Vinyl Lactam-derived Polymers, Compositions Thereof Having Enhanced Water-resistance, And Methods Of Use Thereof Patent Application (2025)

U.S. patent application number 15/301429 was filed with the patent office on 2017-06-22 for vinyl lactam-derived polymers, compositions thereof having enhanced water-resistance, and methods of use thereof. This patent application is currently assigned to ISP Investments LLC. The applicant listed for this patent is ISP Investments LLC. Invention is credited to Hani M. FARES, Mousumi GHOSH, Osama M. Musa, Krishnamurthy NACHARAJU, Donald I PRETTYPAUL, Michael A. TALLON.

VINYL LACTAM-DERIVED POLYMERS, COMPOSITIONS THEREOF HAVING ENHANCEDWATER-RESISTANCE, AND METHODS OF USE THEREOF

Abstract

The invention provides polymers comprising repeating unitsderived from (a) from 16% by weight to about 35% by weight of saidpolymer of at least one N-vinyl lactam monomer; (b) at least onemonomer selected from the group consisting of functionalized andunfunctionalized C.sub.1-C.sub.6 alkyl (meth)acrylates,C.sub.1-C.sub.6 alkyl (meth)acrylamides and combinations thereof;and (c) at least one monomer selected from the group consisting offunctionalized and unfunctionalized C.sub.8-C.sub.30 branched alkyl(meth)acrylates, C.sub.8-C.sub.30 branched alkyl (meth)acrylamides,and combinations thereof; wherein the polymer has a glasstransition temperature of greater than about 45.degree. C. Theinvention further provides various compositions, such as, personalcare, sun care, coatings, and pharmaceutical compositionscomprising the polymers described herein. The invention furthermoreprovides water-resistant sun care compositions comprising thepolymers described herein. Subscripts x, y and z are describedherein. ##STR00001##

Related U.S. Patent Documents

Claims

1. A polymer comprising repeating units derived from: (a) from 16%by weight to about 35% by weight of said polymer of at least oneN-vinyl lactam monomer; (b) at least one monomer selected from thegroup consisting of functionalized and unfunctionalizedC.sub.1-C.sub.6 alkyl (meth)acrylates, C.sub.1-C.sub.6 alkyl(meth)acrylamides and combinations thereof; and (c) at least onemonomer selected from the group consisting of functionalized andunfunctionalized C.sub.8-C.sub.30 branched alkyl (meth)acrylates,C.sub.8-C.sub.30 branched alkyl (meth)acrylamides, and combinationsthereof; wherein said polymer has a glass transistion temperature(Tg) of greater than about 45.degree. C.

2. The polymer according to claim 1 wherein said N-vinyl lactam hasa structure: ##STR00029## wherein Q is a functionalized orunfunctionalized C.sub.1-C.sub.10 alkylene and each R.sub.1,R.sub.2, and R.sub.3 is independently selected from the groupconsisting of hydrogen and functionalized and unfunctionalizedC.sub.1-C.sub.4 alkyl groups.

3. The polymer according to claim 2 wherein said N-vinyl lactam isselected from the group consisting of: N-vinyl-2-pyrrolidone,N-vinyl-2-piperidone, N-vinyl-2-caprolactam,N-vinyl-3-methyl-2-pyrrolidone, N-vinyl-3-methyl-2-piperidone,N-vinyl-3-methyl-2-caprolactam, N-vinyl-4-methyl-2-pyrrolidone,N-vinyl-4-methyl-2-caprolactam, N-vinyl-5-methyl-2-pyrrolidone,N-vinyl-5-methyl-2-piperidone, N-vinyl-5,5-dimethyl-2-pyrrolidone,N-vinyl-3,3,5-trimethyl-2-pyrrolidone,N-vinyl-5-methyl-5-ethyl-2-pyrrolidone,N-vinyl-3,4,5-trimethyl-3-ethyl-2-pyrrolidone,N-vinyl-6-methyl-2-piperidone, N-vinyl-6-ethyl-2-piperidone,N-vinyl-3,5-dimethyl-2-piperidone,N-vinyl-4,4-dimethyl-2-piperidone, N-vinyl-7-methyl-2-caprolactam,N-vinyl-7-ethyl-2-caprolactam, N-vinyl-3,5-dimethyl-2-caprolactam,N-vinyl-4,6-dimethyl-2-caprolactam,N-vinyl-3,5,7-trimethyl-2-caprolactam, and combinationsthereof.

