bio-derived methallylsulfonic acid, bio-derived allyloxybenzenesulfonic acid, bio-derived methallyloxybenzensulfonic acid, bio-derived 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, bio-derived 2-methyl-2-propene-1-sulfonic acid, bio-derived styrene sulfonic acid, bio-derived vinylsulfonic acid, bio-derived 3-sulfopropyl acrylate, bio-derived 3-sulfopropyl methacrylate, bio-derived sulfomethylacrylamide, bio-derived sulfomethylmethacrylamide, and water soluble salts thereof. The unsaturated sulfonic acid monomer is most preferably 2-acrylamido-2-propanesulfonic acid (AMPS).
In the polymers, all or some of the carboxylic or sulfonic acid groups can be present in neutralized form, i.e. the acidic hydrogen atom of the carboxylic and/or sulfonic acid group in some or all acid groups can be replaced with metal ions, preferably alkali metal ions and in particular with sodium ions. Preferably, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 99%, or 100% of the carbon atoms in the polymers are bio-derived.
Hydrophilic Polymer In some of the embodiments of the invention, the sustainable composition may comprise a polymeric material that improves the hydrophilicity of the surface being treated. This increase in hydrophilicity provides improved final appearance by providing "sheeting"
of the water from the surface and/or spreading of the water on the surface, and this effect is preferably seen when the surface is rewetted and even when subsequently dried after the rewetting.
In the context of a product intended to be used as a daily shower product, the "sheeting" effect is particularly noticeable because most of the surfaces treated are vertical surfaces. Thus, benefits have been noted on glass, ceramic and even tougher to wet surfaces such as porcelain enamel. When the water "sheets" evenly off the surface and/or spreads on the surface, it minimizes the formation of, e.g., "hard water spots" that form upon drying. For a product intended to be used in the context of a floor cleaner, the polymer improves surface wetting and assists cleaning performance.
Many materials can provide the sheeting and anti-spotting benefits, but the preferred materials are polymers that contain amine oxide hydrophilic groups. Polymers that contain other hydrophilic groups such a sulfonate, pyrrolidone, and/or carboxylate groups can also be used.
Examples of desirable poly-sulfonate polymers include polyvinylsulfonate, and more preferably polystyrene sulfonate, such as those sold by Monomer-Polymer Dajac (1675 Bustleton Pike, Feasterville, Pa. 19053). A typical formula is as follows.
¨[CH(C6H4S03Na)¨CH2]¨CH(C6H5)¨CH2¨

wherein n is a number to give the appropriate molecular weight as disclosed below.
Polyvinylpyrrolidones may be preferred, particularly bio-derived polyvinylpyrrolidones.
Typical molecular weights are from about 10,000 to about 1,000,000, preferably from about 200,000 to about 700,000. Preferred polymers containing pyrrolidone functionalities include polyvinyl pyrrolidone, quaternized pyrrolidone derivatives (such as Gafquat 755N from International Specialty Products), and co-polymers containing pyrrolidone, such as polyvinylpyrrolidone /dimethylaminoethylmethacrylate (available from ISP) and polyvinyl pyrrolidone/acrylate (available from BASF). Other materials can also provide substantivity and hydrophilicity including cationic materials that also contain hydrophilic groups and polymers that contain multiple ether linkages. Cationic materials include cationic sugar and/or starch derivatives and the typical block copolymer detergent surfactants based on mixtures of polypropylene oxide and ethylene oxide are representative of the polyether materials.
Some non-limiting examples of homopolymers and copolymers which can be used as water-soluble polymers of the present invention are: adipic acid/
dimethylaminohydroxypropyl diethylenetriamine copolymer; adipic acid/epoxypropyl diethylenetriamine copolymer; polyvinyl alcohol; methacryloyl ethyl betaine/methacrylates copolymer; ethyl acrylate/methyl methacrylate/methacrylic acid/acrylic acid copolymer; polyamine resins;
polyquatemary amine resins; poly(ethenylformamide); poly(vinylamine) hydrochloride; poly(vinyl alcohol-co-6%
vinylamine); poly(vinyl alcohol-co-12% vinylamine); poly(vinyl alcohol-co-6%
vinylamine hydrochloride); poly(vinyl alcohol-co-12% vinylamine hydrochloride); and mixtures thereof.
Preferably, said copolymer and/or homopolymers are selected from the group consisting of adipic acid/dimethylaminohydroxypropyl diethylenetriamine copolymer;
poly(vinylpyrrolidone/dimethylaminoethyl methacrylate); polyvinyl alcohol;
ethyl acrylate/methyl methacrylate/methacrylic acid/acrylic acid copolymer;
methacryloyl ethyl betaine/methacrylates copolymer; polyquatemary amine resins;
poly(ethenylformamide);
poly(vinylamine) hydrochloride; poly(vinyl alcohol-co-6% vinylamine);
poly(vinyl alcohol-co-12% vinylamine); poly(vinyl alcohol-co-6% vinylamine hydrochloride);
poly(vinyl alcohol-co-12% vinylamine hydrochloride); and mixtures thereof. Preferably, the all or a portion of the polymer used is bio-derived.
Polymers useful in the present invention can be selected from the group consisting of copolymers of hydrophilic monomers. The polymer can be linear random or block copolymers, and mixtures thereof. Preferably the polymers are formed from bio-derived monomers. The term "hydrophilic" is used herein consistent with its standard meaning of having affinity for water. As used herein in relation to monomer units and polymeric materials, including the copolymers, "hydrophilic" means substantially water soluble. In this regard, "substantially water soluble" shall refer to a material that is soluble in distilled (or equivalent) water, at 25 C., at a concentration of about 0.2% by weight, and are preferably soluble at about 1%
by weight. The terms "soluble", "solubility" and the like, for purposes hereof, correspond to the maximum concentration of monomer or polymer, as applicable, that can dissolve in water or other solvents to form a homogeneous solution, as is well understood to those skilled in the art.
Nonlimiting examples of useful hydrophilic monomers are unsaturated organic mono-and polycarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid and its half esters, and itaconic acid; unsaturated alcohols, such as vinyl alcohol and allyl alcohol; polar vinyl heterocyclics such as vinyl caprolactam, vinyl pyridine, and vinyl imidazole; vinyl amine;
vinyl sulfonate; unsaturated amides such as acrylamides, e.g., N,N-dimethylacrylamide and N-t-butyl acrylamide; hydroxyethyl methacrylate; dimethylaminoethyl methacrylate;
salts of acids and amines listed above; and the like; and mixtures thereof. Some preferred hydrophilic monomers are bio-derived acrylic acid, bio-derived methacrylic acid, bio-derived N,N-dimethyl acrylamide, bio-derived N,N-dimethyl methacrylamide, bio-derived N-t-butyl acrylamide, bio-derived dimethylamino ethyl methacrylate, and mixtures thereof.
Polycarboxylate polymers are those formed by polymerization of monomers, at least some of which contain carboxylic functionality. Common monomers include bio-derived acrylic acid, bio-derived maleic acid, bio-derived ethylene, bio-derived vinyl pyrrolidone, bio-derived methacrylic acid, bio-derived methacryloylethylbetaine, and the like.
Some polymers, especially polycarboxylate polymers, thicken the compositions that are aqueous liquids. This can be desirable. However, when the compositions are placed in Containers with trigger spray devices, the compositions are desirably not so thick as to require excessive trigger pressure. Typically, the viscosity under shear should be less than 200 cp, preferably less than 100 cp, more preferably less than 50 cp. It can be desirable, however, to have thick compositions to inhibit the flow of the composition off the surface, especially vertical surfaces.
The level of polymeric material will normally be less than 0.5%, preferably from about 5 0.01% to about 0.4%, more preferably from about 0.01% to about 0.3%. In general, lower molecular weight materials such as lower molecular weight poly(acrylic acid), e.g., those having molecular weights below about 10,000, and especially about 2,000, do not provide good anti-spotting benefits upon rewetting, especially at the lower levels, e.g., about 0.02%.
The polymers for use in the sustainable compositions preferably are derived from a 10 renewable resource via an indirect route involving one or more intermediate compounds.
Suitable intermediate compounds derived from renewable resources include sugars. Suitable sugars include monosaccharides, disaecharides, trisaccharides, and oligosaccharides. Sugars such as sucrose, glucose, fructose, maltose may be readily produced from renewable resources such as sugar cane and sugar beets. Sugars may also be derived (e.g., via enzymatic cleavage) 15 from other agricultural products such as starch or cellulose. For example, glucose may be prepared on a commercial scale by enzymatic hydrolysis of corn starch. While corn is a renewable resource in North America, other common agricultural crops may be used as the base starch for conversion into glucose. Wheat, buckwheat, arracaha, potato, barley, kudzu, cassava, sorghum, sweet potato, yam, arrowroot, sago, and other like starchy fruit, seeds, or tubers are 20 may also be used in the preparation of glucose.
Other suitable intermediate compounds derived from renewable resources include monofunctional alcohols such as methanol or ethanol and polyfunctional alcohols such as glycerol. Ethanol may be derived from many of the same renewable resources as glucose. For example, cornstarch may be enzymatically hydrolysized to yield glucose and/or other sugars.
25 The resultant sugars can be converted into ethanol by fermentation. As with glucose production, corn is an ideal renewable resource in North America; however, other crops may be substituted. Methanol may be produced from fermentation of biomass. Glycerol is commonly derived via hydrolysis of triglycerides present in natural fats or oils, which may be obtained from renewable resources such as animals or plants.
30 Other intermediate compounds derived from renewable resources include organic acids (e.g., citric acid, lactic acid, alginic acid, amino acids etc.), aldehydes (e.g., acetaldehyde), and esters (e.g., cetyl palmitate, methyl stearate, methyl oleate, etc.).
Additional intermediate compounds such as methane and carbon monoxide may also be derived from renewable resources by fermentation and/or oxidation processes.

Intermediate compounds derived from renewable resources may be converted into polymers (e.g., glycerol to polyglycerol) or they may be converted into other intermediate compounds in a reaction pathway which ultimately leads to a polymer useful in the sustainable compositions. An intermediate compound may be capable of producing more than one secondary intermediate compound. Similarly, a specific intermediate compound may be derived from a number of different precursors, depending upon the reaction pathways used.
Particularly desirable intermediates include bio-derived (meth)acrylic acids and their esters and salts; and olefins. In particular embodiments, the intermediate compound may be bio-derived acrylic acid, bio-derived ethylene, or bio-derived propylene.
For example, acrylic acid is a monomeric compound that may be derived from renewable resources via a number of suitable routes. Examples of such routes are provided below.
Acrylic and methacrylic monomers represent a large portion of the monomers that are used to produce the acrylic polymers. For example, both bio-derived 3-hydroxypropionic acid and bio-derived 2-hydroxyisobutyric acids are available via bio-transformation pathways, see for example, Biotechnology Journal, volume 1, pages 756-769, 2006 and Applied Microbiological Biotechnology, volume 66, pages 131-142, 2004. These bio-derived acids can be dehydrated to form bio-derived acrylic acid and bio-derived methacrylic acid.
The bio-derived acrylic acid and bio-derived acrylic acid monomers, and derivatives thereof, can be used to form numerous bio-derived methacrylic acid, bio-derived alkyl acrylate and bio-derived alkyl methacrylate esters as well as bio-derived acrylamides, bio-derived methacrylamides, bio-derived acrylonitrile and bio-derived methacrylonitrile.
Bio-derived acrylate and bio-derived methacrylate esters can be produced, via esterification reactions with bio-derived alcohols. By incorporating an excess of bio-derived diols into the esterification reaction, hydroxy functional bio-derived acrylate and bio-derived methacrylate esters can be formed. Using at least two equivalents excess of the bio-derived acrylic acid and bio-derived methacrylic acid with bio-derived diols, bio-derived diacrylates and bio-derived dimethacrylates can be formed. These types of monomers find widespread use in the acrylic polymers suitable for use in the sustainable compositions.
A representative sample of bio-derived alcohol, bio-derived acrylic acid, bio-derived acrylic acid, and derivatives thereof, includes, but is not limited to: bio-derived methanol, bio-derived methylacrylate, bio-derived methylmethacrylate, bio-derived ethanol, bio-derived ethyl acrylate, bio-derived ethylmethacrylate, bio-derived I-propanol, bio-derived propyl acrylate, bio-.
derived propyl methacrylate, bio-derived 2-propanol, bio-derived isopropyl acrylate, bio-derived isopropyl methacrylate, bio-derived 1-butanol, bio-derived butyl acrylate, bio-derived butyl methacrylate, bio-derived 2-butanol, bio-derived isobutyl acrylate, bio-derived isobutyl methacrylate, bio-derived ethylene glycol, bio-derived 2-hydroxyethyl acrylate, bio-derived 2-hydroxyethyl methacrylate, bio-derived 1,2-propylene glycol, bio-derived 2-hydroxypropyl acrylate, bio-derived 2-hydroxypropyl methacrylate, bio-derived 1,3-propylene glycol, bio-derived 3-hydroxypropyl acrylate, bio-derived 3-hydroxypropyl methacrylate, bio-derived 1,4-butane diol, bio-derived 4-hydroxybutyl acrylate, bio-derived 4-hydroxybutyl methacrylate, bio-derived 1,2-butane diol, bio-derived 2-hydroxybutyl acrylate, bio-derived 2-hydroxybutyl methacrylate, bio-derived isobornyl alcohol, bio-derived isobornyl acrylate, and bio-derived isobornyl methacrylate.
Bio-epichlorhydrin is also available from bio-derived glycerol via the EPICEROLTM
process developed by Solvay. Bio-derived epichlorohydrin allows the formation of bio-glycidyl acrylate and bio-glycidyl methacrylate monomers.
While bio-derived acrylic and bio-derived methacrylic esters monomers make up the majority of the monomers that are used to produce bio-derived acrylic polymers, other monomers can be copolymerized with these ester monomers to modify the properties of the polymer. These monomers can include, for example, bio-derived acrylamide, bio-derived methacrylamide, bio-derived acrylonitrile and bio-derived methacrylonitrile, bio-derived styrene and styrene derivatives, or combinations thereof are often used. Bio-acrylamides and bio-methacrylamides can be derived from the corresponding bio-derived acrylic acid and bio-derived methacrylic acid, for example, by the formation of bio-derived acid chlorides, followed by amination with ammonia or other primary and/or secondary amines.
Bio-derived acrylonitrile and bio-derived methacrylonitrile can be produced by the dehydration of bio-derived acrylamide and bio-derived methacrylamide using, for example, phosphorus pentoxide. Bio-derived styrene can be produced from phenylalanine by the deamination using phenylalanine ammonia lyase, which results in the formation of cinnamic acid. The formed cinnamic acid can then be decarboxylated using a variety of methods, including bio-synthetic pathways. See for example, The Chemical and Pharmaceuticals Bulletin, Volume 49(5), pages 639-641 , 2001. Another group of monomers that are important to the for formation of bio-derived polymers are the bio-derived monomers that produce polyesters. These bio-derived monomers include monoalcohols, diols, triols and higher polyols;
bio-derived monocarboxylic acids, bio-derived dicarboxylic acids, and bio-derived higher carboxylic acids;
as well as bio-derived hydroxy-functional carboxylic acids, for example, bio-derived I2-hydroxy stearic acid. There exist processes for many of these monomers to be produced from bio-mass sources, thereby providing a route to bio-derived monomers that can be used to form bio-derived polyesters. Bio-derived alcohols and some bio-derived acids have been discussed above. Bio-derived diacids are also available. References can be found to produce bio-derived adipic acid as well as other diacids; see for example, US 4,400,468 and US 4,965,201. It is preferable for the sustainable compositions that all of the carbon atoms of the monomers used to form the polymer components to be bio-derived.
As an example route to obtaining bio-derived acrylic acid, glycerol starting material may be derived from a renewable resource (e.g., via hydrolysis of soybean oil and other triglyceride oils) and converted into acrylic acid according to a two-step process. In a first step, the glycerol may be dehydrated to yield acrolein. A particularly suitable conversion process involves subjecting glycerol in a gaseous state to an acidic solid catalyst such as H3PO4 on an aluminum oxide carrier (which is often referred to as solid phosphoric acid) to yield acrolein. Specifics relating to dehydration of glycerol to yield acrolein are disclosed, for instance, in U.S. Patent Nos. 2,042,224 and 5,387,720. In a second step, the acrolein is oxidized to form acrylic acid. A
particularly suitable process involves a gas phase interaction of acrolein and oxygen in the presence of a metal oxide catalyst. A molybdenum and vanadium oxide catalyst may be used.
Specifics relating to oxidation of acrolein to yield acrylic acid are disclosed, for instance, in U.S.
Patent No. 4,092,354.
Alternatively, glucose derived from a renewable resource (e.g., via enzmatic hydrolysis of corn starch) may be converted into acrylic acid via a two step process with lactic acid as an intermediate product. In the first step, glucose may be biofermented to yield lactic acid. Any suitable microorganism capable of fermenting glucose to yield lactic acid may be used including members from the genus Lactobacillus such as Lactobacillus lactis as well as those identified in U.S. Patent Nos. 5,464,760 and 5,252,473. In the second step, the lactic acid may be dehydrated to produce acrylic acid by use of an acidic dehydration catalyst such as an inert metal oxide carrier which has been impregnated with a phosphate salt. This acidic dehydration catalyzed method is described in further detail in U.S. Patent 4,729,978. In an alternate suitable second step, the lactic acid may be converted to acrylic acid by reaction with a catalyst comprising solid aluminum phosphate. This catalyzed dehydration method is described in further detail in U.S.
Patent 4,786,756.
Another suitable reaction pathway for converting glucose into acrylic acid involves a two step process with 3-hydroxypropionic acid as an intermediate compound. In the first step, glucose may be biofermented to yield 3-hydroxypropionic acid. Microorganisms capable of fermenting glucose to yield 3-hydroxypropionic acid have been genetically engineered to express the requisite enzymes for the conversion. For example, a recombinant microorganism expressing the dhaB gene from Klebsiella pneumoniae and the gene for an aldehyde dehydrogenase has been shown to be capable of converting glucose to 3-hydroxypropionic acid.
Specifics regarding the production of the recombinant organism may be found in U.S. Patent No.
6,852,517. In the second step, the 3-hydroxypropionic acid may be dehydrated to produce acrylic acid.
Glucose derived from a renewable resource (e.g., via enzymatic hydrolysis of corn starch obtained from the renewable resource of corn) may be converted into acrylic acid by a multistep reaction pathway. Glucose may be fermented to yield ethanol, which itself may be obtained from bio-derived sources of carbon. Ethanol may be dehydrated to yield ethylene. At this point, ethylene may be polymerized to form polyethylene. However, ethylene may be converted into prop ionaldehyde by hydroformylation of ethylene using carbon monoxide and hydrogen in the presence of a catalyst such as cobalt octacarbonyl or a rhodium complex.
Propan-l-ol may be formed by catalytic hydrogenation of propionaldehyde in the presence of a catalyst such as sodium borohydride and lithium aluminum hydride. Propan-l-ol may be dehydrated in an acid catalyzed reaction to yield propylene. At this point, propylene may be polymerized to form polypropylene. However, propylene may be converted into acrolein by catalytic vapor phase oxidation. Acrolein may then be catalytically oxidized to form acrylic acid in the presence of a molybdenum- vanadium catalyst.
While the above reaction pathways yield acrylic acid, a skilled artisan will appreciate that acrylic acid may be readily converted into an ester (e.g., methyl acrylate, ethyl acrylate, etc.) or salt. Thereby, the bio-derived acrylic acid becomes an intermediate in a pathway to bio-derived esters such as bio-derived methyl acrylate and bio-derived ethyl acrylate.
Scale formation is sometimes a problem, particularly in nil-phosphate formulation. Anti-sealants include polyacrylates and polymers based on acrylic acid combined with other moieties, preferably from bio-derived sources. Sulfonated varieties of these polymers are particular effective in nil phosphate formulation executions. Examples of anti-scalants include those described in US 5,783,540, column 15, line 20 through column 16, line 2; and EP 0 851 022 A2, page 12, lines 1-20. Commercially available examples may include Acusol series (e.g., Acusol 588) of polymers from Dow and sulfonated polymers from Nippon Shukobai.
Olefins such as ethylene and propylene may be derived from renewable resources. For example, methanol derived from fermentation of biomass may be converted to ethylene and/or propylene, which are both suitable monomeric compounds, as described in U.S.
Patent Nos.
4,296,266 and 4,083,889. Ethanol derived from fermentation of a renewable resource may be converted into monomeric compound of ethylene via dehydration as described in U.S. Patent No.
4,423,270. Similarly, propanol or isopropanol derived from a renewable resource can be dehydrated to yield the monomeric compound of propylene as exemplified in U.S.
Patent No.
5,475,183. Propanol is a major constituent of fusel oil, a by-product formed from certain amino acids when potatoes or grains are fermented to produce ethanol.
Charcoal derived from biomass can be used to create syngas (i.e., CO/H2) from which 5 hydrocarbons such as ethane and propane can be prepared (Fischer-Tropsch Process). Ethane and propane can be dehydrogenated to yield the monomeric compounds of ethylene and propylene.
Acrylic acid having a 100% bio-derived carbon isotope ratio may be produced from bioderived glycerol, bio-derived lactic acid, and/or bio-derived lactate esters, as described in U.S.
10 Pat. App!. Pub. No. 2009/0018300. In turn, the bioderived glycerol may be converted to other useful chemical feedstocks, such as, acrylic acid (2-propenoic acid), allyl alcohol (2-propen-1-01), and 1,3-propanediol, having a 100% biobased carbon isotope ratio. For example, bioderived glycerol may be dehydrated to give acrolein (2-propenal). The acrolein may be oxidized to afford acrylic acid (2-propenoic acid). Alternatively, acrolein may be reduced to give ally!
15 alcohol (2-propen-1-o1). Suitable methods for the conversion of acrolein to ally! alcohol include, but are not limited to, reactions catalyzed by a silver indium catalyst as described by Lucas et al.
in Chemie Ingenieur Technik, 2005, 77, 110-113, the disclosure of which is incorporated by reference herein in its entirety. Further, acrolein may be converted to 1,3-propanediol. One suitable method for the conversion of acrolein to 1,3-propanediol includes hydration followed by 20 hydrogenation as described in U.S. Pat. No. 5,171,898, the disclosure of which is incorporated by reference herein in its entirety. The industrial/chemical feedstocks produced from glycerol, via acrolein, as set forth herein, will have a carbon isotope ratio that can be identified as being derived from biomass (i.e., bio-derived). Bio-derived 1,3-propanediol may be prepared as disclosed in U.S. Pat. App!. Pub. No. 2007/0213247. Moreover, sustainable compositions herein 25 may comprise bio-derived 1,3-propanediol prepared as disclosed in U.S.
Pat. App!. Pub. No.
2007/0213247.
Alternatively, bio-derived acrylic acid or acrylate esters may be synthesized from bio-derived lactic acid or lactate esters. Biobased lactic acid derivatives may be bio-synthesized, for example, by fermentation of a carbohydrate material. Conversion of lactic acid and lactate esters 30 into acrylic acid and acrylate esters, respectively, may be accomplished by dehydration of the alcohol group of the lactate moiety. Suitable methods for the conversion of lactic acid and lactate esters, for example, lactic acid/lactate esters from the fermentation of carbohydrate material in the presence of ammonia, into an acrylate ester or acrylic acid are disclosed in U.S.
=

Pat. Nos. 5,071,754 and 5,252,473, the disclosures of which are incorporated by reference herein in their entirety.
The bio-derived monomers described herein may be used for the synthesis of polymers having up to a 100% bio-derived carbon isotope ratio. Thus, the bio-derived monomers may be used for the synthesis of polymers having from 1% to 99.9% bio-derived carbon.
The bio-derived polymers, then, are suited for use in the sustainable composition.
According to other embodiments, the bio-derived monomers may be used for the synthesis of polymers having from 50% to 99.9% biobased carbon. Thus, the glycerol and carbohydrate starting materials described herein will necessarily be derived from biological sources. For example, bio-derived glycerol containing 100% bio-derived carbon, as determined by ASTM Method D 6866, may be obtained from triglycerides (triacylglycerols) from biological sources, for example, a vegetable oil or an animal fat, by splitting the triglyceride into the corresponding fatty acids and glycerol.
Triglycerides may be converted into the corresponding fatty acids and glycerol by acidic hydrolysis, basic hydrolysis (saponification) or by a catalytic de-esterification. Suitable triglycerides for use in the formation of bio-derived glycerol include, but are not limited to, corn oil, soybean oil, canola oil, vegetable oil, safflower oil, sunflower oil, nasturtium seed oil, mustard seed oil, olive oil, sesame oil, peanut oil, cottonseed oil, rice bran oil, babassu nut oil, castor oil, palm oil, palm kernel oil, rapeseed oil, low erucic acid rapeseed oil, lupin oil, jatropha oil, coconut oil, flaxseed oil, evening primrose oil, jojoba oil, tallow, beef tallow, butter, chicken fat, lard, dairy butterfat, shea butter, biodiesel, used frying oil, oil miscella, used cooking oil, yellow trap grease, hydrogenated oils, derivatives of these oils, fractions of these oils, conjugated derivatives of these oils, and mixtures of any thereof.
Suitable bioderived olefins include, but are not limited to monoacrylates, diacrylates, and ally' esters.
Alternatively, bio-derived glycerol may be produced as a co-product of biodiesel production. Glycerol produced by these methods will have a carbon isotope ratio consistent with a 100% bio-derived product and will provide a renewable source of acrolein and acrylic acid that may be used as a feedstock for the bio-derived monomers and polymers for use in the sustainable compositions. Non-limiting examples of methods and processes for producing biodiesel may be found in U.S. Pat. No. 5,354,878; U.S. Patent Application Publication Nos.
20050245405A1;
2007-0181504; and 20070158270A1; Provisional Patent Application Ser. No.
60/851,575, the disclosures of which are incorporated in their entirety by reference herein.
The monomers and polymers, as set forth herein, may have up to 100% biobased carbon isotope ratio as determined by ASTM Method D 6866. The monomers and polymers may be -differentiated from, for example, similar monomers and polymers comprising petroleum derived components by comparison of the carbon isotope ratios, for example, the 14C/12C or the 13c/12c carbon isotope ratios, of the materials. As described herein, isotopic ratios may be determined, for example, by liquid scintillation counting, accelerator mass spectrometry, or high precision isotopic ratio mass spectrometry.
Bio-derived acrylic acid (or acrylate esters), for example acrylic acid and esters synthesized by any of the embodiments described herein, may be esterified (or transesterified) with other bio-derived alcohols, diols, or polyols. Non-limiting suitable bio-derived alcohols and diols include, for example, methanol; ethanol; n-butanol, for example from an acetone/butanol fermentation; fusel oil alcohols (n-propanol, isobutyl alcohol, isoamyl alcohol, and/or furfural);
and alcohol and diol derivatives derived from carbohydrates or their derivatives.
Non-limiting examples of carbohydrate derived diols include hydroxymethylfurfuryl, 2,5-bis(hydroxymethyl)furan, 2,5-bis(hydroxymethyl)tetrahydrofuran, and isosorbide (dianhydrohexitol), isomannide, mannitol, xylitol, maltitol, maltitol syrup, lactitol, erythritol, isomalt, isoidide (the dianhydrohexitol of iditol), or ethoxylated or propoxylated derivatives of these.
Diacrylate esters may be produced from carbohydrate derived diols and may act as monomers or co-monomers having 100% bio-derived carbons, as determined by ASTM
Method D 6866, for the synthesis of polymers having up to 100% biobased carbon and being suitable for use in the sustainable compositions.
Other embodiments of bio-derived diols suitable for producing diacrylate esters having 100% biobased carbon may be produced from fatty acids, such as, for example, unsaturated fatty acids. For example, hydroformylation of unsaturated fatty acids and their derivatives to produce fatty acid derivatives having a hydroxymethylene group is described in U.S.
Pat. No. 3,210,325 to De Witt et al., the disclosure of which is incorporated in its entirety by reference herein.
Reduction of the carbonyl of the fatty acid derivative, for example, by hydrogenation, produces a biobased diol suitable for esterification or transesterification with acrylic acid or an acrylate ester, as produced herein, to form a biobased diacrylate monomer.
Additionally, bio-derived diols suitable for producing diacrylate esters having 100% bio-derived carbon may be produced by epoxidation of at least one of the double bonds of an unsaturated fatty acid/ester or unsaturated fatty alcohol. One non-limiting example of the epoxidation procedure is described by Rao et al., Journal of the American Oil Chemists' Society, (1968), 45(5), 408, the disclosure of which is incorporated in its entirety by reference herein.
The epoxidation may be followed by reduction, for example, by hydrogenation, to open the epoxide to the alcohol, which may also include reduction of the carbonyl of the fatty acid/ester to the alcohol. Any biobased diol may then be esterified or transesterified with acrylic acid or an acrylate ester, as produced herein, to form a diacrylate monomer having 100%
biobased carbon.
Still further, diols suitable for producing diacrylate esters having 100%
biobased carbon may be produced by reduction of a,w-dicarboxylic acids. As used herein, the term a,w-dicarboxylic acid" includes organic molecules comprising a carbon chain of at least 1 carbon atom and two carboxylic acid functional groups, each of which is positioned at opposite ends of the carbon chain. For example, a,w-dicarboxylic acids may be produced by a fermentation process involving biobased fatty acids, such as, by a fermentation process as described in Craft, et al., Applied and Environmental Microbiology, (2003), 69(10), 5983-5991 and/or U.S. Pat. No.
6,569,670 to Anderson et al., the disclosures of which are incorporated in their entirety by reference herein. Other a,co-dicarboxylic acids from biobased sources, such as, for example, maleic acid, fumaric acid, oxalic acid, malonic acid, adipic acid, succinic acid, and glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid may also be used in the sustainable compositions. According to certain embodiments, the a,w-dicarboxylic acid may be an unsaturated a,w-dicarboxylic acid or a saturated a,w-dicarboxylic acid.
Reduction of the carbonyls of the a,w-dicarboxylic acids provides a biobased diol which may then be esterified or transesterified with acrylic acid or an acrylate ester, as produced herein, to form a biobased diacrylate monomer.
Still further, bioderived diacrylamide derivatives may serve as monomers for the polymerization reactions described herein. For example, according to certain embodiments, the diol component in the formation of the diacrylate esters described herein, may be chemically converted to a bio-derived diamine, for example, by a double Mitsunobu-type reaction. Non-limiting examples of resulting biobased diamines may include, for example, bis-amino isosorbide, 2,5-bisaminomethyltetrahydrofuran, 2,5-bisaminomethylfuran.
Alternatively, naturally occurring bioderived diamines, such as, for example, 1,4-diaminobutane, 1,5-diaminopentane, or other alkyldiamines or diamine containing alkaloid derivatives, may be replace the diol reactant in the reaction with the bioderived acrylate derivative to form a diacryl amide compound. Further, it is also contemplated that bioderived amino alcohols may replace the diol component in the formation of the biobased monomers. According to these embodiments, the bioderived amino alcohols may be reacted with the bioderived acrylic acid or bioderived acrylate esters to form a bioderived monomer possessing both an acrylate ester and an acrylamide functionality.

Bioderived diacryl derivatives, such as the diacrylate esters, diacrylamides, and acrylate/acrylamide monomers may serve as monomers or co-monomers in a polymerization reaction to produce a bio-derived polymer for inclusion in the sustainable compositions. For example, an olefin metathesis polymerization reaction may be used to produce the biobased polymer. As used herein, the term "metathesis polymerization" includes an olefin metathesis reaction involving a metal carbene acting as a catalyst to metathesize alkene monomers or co-monomers into a polyunsaturated polymer through a metallocyclobutane intermediate. Thus, a polymer comprising a product from an olefin metathesis polymerization reaction of a bioderived olefin and a diacrylate ester of a bioderived diol may be used, wherein the diacrylate ester is produced by reacting a bioderived diol with at least two equivalents of bio-derived acrylic acid or an acrylate ester derived from a bioderived glycerol. The olefin metathesis polymerization reaction may be catalyzed by an olefin metathesis catalyst, such as a metal carbene catalyst, for example, metal carbenes of molybdenum or ruthenium. Commercially available olefin metathesis catalysts suitable for use in the polymerization reactions of the present disclosure include, but are not limited to, the "Schrock catalyst" (i.e., [Mo(=CHMe2Ph)(=N¨
Ar)(0CMe(CF3)2)21), the "1st generation Grubb's catalyst" (i.e., [Ru(=CHPh)C12(PCy3)2]), and the "2nd generation Grubb's catalyst" (i.e, [Ru(=CHPh)C12PCy3(N,N'-diary1-2-imidazolidiny1)]) (Me=methyl, Ph=phenyl, Ar=aryl, and Cy=cyclohexyl). Other olefin metathesis catalysts that may be suitable include those catalysts set forth in U.S. Pat. 7,034,096 to Choi et al. at column 12, line 27 to column 19, line 2, the disclosure of which is incorporated in its entirety by reference herein. It should be noted that the polymers and polymerization process described in the present disclosure are not limited to a particular olefin metathesis catalyst(s) and that any olefin metathesis catalyst, either currently available or designed in the future, may be suitable for use in various embodiments of the present disclosure.
Additionally, the bio-derived olefin component of the metathesis polymerization may be a bioderived cyclic olefin, wherein the metathesis polymerization reaction is a ring opening metathesis polymerization ("ROMP") reaction. As used herein, the term "ring opening metathesis polymerization reaction" includes olefin metathesis polymerization reactions wherein at least one of the monomer alkene units comprises a cyclic olefin. Thus, the ROMP reaction may react a bioderived diacryl derivative with a bioderived cyclic olefin to produce a polymer that is up to 100% biobased as determined by ASTM Method D 6866. Bio-derived cyclic olefins may be prepared, for example, from palmitoleic acid, oleic acid, erucic acid, linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid, docosahexaenoic acid, and other unsaturated fatty acids.