4. The polymer according to claim 1 wherein said C.sub.1-C.sub.6alkyl (meth)acrylate is selected from the group consisting ofmethyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate,iso-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl(meth)acrylate, n-pentyl (meth)acrylate, iso-amyl (meth)acrylate,n-hexyl (meth)acrylate, and combinations thereof.

5. The polymer according to claim 1 wherein said C.sub.1-C.sub.6alkyl (meth)acrylamide is selected from the group consisting ofmethyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide, ethyl(meth)acrylamide, propyl (meth)acrylamide, iso-butyl(meth)acrylamide, sec-butyl (meth)acrylamide, tert-butyl(meth)acrylamide, n-pentyl (meth)acrylamide, iso-amyl(meth)acrylamide, n-hexyl (meth)acrylamide, and combinationsthereof.

6. The polymer according to claim 1 wherein said C.sub.8-C.sub.30branched alkyl (meth)acrylate is selected from the group consistingof 2-ethylhexyl (meth)acrylate; 1,1,3,3-tetramethylbutyl(meth)acrylate; 1,1-dimethylhexyl (meth)acrylate; 6-methylheptyl(meth)acrylate; 7-methyloctyl (meth)acrylate; 2-propylheptyl(meth)acrylate; 8-methylnonyl (meth)acrylate; 9-methyldecyl(meth)acrylate; 10-methylundecyl (meth)acrylate; 11-methyldodecyl(meth)acrylate; 12-methyltridecyl (meth)acrylate;13-methyltetradecyl (meth)acrylate; 14-methylpentadecyl(meth)acrylate; 15-methylhexadecyl (meth)acrylate;16-methylheptadecyl (meth)acrylate; 17-methyloctadecyl(meth)acrylate; and combinations thereof.

7. The polymer according to claim 1 wherein said C.sub.8-C.sub.30branched alkyl (meth)acrylamide is selected from the groupconsisting of N-2-ethylhexyl (meth)acrylamide;N-1,1,3,3-tetramethylbutyl (meth)acrylamide; N-1,1-dimethylhexyl(meth)acrylamide; N-6-methylheptyl (meth)acrylamide;N-7-methyloctyl (meth)acrylamide; N-2-propylheptyl(meth)acrylamide; N-8-methylnonyl (meth)acrylamide; N-9-methyldecyl(meth)acrylamide; N-10-methylundecyl (meth)acrylamide;N-11-methyldodecyl (meth)acrylamide; N-12-methyltridecyl(meth)acrylamide; N-13-methyltetradecyl (meth)acrylamide;N-14-methylpentadecyl (meth)acrylamide; N-15-methylhexadecyl(meth)acrylamide; N-16-methylheptadecyl (meth)acrylamide;N-17-methyloctadecyl (meth)acrylamide; and combinationsthereof.

8. The polymer according to claim 1 comprising repeating unitsderived from: (a) from 18% by weight to about 25% by weight of saidpolymer of at least one monomer selected from the group consistingof N-vinyl-2-pyrrolidone, N-vinyl-2-caprolactam, and combinationsthereof; (b) at least one monomer selected from the groupconsisting of methyl (meth)acrylate, methyl (meth)acrylamide,tert-butyl (meth)acrylate, tert-butyl (meth)acrylamide,N,N-dimethyl (meth)acrylamide, and combinations thereof; and (c) atleast one monomer selected from the group consisting of2-ethylhexyl (meth)acrylate; N-2-ethylhexyl (meth)acrylamide;1,1,3,3-tetramethylbutyl (meth)acrylate; N-1,1,3,3-tetramethylbutyl(meth)acrylamide; and combinations thereof.