Further processes for producing bio-derived acrylic acid, acrylic acid esters, and acrylate polymers are disclosed in WO 2011/002284; US 7,928,148; US 2009/0018300; EP
1710227, and Xu et al, "Advances in the Research and Development of Acrylic Acid Production from Biomass," Chinese J. Chem. Eng., vol. 14, pp. 419-427 (2006), all of which are incorporated 5 herein in their entirety.
Thickening Agent The sustainable compositions may comprise a thickener system. A particularly preferred thickener for use in the compositions herein comprises xanthan gum or similar material and a co-thickener such as an associative polymer or water soluble silicates. The thickener system may 10 constitute from about 0.1% to about 15% by weight of the composition.
Suitable thickening agents are viscoelastic, thixotropic thickening agents.
The viscoelastic, thixotropic thickening agent in the compositions of the present invention is from about 0.1% to about 10%, preferably from about 0.25% to about 8%, most preferably from about 0.5% to about 5%, by weight of the detergent composition. Preferably, the thickening agents are 15 bio-derived.
Suitable thickeners which can be used in this composition include natural gums, such as xanthan gum, locust bean gum, guar gum, and the like. In one embodiment, xanthan gums are utilized. Xanthan gums are biopolysaccharides and suitable xanthan gums include, without limitation, products sold by Kelco Corporation under the trade names KELTROL , such as 20 KETROL RD and KELTROL CG-SFT and KELZAN as well as products sold by Rhodia under the trade names RHODIPOL , RHODIGEL" and RHODICARE", such as RHODICAREe T.
The cleaning detergent composition may comprise water-soluble silicates. Water-soluble silicates herein are any silicates which are soluble to the extent that they do not adversely affect 25 spotting/filming characteristics of the sustainable composition.
Aluminosilicate builders can be used in the present compositions though are not preferred for automatic dishwashing detergents.
The soluble silicate is typically used in an amount of about 0.4% to about 4.0% by weight; more preferably is present in an amount of about 0.75% to about 3% by weight and most preferably present in an amount of about 1% to about 2% by weight, based on the total weight of 30 the composition.
The associative thickener is typically an addition polymer of three components: (1) an alpha-beta-monoethylenically unsaturated monocarboxylic acid or dicarboxylic acid of from 3 to 8 carbon atoms such as bio-derived acrylic acid or bio-derived methacrylic acid to provide water solubility; (2) a monoethylenically unsaturated copolymerizable monomer lacking surfactant capacity such as bio-derived methyl acrylate or bio-derived ethyl acrylate to obtain the desired polymer backbone and body characteristics; and (3) a monomer possessing surfactant capacity which provides the pseudo plastic properties to the polymer and is the reaction product of a monoethylenically unsaturated monomer with a nonionic surfactant compound wherein the monomer is copolymerizable with the foregoing monomers such as the reaction product of bio-derived methacrylic acid with a monohydric nonionic surfactant to obtain a monomer such as CH3(CH2)is-17(OCH2CH2)e0OCC(CH3)=CH2, where "e" has an average value of about 10 or 20.
Optionally, up to about 2.0% of a polyethylenically unsaturated monomer sloth as bio-derived ethylene glycol diacrylate or dimethacrylate or divinylbenzene can be included if a higher molecular weight polymer is desired.
Additional associative thickeners include bio-derived maleic anhydride copolymers reacted with nonionic surfactants such as bio-derived ethoxylated C12-C14 primary alcohol, similar to the compounds available under the tradename Surfonic L Series from Texaco Chemical Co. and the tradename Gantrez AN-119 from ISP.
The associative thickeners may include C10¨C22 alkyl groups in an alkali-soluble acrylic emulsion polymer such as those available under the trademark AcusoI from Rohm & Haas Co. of Philadelphia, Pa. The most preferred associative thickeners are Acusol 820 ("820") and 1206A ("1206A"). Acusol 820 is a 30.0% active emulsion polymer of 40.0%
methacrylic acid, 50% ethyl acrylate and 10.0% stearyl oxypoly ethyl methacrylic emulsion polymer having approximately 20 moles of ethylene oxide. Acusol 1206A is a 30% active emulsion polymer with 44% methacrylic acid, 50% ethyl acrylate and 6% stearyl methacrylate polymer having about 10 moles of ethylene oxide. These polymers are described in U.S. Pat.
No. 4,351,754 to Dupre. Most preferably, the associative thickeners are provided as 100% bio-derived analogs of these commercially available products.
The associative thickener is typically used in an amount of about 0.01% to about 1.0% by weight; more preferably is present in an amount of about 0.05% to about 0.5%
by weight and most preferably present in an amount of about 0.1% to about 0.3% by weight, based on the total weight of the sustainable composition.
In addition to the xanthan gum thickener, other thickeners may be utilized.
Suitable are various carboxyvinyl polymers, homopolymers and copolymers are commercially available from B. F. Goodrich Company, New York, N.Y., under the trade name CARBOPOLe. These polymers are also known as carbomers or polyacrylic acids. Carboxyvinyl polymers useful in formulations of the present invention include CARBOPOL 910 having a molecular weight of about 750,000, CARBOPOL 941 having a molecular weight of about 1,250,000, and CARBOPOLe 934 and 940 having molecular weights of about 3,000,000 and 4,000,000, respectively. More preferred are the series of CARBOPOL which use ethyl acetate and cyclohexane in the manufacturing process, for example, CARBOPOL 981, 2984, 980, and 1382. Analogous compounds may be produced from bio-derived carbon sources and may be used in the sustainable compositions in preferred embodiments.
Further suitable additional thickeners include polycarboxylate polymers of the invention are non-linear, water-dispersible, polyacrylic acid cross-linked with a polyalkenyl polyether and having a molecular weight of at lease 750,000, preferably from about 750,000 to about 4,000,000, all preferably bio-derived. Suitable examples of these polycarboxylate polymers include are SOKALAN PHC-25 , a polyacrylic acid available from BASF
Corporation and the POLYGEL series available from 3-V Chemical Corporation. Mixtures of polycarboxylate polymers may also be used.
Semi-synthetic thickeners such as the cellulosic type thickeners: hydroxyethyl and hydroxymethyl cellulose (ETHOCEL and METHOCEL available from Dow Chemical) can also be used. Preferably the semi-synthetic thickeners are obtained from bio-derived sources of carbon. Mixtures of inorganic clays (e.g., aluminum silicate, bentonite, fumed silica) are also suitable for use as a thickener herein. The preferred clay thickening agent can be either naturally occurring or synthetic. An example of a suitable synthetic clay is disclosed in the U.S. Pat. No.
3,843,598. Naturally occurring clays further include some smectite and attapulgite clays as disclosed in U.S. Pat. No. 4,824, 590.
Other suitable organic polymer for use herein includes a polymer comprising an acrylic acid backbone and alkoxylated side chains, the polymer having a molecular weight of from about 2,000 to about 20,000, and said polymer having from about 20 wt% to about 50 wt% of an alkylene oxide, preferably a bio-derived alkylene oxide. The polymer should have a molecular weight of from about 2,000 to about 20,000, or from about 3,000 to about 15,000, or from about 5,000 to about 13,000. The alkylene oxide (AO) component of the polymer is generally propylene oxide (PO) or ethylene oxide (E0), preferably bio-derived EO and/or bio-derived PO, and generally comprises from about 20 wt% to about 50 wt%, or from about 30 wt% to about 45 wt%, or from about 30 wt% to about 40 wt% of the polymer. The alkoxylated side chains of the water soluble polymers may comprise from about 10 to about 55 AO units, or from about 20 to about 50 AO units, or from about 25 to 50 AO units. The polymers, preferably water. soluble, may be configured as random, block, graft, or other known configurations.
Methods for forming alkoxylated acrylic acid polymers are disclosed in U.S. Patent No. 3,880,765.
Further methods for producing bio-based glycol compositions as synthetic feedstocks for bio-derived monomers and bio-derived polymers are disclosed in WO 2008/057220, incorporated herein by reference.
Polyvalent Metal Compounds The sustainable composition may comprise a polyvalent metal compound. Any suitable polyvalent metal compound may be used in any suitable amount or form. Suitable polyvalent metal compounds include, but are not limited to: polyvalent metal salts, oxides, hydroxides, and mixtures thereof. Suitable polyvalent metals include, but are not limited to:
Groups IIA, IIIA, IVA, VA, VA, VIIA, IIB, IIIB, IVB, VB and VIII of the Periodic Table of the Elements. For example, suitable polyvalent metals may include Al, Mg, Co, Ti, Zr, V, Nb, Mn, Fe, Ni, Cd, Sn, Sb, Bi, and Zn. These polyvalent metals may be used in any suitable oxidation state. Suitable oxidation states are those that are stable in the cleaning sustainable compositions described herein.
Any suitable polyvalent metal salt may be used in any suitable amount or form.
Suitable salts include but are not limited to: organic salts, inorganic salts, and mixtures thereof. For example, suitable polyvalent metal may include: water-soluble metal salts, slightly water-soluble metal salts, water-insoluble metal salts, slightly water-insoluble metal salts, and mixtures thereof.
Suitable water-soluble aluminum salts may include, but are not limited to:
aluminum acetate, aluminum ammonium sulfate, aluminum chlorate, aluminum chloride, aluminum chlorohydrate, aluminum diformate, aluminum fluoride, aluminum formoacetate, aluminum lactate, aluminum nitrate, aluminum potassium sulfate, aluminum sodium sulfate, aluminum sulfate, aluminum tartrate, aluminum triformate, and mixtures thereof.
Suitable water-insoluble aluminum salts may include, but are not limited to: aluminum silicates, aluminum salts of fatty acids (e.g., aluminum stearate and aluminum laurate), aluminum metaphosphate, aluminum monostearate, aluminum oleate, aluminum oxylate, aluminum oxides and hydroxides (e.g., activated alumina and aluminum hydroxide gel), aluminum palmitate, aluminum phosphate, aluminum resinate, aluminum salicylate, aluminum stearate, and mixtures thereof.
Suitable water-soluble magnesium salts may include, but are not limited to:
magnesium acetate, magnesium acetylacetonate, magnesium ammonium phosphate, magnesium benzoate, magnesium biophosphate, magnesium borate, magnesium borocitrate, magnesium bromate, magnesium bromide, magnesium calcium chloride, magnesium chlorate, magnesium chloride, magnesium citrate, magnesium fluosilicate, magnesium formate, magnesium gluconate, magnesium glycerophosphate, magnesium lauryl sulfate, magnesium nitrate, magnesium phosphate monobasic, magnesium salicylate, magnesium stannate, magnesium stannide, magnesium sulfate, magnesium sulfite, and mixtures thereof. Suitable water-insoluble inagnesium salts may include, but are not limited to: magnesium aluminate, magnesium fluoride, magnesium oleate, magnesium perborate, magnesium phosphate dibasic, magnesium phosphate tribasic, magnesium pyrophosphate, magnesium silicate, magnesium trisilicate, magnesium sulfide, magnesium tripolyphosphate, and mixtures thereof.
Suitable water-soluble zinc salts may include, but are not limited to: zinc acetate, zinc benzoate, zinc borate, zinc bromate, zinc bromide, zinc chlorate, zinc chloride, zinc ethysulfate, zinc fluorosilicate, zinc formate, zinc gluconate, zinc hydrosulfite, zinc lactate, zinc linoleate, zinc malate, zinc nitrate, zinc perborate, zinc salicylate, zinc sulfate, zinc sulfamate, zinc tartrate, and mixtures thereof. Suitable water-insoluble zinc salts may include, but are not limited to: zinc bacitracin, zinc carbonate, zinc basic carbonate or basic zinc carbonate, hydrozincite, zinc laurate, zinc phosphate, zinc tripolyphosphate, sodium zinc tripolyphosphate, zinc silicate, zinc stearate, zinc sulfide, zinc sulfite, and mixtures thereof.
Any suitable polyvalent metal oxide and/or hydroxide may be used in any suitable amount or form. Suitable polyvalent metal oxides may include, but are not limited to: aluminum oxide, magnesium oxide, and zinc oxide. Suitable polyvalent metal hydroxides may include, but are not limited to: aluminum hydroxide, magnesium hydroxide, and zinc hydroxide.
In certain non-limiting embodiments, polyvalent metal compounds may be used in their water-insoluble form. The presence of the polyvalent metal compounds in an essentially insoluble but dispersed form may inhibit the growth of large precipitates from within cleaning detergent product and/or wash liquor solution. Not to be bound by theory, it is believed that because the water-insoluble polyvalent metal compound is in a form in product that is essentially insoluble, the amount of precipitate, which will form in the wash liquor of the dishwashing process, is greatly reduced. Although the insoluble polyvalent metal compound will dissolve only to a limited extent in the wash liquor, the dissolved metal ions are in sufficient concentration to impart the desired glasscare benefit to treated dishware. Hence, the chemical reaction of dissolved species that produce precipitants in the dishwashing process is controlled. Thus, use of water-insoluble polyvalent metal compounds allows for control of the release of reactive metal species in the wash liquor, as well as, the control of unwanted precipitants.
In certain non-limiting embodiments, the amount of polyvalent metal compound may be provided in a range of from about 0.01% to about 60%, from about 0.02% to about 50%, from about 0.05% to about 40%, from about 0.05% to about 30%, from about 0.05% to about 20%, from about 0.05% to about 10%, and alternatively, from about 0.1% to about 5%, by weight, of the sustainable composition.
Natural Thickener The sustainable compositions can also comprise an auxiliary nonionic or anionic 5 polymeric thickening component, especially cellulose thickening polymers, especially a water-soluble or water dispersible polymeric materials, having a molecular weight greater than 20,000.
The cellulose thickening polymers preferably contain bio-derived cellulose. By "water-soluble or water dispersible polymer" is meant that the material will form a substantially clear solution in water at a 0.5 to 1 weight percent concentration at 25 C and the material will increase the 10 viscosity of the water either in the presence or absence of surfactant.
Examples of water-soluble polymers which may desirably be used as an additional thickening component in the present compositions, are hydroxyethylcellulose, hydroxypropyl cellulose, hydroxypropyl methylcellulose, dextrans, for example Dextran purified crude Grade 2P, available from D&O
Chemicals, carboxymethyl cellulose, plant exudates such as acacia, ghatti, and tragacanth, 15 seaweed extracts such as sodium alginate, and sodium carrageenan.
Preferred as the additional thickeners for the present compositions are bio-derived polysaccharide or cellulose materials.
Examples of such materials include, but are limited to, guar gum, locust bean gum, xanthan gum and mixtures thereof. The sustainable composition also may contain an anti-redeposition polymer. Examples of anti- redeposition polymers include, but are not limited to, inulin, 20 derivatized inulin, guar and derivatized guar. Also suitable for use in the sustainable compositions is hydroxyethyl cellulose, preferably bio-derived, having a molecular weight of about 700,000. The thickeners are generally present in amounts of about 0.05 to about 2.0 weight percent, or about 0.1 to about 2.0 weight percent.
Low levels of polymer can also be used to thicken the preferred aqueous compositions of 25 the present invention. In general, the level of thickening polymer is kept as low as possible so as not to hinder the product's end result properties. Xanthan gum is a particularly preferred thickening agent as it can also enhance end result properties, particularly when used in low concentrations. Moreover, xanthan gum is bio-derived. The thickening polymer agent is present in from about 0.001% to about 0.1%, more preferably from about 0.0025% to about 0.05%, most 30 preferably from about 0.005% to about 0.025%, by weight of the composition.

=
Natural Essence The sustainable compositions of the present invention may include a bio-derived "natural essence". As used herein, "natural essence" is intended to include a broader class of natural products comprising natural oils extracted from plants and trees and their fruits, nuts and seeds, (for example by steam or liquid extraction of ground-up plant/tree material), natural products that may be purified by distillation, (i.e., purified single organic molecules or close boiling point "cuts" of organic materials such as terpenes and the like), and synthetic organic materials that are the synthetic versions of naturally occurring materials (e.g., either identical to the natural material, or the optical isomer, or the racemic mixture). Synthetic versions of naturally occurring materials preferably are synthesized from bio-derived carbon sources. An example of the synthetic essence is D,L-limonene that is synthetically prepared and is a good and eco-friendly substitute for natural orange oil (mostly D-limonene) when citrus is expensive, for example, because of crop freezes.
Thus, it should be understood that "natural essence" incorporates a wide range of pure organic materials either natural or synthetic versions thereof, mixtures of these previously purified individual materials or distillate cuts of materials, and complex natural mixtures directly extracted from plant/tree materials through infusion, steam extraction, etc.
Also, it should be understood that these natural essence ingredients may double as fragrance materials for the sustainable composition, and in fact many natural extracts, oils, essences, infusions and such are very fragrant materials. However, for use in the present sustainable compositions, these materials are used at higher levels than would be typical for fragrance purposes, and it should be also understood that depending on optical isomers used, there may be no smell or a reduced smell, or even a masking effect to the human sensory perception. Thus by judicious choice of natural essence mixtures, performance boosting may be effected without making the compositions overwhelmingly scented. Also, actual fragrance masking materials (such as used for household cleaners and available from the fragrance supply houses such as International Flavors & Fragrances, Symrise, Givaudan, Firmenich, and others) may be added to mask the smells of the natural essences.
Some of the naturally derived essences for use in the sustainable compositions include, but are not limited to, musk, civet, ambergis, castoreum and similar animal derived oils; abies oil, ajowan oil, almond oil, ambrette seed absolute, angelic root oil, anise oil, basil oil, bay oil, benzoin resinoid, bergamot oil, birch oil, bois de rose oil, broom abs., cajeput oil, cananga oil, capsicum oil, caraway oil, cardamon oil, carrot seed oil, cassia oil, cedar leaf oil, cedar wood oil, celery seed oil, cinnamon bark oil, citronella oil, clary sage oil, clove oil, cognac oil, coriander oil, cubeb oil, cumin oil, camphor oil, dill oil, elemi gum, estragon oil, eucalyptol nat., eucalyptus oil, fennel sweet oil, galbanum res., garlic oil, geranium oil, ginger oil, grapefruit oil, hop oil, hyacinth abs., jasmin abs., juniper berry oil, labdanum res., lavender oil, laurel leaf oil, lavender Synthetic essences include but are not limited to pinene, limonene and like hydrocarbons;
3,3,5-trimethylcyclohexanol, linalool, geraniol, nerol, citronellol, menthol, borneol, borneyl methoxy cyclohexanol, benzyl alcohol, anise alcohol, cinnamyl alcohol, 3-phenyl ethyl alcohol, acetate, methyl anthranilate, methyl dihydrojasmonate, nopyl acetate, P-phenylethyl acetate, trichloromethylphenyl carbinyl acetate, terpinyl acetate, vetiveryl acetate, and the like.
Suitable essence mixtures may produce synergistic performance attributes for the sustainable composition and may help to impart an overall fragrance perception as well to the composition including but not limited to, fruity, musk, floral, herbaceous (including mint), and woody, or perceptions that are in-between (fruity-floral for example).
Typically these essence or essential oil mixtures may be compounded by mixing a variety of these active extract or synthetic materials along with various solvents to adjust cost, viscosity, flammability, ease of handling, etc.
Since many natural extract ingredients are compounded into fragrances, the essential oils, infusions, distillates, etc. that are considered "natural essences" are also available from the fragrance companies such as International Flavors & Fragrances, Givaudan, Symrise, Firmenich, Robertet, and many others. The natural essences are preferably incorporated at a level of from about 0.1% to about 5% as the 100% neat substance or mixture of substances. It is important to note that these levels tend to be greater than those levels used for scenting a product with a perfume.
Fragrances The sustainable compositions can contain fragrances, especially fragrances containing essential oils, and especially fragrances containing D-limonene or lemon oil;
or natural essential oils or fragrances containing D-limonene or lemon oil. Lemon oil and D-limonene compositions which are useful in the sustainable compositions include mixtures of terpene hydrocarbons obtained from the essence of oranges, e.g., cold-pressed orange terpenes and orange terpene oil phase from fruit juice, and the mixture of terpene hydrocarbons expressed from lemons and grapefruit. The essential oils may contain minor, non-essential amounts of hydrocarbon carriers.
Suitably, the fragrance contains essential oil or lemon oil or D-limonene in the sustainable composition in an amount ranging from about 0.01 wt.% to about 5.0 wt.%, from about 0.01 wt.% to about 4.0 wt.%, from about 0.01 wt.% to about 3.0 wt.%, from about 0.01 wt.% to about 2.0 wt.%, from about 0.01 wt.% to about 1.0 wt.%, or from about 0.01 wt.% to about 0.50 wt.%, or from about 0.01 wt.% to about 0.40 wt.%, or from about 0.01 wt.%
to about 0.30 wt.%, or from about 0.01 wt.% to about 0.25 wt.%, or from about 0.01 wt.%
to about 0.20 wt.%, or from about 0.01 wt.% to about 0.10 wt.%, or from about 0.05 wt.%
to about 2.0 wt.%, or from about 0.05 wt.% to about 1.0 wt.%, or from about 0.5 wt.% to about 1.0 wt.%, or from about 0.05 wt.% to about 0.40 wt.%, or from about 0.05 wt.% to about 0.30 wt.%, or from about 0.05 wt.% to about 0.25 wt.%, or from about 0.05 wt.% to about 0.20 wt.%, or from about 0.05 wt.% to about 0.10 wt.%.
The sustainable compositions may further comprise a perfume. In a particularly preferred embodiment the sustainable compositions comprise different perfumes such that the user will gain a different olfactory experience, for example, when the sustainable compositions are contained within different types of dosing devices such as pouches.
The sustainable compositions may also comprise a blooming perftime. A blooming perfume composition is one which comprises blooming perfume ingredients. A
blooming perfume ingredient may be characterized by its boiling point (B.P.) and its octanol/water partition coefficient (P). As used in this context, "boiling point" refers to boiling point measured under normal standard pressure of 760 mmHg. The boiling points of many perfume ingredients, at standard 760 mm Hg are given in, e.g., "Perfume and Flavor Chemicals (Aroma Chemicals),"
Steffen Arctander, published by the author, 1969, incorporated herein by reference.
The octanol/water partition coefficient of a perfume ingredient is the ratio between its equilibrium concentrations in octanol and in water. The partition coefficients of the preferred perfume ingredients may be more conveniently given in the form of their logarithm to the base 10, logP. The logP values of many perfume ingredients have been reported; for example, the Pomona92 database, available from Daylight Chemical Information Systems, Inc.
(Daylight CIS), Irvine, Calif., contains many, along with citations to the original literature. However, the logP values are most conveniently calculated by the "CLOGP" program, also available from Daylight CIS. This program also lists experimental logP values when they are available in the Pomona92 database. The "calculated logP" (ClogP) is determined by the fragment approach of Hansch and Leo (cf., A. Leo, in Comprehensive Medicinal Chemistry, Vol. 4, C.
Hansch, P. G.
Sammens, J. B. Taylor and C. A. Ramsden, Eds., p. 295, Pergamon Press, 1990, incorporated herein by reference). The fragment approach is based on the chemical structure of each perfume ingredient, and takes into account the numbers and types of atoms, the atom connectivity, and chemical bonding. The ClogP values, which are the most reliable and widely used estimates for this physicochemical property, are preferably used instead of the experimental logP values in the selection of perfume ingredients which are useful in sustainable compositions.
The perfume, if present in the sustainable composition, may preferably comprise at least two perfume ingredients. The first perfume ingredient is characterized by a boiling point of 250 C or less and ClogP of 3.0 or less. More preferably the first perfume ingredient has boiling point of 240 C or less, most preferably 235 . C or less. More preferably the first perfume ingredient has a ClogP value of less than 3.0, more preferably 2.5 or less.
The first perfume ingredient is present at a level of at least 7.5% by weight of the composition, more preferably at least 8.5% and most preferably at least 9.5% by weight of the composition.
The second perfume ingredient, if present in the sustainable composition, may be characterized by a boiling point of 250 C or less and ClogP of 3.0 or more.
More preferably the 5 second perfume ingredient has boiling point of 240 C or less, most preferably 235 C or less.
More preferably the second perfume ingredient has a ClogP value of greater than 3.0, even more preferably greater than 3.2. The second perfume ingredient is present at a level of at least 35%
by weight of the composition, more preferably at least 37.5% and most preferably greater than 40% by weight of the perfume composition.
10 More preferably the perfume, when present in the sustainable composition, may comprise a plurality of ingredients chosen from the first group of perfume ingredients and a plurality of ingredients chosen from the second group of perfume ingredients. In addition to the above, it is the sustainable composition may comprise at least one perfume ingredient selected from either first and/or second perfume ingredients, which are present in an amount of at least 7% by weight 15 of the perfume composition, preferably at least 8.5% of the perfume composition, and most preferably, at least 10% of the perfume composition.
The first and second perfume ingredients may be selected from the group consisting of esters, ketones, aldehydes, alcohols, derivatives thereof and mixtures thereof. Preferred examples of the first and second perfume ingredients can be found in PCT
application number 20 US00/19078 (Applicants case number CM2396F). Preferably, the perfume ingredients comprise or consist of natural or bio-derived substances.
In the perfume art, some auxiliary materials having no odor, or a low odor, are used, e.g., as solvents, diluents, extenders or fixatives. Non-limiting examples of these materials are ethyl alcohol, carbitol, diethylene glycol, dipropylene glycol, diethyl phthalate, triethyl citrate, 25 isopropyl myristate, and benzyl benzoate, any or all of which may be bio-derived substances.
These materials are used for, e.g., solubilizing or diluting some solid or viscous perfume ingredients to, e.g., improve handling and/or formulating. These materials are useful in the blooming perfume compositions, but are not counted in the calculation of the limits for the definition/formulation of the blooming perfume compositions of the present invention.
30 It can be desirable to use blooming and delayed blooming perfume ingredients and even other ingredients, preferably in small amounts, in the blooming perfume compositions of the present invention, that have low odor detection threshold values. The odor detection threshold of an odorous material is the lowest vapor. concentration of that material which can be detected. The odor detection threshold and some odor detection threshold values are discussed in, e.g., "Standardized Human Olfactory Thresholds", M. Devos et al, IRL Press at Oxford University Press, 1990, and "Compilation of Odor and Taste Threshold Values Data", F. A.
Fazzalari, editor, ASTM Data Series DS 48A, American Society for Testing and Materials, 1978, both of said publications being incorporated by reference. The use of small amounts of non-blooming perfume ingredients that have low odor detection threshold values can improve perfume odor character, without the potential negatives normally associated with such ingredients, e.g., spotting and/or filming on, e.g., dish surfaces. Non-limiting examples of perfume ingredients that have low odor detection threshold values useful in the present invention include coumarin, vanillin, ethyl vanillin, methyl dihydro isojasmonate, 3-hexenyl salieylate, isoeugenol, lyral, gamma-undecalactone, gamma-dodecalactone, methyl beta naphthyl ketone, and mixtures thereof. These materials are preferably present at low levels in addition to the blooming and optionally delayed blooming ingredients, typically less than 5%, preferably less than 3%, more preferably less than 2%, by weight of the blooming perfume compositions of the present invention. Preferably, these materials are obtained from sources of bio-derived carbon.
The perfumes suitable for use in the sustainable compositions herein can be formulated from known fragrance ingredients and for purposes of enhancing environmental compatibility, the perfume compositions used herein are preferably substantially free of halogenated fragrance materials and nitromusks.
Alternatively the perfume ingredients or a portion thereof, when present in the sustainable composition, may be complexed with a complexing agent. Complexing agents may include any compound which encapsulate or bind perfume raw materials in aqueous solution.
Binding can result from one or more of strong reversible chemical bonding, reversible weak chemical bonding, weak or strong physical absorption or adsorption and, for example, may take the form of encapsulation, partial encapsulation, or binding. Complexes formed can be 1:1, 1:2, 2:1 complexant:perfume ratios, or can be more complex combinations. It is also possible to bind perfumes via physical encapsulation via coating (e.g. starch coating), or coacervation. Key to effective complexation for controlled perfume release is an effective de-complexation mechanism, driven by use of the product for washing dishes or hard surfaces.
Suitable de-complexation mechanisms can include dilution in water, increased or decreased temperature, increased or decreased ionic strength. It is also possible to chemically or physically decompose a coated perfume, eg via reaction with enzyme, bleach or alkalinity, or via solubilization by surfactants or solvents. Preferred complexing agents include cyclodextrin, zeolites, coacervates starch coatings, and mixtures thereof.

Cyclodextrin molecules are known for their ability to form complexes with perfume ingredients and have typically been taught as a perfume carrier. In addition, cyclodextrin molecules also appear to be surprisingly effective at reducing malodors generated by nitrogenous compounds, such as amines. Cyclodextrins for use herein preferably are bio-derived molecules and may be obtained, for example, by enzymatic conversion of natural or plant-derived starches.
Suitable cyclodextrins are discussed in U.S. Pat. No. 5,578,563, issued Nov.
26, 1996, to Trinh et al., which is hereby incorporated by reference. The cavity of a cyclodextrin molecule has a substantially conical shape. It is preferable in the present invention that the cone-shaped cavity of the cyclodextrins have a length (altitude) of 8 A and a base size of from 5 A to 8.5 A.
Thus the preferred cavity volume for cyclodextrins of the present invention is from 65 A3 to 210 A3.
Suitable cyclodextrin species include any of the known cyclodextrins such as unsubstituted cyclodextrins containing from six to twelve glucose units, especially, alpha-cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin and/or their derivatives and/or mixtures thereof. The alpha-cyclodextrin consists of six glucose units, the beta-cyclodextrin consists of seven glucose units, and the gamma-cyclodextrin consists of eight glucose units arranged in a donut-shaped ring. The specific coupling and conformation of the glucose units give the cyclodextrins a rigid, conical molecular structure with a hollow interior of a specific volume.
The "lining" of the internal cavity is formed by hydrogen atoms and glycosidic bridging oxygen atoms, therefore this surface is fairly hydrophobic. The unique shape and physical-chemical property of the cavity enable the cyclodextrin molecules to absorb (form inclusion complexes with) organic molecules or parts of organic molecules which can fit into the cavity. Many perfume molecules can fit into the cavity.
The cyclodextrin molecules are preferably water-soluble. The water-soluble cyclodextrins preferably have a water solubility of at least 10 g in 100 mL
water, more preferably at least 25 g in 100 mL of water at standard temperature and pressure.
Examples of preferred water-soluble cyclodextrin derivative species are hydroxypropyl alpha-cyclodextrin, methylated alpha-cyclodextrin, methylated beta-cyclodextrin, hydroxyethyl beta-cyclodextrin, and hydroxypropyl beta-cyclodextrin. Hydroxyalkyl cyclodextrin derivatives preferably have a degree of substitution of from 1 to 14, more preferably from 1.5 to 7, wherein the total number of OR groups per cyclodextrin is defined as the degree of substitution.
Methylated cyclodextrin derivatives typically have a degree of substitution of from 1 to 18, preferably from 3 to 16. A
known methylated beta-cyclodextrin is heptakis-2,6-di-O-methyl-,13-cyclodextrin, commonly known as DIMEB, in which each glucose unit has 2 methyl groups with a degree of substitution of 14. A preferred, more commercially available methylated beta-cyclodextrin is a randomly methylated beta-cyclodextrin having a degree of substitution of 12.6. The preferred cyclodextrins are available, e.g., from American Maize-Products Company and Wacker Chemicals (USA), Inc. Preferably, the cyclodextrins themselves, as well as any alkyl functionality, contain only bio-derived carbon.
Further cyclodextrin species suitable for use in the present invention include alpha-cyclodextrin and derivatives thereof, gamma-cyclodextrin and derivatives thereof, derivatized beta-cyclodextrins, and/or mixtures thereof. Other derivatives of cyclodextrin suitable for use in the sustainable compositions are discussed in U.S. Pat. No. 5,578,563, incorporated above. It should be noted that two or more different species of cyclodextrin may be used in the same liquid detergent composition.
The complexes may be formed in any of the ways known in the art. Typically, the complexes are formed either by bringing the fragrance materials and the cyclodextrin together in a suitable solvent e.g. water and ethanol mixtures, propylene glycol, preferably bio-derived propylene glycol. Additional examples of suitable processes as well as further preferred processing parameters and conditions are disclosed in U.S. Pat. No. 5,234,610, to Gardlik et al., issued Aug. 10, 1993, which is hereby incorporated by reference. After the cyclodextrin and fragrance materials are mixed together, this mixture is added to the sustainable composition.
Generally, only a portion (not all) of the fragrance materials mixed with the cyclodextrin will be encapsulated by the cyclodextrin and form part of the cyclodextrin/perfume complex; the remaining fragrance materials will be free of the cyclodextrin and when the cyclodextrin/perfume mixture is added to the detergent composition they will enter the detergent composition as free perfume molecules. A portion of free cyclodextrin molecules which are not complexed with the fragrance materials may also be present. In an alternative embodiment of the present invention, the fragrance materials and cyclodextrins are added uncomplexed and separately to the liquid sustainable compositions. Consequently, the cyclodextrins and fragrance materials will come into the presence of each other in the composition, and a portion of each will combine to form the desired fragrance materials/cyclodextrin complex.
In general, perfume/cyclodextrin complexes have a molar ratio of perfume compound to cyclodextrin of 1:1. However, the molar ratio can be either higher or lower, depending on the size of the perfume compound and the identity of the cyclodextrin compound.
For example, the the molar ratio of fragrance materials to cyclodextrin may be from 4:1 to 1:4, preferably from 1.5:1 to 1:2, more preferably from 1:1 to 1:1.5. The molar ratio can be determined easily by forming a saturated solution of the cyclodextrin and adding the perfume to form the complex. In general the complex will precipitate readily. If not, the complex can usually be precipitated by the addition of electrolyte, change of pH, cooling, etc. The complex can then be analyzed to determine the ratio of perfume to cyclodextrin.
The actual complexes are determined by the size of the cavity in the cyclodextrin and the size of the perfume molecule. Although the normal complex is one molecule of perfume in one molecule of cyclodextrin, complexes can be formed between one molecule of perfume and two molecules of cyclodextrin when the perfume molecule is large and contains two portions that can fit in the cyclodextrin. Highly desirable complexes can be formed using mixtures of cyclodextrins since perfumes are normally mixtures of materials that vary widely in size. It is usually desirable that at least a majority of the material be beta- and/or gamma-cyclodextrin.
Odor Control Agents The sustainable compositions may comprise one or more odor control agents, of which all or a substantial portion of the carbon atoms in the odor control agents are bio-derived.
Cyclodextrins are particularly preferred, and may be bio-derived from sources such as those described above with respect to the cyclodextrins for complexing perfumes.
For the odor control agents, the term "cyclodextrin" includes any of the known cyclodextrins such as unsubstituted cyclodextrins containing from six to twelve glucose units, especially, alpha-cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin and/or their derivatives and/or mixtures thereof. The alpha-cyclodextrin consists of six glucose units, the beta-cyclodextrin consists of seven glucose units, and the gamma-cyclodextrin consists of eight glucose units arranged in donut-shaped rings. The specific coupling and conformation of the glucose units give the cyclodextrins rigid, conical molecular structures with hollow interiors of specific volumes. The "lining" of each internal cavity is formed by hydrogen atoms and glycosidic bridging oxygen atoms; therefore, this surface is fairly hydrophobic.
The unique shape and physical-chemical properties of the cavity enable the cyclodextrin molecules to absorb (form inclusion complexes with) organic molecules or parts of organic molecules which can fit into the cavity. Many odorous molecules can fit into the cavity including many malodorous molecules and perfume molecules. Therefore, cyclodextrins, and especially mixtures of cyclodextrins with different size cavities, can be used to control odors caused by a broad spectrum of organic odoriferous materials, which may, or may not, contain reactive functional groups. The complexation between cyclodextrin and odorous molecules occurs rapidly in the presence of water. However, the extent of the complex formation also depends on the polarity of the absorbed molecules. In an aqueous solution, strongly hydrophilic molecules (those which are highly water-soluble) are only partially absorbed, if at all. Therefore, cyclodextrin does not complex effectively with some very low molecular weight organic amines and acids when they are present at low levels on wet surfaces. As the water is being removed 5 however, e.g., the surface is being dried off, some low molecular weight organic amines and acids have more affinity and will complex with the cyclodextrins more readily.
The cavities within the cyclodextrin in the solution of the present invention should remain essentially unfilled (the cyclodextrin remains uncomplexed) while in solution, in order to allow the cyclodextrin to absorb various odor molecules when the solution is applied to a surface.
10 Non-derivatised (normal) beta-cyclodextrin can be present at a level up to its solubility limit of about 1.85% (about 1.85g in 100 grams of water) at room temperature. Beta-cyclodextrin is not preferred in compositions which call for a level of cyclodextrin higher than its water solubility limit. Non-derivatised beta-cyclodextrin is generally not preferred when the composition contains surfactant since it affects the surface activity of most of the preferred surfactants that are 15 compatible with the derivatised cyclodextrins.
Preferably, the compositions of the present invention are clear. The term "clear" as defined herein means transparent or translucent, preferably transparent, as in "water clear," when observed through a layer having a thickness of less than 10 cm.
Preferably, the cyclodextrins used in the present invention are highly water-soluble such 20 as, alpha-cyclodextrin and/or derivatives thereof, gamma-cyclodextrin and/or derivatives thereof, derivatised beta-cyclodextrins, and/or mixtures thereof. The derivatives of cyclodextrin consist mainly of molecules wherein some of the OH groups are converted to OR groups.
Cyclodextrin derivatives include, e.g., those with short chain alkyl groups such as methylated cyclodextrins, and ethylated cyclodextrins, wherein R is a methyl or an ethyl group; those with hydroxyalkyl 25 substituted groups, such as hydroxypropyl cyclodextrins and/or hydroxyethyl cyclodextrins;
branched cyclodextrins such as maltose-bonded cyclodextrins; cationic cyclodextrins such as those containing 2-hydroxy-3-(dimethylamino)propyl ether; quaternary ammonium,; anionic cyclodextrins such as carboxymethyl cyclodextrins, cyclodextrin sulfates, and cyclodextrin succinylates; amphoteric cyclodextrins such as carboxymethyliquaternary ammonium 30 cyclodextrins; cyclodextrins wherein at least one glucopyranose unit has a 3-6-anhydro-cyclomalto structure, e.g., the mono-3-6-anhydrocyclodextrins.
Highly water-soluble cyclodextrins are those having water solubility of at least 10 g in 100 ml Of water at room temperature, preferably at least 20 g in 100 mL of water, more preferably at least 25 g in 100 mL of water at room temperature. The availability of solubilized, uncomplexed cyclodextrins is essential for effective and efficient odor control performance.
Solubilized, water-soluble cyclodextrin can exhibit more efficient odor control performance than non-water-soluble cyclodextrin when deposited onto surfaces.
Examples of preferred water-soluble cyclodextrin derivatives suitable for use herein are hydroxypropyl alpha-cyclodextrin, methylated alpha-cyclodextrin, methylated beta-cyclodextrin, hydroxyethyl beta-cyclodextrin, and hydroxypropyl beta-cyclodextrin.
Hydroxyalkyl cyclodextrin derivatives preferably have a degree of substitution of from about 1 to about 14, more preferably from about 1.5 to about 7, wherein the total number of OR
groups per cyclodextrin is defined as the degree of substitution. Methylated cyclodextrin derivatives typically have a degree of substitution of from about 1 to about 18, preferably from about 3 to about 16. A known methylated beta-cyclodextrin is heptakis-2,6-di-O-methyl-f3-cyclodextrin, commonly known as DIMEB, in which each glucose unit has about 2 methyl groups with a degree of substitution of about 14. A preferred, more commercially available, methylated beta-cyclodextrin is a randomly methylated beta-cyclodextrin, commonly known as RAMEB, having different degrees of substitution, normally of about 12.6. RAMEB is more preferred than DIMEB, since DIMEB affects the surface activity of the preferred surfactants more than RAMEB. The preferred cyclodextrins are available, e.g., from Cerestar USA, Inc. and Wacker Chemicals (USA), Inc.
It is also preferable to use a mixture of cyclodextrins. Such mixtures absorb odors more broadly by complexing with a wider range of odoriferous molecules having a wider range of molecular sizes. Preferably at least a portion of the cyclodextrin is alpha-cyclodextrin and/or its derivatives, gamma-cyclodextrin and/or its derivatives, and/or derivatised beta-cyclodextrin, more preferably a mixture of alpha-cyclodextrin, or an alpha-cyclodextrin derivative, and derivatised beta-cyclodextrin, even more preferably a mixture of derivatised alpha-cyclodextrin and derivatised beta-cyclodextrin, most preferably a mixture of hydroxypropyl alpha-cyclodextrin and hydroxypropyl beta-cyclodextrin, and/or a mixture of methylated alpha-cyclodextrin and methylated beta-cyclodextrin.
It is preferable that the usage compositions of the present invention contain low levels of cyclodextrin so that no visible residue appears at normal usage levels.
Preferably, the solution used to treat the surface under usage conditions is virtually not discernible when dry. Typical levels of cyclodextrin in usage compositions for usage conditions are from about 0.01% to about 1%, preferably from about 0.05% to about 0.75%, more preferably from about 0.1% to about 0.5% by weight of the composition. Compositions with higher concentrations can leave unacceptable visible residues.

Optional Additional Sustainable Surfactants Optionally, additional surfactants, in addition to the low-residue surfactant, may be present in the sustainable composition. Additional surfactants suitable for use herein may include bio-derived surfactants and, optionally, non-bio-derived surfactants.
The bio-derived surfactants may include bio-derived anionic surfactants, bio-derived nonionic surfactants, bio-derived cationic surfactants, or combinations thereof. Additional surfactants may be present in amounts from 0% to 10% by weight, preferably from 0.1% to 10%, and most preferably from 0.25% to 6% by weight of the total composition. Of all the surfactants in the sustainable composition, preferably at least 50% by weight, at least 60% by weight, at least 70% by weight, at least 80% by weight, at least 90% by weight, at least 99% by weight, or 100% by weight are bio-derived surfactants.
Surfactants generally comprise at least one hydrophilic portion and one hydrophobic portion. In the surfactants in the sustainable composition, either or both portions may be biobased. Bio-derived surfactants containing biologically derived carbon may include, without limitation, glycosides of fatty acids and alcohols, polyether glycosidic ionophores, macrocyclic glycosides, carotenoid glycosides, isoprenoid glycosides, fatty acid amide glycosides and analogues and derivatives thereof, glycosides of aromatic metabolites, alkaloid glycosides, hemiterpenoid glycosides, monoterpenoid glycosides, phospholipids, lysophospholipids, ceramides, gangliosides, sphingolipids, fatty acid amides, alkylpolyglucosides, polyol alkyl ethoxylates, anhydrohexitol alkyl ethoxylates, and combinations of any thereof.
The hydrophilic portions of bio-derived surfactants in the sustainable compositions include, without limitation, a polyol alkyl ethoxylate containing biobased carbon (bioderived polyol alkyl ethoxylate). The polyol portions of polyol alkyl ethoxylates may be biologically derived polyols from biological or botanical sources. Biobased polyols suitable as a starting material for polyols suitable for use in polyol alkyl ethoxylates include, but are not limited to, anhydrohexitols, saccharides, such as monosaccharides including but not limited to dioses, such as glycolaldehyde; trioses, such as glyceraldehyde and dihydroxyacetone;
tetroses, such as erythrose and threose; aldo-pentoses such as arabinose, lyxose, ribose, deoxyribose, xylose; keto-pentoses, such as ribulose and xylulose; aldo-hexoses such as allose, altrose, galactose, glucose (dextrose), gulose, idose, mannose, talose; keto-hexoses, such as fructose, psicose, sorbose, tagatose; heptoses, such as mannoheptulose and sedoheptulose; octoses, such as octolose and 2-. keto-3-deoxy-manno-octonate; and nonoses, such as sialose; disaccharides including but not limited to sucrose (table sugar, cane sugar, saccharose, or beet sugar), lactose (milk sugar), 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, I7-methyloctadecanoic acid, isoarachic acid, 19-methyl-eicosanoic acid, a-ethyl-hexanoic acid, a-hexyldecanoic acid, a-heptylundecanoic acid, 2-decyltetradecanoic acid, 2-undecyltetradecanoic acid, 2-decylpentadecanoic acid, 2-undecylpentadecanoic acid, 6-methyl-octanoic acid, 8-methyl-decanoic acid, 10-methyl-dodecanoic acid, 12-methyl-tetradecanoic acid, 14-methyl-hexadecanoic acid, 16-methyl-octadecanoic acid, 18-methyl-eicosanoic acid, 20-methyl-docosanoic acid, 22-methyl-tetracosanoic acid, 24-methyl-hexacosanoic, . _ methyloctacosanoic acid; unsaturated fatty acids, such as 4-decenoic acid, caproleic acid, 4-dodecenoic acid, 5-dodecenoic acid, lauroleic acid, 4-tetradecenoic acid, 5-tetradecenoic acid, 9-tetradecenoic acid, palmitoleic acid, 6-octadecenoic acid, oleic acid, 9-octadecenoic acid, 11-octadecenoic acid, 9-eicosenoic acid, cis-11-eicosenoic acid, cetoleic acid, 13-docosenoic acid, 5 15-tetracosenoic acid, 17-hexacosenoic acid, 6,9,12,15-hexadecatetraenoic acid, linoleic acid, linolenic acid, gamma linolenic acid, a-eleostearic acid, gadoleic acid, a-eleostearic acid, punicic acid, 6,9,12,15-octadecatetraenoic acid, parinaric acid, 5,8,1 1 ,14-eicosatetraenoic acid, erucic acid, 5,8,11,14,17-eicosapentaenoic acid (EPA), 7,10,13,16,19-docosapentaenoic acid, 4,7,10,13,16,19-docosahexaenoic acid (DHA); hydroxylated fatty acids, such as a-hydroxylauric 10 acid, a-hydroxymyristic acid, a-hydroxypalmitic acid, a-hydroxystearic acid, co-hydroxylauric acid, a-hydroxyarachic acid, 9-hydroxy-12-octadecenoic acid, ricinoleic acid, a-hydroxybehenic acid, 9-hydroxy-trans-10,12-octadecadienic acid, kamolenic acid, ipurolic acid, 9,10-dihydroxystearic acid, 12-hydroxystearic acid, the corresponding alcohol of any thereof, derivatives of any thereof, and combinations of any thereof. These fatty acids may be reduced to 15 their corresponding fatty alcohols.
The alkyl portion of the polyol alkyl ethoxylate may comprise a bio-derived fatty acid alkyl portion, such as from the group consisting of animal oil, vegetable oil, biodiesel, triacylglycerols, diacylglycerols, monoacylglycerols, fatty acids, fatty alcohols, branched dicarboxylic acids, dicarboxylic acid ethers, phospholipids, soapstock, deodorizer distillate, acid 20 oil, polymerized oil, heat-bodied oil, blown oil, derivatives of any thereof, and combinations of any thereof. Fatty acids may comprise a mixture of bio-derived fatty acids, such as from the group consisting of animal fat, beef tallow, biodiesel, borne tallow, butterfat, camelina oil, candlefish oil, canola oil, castor oil, ceramides, cocoa butter, cocoa butter substitutes, coconut oil, cod-liver oil, coriander oil, corn oil, cottonseed oil, diacylglycerols, flax oil, float grease from 25 wastewater treatment facilities, hazelnut oil, hempseed oil, herring oil, illipe fat, jatropha oil, kokum butter, lanolin, lard, linseed oil, mango kernel oil, marine oils, meadowfoam oil, menhaden oil, milk fat, monoacylglycerols, mowrah fat, mustard oil, mutton tallow, neat's foot oil, olive oil, orange roughy oil, palm oil, palm kernel oil, palm kernel olein, palm kernel stearin, palm olein, palm stearin, peanut oil, phospholipids, phulwara butter, pile herd oil, pork lard, 30 rapeseed oil, rice bran oil, safflower oil, sal fat, sardine oil, sasanqua oil, shea fat, shea butter, soybean oil, sphingolipids, sunflower seed oil, tall oil, tallow, tsubaki oil, tung oil, triacylglycerols, triolein, used cooking oil, vegetable oil, whale oil, white grease, yellow grease, and derivatives, conjugated derivatives, genetically-modified derivatives, and mixtures of any thereof.