9. The polymer according to claim 8 comprising repeating unitsderived from: from 18% by weight to about 25% by weight of saidpolymer of N-vinyl-2-pyrrolidone, from about 25% by weight to about50% by weight of said polymer of methyl (meth)acrylate, and fromabout 30% by weight to about 70% by weight of said polymer of2-ethylhexyl (meth)acrylate.

10. The polymer according to claim 1 having a structure selectedfrom the group consisting of ##STR00030## ##STR00031## ##STR00032####STR00033## wherein x has a value ranging from 18% by weight toabout 35% by weight of said polymer, and y and z are independentlyselected non-zero weight % values such that sum of said x, y and zfor each said polymer equals 100.

11. The polymer according to claim 1 having a glass transistiontemperature (Tg) from about 45.degree. C. to about 85.degree.C.

12. A composition comprising a polymer comprising repeating unitsderived from: (a) from 16% by weight to about 35% by weight of saidpolymer of at least one N-vinyl lactam monomer; (b) at least onemonomer selected from the group consisting of functionalized andunfunctionalized C.sub.1-C.sub.6 alkyl (meth)acrylates,C.sub.1-C.sub.6 alkyl (meth)acrylamides and combinations thereof;and (c) at least one monomer selected from the group consisting offunctionalized and unfunctionalized C.sub.8-C.sub.30 branched alkyl(meth)acrylates, C.sub.8-C.sub.30 branched alkyl (meth)acrylamides,and combinations thereof; wherein said polymer has a glasstransistion temperature of greater than about 45.degree. C.

13. The composition according to claim 12 wherein said compositionis a personal care composition, pharmaceutical composition, coatingcomposition, household, industrial and institutional composition,cementing fluid, oilfield composition, construction composition,servicing fluid, gravel packing mud, fracturing fluid, completionfluid, workover fluid, spacer fluid, drilling mud, foodcomposition, biocide, adhesive, ink, paper, polish, membrane, metalworking fluid, plastic, textile, printing composition, lubricant,preservative, agricultural, or wood-care composition.

14. A personal care composition comprising a polymer comprisingrepeating units derived from: (a) from 16% by weight to about 35%by weight of said polymer of at least one N-vinyl lactam monomer;(b) at least one monomer selected from the group consisting offunctionalized and unfunctionalized C.sub.1-C.sub.6 alkyl(meth)acrylates, C.sub.1-C.sub.6 alkyl (meth)acrylamides andcombinations thereof; and (c) at least one monomer selected fromthe group consisting of functionalized and unfunctionalizedC.sub.8-C.sub.30 branched alkyl (meth)acrylates, C.sub.8-C.sub.30branched alkyl (meth)acrylamides, and combinations thereof; whereinsaid polymer has a glass transistion temperature of greater thanabout 45.degree. C.

15. The personal care composition according to claim 14 whereinsaid personal care composition is a sun care composition, a facecare composition, a lip care composition, an eye care composition,a skin care composition, an after-sun composition, a body carecomposition, a nail care composition, an anti-aging composition, aninsect repellant, an oral care composition, a deodorantcomposition, a hair care composition, a conditioning composition, acolor cosmetic composition, a color-protection composition, aself-tanning composition, or a foot care composition.

16. The personal care composition according to claim 15 whereinsaid personal care composition is a sun care composition.

17. The personal care composition according to claim 16 whereinsaid sun care composition is a water-resistant sun carecomposition.

18. The personal care composition according to claim 17 whereinsaid water-resistant sun care composition further comprises atleast one UV active.

19. The personal care composition according to claim 18 whereinsaid water-resistant sun care composition further comprises atleast one additive selected from the group consisting of secondarypolymers for improving water-resistance, UV active solubilizers,oils, waxes, solvents, emulsifiers, preservatives, antioxidants,antiradical protecting agents, vitamins, perfumes, insectrepellants, dyes, pigments, humectants, fillers, thickeners, filmformers, stabilizers, buffers, spreading agents, pearlizing agents,electrolytes, acids, bases, pharmaceutically or dermatologically orcosmetically acceptable excipients, and combinations thereof.