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 sustainable compositions described herein.
Bio-derived surfactants also may be obtained, in whole or in significant part, from bioorganic substances directly obtainable from algae (from direct extraction for example), and/or through standard synthetic organic transformations starting from bioorganic molecules that are in turn obtainable from algae. Some of the more practical starting materials directly obtainable from algae include lipids and polysaccharides, which are useful bio-derived feedstocks for bio-derived surfactants. High yield, lipid-rich algae can be grown in water-ponds in temperature and environmentally controlled greenhouses and bioreactors. Through autotrophic and/or heterotrophic processes, the lipid oil can be extracted through known mechanical, chemical, and biological techniques. Through algae strain selection, and technologies to influence the algae metabolic pathways, algae is also capable of producing high percentages of starch and cellulose via autotrophic and heterotrophic routes, giving additional feedstocks for specialty chemicals such as bio-derived for use in consumer products. In particular, hydrogenolysis, hydrolysis, amidation, esterification, ethoxylation and transesterification processes from algal lipid starting materials, along with the hydrolysis, enzymolysis, and/or fermentation of algal polysaccharides are available routes to the production of the bio-derived surfactants. Also the direct production of glucose, cellulose, and sucrose as metabolites from living cyanobacteria give useful bioorganic ingredients and bio-feedstock for bio-derived surfactants.
Algae that may be used to produce bioorganic substances that are directly incorporable into bio-derived surfactants, or which are useful as precursors to bio-derived surfactants include, but are not limited to, Chlorophyta (green algae), Charophyta (Stoneworts and Brittleworts), Euglenophyta (Euglenoids), Chrysophyta (golden-brown and yellow-green algae and diatoms), Phaeophyta (brown algae), Rhodophyta (red algae), Cyanophyta (blue-green algae, same as blue-green bacteria or cyanobacteria), and the Pyrrhophyta (dinoflagellates). Most algae are photoautotrophs, and most dried algae mass, wet algae colonies, or algae metabolites will provide some levels of lipid, saccharidic substances including polysaccharides and sulfated materials (cellulose, hemicellulose, pectin, alginic acid, carrageenan, agarose, porphyran, fucelleran, funoran, starch, simple sugars, and the like), glycoproteins, and a variety of photosynthetic pigments (chlorophyll, astaxanthin, etc).
For algal lipid feedstock, some species of algae and diatom algae that may produce commercially significant levels of lipids include, but are not limited to;
Actinastnim;
Actinochloris; Anabaena; Ankistrodesnnis; Apatococcus; Asterarcys;
Auzenochlorella;
Bacilliarophy; Botrydiopsis; Botiyococciis; Bracteacoccus; Biimilleriopsis;
Chaetophorcr, Chant ransia; Charachtm; Chlamydomonas', Chlorella; Chlorideilcr, Chlorobotrys;
Chlorococcum;
Chlorokybns; Chloroliimula; Chlormonas; Chlorophyceae; Chlorosarcinopsis;
Chlorotetraedron;
Chloricystis; Coccomyxa; Coelasirella; Coelastropsis; Coelastrum;
Coenochloris; Coleochlemys;
Cosmarivm; Crucigenia; Crucigeniella; Desmodesmus; Diadesmis; Dictyococciis;
Dictyosphaenum; Dipfosphaera; Dunaliella; Ellipsoidion; Ena/lax; Ettlia;
Euglena; Fortiea;
Geminella; Gonium; Graesiella; Haematococcus; Heterococcus; Interfilum;
Isochrysis;
Kentrosphaera; Keratococcus; Klebsormidium; Koliella; Lagerheimia;
Lobosphaera;
Macrochloris; Microthamnion; Monodus; Monoraphidium; Mougeotia; Muriel la;
Mychonastes;

Myrmecia; Nannochlolis; Nannochloropsis; Nautococcus; navicular, Navioua;
Neochloris;
Neodesmus; Neospongiococcum; Nephrochlamys; Oocyst is; Oonephris;
Orthotrichum;
Pediastrum; Phaeodactylum; Pithophora; Pleurastrum; Pleurochrysis;
Porphyridium; Possonia;
Prasiolopsis; Protosiphon; Prymnesium, Pseudollipsoidion; Pseudendoclonium;
Pseudocharaciopsis; Pseudococcomyxa; Pseudoendoclonium; Raphidocelis;
Raphidonema;
Rhexinema; Rhopalocystis; Scenedesmus; Schroederiella; Scotiella;
Scotiellopsis; Selenastrum, Sphaerocystis; Spirogyra; Spirulina; Spongiochloris; Stichococcus;
Stigeoclonium; Synechoccus;
Tetradesmus; Tetrahedron; Tetraselmis; Tetrastrum; Tribonema; Vischeria;
Willea; Xanthonema;
and Zygnema.
From these and other algae and diatom algae may be obtained lipid (or "algal fat") high in C14 through C22 triglycerides including saturated and unsaturated fatty acid chains. Other lipid and oil producing algae include blue algae, green algae, blue-green algae, and golden-brown algae, often collectively referred to as micro-algae. This lipid constitution is similar to fresh water fish oils. Brown algae and red algae produce longer chain triglycerides, for example with carbon chains greater than 24-carbons.
The algae-derived lipid oils (triglycerides), starch, and cellulose may be converted to algae-derived surfactants through established chemical synthetic routes, such as:
(1) Algae ¨> Lipid Triglycerides ¨> Surfactants;
(2) Algae ¨> Starch or Cellulose ¨> Sugar ¨> Surfactants;
(3) Algae ¨> Starch or Cellulose ¨> Surfactants; and, combinations of the intermediates and end molecules obtainable from these basic routes, (e.g., a sugar from route 2 combined with a fatty acid from route I to produce an alkylpolyglycoside surfactant).
Examples of bio-derived surfactants having carbon chains traceable back to algae may include, but are not limited to, alkyl glycosides and alkyl polyglycosides, fatty alcohol ethoxylates, fatty acid soaps, fatty acid amides and alkanolamides, fatty amines and ethoxylated amines, quaternary ammonium compounds (cationic surfactants), fatty acid esters and ethoxylated esters, alpha-sulfonated fatty acid esters, fatty acid phosphates, glyceryl esters, glucamides, polyglycerol esters, lecithins, lignin sulfonates, proteins and protein derivatives, saponins, sorbitol and sorbitan esters, sucroglycerides, sucrose esters, alkyl sulfates and alcohol ether sulfates.
Some bioorganic materials, such as alkylglycoside, lignin, saponins, glycolipids (such as ascarosides, simplexides, plakopolyprenos ides, and the like), etc. may or may not be found in algae species currently known to date; however, some of these materials are known to be plant derived and may eventually be sourced from alga species that are currently undiscovered or not yet bio-engineered. For example, certain alkylglycosides are found naturally in cyanobacteria, but lignin is primarily found in wood.
Anionic Surfactants¨In view of the above-mentioned sources and production methods for obtaining bio-derived surfactants generally, bio-derived anionic surfactants useful in the present sustainable composition are preferably selected from the group consisting of, bio-derived linear alkylbenzene sulfonate, bio-derived alpha olefin sulfonate, bio-derived paraffin sulfonates, bio-derived methyl ester sulfonates, bio-derived alkyl sulfates, bio-derived alkyl alkoxy sulfate, bio-derived alkyl sulfonates, bio-derived alkyl alkoxy carboxylate, bio-derived alkyl alkoxylated sulfates, bio-derived sarcosinates, bio-derived taurinates, and mixtures thereof. An effective amount, typically from 0% to 10%, preferably from 0.1% to 10%, and most preferably from 0.25% to 6% by weight of the total sustainable composition, of anionic surfactant can be used.
Of all the anionic surfactants in the sustainable composition, preferably at least 50% by weight, at least 60% by weight, at least 70% by weight, at least 80% by weight, at least 90% by weight, at least 99% by weight, or 100% by weight are bio-derived anionic surfactants.
The anionic surfactant may include alkyl ester sulfonates. These are desirable because they can be made with renewable, non-petroleum resources. Preparation of alkyl ester sulfonate surfactants can be effected according to known methods disclosed in the technical literature. For example, linear esters of C8-C2ocarboxylic acids can be sulfonated with gaseous SO3 according to "The Journal of the American Oil Chemists Society," vol. 52, pp. 323-329 (1975). Suitable starting materials include natural fatty substances as derived from tallow oils, palm oils, and coconut oils, for example.
Preferred alkyl ester sulfonate surfactant comprise alkyl ester sulfonate surfactants of the structural formula:

R3¨al¨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 C10¨C16 alkyl, and R4 is methyl, ethyl, or isopropyl. Especially preferred are the methyl ester sulfonates wherein R3 is C14¨C16 alkyl.
Bio-derived alkyl sulfate surfactants are another type of bio-derived anionic surfactant of importance for use herein. In addition to providing excellent overall cleaning ability when used in combination with polyhydroxy fatty acid amides (see below), including good grease/oil cleaning over a wide range of temperatures, wash concentrations, and wash times, dissolution of alkyl sulfates can be obtained, as well as improved formulability in sustainable compositions are water soluble salts or acids of the formula ¨ROSO3M, where R preferably is a Cio¨C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C10¨C20 alkyl component, more preferably a C12¨C18 alkyl or hydroxyalkyl, and M is H or a cation, e.g., an alkali or alkaline (Group IA or Group IIA) metal cation (e.g., sodium, potassium, lithium, magnesium, calcium), substituted or unsubstituted ammonium cations such as methyl-, dimethyl-, and trimethyl ammonium and quaternary ammonium cations, e.g., tetramethyl-ammonium and dimethyl piperdinium, and cations derived from alkanolamines such as ethanolamine, diethanolamine, triethanolamine, and mixtures thereof, and the like. Typically, alkyl chains of C12¨C15 are preferred.
Bio-derived alpha-sulfonated alkyl esters may be include linear esters of C6-carboxylic acids sulfonated with gaseous S03. Alpha, (or a-, used interchangeably herein), pertains to the first position on the carbon chain adjacent to the carboxylate carbon, as per standard organic chemistry nomenclature. The alpha-sulfonated alkyl esters may be pure alkyl ester or a blend of (1) a mono-salt of an alpha-sulfonated alkyl ester of a fatty acid having from 8 to 20 carbon atoms where the alkyl portion forming the ester is straight alkyl chain of 1 to 6 carbon atoms; and (2) a di-salt of an alpha-sulfonated fatty acid, the ratio of mono-salt to di-salt being at least 2:1. The alpha-sulfonated alkyl esters useful herein are typically prepared by sulfonating an alkyl ester of a fatty acid with a sulfonating agent such as S03. As an example, the bio-derived fatty acid esters are readily available by transesterification of algae lipids, or alternatively by esterification of the fatty acids obtained by hydrolysis of the algae lipids. When prepared by sulfonation of fatty acid esters, the alpha-sulfonated alkyl esters normally contain a minor amount, (typically less than 33% by weight), of the di-salt of the alpha-sulfonated fatty acid which results from saponification of the ester. Preferred alpha-sulfonated alkyl esters contain less than 10% by weight of the di-salt of the corresponding alpha-sulfonated fatty acid.
The alpha-sulfonated fatty acid ester surfactants that may be incorporated into the sustainable compositions may comprise alkyl ester sulfonate surfactants of the structural formula R3¨CH(S03M)¨0O2R4, where R3 is a C8¨C20 algae-sourced carbon chain, R4 is a straight or branched chain C1¨C6 alkyl group, and M is a cation that forms a water-soluble salt with the alkyl ester sulfonate, including sodium, potassium, magnesium, and ammonium cations.
Preferably, R3 is C10¨C16 fatty alkyl, and R4 is ethyl, in turn indirectly derived from algal polysaccharides (transesterification of the algae-lipid with ethanol obtained through algae cellulose fermentation).
Other anionic surfactants that may be included in the sustainable compositions herein include bio-derived alkyl sulfates, also known as alcohol sulfates. These bio-derived surfactants have the general formula R¨O¨SO3Na, where R is a hydrocarbyl having from about 10 to 18 carbon atoms, and these materials may also be denoted as sulfuric monoesters of C10¨C18 alcohols, examples being sodium decyl sulfate, sodium palmityl alkyl sulfate, sodium myristyl alkyl sulfate, sodium dodecyl sulfate, sodium tallow alkyl sulfate, sodium coconut alkyl sulfate, and mixtures of these surfactants, or of C10¨C20 oxo alcohols, and those monoesters of secondary alcohols of this chain length. The alkyl sulfates are readily obtainable by sulfonation of the bio-derived fatty alcohols described above, which can be directly synthesized through hydrogenolysis of algae lipids, or less directly through transesterification of algae lipids and hydrogenation of the intermediate fatty acid esters.
Fatty alkylamidopropyl betaines may be present in the sustainable compositions and represent an important class of mild detergents. For example, cocamidopropyl betaine, with or without sodium laureth sulfate as co-surfactant, is the surfactant system of choice for most shampoo and bodywash compositions. The synthesis of betaines is well known and is described in U.S. Patent No. 5,354,906 (Weitemeyer, et al.) incorporated herein in its entirety by reference.
The amidoamine intermediates described by Weitemeyer as obtainable from coconut fatty acid are just as easily be obtainable from a fatty acid blend derived from hydrolysis or hydrogenolysis of algal lipids. Alternatively, algae lipids may be directly amidated using bio-derived 1,3-propanediamine to give fatty amidoamines that then may be converted to alkylamidopropyl betaines using the methods described in the '906 patent.
The bio-derived anionic surfactants may include alkyl alkoxylated sulfate surfactants.
These surfactants are water-soluble salts or acids typically of the formula RO(A)1,S03M, where R is an unsubstituted C10¨C24 alkyl or hydroxyalkyl group having a C10¨C24 alkyl component, preferably a C12¨C20 alkyl or hydroxyalkyl, more preferably C12¨C18 alkyl or hydroxyalkyl; A is an ethoxy or propoxy unit; m is greater than zero, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3; and M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted-ammonium cation. Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein. Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethyl-ammonium and quaternary ammonium cations, such as tetramethyl-ammonium, dimethyl piperidinium and cations derived from alkanolamines, e.g.
monoethanolamine, diethanolamine, and triethanolamine, and mixtures thereof.
Exemplary surfactants include C12-C18 alkyl polyethoxylate (1.0) sulfate, C12-C18 alkylpolyethoxylate (2.25) sulfate, C12¨C18 alkyl polyethoxylate (3.0) sulfate, and C12-C18 alkyl polyethoxylate (4.0) sulfate where M is selected from sodium and potassium. Surfactants for use herein can be made from natural or synthetic alcohol feedstocks. Chain lengths represent average hydrocarbon distributions, including branching.
Preferred anionic surfactants for use in the sustainable composition include the alkyl ether sulfates, also known as alcohol ether sulfates. Alcohol ether sulfates are the sulfuric monoesters of the straight chain or branched alcohol ethoxylates and have the general formula R¨(OCH2CH2)x¨O¨S03M, where R preferably comprises C7¨C21 alcohol ethoxylated with from about 0.5 mol to about 9 mol of ethylene oxide (i.e., x=0.5 to 9 EO), such as C12¨C18 alcohols containing from 0.5 to 9 EO, and where M is alkali metal or ammonium, alkyl ammonium or alkanol ammonium counterion. Preferred alkyl ether sulfates are C8¨C18 alcohol ether sulfates with a degree of ethoxylation of from about 0.5 to about 9 ethylene oxide moieties and most preferred are the C12¨C15 alcohol ether sulfates with ethoxylation from about 4 to about 9 ethylene oxide moieties, with 7 ethylene oxide moieties being most preferred.
In another embodiment, the C12-C15 alcohol ether sulfates with ethoxylation from about 0.5 to about 3 ethylene oxide moieties are preferred. In keeping with the spirit of only using natural feedstock for ingredients for the sustainable composition, the fatty alcohol portion of the surfactant is preferably animal or vegetable derived, rather than petroleum derived.
Therefore the fatty alcohol portion of the surfactant will comprise distributions of even number carbon chains, e.g.
C12, C14, C16, C18, and so forth. It is understood that when referring to alkyl ether sulfates, these substances are already salts (hence "sulfate" nomenclature), and most preferred and most readily available are the sodium alkyl ether sulfates (also referred to as NaAES, or simply FAES).
Commercially available alkyl ether sulfates include the CALFOAM alcohol ether sulfates from Pilot Chemical, the EMAL , LEVENOL and LATEMAL products from Kao Corporation, and the POLYSTEP products from Stepan, most of these with fairly low EO
content (e.g., average 3 or 4-E0). Alternatively, the alkyl ether sulfates may be prepared by sulfonation of alcohol ethoxylates (i.e., nonionic surfactants) if the commercial alkyl ether sulfate with the desired chain lengths and EO content are not easily found, but perhaps where the nonionic alcohol ethoxylate starting material may be. For example, sodium lauryl ether sulfate ("sodium laureth sulfate", having about 2-3 ethylene oxide moieties) is very readily available commercially and quite common in shampoos and detergents. Depending on the degree of ethoxylation desired, it may be more practical to sulfonate a commercially available nonionic surfactant such as Neodol 25-7 Primary Alcohol Ethoxylate (a C12-C15/7E0 nonionic from Shell) to obtain for example the C12-C15/7E0 alkyl ether sulfate that may have been more include the alpha-sulfonated alkyl esters of C12-C16 fatty acids. The alpha-sulfonated alkyl esters may be pure alkyl ester or a blend of (1) a mono-salt of an alpha- sulfonated alkyl ester of a fatty acid having from 8 to 20 carbon atoms where the alkyl portion forming the ester is straight or However, the methyl esters are derived from methanol sources. Thus, the ethyl esters, which are currently not commercially available, would be the most preferred alpha-sulfonated fatty acid esters. When used in the present sustainable compositions, the alpha-sulfonated alkyl ester is preferably incorporated at from about 3% to about 15% by weight actives.
The sustainable compositions may also include bio-derived fatty acid soaps as an anionic surfactant ingredient. The fatty acids that may be represented by the general formula R¨COOH, where R represents a linear or branched alkyl or alkenyl group having between about 8 and 24 carbons. It is understood that within the sustainable compositions, the free fatty acid form (the carboxylic acid) will be converted to the carboxylate salt in-situ (that is, to the fatty acid soap), by the excess alkalinity present in the composition from added alkaline builder. As used herein, "soap" means salts of fatty acids. Thus, after mixing and obtaining the compositions of the present invention, the fatty acids will be present in the composition as R¨COOM, where R
represents a linear or branched alkyl or alkenyl group having between about 8 and 24 carbons and M represents an alkali metal such as sodium or potassium.
The fatty acid soap, which is often a desirable component having suds-reducing effect in the dishwasher, is preferably comprised of higher fatty acid soaps. The fatty acids that are added directly into the sustainable compositions may be derived from natural fats and oils, such as those from animal fats and greases and/or from vegetable and seed oils, for example, tallow, hydrogenated tallow, whale oil, fish oil, grease, lard, coconut oil, palm oil, palm kernel oil, olive oil, peanut oil, corn oil, sesame oil, rice bran oil, cottonseed oil, babassu oil, soybean oil, castor oil, and mixtures thereof. Although fatty acids can be synthetically prepared, for example, by the oxidation of petroleum, or by hydrogenation of carbon monoxide by the Fischer-Tropsch process, the naturally obtainable fats and oils are preferred. The fatty acids of particular use in the sustainable compositions are linear or branched and contain from about 8 to about 24 carbon atoms, preferably from about 10 to about 20 carbon atoms and most preferably from about 14 to about 18 carbon atoms. Preferred fatty acids include coconut, tallow or hydrogenated tallow fatty acids, and most preferred is to use entirely coconut fatty acid.
Preferred salts of the fatty acids are alkali metal salts, such as sodium and potassium or mixtures thereof and, as mentioned above, preferably the soaps generated in-situ by neutralization of the fatty acids with excess alkali from the silicate. Other useful soaps are ammonium and alkanol ammonium salts of fatty acids, with the understanding that these soaps would necessarily be added to the compositions as the preformed ammonium or alkanol ammonium salts and not neutralized in-situ within the added alkaline builders of the present invention. The bio-derived fatty acids that may be included in the present compositions will preferably be chosen to have desirable detergency and suds-reducing effect. Fatty acid soaps may be incorporated in the sustainable compositions of the present invention at from about 1% to about 10% by weight of the sustainable composition.
The sustainable compositions may also include alkyl sulfate as the sole anionic surfactant component, or in combination with one of more other anionic surfactants mentioned above. Fatty alkyl sulfates have the general formula R-S03M, where R preferably comprises a C7-C21 fatty alkyl chain, and where M is alkali metal or ammonium, alkyl ammonium or alkanol ammonium counterion. Preferred alkyl sulfates for use in the present invention are C8¨C18 fatty alkyl sulfate.
Most preferred is to incorporate sodium lauryl sulfate, such as Standapol WAQ-LC marketed by Cognis, and to have from about 1% to about 10% by actives weight basis in the cleaningcomposition.
Other Anionic Surfactants¨Other anionic surfactants useful for detersive purposes can also be included in the sustainable compositions. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di-and triethanolamine salts) of soap, C9-C20 linear alkylbenzenesulfonates, C8-C22 primary or secondary alkanesulfonates, Cg ¨C24olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British patent specification No. 1,082,179, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty ()ley] glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isothionates such as the acyl isothionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C12¨C18 monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C6¨C14 diesters), N-acyl sarcosinates, sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described below), branched primary alkyl sulfates, alkyl polyethoxy carboxylates such as those of the formula RO(CH2CH20)kCH2COOM4- , where R is a C8-C22 alkyl, k is an integer from 0 to 10, and M is a soluble salt-forming cation, and fatty acids esterified with isethionic acid and neutralized with sodium hydroxide. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil. Further examples are given in "Surface Active Agents and Detergents"
(Vol. I and II by Schwartz, Perry and Berch). A variety of such surfactants are also generally disclosed in U.S. Pat. No. 3,929,678, issued Dec. 30, 1975 to Laughlin, et al.
at Column 23, line 58 through Column 29, line 23. Preferably, the other anionic surfactants are bio-derived.
Specific examples of bio-derived anionic surfactants suitable herein include Caflon 2L28U by Univar, a sodium lauryl ether sulfate from bio-derived C12¨C14 alcohols; Akypo LF I

and Akypo LF 2 by Kao, low-foaming bio-derived anionic surfactants from palm kernal oil and comprising capryleth carboxylic acids; and Akypo RLM bio-derived surfactants by Kao, laureth carboxylic acids from bio-derived C12¨C14 alcohols.
Secondary Surfactants¨Secondary detersive surfactants can be selected from the group consisting of nonionics, cationics, ampholytics, zwitterionics, and mixtures thereof. By selecting the type and amount of detersive surfactant, along with other adjunct ingredients disclosed herein, the present sustainable compositions can be formulated to be used in the context of dishwashing. The particular surfactants used can therefore vary widely depending upon the particular end-use envisioned. Suitable secondary surfactants are described below.
Nonionic Detergent Surfactants¨Suitable nonionic detergent surfactants are generally disclosed in U.S. Pat. No. 3,929,678, Laughlin et at., issued Dec. 30, 1975, at column 13, line 14 through column 16, line 6, incorporated herein by reference. Exemplary, non-limiting classes of useful nonionic surfactants include: alkyl dialkyl amine oxide, alkyl ethoxylate, alkanoyl glucose amide, the so-called narrow peaked alkyl ethoxylates, C 6-C 12 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy) and mixtures thereof. In the present sustainable compositions, preferably the nonionic surfactants are bio-derived.
The nonionic surfactants for use herein may include, for example, the polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols. In general, the polyethylene oxide condensates are preferred. These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to about 12 carbon atoms in either a straight-chain or branched-chain configuration with the alkylene oxide. In a preferred embodiment, the ethylene oxide is present in an amount equal to from about 5 to about moles of ethylene oxide per mole of alkyl phenol. Commercially available nonionic surfactants of this type include Igepal CO-630, marketed by the GAF
Corporation; and Triton 25 X-45, X-114, X-100, and X-102, all marketed by the Rohm & Haas Company.
These compounds are commonly referred to as alkyl phenol alkoxylates, (e.g., alkyl phenol ethoxylates).
Specific examples of bio-derived nonionic surfactants suitable herein include Ecosurf SA
surfactants by Dow, alcohol ethoxylates made from bio-derived modified seed oils; Amidet N by Kao, a bio-derived amine surfactant made from polyethylene glycol and rapeseed oil; Levenol by Kao, glycereth cocoate surfactants made from bio-derived glycerine of vegetable origin; Emanon XLf by Kao, comprising vegetable-derived glycereth caprylate; Caflon SP20 by Kao/Univar, vegetable-derived sorbitan laurate; Canon SP60 by Kao/Univar, vegetable-derived sorbitan stearate; Kaopan SP-010, vegetable-derived sorbitan oleate; Kaopan TX and Caflon TW

surfactants, vegetable-derived polyethylene glycol¨sorbitan surfactants; and Caflon LF, Triton BG, and Triton CG by Univar/Dow, all vegetable-derived alkyl polyglucoside surfactants.
The nonionic surfactants for use herein further may include, for example, the condensation products of bio-derived aliphatic alcohols with from about 1 to about 25 moles of bio-derived ethylene oxide. The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms.
Particularly preferred are the condensation products of alcohols having an alkyl group containing from about 10 to about 20 carbon atoms with from about 2 to about 18 moles of ethylene oxide per mole of alcohol. Examples of commercially available nonionic surfactants of this type include Tergitol 15-S-9 (the condensation product of Cu¨Cis linear secondary alcohol with 9 moles ethylene oxide), Tergitol 24-L-6 NMW (the condensation product of C12¨C14 primary alcohol with 6 moles ethylene oxide with a narrow molecular weight distribution), both marketed by Union Carbide Corporation; Neodol 45-9 (the condensation product of C14¨C15 linear alcohol with 9 moles of ethylene oxide), Neodol 23-6.5 (the condensation product of C12¨C13 linear alcohol with 6.5 moles of ethylene oxide), Neodol 45-7 (the condensation product of C14¨C15 linear alcohol with 7 moles of ethylene oxide), Neodol el 45-4 (the condensation product of C14¨C15 linear alcohol with 4 moles of ethylene oxide), marketed by Shell Chemical Company, and Kyro BOB (the condensation product of C13-C15 alcohol with 9 moles ethylene oxide), marketed by The Procter & Gamble Company. Other commercially available nonionic surfactants include Dobanol 91-80 marketed by Shell Chemical Co. and Genapol 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 sustainable compositions may also include bio-derived amide type nonionic surfactants, for example alkanolamides that are condensates of algae-derived fatty acids with alkanolamines such as bio-derived monoethanolamine (MEA), bio-derived diethanolamine (DEA) and bio-derived monoisopropanolamine (MIPA), that have previously found widespread use in cosmetic, personal care, household and industrial formulations. Useful alkanolamides include bin-derived ethanolamides and/or bin-derived isopropanolamides such as monoethanolamides, diethanolamides and isopropanolamides in which the fatty acid acyl radical typically contains from 8 to 18 carbon atoms. Especially satisfactory alkanolamides have been mono- and diethanolamides such as those derived from mixed fatty acids or special fractions containing, for instance, predominately C12 to C14 fatty acids. For example, bio-derived fatty acids may be obtained from algae lipids through a number of routes, and these may be amidated with the required alkanolamine. Alternatively, and more directly, the nonionic alkanolamides may be obtained by direct amidation of the algae lipid (e.g., the crude algae fat).
Additional classes of bio-derived nonionic surfactants that may be used in the sustainable compositions herein include bio-derived ethoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, especially bio-derived fatty acid ethyl esters. An algae-sourced fatty acid ester may be ethoxylated, for example, with bio-derived ethylene oxide, such as ethylene oxide obtained from algae-sourced ethanol. Additionally, ethoxylated fatty amines may be obtained by ethoxylation of fatty amines, wherein these starting materials are obtained from bio-derived ethanol and algae lipid, respectively.
Further examples of suitable nonionic surfactants are alcohol ethoxylates containing linear radicals from alcohols of natural origin having 12 to 18 carbon atoms, e.g., from coconut, palm, tallow fatty or oley1 alcohol and on average from 4 EO to about 12 EO
per mole of alcohol.
Also useful as a nonionic surfactant is the C12¨C14 alcohol ethoxylate-7E0, and the C12¨C14 alcohol ethoxylate-12E0 incorporated in the composition at from about 1 wt% to about 10 wt%.
Preferred nonionic surfactants for use in this invention include for example, Neodol 45-7, Neodol 25-9, or Neodol 25-12 from Shell Chemical Company and most preferred are Surfonic L24-7, which is a CU- CI4 alcohol ethoxylate-7E0, and Surfonic L24-12, which is a C12¨C14 alcohol ethoxylate-12E0, both available from Huntsman. Combinations of more than one alcohol ethoxylate surfactant may also be desired in the sustainable composition to maximize cleaning performance.
The nonionic surfactants for use herein further may include, for example, the condensation products of bio-derived ethylene oxide with the product resulting from the reaction of bio-derived propylene oxide and bio-derived ethylenediamine. The hydrophobic moiety of these products consists of the reaction product of bio-derived ethylenediamine and excess bio-derived propylene oxide, and generally has a molecular weight of from about 2500 to about 3000. This hydrophobic moiety is condensed with bio-derived ethylene oxide to the extent that the condensation product contains from about 40% to about 80% by weight of bio-derived polyoxyethylene and has a molecular weight of from about 5,000 to about 11,000. Examples of this type of nonionic surfactant include bio-derived analogs of the commercially available Tetronice compounds, marketed by BASF.
Fatty alcohol ethoxylates may be obtained additionally through synthetic organic transformations starting from algae bioorganic materials. Algae-derived examples may include alcohol ethoxylates containing linear radicals from bio-derived alcohols having 14 to 24 carbon atoms, e.g., from the hydrogenation of fatty acids and/or fatty acid esters that are in turn derived from algal lipids through hydrolysis or transesterification, respectively.
Fatty alcohols may also be obtained by direct high-pressure hydrogenation of the algae lipid mass and separation of the fatty alcohols from the propane diol. The ethoxylation or the propoxylation (preferably on average from 4 to about 12 EO, PO, or E0/P0 per mole of alcohol) does not necessarily have to come from bio-sources, although that would be preferred. So for example, a fatty alcohol with carbon chain directly from algae sources may be conventionally ethoxylated with ethylene oxide obtained from petroleum sources (cracked ethylene and oxygen). In this way, a preferred detergent surfactant such as C14¨C16 alcohol ethoxylate-7E0 would at least have about 50% of the carbon (the C14¨C16 chain) obtained from algae, and about 50% of the carbon from petroleum sources (the 7E0, or 14-carbons from the 7-moles of ethylene oxide). More preferred is to incorporate bio-derived ethylene oxide as the building blocks for the ethoxylate (EC)) chains of these nonionic surfactants to create molecules having all of the carbon bio-derived. In known processes, bio-derived ethanol may be dehydrated to ethylene, which may in turn be oxidized to ethylene oxide with oxygen. Additionally, once fatty alcohols are obtained from algae lipids, the alcohols may be reacted in a Guerbet Reaction ("Guerbetization") to produce the branched "Guerbet Alcohols", which then may be ethoxyIated to give bio- derived branched chain alcohol ethoxylate surfactants.
Semi-polar nonionic surfactants are a special category of nonionic surfactants that include water-soluble amine oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about I to about 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of from about 10 to about 1 8 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms.
Semi-polar nonionic detergent surfactants include the amine oxide surfactants having the formula 0\
R3(0R4)11N(R5)2 where R3 is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures thereof containing from about 8 to about 22 carbon atoms; R4 is an alkylene or hydroxyalkylene group containing from about 2 to about 3 carbon atoms or mixtures thereof; x is from 0 to about 3;
and each R5 is an alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms or a polyethylene oxide group containing from about 1 to about 3 ethylene oxide groups. The R5 groupscan be attached to each other, e.g., through an oxygen or nitrogen atom, to form a ring structure.
Preferably, a substantial portion or, more preferably, all of the carbon atoms in these groups are bio-derived.
The amine oxide surfactants in particular include C10¨C18 alkyl dimethyl amine oxides and C8¨C12 alkoxy ethyl dihydroxy ethyl amine oxides. Spectic examples of bio-derived amine oxide surfactants suitable herein include ChemoxideTM SO Surfactant by Lubrizol, a soy-based amine oxide, and Genaminox CHE by Clariant.
The nonionic surfactants for use herein further may include, for example, bio-derived analogs of alkylpolysaccharides disclosed in U.S. Pat. No. 4,565,647, Llenado, issued Jan. 21, 1986, having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containing from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7 saccharide units. Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties. (Optionally the hydrophobic group is attached at the 2-, 3-, 4-, etc.
positions thus giving a glucose or galactose as opposed to a glucoside or galactoside.) The intersaccharide bonds can be, e.g., between the one position of the additional saccharide units and the 2-, 3-, 4-, and/or 6- positions on the preceding saccharide units. The sacchrides may be bio-derived, such as from algae or from another renewable resource.

Optionally, and less desirably, there can be a polyalkylene-oxide chain joining the hydrophobic moiety and the polysaccharide moiety. The preferred alkyleneoxide is ethylene oxide, such as bio-derived ethylene oxide. Typical hydrophobic groups include alkyl groups, either saturated or unsaturated, branched or unbranched containing from about 8 to about 18, preferably from about 10 to about 16, carbon atoms. Preferably, the alkyl group is a straight chain saturated alkyl group. The alkyl group can contain up to about 3 hydroxy groups and/or the polyalkyleneoxide chain can contain up to about 10, preferably less than 5, alkyleneoxide moieties. Suitable alkyl polysaccharides are octyl, nonyl, decyl, undecyldodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl, di-, tri-, tetra-, penta-, and hexaglucosides, galactosides, lactosides, glucoses, fructosides, fructoses and/or galactoses.
Suitable mixtures include coconut alkyl, di-, tri-, tetra-, and pentaglucosides and tallow alkyl tetra-, penta-, and hexa-glucosides. Preferably, these groups are obtained from natural sources so as to produce bio-derived surfactants.
Polyhydroxy Fatty Acid Amide Surfactant¨The sustainable compositions may also contain an effective amount of polyhydroxy fatty acid amide surfactant. By "effective amount"
is meant that the formulator of the composition can select an amount of polyhydroxy fatty acid amide to be incorporated into the compositions that will improve the cleaning performance of the detergent composition. In general, for conventional levels, the incorporation of about 1%, by weight, polyhydroxy fatty acid amide will enhance cleaning performance.
The sustainable compositions herein may comprise about 1% weight basis, polyhydroxy fatty acid amide surfactant, preferably from about 3% to about 30%, of the polyhydroxy fatty acid amide. The polyhydroxy fatty acid amide surfactant component comprises compounds of the structural formula:

II I
R2¨C¨N¨Z
where: R1 is H, C1¨C4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, or a mixture thereof, preferably C1 -C4 alkyl, more preferably C1 or C2 alkyl, most preferably C1 alkyl (i.e., methyl);
and R2 is a C5¨C31 hydrocarbyl, preferably straight-chain C7¨C19 alkyl or alkenyl, more preferably straight chain C9¨C17 alkyl or alkenyl, most preferably straight chain C11¨C15 alkyl or alkenyl, or mixtures thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z will be a glycityl.
Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose. As raw materials, high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup can be utilized as well as the individual sugars listed above. These corn syrups may yield a mix of sugar components for Z. It should be understood that it is by no means intended to exclude other suitable raw materials. Z preferably will be selected from the group consisting of ¨CH2¨(CHOH)õ¨CH2OH; ¨CH(CH2OH)¨(CHOH)n; ¨CH2OH, ¨CH2¨(CHOH)2(CHOR')(CHOH) ¨CH2OH, and alkoxylated derivatives thereof, where n is an integer from 3 to 5, inclusive, and R' is H or a cyclic or aliphatic monosaccharide. Most preferred are glycityls wherein n is 4, particularly ¨CH2¨(CHOH)4CH2OH. RI can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-2-hydroxyethyl, or N-2-hydroxypropyl. R2¨CO¨N< can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallowamide, etc. Z can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 1-deoxylactityl, 1-deoxygalactityl, 1-deoxymannityl, 1-deoxymaltotriotityl, etc.
Methods for making polyhydroxy fatty acid amides are known in the art. In general, they can be made by reacting an alkyl amine with a reducing sugar in a reductive anation reaction to form a corresponding N-alkyl polyhydroxyarine, and then reacting the N-alkyl polyhydroxyamine with a fatty aliphatic ester or triglyceride in a condensation/amidation step to form the N-alkyl, N-polyhydroxy fatty acid amide product. Processes for making compositions containing polyhydroxy fatty acid amides are disclosed, for example, in G.B.
Patent Specification 809,060, published Feb. 18, 1959, by Thomas Hedley & Co., Ltd.; U.S. Pat. No.
2,965,576, issued Dec. 20, 1960 to E. R. Wilson; and U.S. Pat. No. 2,703,798, Anthony M.
Schwartz, issued Mar. 8, 1955; and U.S. Pat. No. 1,985,424, issued Dec. 25, 1934 to Piggott, each of which is incorporated herein by reference.
Fatty acid surfactants are also derivable from algae sources. For example, the fatty acid surfactants that may be used here have general formula R¨0O2M, where R
represents an algae-derived linear alkyl (saturated or unsaturated) group having between about 8 and 24 carbons and M represents an alkali metal such as sodium or potassium or ammonium or alkyl-or dialkyl- or trialkyl-ammonium or alkanolammonium cation. The fatty acids of particular use in the sustainable compositions include carbon chains of from about 8 to about 24 carbon atoms, preferably from about 10 to about 20 carbon atoms and most preferably from about 14 to about 18 carbon atoms. Preferred fatty acids should have similar structure to the animal derived tallow or hydrogenated tallow fatty acids and their preferred salts (soaps) are alkali metal salts, such as sodium and potassium or mixtures thereof. That being said, hydrolysis of algae lipids will produce a mixture of unsaturated fatty acids and glycerol and the unsaturated fatty acids may in turn be hydrogenated as necessary to arrive at more saturated fats. Well known are purification processes such as distillation to arrive at particular fatty acid distribution. So for example, crude algae triglyceride may be transesterified with methanol and the resulting fatty acid methyl esters mixture may be fractionally distilled. The resulting methyl ester distillate "cuts" may then be hydrolyzed to yield fatty acids with narrower carbon chain distributions.
Cationic Surfactants¨Cationic detersive surfactants can also be included in sustainable compositions of the present invention. Cationic surfactants include the ammonium surfactants such as alkyldimethylammonium halogenides, and those surfactants having the formula:
{R2(0R3)3,}[R4(0R3)5,12R5N+X-where R2 is an alkyl or alkyl benzyl group having from about 8 to about 18 carbon atoms in the alkyl chain; each R3 isselected from the group consisting of ¨CH2CH2¨, ¨CH2CH(CH3) ¨CH2CH(CH2OH) ¨CH2CH2CH2¨, and mixtures thereof; each R4 is selected from the group consisting of Ci-Caalkyl, CI-Ca hydroxyalkyl, benzyl, ring structures formed by joining the two R4 groups, ¨CH2CHOHCHOHCOR6CHOH¨CH 20H wherein R6 is any hexose or hexose polymer having a molecular weight less than 1000, and hydrogen when y is not 0; R5 is the same as R4 or is an alkyl chain wherein the total number of carbon atoms of R2 plus R5 is not more than about 18; each y is from 0 to about 10 and the sum of the y values is from 0 to about 15; and X is any compatible anion. Preferably at least 50%, more preferably all of the carbon atoms in the cationic surfactants are bio-derived.
Other cationic surfactants useful herein are also described in U.S. Pat. No.
4,228,044, Cambre, issued Oct. 14, 1980, incorporated herein by reference.
Other Surfactants¨In addition to the above-mentioned surfactants, ampholytic surfactants can be incorporated into the sustainable compositions hereof.
These surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical can be straight chain or branched. One of the aliphatic substituents contains at least 8 carbon atoms, typically from about 8 to about 18 carbon atoms, and at least one contains an anionic water-solubilizing group, e.g., carboxy, sulfonate, sulfate. See U.S. Pat. No.
3,929,678 to Laughlin et al., issued Dec. 30, 1975 at column 19, lines 18-35 for examples of ampholytic surfactants.
Preferred amphoteric include C12-C18 betaines and sulfobetaines ("sultaines"), C fo -C 18 amine oxides, and mixtures thereof. The ampholytic surfactants preferably contain carbon atoms that are bio-derived.
The bio-derived surfactants described above may be formed from a naturally occurring lipid by any known method such as by esterification, Fischer esterification, epoxidation, etc.
Prior to the formation of a bio-derived surfactant, bio-derived fatty acids may be liberated from natural lipids by, for example, triglyceride hydrolysis, which separates the fatty acids from glycerol. The fatty acids may then be reacted to yield the bio-derived surfactants, including fatty alcohol ethoxylates or other high HLB-value surfactants derived from fatty alcohols. In one version, a reaction is performed of fatty acids is with an alcohol or an epoxide. Exemplary alcohols include methanol, ethanol, propanol, and other primary or secondary alkyl alcohols.
In ethoxylation, bio-derived ethylene oxide is added to bio-derived fatty acids or fatty alcohols, typically in the presence of potassium hydroxide, resulting in the addition of multiple ethoxy groups to the molecule. To obtain a bio-derived surfactant with a relatively high HLB
value that is the product of a natural lipid, ethoxylation is a useful technique because a chain of hydrophilic ethoxy groups can be readily added to the molecule. Thus, the bio-derived surfactants are preferably obtained through a simple operation or small number of operations from the natural raw materials themselves, such as via hydrolysis and esterification (e.g., ethoxylation) or via esterification alone. A hydrogenation step may also be included prior to or after esterification (e.g, in the formation of alcohols, hydrogenation may follow methylation of a fatty acid). Bio-derived surfactants may be produced from any known method of ethoxylating triglycerides such as vegetable oils, including the methods discussed in U.S.
Pat. No. 6,268,517, "Method for Producing Surfactant Compositions."
For example, if the bio-derived surfactant is an ethoxylated mono-, di-, or triglyceride, it may be prepared by the condensation of bio-derived ethylene oxide with a mono-, di-, or triglyceride. The reaction may be performed using from 5 to 70 moles, 10 to 50 moles, or 20 to 50 moles of preferably bio-derived ethylene oxide per mole of mono-, di-, or triglyceride. The resulting condensation product may have a melting point of at least 15 C, at least 25 C, or at least 30 C. As discussed by Ernst W. Flick in Industrial Surfactants, 2nd ed., p. 230, ethoxylated fatty acids and polyethylene glycol fatty acid esters are nonionic mono and diesters of various fatty acids, typically prepared by the condensation or addition of ethylene oxide to a fatty acid at the site of the active hydrogen or by esterification of the fatty acid with polyethylene glycol. The chemical structure of the monoester product is generally R¨00¨(0¨CH2CH2)n¨OH
where R:CO represents the hydrophobic base and n denotes the mole ratio of oxyethylene to the base. The diester product has a chemical structure of R¨00¨(0¨CH2CH2)n¨O¨CO¨R.

U.S. Pat. No. 6,300,508, "Thickened Aqueous Surfactant Solutions," issued Oct.
9, 2001 to Raths, Milstein, and Seipel, herein incorporated by reference to the extent it is compatible herewith, describes a method for the production of fatty acid esters of an ethylene-propylene glycol of the formula RICOO(E0)õ(PO)y(E0),H where RICO is a linear aliphatic, saturated or unsaturated acyl group, or a combination thereof, having from about 6 to about 22 carbon atoms (though a more specific range of 14 to 22 or 16 to 22 carbon atoms may be considered), EO is ¨CH2CH2¨, and PO is ¨CH2CH(CH3)0¨ or ¨CH2CH2CH20¨ or a combination thereof.
The method of U.S. Pat. No. 6,300,508 comprises reacting a fatty acid having from about 6 to about 22 carbon atoms with an alkylene oxide selected from the group consisting of propylene oxide, ethylene oxide or a combination thereof, in the presence of an alkanolamine.
For some embodiments of the present invention, the use of additional moles of alkylene oxide reactants relative to the recommendations of U.S. Pat. No. 6,300,508 may be considered to increase the degree of ethoxylation or propoxylaytion and thereby increase HLB. Preferably, each of the reactants in these processes is bio-derived.
U.S. Pat. No. 6,221 ,919, "Utilization of Ethoxylated Fatty Acid Esters as Self-Emulsifiable Compounds," issued April 24, 2001, to G. Trouve, herein incorporated by reference to the extent that it is noncontradictory herewith, discloses methods of producing ethoxylated fatty acid esters that may have one or more of the following three formulas:
(A) RI¨00¨ (0¨CH2¨CH2)k-0R2 (B) R3¨00¨ (0¨CH2¨CH2)10R40¨ (CH2¨CH2-0),,¨CO¨R5 (C) R6¨00¨ (0¨CH2¨CH2)n¨O¨R7¨CHRI I¨R9-0¨ (CH2¨CH2-0)q¨CO¨RI
where R" is ¨0¨((0¨CH2¨CH2)n¨CO¨R8; RI , R3, R5, R6, R8 and RI each represent a linear or branched, saturated or unsaturated hydrocarbon chain having from 5 to 30 carbon atoms, preferably from 14 to 30 carbon atoms; and R2, R4, R7 and R9 each represent a linear or branched, saturated or unsaturated hydrocarbon chain having from 1 to 5 carbon atoms. US
6,221 ,919 teaches that the values of k, l+m, and n+p+q should be adapted to give HLB
values between about 4 and about 10, preferably neighboring 5, although higher HLB values are within the scope of the present invention, so elevated values of k, l+m, and n+p+q may be useful.
Example 2 described by U.S. 6,221,919 is specifically incorporated herein by reference, for it describes ethoxylation of rapeseed oil via a process that may be useful for a variety of other vegetable oils. Ethoxylation is most easily performed by direct condensation reactions with ethylene oxide with fatty acids or fats themselves. Ethoxylation can also be carried out on fatty acid methyl esters if the appropriate catalysts are used, as described by I.
Hama, T. Okamoto and H. Nakamura of Lion Corporation, Tokyo, Japan, in "Preparation and Properties of Ethoxylated Fatty Methyl Ester Nonionics," Journal of the American Oil Chemists' Society, Vol. 72, No. 7, July, 1995, pp. 781-784. Their method directly inserts EO into fatty methyl esters (RCOOCH3) to give [RCO(OCH2CH2)õOCH3] using a solid catalyst modified by metal cations.
Ethoxylates of fatty methyl esters obtained by this method were homogeneous monoesters and had good properties as nonionic surfactants.
Fischer esterification involves forming an ester by refluxing a carboxylic acid and an alcohol in the presence of an acid catalyst. Typical catalysts for a Fischer esterification include sulfuric acid, tosic acid, and lewis acids such as scandium(III) triflate or dicyclohexylcarbodiimide.
Vegetable oils, after basic purification, can be processed to produce methylated or ethylated seed oils, commonly referred by the abbreviations MSO and ESO, respectively, which typically have a single moiety added, unlike epoxidation reactions which can add numerous groups. MSOs and ESOs are created by hydrolysis of the glycerol molecule from the fatty acids, and the acids are then esterified with methanol or ethanol. Such compounds can be used as bio-derived surfactants in the sustainable composition, but when higher HLB values are desired, additional hydrophilic groups should be added.
Examples of commercially available compositions comprising bio-derived surfactants that may be used within the sustainable compositions described herein include, without limitation, the following:
SC-1000TM, a surface washing agent marketed by GemTek Products (Phoenix, AZ).
SC1000TM is part of GemTek's SAFE CARE product series, that are said to contain alcohols, fatty acids, esters, waxes, saponifiers, chelators, enzymes and other fractions from soy, corn, palm kernel, peanut, walnut, safflower, sunflower, Canola, and cotton seed.
SoyFastTM Manufacturer's Base marketed by Soy Technologies (Nicholasville, Kentucky) as a soy-based biodegradable all-purpose cleaner, and related soy-based products such as SoyFastTM Cleaner and SoyGreenTM Solvents. Manufacturer's Base, according to its MSDS, comprises two bio-derived surfactants, ethoxylated castor oil (average degree of ethoxylation said to be about 30) and soybean oil methyl ester (formed by reaction of soybean oil with methanol, resulting in hydrolysis of the triglyceride to yield methylated fatty acids and glycerol).
It also comprises pentanedioic acid, dimethyl ester; butanedioic acid, dimethyl ester; hexanedioic acid, dimethyl ester; and polyoxyethylene tridecyl ester.
Soy-Dex Plus marketed by Helena Chemical Co. (Memphis, Tennessee), said to be a proprietary blend of vegetable oil, polyol fatty acid ester, polyethoxylated esters thereof, and ethoxylated alkylaryl phosphate ester.

Esterified vegetable oils, for example from Cognis Corp. (Monheim, Germany), including AGNIQUE SBO-10 Ethoxylated Soybean Oil, POE 10; AGNIQUE SBO-30 Ethoxylated Soybean Oil POE 30; AGNIQUE SBO-42 (Trylox 5919-C) Ethoxylated Soybean Oil, POE 42;
AGNIQUE SBO- 60 Ethoxylated Soybean Oil POE 60; AGNIQUE CSO-44 (Mergital EL
44) Ethoxylated Castor Oil, POE (polyoxyethylene) 44; AGNIQUE CSO-60H (Eumulgin HRE 60) Hydrogenated Ethoxylated Castor Oil, POE 60; AGNIQUE CSO-200 (Etilon R 200) Ethoxylated Castor Oil, POE 200; AGNIQUE RS0-0303 (Eumulgin CO 3522) Alkoxylated Rapeseed Oil, POE 3, POP (polyoxypropylene) 3; AGNIQUE RSO-2203 (Eumulgin CO 3526) Alkoxylated Rapeseed Oil, POE 3, POP 22; AGNIQUE RSO-30 (Eumulgin CO 3373) Ethoxylated Rapeseed Oil, POE 30. Also, Ethoxolated Soybean Oil, marketed by Adjuvants Unlimited of Memphis, TN, as AU970 could be used.
TOXIMUL ethoxylated castor oils from Stepan Chemical (Northfield, Illinois), including TOXIMUL 8240 (P0E-36), TOXIMUL 8241 (POE- 30), and TOXIMUL 8242 (P0E-40).
Genapol surfactants by Hoechst Chemical, such as Genapol OXD-080, a fatty alcohol polyglycol ether.
Ethoxylated castor oil is available as Shree Chem-Co 35 from Shree Vallabh Chemicals (Gujarat, India). In Shree Chem-Co 35, the hydrophobic constituents comprise about 83% of the total mixture, the main component being glycerol polyethylene glycol ricinoleate. Other hydrophobic constituents include fatty acid esters of polyethylene glycol along with some unchanged castor oil. The hydrophilic part (17%) consists of polyethylene glycols and glycerol ethoxylates. In a related compound, Shree Chem-Co 40, approximately 75% of the components of the mixture are hydrophobic. These comprise mainly fatty acid esters of glycerol polyethylene glycol and fatty acid esters of polyethylene glycol. The hydrophilic portion consists of polyethylene glycols and glycerol ethoxylates.
Ethoxylated castor oil and hydrogenated castor oil products marketed by Global Seven Corp. (Franklin, NJ). These products, marketed as emulsifiers, solubilizers, and conditioners, include HETOXIDE C-200, a PEG-200 castor oil compound having an HLB of 18.1;
HETOXIDE C-81, a PEG-81 castor oil compound said to have an HLB of 15.9;
HETOXIDE C-40, a PEG-40 castor oil compound having an HLB of 13.0; HETOXIDE C-30, a PEG-30 castor oil compound having an HLB of 11.8; HETOXIDE C25, a PEG-25 castor oil compound having an HLB of 10.8; HETOXIDE C-16, a PEG-16 castor oil compound having an HLB of 8.6; and I IETOXIDE C-5, a PEG-5 castor oil compound having an HLB of 4Ø