20. The personal care composition according to claim 17 whereinsaid water-resistant sun care composition is in the form of anoil-in-water emulsion, a water-in-oil emulsion, an oil-water-oilemulsion, a water-oil-water emulsion, a water-in-silicone emulsion,an oily solution, a lipid fusion, a hydro-alcoholic gel, ananhydrous formulation, an anhydrous gel, an aqueous gel, analcoholic solution or a hydro-alcoholic solution.

21. A method for protecting a keratinous substrate from UVradiation comprising applying onto said substrate a water-resistantsun care composition comprising: (a) a polymer comprising repeatingunits derived from: from 16% by weight to about 35% by weight ofsaid polymer of at least one N-vinyl lactam monomer; at least onemonomer selected from the group consisting of functionalized andunfuctionalized C.sub.1-C.sub.6 alkyl (meth)acrylates,C.sub.1-C.sub.6 alkyl (meth)acrylamides and combinations thereof;and at least one monomer selected from the group consisting offunctionalized and unfunctionalized C.sub.8-C.sub.30 branched alkyl(meth)acrylates, C.sub.8-C.sub.30 branched alkyl (meth)acrylamides,and combinations thereof, wherein said polymer has a glasstransistion temperature of greater than about 45.degree. C.; and(b) at least one UV active.

Description

FIELD OF THE INVENTION

[0001] The invention provides vinyl lactam-derived polymers. Theinvention further provides compositions comprising the vinyllactam-derived polymers. The invention furthermore providespersonal care compositions, such as water-resistant sun carecompositions comprising the vinyl lactam-derived polymers, andmethods of use thereof.

DESCRIPTION OF RELATED ART

[0002] Aging skin is the result of more than just chronologicalage. Skin is exposed to various environmental stresses, such asultraviolet (UV) rays, which cause free radicals to form in theskin. Free radicals include, for example, singlet oxygen, hydroxylradical, the superoxide anion, nitric oxide and hydrogen radicals.Free radicals attack DNA, membrane lipids and proteins, generatingcarbon radicals. These in turn react with oxygen to produce aperoxyl radical which may attack adjacent fatty acids to generatenew carbon radicals. This process can lead to a chain reactionproducing lipid peroxidation products. Damage to the cell membranecan result in loss of cell permeability, increased intercellularionic concentration and/or decreased ability to excrete or detoxifywaste products. The end result is a loss of elasticity of the skinand the appearance of wrinkles leading to premature ageing of theskin. This process is commonly referred to as photo-aging.

[0003] One of the requirements of commercial sun care compositionsis to possess water-resistance properties in order to inhibit theprotective composition from being easily removed from a keratinoussubstrate surface by sweat and exposure to water.

[0004] U.S. Pat. No. 4,978,527 teaches film-forming emulsioncontaining iodine and methods of use. The film-forming emulsioncomprises: (a) a substantially water resistant film-formingcopolymer phase comprising A, B and C monomers wherein A is a"soft" monomer wherein the corresponding homopolymer has a glasstransition temperature (Tg) of less than about -15.degree. C., andis present as about 15 to 80% of the total weight of all monomersin the copolymer, B is a "hard" monomer wherein the correspondinghomopolymer has a Tg of more than about -5.degree. C., and ispresent as about 20 to 70% of the total weight of all monomers inthe copolymer, and C is a monomer capable of complexing iodine anddelivering it to the skin and is present as about 1 to 15% of thetotal weight of all monomers in the copolymer; (b) about 0.05 to15% of iodine based on total emulsion weight; (c) an effectiveamount of an emulsifying agent; and (d) about 30 to 95% by weightof water.