In an example embodiment, the bio-derived surfactants of the present sustainable compositions comprise surfactants obtained by esterification of vegetable lipids. In a particular embodiment, the lipids are selected from soybean oil and castor oil. These may also be derived from single cell organisms, such as bacteria, algae, yeast, and fungi. The major unsaturated fatty acids in soybean oil triglycerides are 7% linolenic acid (C-18:3); 51%
linoleic acid (C-18:2); and 23% oleic acid (C-18:1). Castor oil is a triglyceride in which about 85% to 95% of the fatty acids are ricinoleic acid (C18:1-0H), about 2% to 6% are oleic acid (C-18:1), about 1% to 5% is linoleic acid (C-18:2), with there being about 0.3% to 1% each of linolenic acid (C18:3), stearic acid (C18:0), palmitic acid (C16:0), and dihydroxystearic acid, with small amounts of some other acids.
Additional steps, such as hydrogenation and dehydrogenation may be contemplated. In one embodiment, the bio-derived compound comprises an ester of a fatty acid, wherein the fatty acid has not been chemically modified apart from the formation of an ester bond to join the fatty acid to a hydrophilic moiety. Alternatively, a bio-derived surfactant may be the ethoxylated product of a naturally occurring fatty acid or lipid.
Other bio-derived or natural surfactants may be included in the sustainable composition, such as the rhamnolipids and rhamnolipid derivatives marketed by Jeneil Biosurfactant Company (Saukville, Wisconsin), such as JBR425 (CAS Number: 147858-26-2) as well as those described in U.S. Pat. No. 5,455,232, "Pharmaceutical Preparation Based in Rhamnolipid,"
issued Oct. 3, 1995 to Piljac and Piljac, or in U.S. Pat. No. 7,129,218, "Use of Rhamnolipids in Wound Healing, Treatment and Prevention of Gum Disease and Periodontal Regeneration," issued Oct.
31, 2006 to Stipcevic et al. Lipopeptide biosurfactants such as those produced by Bacillus species may also be included. Natural plant oils may be provided in the form of oil cakes that can be used.
Adjuncts The sustainable compositions optionally contain one or more of the following adjuncts:
enzymes such as protease, amylase, mannanase, and lipase, stain and soil repellants, lubricants, odor control agents, perfumes, builders, fragrances and fragrance release agents, reducing agents such as sodium sulfite, and bleaching agents. Other adjuncts include, but are not limited to, acids, pH adjusting agents, electrolytes, dyes and/or colorants, solubilizing materials, stabilizers, thickeners, defoamers, hydrotropes, cloud point modifiers, preservatives, and other polymers.
Electrolytes, when used, include, calcium, sodium and potassium chloride.
Preferably the adjuncts are bio-derived. Optional pH adjusting agents include inorganic acids and bases such as sodium hydroxide, and organic agents such as monoethanolamine, diethanolamine, and triethanolamine, preferably bio-derived. Thickeners, when used, include, but are not limited to, polyacrylic acid, xanthan gum, calcium carbonate, aluminum oxide, alginates, guar gum, methyl, ethyl, clays, and/or propyl hydroxycelluloses, preferably bio-derived.
Defoamers, when used, include, but are not limited to, silicones, aminosilicones, silicone blends, and/or silicone/hydrocarbon blends, all preferably bio-derived. Bleaching agents, when used, include, but are not limited to, peracids, hypohalite sources, hydrogen peroxide, and/or sources of hydrogen peroxide. In a preferred embodiment, the sustainable composition includes a builder such as ethylenediamine disuccinate. In a suitable embodiment the compositions contain an effective amount of one or more of the following bio-derived enzymes:
protease, lipase, amylase, cellulase, and mixtures thereof Suitable enzymes are available from manufacturers including, but not limited to, Novozymese and Genencor .
Any suitable adjunct ingredient in any suitable amount may be used in the cleaning detergent composition. Suitable adjunct ingredients as described herein may be substantially sodium ion-free. Suitable adjunct ingredients may include, but are not limited to: co-surfactants;
suds suppressors; builders; enzymes; bleaching systems; dispersant polymers;
carrier media;
thickeners and mixtures thereof.
Other suitable adjunct ingredients may include, but are not limited to: enzyme stabilizers, such as calcium ion, boric acid, bio-derived propylene glycol, bio-derived short-chain carboxylic acids, boronic acids, and mixtures thereof chelating agents, such as, alkali metal bio-derived ethane 1-hydroxy diphosphonates (HEDP), bio-derived alkylene poly (alkylene phosphonate), as well as, amino phosphonate compounds, including amino aminotri(methylene phosphonic acid) (ATMP), bio-derived nitrilo trimethylene phosphonates (NTP), bio-derived ethylene diamine tetra methylene phosphonates, and bio-derived diethylene triamine penta methylene phosphonates (DTPMP); alkalinity sources; water softening agents; secondary solubility modifiers; soil release polymers; hydrotropes; binders; antibacterial actives, such as bio-derived citric acid, bio-derived benzoic acid, bio-derived benzophenone, bio-derived thymol, bio-derived eugenol, bio-derived menthol, bio-derived geraniol, bio-derived vertenone, bio-derived eucalyptol, bio-derived pinocarvone, bio-derived cedrol, bio-derived anethol, bio-derived carvacrol, bio-derived hinokitiol, bio-derived berberine, bio-derived ferulic acid, bio-derived cinnamic acid, bio-derived methyl salicylic acid, bio-derived methyl salicylate, bio-derived terpineol, bio-derived limonene, and halide-containing compounds; detergent fillers, such as potassium sulfate; abrasives, such as, quartz, pumice, pumicite, titanium dioxide, silica sand, calcium carbonate, zirconium silicate, diatomaceous earth, whiting, and feldspar; anti-redeposition agents, such as organic phosphate; anti-oxidants; metal ion sequestrants; anti-tarnish agents, such as benzotriazole; anti-corrosion agents, such as, aluminum-, magnesium-, zinc-containing materials (e.g. hydrozincite and zinc oxide); processing aids;
plasticizers, such as, bio-derived propylene glycol, and bio-derived glycerine; thickening agents, such as bio-derived cross-linked polycarboxylate polymers with a weight-average molecular weight of at least 500,000 (e.g. CARBOPOLO 980 from B. F. Goodrich), naturally occurring or synthetic clays, bio-derived starches, bio-derived celluloses, bio-derived alginates, and natural gums, (e.g.
xanthum gum); aesthetic enhancing agents, such as bio-derived dyes, bio-derived colorants, bio-derived pigments, bio-derived speckles, bio-derived perfume, and bio-derived oils; preservatives;
and mixtures thereof. Suitable adjunct ingredients may contain low levels of sodium ions by way of impurities or contamination. In certain non-limiting embodiments, adjunct ingredients may be added during any step in the process in an amount from about 0.0001% to about 91.99%, by weight of the composition.
Adjunct ingredients suitable for use are disclosed, for example, in U.S. Pat.
Nos.:
3,128,287; 3,159,581; 3,213,030; 3,308,067; 3,400,148; 3,422,021; 3,422,137;
3,629,121;
3,635,830; 3,835,163; 3,923,679;3,929,678; 3,985,669; 4,101,457; 4,102,903;
4,120,874;
4,141,841; 4,144,226; 4,158,635; 4,223,163; 4,228,042; 4,239,660; 4,246,612;
4,259,217;
4,260,529; 4,530,766; 4,566,984; 4,605,509; 4,663,071; 4,663,071; 4,810,410;
5,084,535;
5,114,611; 5,227,084; 5,559,089; 5,691,292; 5,698,046; 5,705,464; 5,798,326;
5,804,542;
5,962,386; 5,967,157; 5,972,040; 6,020,294; 6,113,655; 6,119,705; 6,143,707;
6,326,341;
6,326,341; 6,593,287; and 6,602,837; European Patent Nos.: 0,066,915;
0,200,263; 0332294;
0414 549; 0482807; and 0705324; PCT Pub. Nos.: WO 93/08876; and WO 93/08874.
Builders The sustainable compositions optionally may comprise one or more builders.
Builders for use in the sustainable compositions include non-phosphate builders. If present, builders are used in a level of from 5% to 60%, preferably from 10% to 50% by weight of the sustainable composition. In another embodiment, the builders are present in an amount of up to 50%, more preferably up to 45%, even more preferably up to 40%, and especially up to 35%
by weight of the composition. The compositions of the present invention are preferably phosphate free or essentially free, and most preferably comprise carbon atoms that are bio-derived.

One example of a builder is an aminocarboxylic builder. Preferably the aminocarboxylic builder is an aminopolycarboxylic builder, more preferably a glycine-N,N-diacetic acid or derivative of general formula MO0C-CHR-N(CH2COOM)2, where R is a C1-12 alkyl and M is alkali metal. Aminocarboxylic builders may include MGDA (methyl-glycine-diacetic acid), GLDA (glutamic-N,N-diacetic acid), iminodisuccinic acid (IDS), carboxymethyl inulin and salts and derivatives thereof. MGDA (salts and derivatives thereof) is especially preferred according to the invention, with the tri-sodium salt thereof being preferred and a sodium/potassium salt being specially preferred for the low hygroscopicity and fast dissolution properties of the resulting particle. Preferably, the aminocarboxylic acid builders are obtained from bio-derived sources of carbon.
Other suitable aminocarboxylic builders include; for example, aspartic acid-N-monoacetic acid (ASMA), aspartic acid-N,N-diacetic acid (ASDA), aspartic acid-N-monopropionic acid (ASMP) , iminodisuccinic acid (IDA), N-(2-sulfomethyl) aspartic acid (SMAS), N-(2-sulfoethyl) aspartic acid (SEAS), N-(2-sulfomethyl) glutamic acid (SMGL), N-(2-sulfoethyl) glutamic acid (SEGL), IDS (iminodiacetic acid) and salts and derivatives thereof such as N-methyliminodiacetic acid (MIDA), alpha-alanine-N,N-diacetic acid (alpha-ALDA), serine-N,N-diacetic acid (SEDA), isoserine-N,N-diacetic acid (ISDA), phenylalanine-N,N-diacetic acid (PHDA), anthranilic acid-N,N-diacetic acid (ANDA), sulfanilic acid-N,N-diacetic acid (SLDA), taurine-N,N-diacetic acid (TUDA) and sulfomethyl-N,N-diacetic acid (SMDA), and alkali metal salts and derivative thereof.
In addition to the aminocarboxylic builders in the sustainable article, the composition can comprise carbonate and/or citrate.
Other non-phosphate builders include homopolymers and copolymers of polycarboxylic acids and their partially or completely neutralized salts, monomeric polycarboxylic acids and hydroxycarboxylic acids and their salts. Preferred salts of the abovementioned compounds are the ammonium and/or alkali metal salts, i.e. the lithium, sodium, and potassium salts, and particularly preferred salts are the sodium salts.
Suitable polycarboxylic acids are acyclic, alicyclic, heterocyclic and aromatic carboxylic acids, in which case they contain at least two carboxyl groups which are in each case separated from one another by, preferably, no more than two carbon atoms.
Polycarboxylates which comprise two carboxyl groups include, for example, water-soluble salts of, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid. Polycarboxylates which contain three carboxyl groups include, for example, water-soluble citrate. Correspondingly, a suitable hydroxycarboxylic acid is, for example, citric acid.

Another suitable polycarboxylic acid is the homopolymer of acrylic acid. Other suitable builders are disclosed in WO 95/01416. Carboxylic acids and, particularly acrylic acid derivatives, preferably are obtained from bio-derived sources.
Enzymes Enzymes may be included in the sustainable compositions. One such enzyme includes a protease. Suitable proteases include metalloproteases and serine proteases, including neutral or alkaline microbial serine proteases, such as subtilisins (EC 3.4.21.62).
Suitable proteases include those of animal, vegetable or microbial origin. Another enzyme for use herein includes alpha-amylases, including those of bacterial or fungal origin. Chemically or genetically modified mutants (variants) are included. Additional enzymes suitable for use in the sustainable composition can comprise one or more enzymes selected from the group comprising hemicellulases, cellulases, cellobiose dehydrogenases, peroxidases, proteases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, mannanases, pectate lyases, keratinases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases,13-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase, amylases, and mixtures thereof.
SUSTAINABLE CONSUMER PRODUCTS
A sustainable consumer product may comprise a sustainable container, as described above, and a sustainable composition, as also described above. The sustainable consumer product may further comprise secondary packaging around the sustainable container having the sustainable composition therein. The secondary packaging, as well as any label on the sustainable container, may comprise a suitable consumer message in the form of printed indicia, for example.
Secondary Packaging The sustainable article as a whole or, alternatively, components of the sustainable article such as the sustainable container, the sustainable closure, the sustainable dispenser, or combinations thereof, may be packaged within a secondary packaging such as a tub, a bag, a shrink-wrapped bundle, a display pack comprising an outer package such as a see-through container, for example a transparent or translucent carton or bottle which contains a plurality of sustainable containers or other associated products (such as a cleaning implement having a cleaning pad for spreading the sustainable composition, for example) in a multiplicity of visually or otherwise sensorially distinctive groups. By visually distinctive herein is meant that the groups can be distinguished in terms of shape, color, size, pattern, ornament, etc. Otherwise the groups are distinctive in terms of providing a unique sensorial signal such as smell, sound, feel, etc.
The secondary packaging can be made of plastic or any other suitable material, provided the material is strong enough to protect the sustainable container during transport. Preferably, the plastic or other suitable material comprises at least 50%, at least 75%, at least 90%, at least 95%, at least 99%, or even 100% bio-derived material. Alternatively, the pack can have non-see-through outer packaging, perhaps with indicia or artwork representing the contents of the pack.
In further embodiments, when multiple sustainable containers are stored in a container or containers through at least a portion of which the sustainable containers contained therein may be seen, preferably as images on the printed material. Preferably the optional image is linked conceptually to graphic on the portions of the container through which the sustainable container may not be seen through. For example, the printed image may be of a lemon the graphic on the outside of the container may include images of lemons or odor-control functionality and/or a written reference to the lemon or citrus themes or odor-control functionality.
This provides a strong and reinforced message to the consumer about the benefits of using the product.
The printed images preferably are formed with bio-derived inks. The inks can be solvent-based or water-based. In some embodiments, the ink is derived from a renewable resource, such as soy, a plant, or a mixture thereof. The ink can be cured using heat or ultraviolet radiation (UV). In some preferred embodiments, the ink is cured by UV, which results in a reduction of curing time and energy output. Nonlimiting examples of bio-derived inks include ECO-SURE!TM from Gans Ink & Supply Co. and the solvent-based VUTEke and BioVuTM
inks from EFI, all of which are derived completely from renewable resources (e.g., corn).
The secondary packaging or containers preferably are made from bio-derived and/or biodegradable products such as from bio-derived paper or bio-derived plastic, and from biodegradable or bioplastic resins. Bioplastic resins may include bio-derived polyhydroxyalkanoate (PHA), bio-derived poly 3-hydroxybutrate-co-3-hydroxyhexanote (PHBH), bio-derived polyhydroxybutyrate-co -valerate (PHB/V), bio-derived poly-hydroxybutyrate (PHB), chemical synthetic polymer such as bio-derived polybutylene succinate (PBS), bio-derived polybutylene succinate adipate (PBSA), bio-derived polybutylene succinate carbonate, bio-derived polycaprolactone (PCL), bio-derived cellulose acetate (PH), bio-derived polylactic acid/chemical synthetic polymer such as bio-derived polylactic polymer (PLA) or bio-.

derived copoly-L-lactide (CPLA), and naturally occurring polymer, such as starch modified PVA+aliphatic polyester, or corn starch.
Polylactic acid (PLA) is a transparent bioplastic produced from corn, beet and cane sugar.
It not only resembles conventional petrochemical mass plastics, such as polyethelene (PE), polyethylene terephthalate (PET or PETE), high density polyethylene (HDPE) and polypropene (PP) in its characteristics, but it can also be processed easily on standard equipment that already exists for the production of conventional plastics. PLA and PLA-blends generally come in the form of PA010-103 granulates with various properties and are used in the plastic processing industry for the production of foil, molds, cups, bottles and other packaging.
The bio-derived polymer poly-3-hydroxybutyrate (PHB) is polyester produced by certain bacteria processing glucose or starch. Its characteristics are similar to those of the petro plastic polypropylene. The South American sugar industry, for example, has decided to expand PHB
production to an industrial scale. PHB is distinguished primarily by its physical characteristics.
It produces transparent film at a melting point higher than 130 C, and is biodegradable without residue.
Biodegradable resins may be made into products that are relatively rigid with good transparency, and thus use of these resins may be appropriate for rigid molded products, such as the secondary packaging described above.
The bio-derived plastic material may include a single, composite layer of bioplastic resin mixed with plasticizer. This material may be provided as a resin, which can be formed into the desired shape. Here, the plasticizer and resin cooperate to form a bio-derived plastic material that may be generally impermeable to fluids. The bioplastic resin may, for example, be PLA, PHA, PUB, PHBH, PBS, PBSA, PCL, PH, CPLA or PVA. The plasticizer may be a silicone such as, but not limited to, polydimethyl siloxane with filler and auxiliary agents, alkylsilicone resin with alkoxy groups with filler and auxiliary agents and isooctyltrimethoxysilane or silicone oxide, and silicone dioxide. The bioplastic resin and silicone may be mixed to form a new resin.
This resin may have been shown to have improved barrier properties, resulting in permeability rates to less than or equal to from 0.5 to 3 units for water vapor, oxygen from 75 to 1400 units, and carbon dioxide from 200 to! 800 units, measured; at g-mil/100 square inch per day for water at 100% RH, and cc-mill/100 sq inch day atm at 20 C and 0% RH for at 100%
oxygen and carbon dioxide.
Additionally, bio-derived paper and bio-derived plastic resins (namely, for example, PLA, PHA, PHB, PHBH, PBS, PBSA, PCL, PH, CPLA and PVA) may be coated with ultraviolet curable acrylates, preferably bio-derived acrylates, to form a bio degradable container. Some of these ultraviolet curable acrylates are suitable for storing consumable materials and are Food and Drug Administration (FDA) approved, namely tripropylene glycol diacrylate, trimethylolpropane triacrylate, and bisphenol A diglycidal ether diacrylate. Other ultraviolet cured materials might not be FDA approved, but could still be used to coat a biodegradable container.
In some embodiments, one or more sustainable articles described herein and packaged in a sustainable secondary packaging material may be further packaged or bundled in a sustainable tertiary packaging, for example, in a multi-pack or in a suitable shipping container. In such embodiments, the materials for the tertiary packaging preferably are bio-derived and are made from one or more of the materials described above with regard to the secondary packaging. The material of the tertiary packaging may be the same as or different from the material of the secondary packaging. The tertiary packaging can be labeled independently from the secondary packaging, preferably using the sustainable labels described above, the bio-derived inks described above, or both.
Consumer Message The sustainable article or container, the sustainable label thereon, the secondary pacakging, or a combination thereof, may further comprise a related environmental message that communicates a related environmental message to a consumer. The related environmental message may convey the benefits or advantages of the sustainable composition contained in the sustainable article or container, particularly that the sustainable composition, the packaging, or both, comprise or consist of a polymer derived from a renewable resource. The related environmental message may identify the sustainable composition and its packaging as: being environmentally friendly or Earth friendly; having reduced petroleum (or oil) dependence or content; having reduced foreign petroleum (or oil) dependence or content;
having reduced petrochemicals or having components that are petrochemical free; and/or being made from renewable resources or having components made from renewable resources. This communication is of importance to consumers that may have an aversion to petrochemical use (e.g., consumers concerned about depletion of natural resources or consumers who find petrochemical based products unnatural or not environmentally friendly) and to consumers that are environmentally conscious. Without such a communication, the benefit of the present invention maybe lost on some consumers.
The communication may be effected in a variety of communication forms.
Suitable communication forms include store displays, posters, billboard, computer programs, brochures, package literature, shelf information, videos, advertisements, Internet web sites, pictograms, iconography, or any other suitable form of communication. The information could be available at stores, on television, in a computer-accessible form, in advertisements, or any other appropriate venue. Ideally, multiple communication forms may be employed to disseminate the related environmental message.
The communication may be written, spoken, or delivered by way of one or more pictures, graphics, or icons. For example, a television or Internet based-advertisement may have narration, a voice-over, or other audible conveyance of the related environmental message. Likewise, the related environmental message may be conveyed in a written form using any of the suitable communication forms listed above. It may be desirable to quantify the reduction of petrochemical usage of the sustainable composition compared to other sustainable compositions that are presently commercially available. The communication form may be one or more icons, such as those shown in FIGS. 3A-3F of WO 2007/109128, hereby incorporated by reference.
The one or more icons may be used to convey the related environmental message of reduced petrochemical usage. Icons communicating the related environmental message of environmental friendliness or renewable resource may be used. The icons may be located on the unit-dose pouch, on the secondary packaging, or both. Preferably, the icons and any graphics on the pouch or packaging are printed with biodegradable and/or bio-derived inks.
The related environmental message may also include a message of petrochemical equivalence. Because many renewable, naturally occurring, bio-derived, or non-petroleum derived polymers often are perceived to lack the performance characteristics that consumers have come to expect when used in absorbent articles, a message of petroleum equivalence may be necessary to educate consumers that the polymers derived from renewable resources, as described above, exhibit equivalent or better performance characteristics as compared to petroleum derived polymers. Thus, a suitable petrochemical equivalence message can include comparison to a sustainable composition that does not have a polymer derived from a renewable resource. For example, a suitable combined message may be, "Sustainable Composition A with bio-derived ingredients is just as effective as Petroleum-Derived Composition B." This message conveys both the related environmental message and the message of petrochemical equivalence.
The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as "40 mm" is intended to mean "about 40 mm".

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.

Claims

1. A sustainable container for a consumer product, the sustainable container comprising at least one bio-derived polymer selected from the group consisting of bio-derived polyethylene, bio-derived high-density polyethylene, bio-derived polypropylene, bio-derived polyethylene terephthalate, and mixtures thereof.

2. The sustainable container of claim 1, comprising a portion that holds a liquid composition, a closure, a label, and optionally a sustainable dispenser or delivery apparatus.

3. A consumer product comprising at least one sustainable container and a liquid composition contained in one or more of the at least one the sustainable container, wherein each sustainable container comprises at least one bio-derived polymer selected from the group consisting of bio-derived polyethylene, bio-derived high-density polyethylene, bio-derived polypropylene, bio-derived polyethylene terephthalate, and mixtures thereof.

4. The consumer product of claim 3, further comprising sustainable secondary packaging materials that enclose the consumer product and, optionally, sustainable tertiary packaging materials that enclose multiple consumer products enclosed in the sustainable secondary packaging.

5. A consumer product comprising a sustainable container and a sustainable composition, wherein:
the sustainable container comprises at least one bio-derived polymer selected from the group consisting of bio-derived polyethylene, bio-derived high-density polyethylene, bio-derived polypropylene, bio-derived polyethylene terephthalate, and mixtures thereof; and the sustainable composition comprises at least one bio-derived surfactant.

6. The consumer product of claim 5, wherein the sustainable composition further comprises at least one additional bio-derived ingredient selected from the group consisting of bio-derived solvents, bio-derived chelants, bio-derived polymers, and bio-derived thickeners.

7. The consumer product of claim 5, further comprising sustainable secondary packaging materials that enclose the consumer product and, optionally, sustainable tertiary packaging materials that enclose multiple consumer products enclosed in the sustainable secondary packaging.