[0005] U.S. Pat. No. 4,584,192 teaches a film-forming compositioncontaining an antimicrobial agent and methods of use. Thefilm-forming composition comprises (a) a film-forming copolymerconsisting essentially of copolymerized A, B, and C monomers asfollows: A is a monomeric acrylic or methacrylic acid ester of analkyl alcohol containing a single hydroxyl, the alcohol beingfurther described as having from 2 to about 14 carbon atoms whenthe A monomer is an acrylic acid ester, and about 7 to 18 carbonatoms when the A monomer is a methacrylic acid ester, the amount byweight of A monomer being about 15 to 80% of the total weight ofall monomers in the copolymer; B is a monomeric methacrylic acidester of an alkyl alcohol containing a single hydroxyl, the alcoholbeing further described as having from 1 to about 6 carbon atoms,the amount by weight of B monomer being about 20 to 70% of thetotal weight of all monomers in the copolymer; and C is an N-vinyllactam, the amount by weight of which being about 1 to 15% of thetotal weight of all monomers in the copolymer; (b) an effectiveamount of a broad spectrum antimicrobial agent; the compositionbeing dermatologically-acceptable, and, when applied to skin from afugitive solvent, being capable of forming a clear, substantiallyfluid-resistant, substantially tack-free, flexible film whichadheres to skin and releases the antimicrobial agent to skin.

[0006] U.S. Pat. No. 7,745,505 teaches a UV-curable hot meltpressure sensitive adhesive comprising (a) from about 70 to about95 parts by weight of methyl acrylate, methyl methacrylate, n-butylacrylate, 2-ethylhexyl acrylate, and/or isooctyl acrylate, (b) 0 toabout 30 parts by weight of hydroxyethyl acrylate and/orhydroxypropyl acrylate, (c) 0 to about 20 parts by weight ofacrylic acid or maleic anhydride, (d) 0 to about 30 parts by weightof 1-vinyl-2-pyrrolidinone (NVP), t-octyl acrylamide,2-(tert-butylamino)ethyl methacrylate (t-BAEM), acrylamide,glycidyl methacrylate, 3-Isopropenyl-.alpha.,.alpha.-dimethylbenzyl isocyanate (m-TMI.RTM.), and (e) from about0.01 to about 15 parts by weight of a photoinitiator.

[0007] US published patent application 2008/0138300 teaches acosmetic composition comprising, in a cosmetically acceptablemedium: at least one acrylic polymer resulting from thecopolymerization of: a) at least one monomer A chosen from estersderived from the reaction of (meth)acrylic acid with at least onemonoalcohol comprising from 2 to 20 carbon atoms, b) at least onemonomer B chosen from esters derived from the reaction ofmethacrylic acid with at least one monoalcohol comprising from 1 to10 carbon atoms, and c) at least one monomer C chosen fromN-vinyllactams and derivatives thereof, and at least one organicsolvent phase comprising at least one first organic solvent,wherein the at least one organic solvent phase comprises less thanor equal to 15% by weight of solvents chosen from lowermonoalcohols comprising from 1 to 5 carbon atoms andC.sub.3-C.sub.4 ketones, relative to the total weight of thecomposition. Advantageously, the monomer C is present in anumerical proportion ranging from 1% to 15% and better still from5% to 15% relative to the total number of monomers in thepolymer.

[0008] US published patent application 2010/0282409 teaches anantimicrobial composition comprising: a) a C.sub.2-C.sub.5 loweralcohol present in an amount of at least 35 wt-%; b) a hydrophobicpolymer soluble or dispersible in the lower alcohol; c) anemollient ester; and d) a cationic antimicrobial agent; wherein theantimicrobial composition is free of surfactants with an HLBgreater than 6; and wherein the antimicrobial composition isessentially free of hydrophilic polymers.

[0009] We have found that polymers according to the inventionprovide, among many other benefits, the important benefits ofenhanced water-resistance and good skin feel. The polymers may beformulated into a wide variety of compositions for many importantapplications, non-limiting examples of which include personal care,sun care, coatings, agricultural, and pharmaceuticals.

SUMMARY

[0010] In a first aspect, the invention provides a polymercomprising repeating units derived from (a) from 16% by weight toabout 35% by weight of said polymer of at least one N-vinyl lactammonomer; (b) at least one monomer selected from the groupconsisting of functionalized and unfunctionalized C.sub.1-C.sub.6alkyl (meth)acrylates, C.sub.1-C.sub.6 alkyl (meth)acrylamides andcombinations thereof; and (c) at least one monomer selected fromthe group consisting of functionalized and unfunctionalizedC.sub.8-C.sub.30 branched alkyl (meth)acrylates, C.sub.8-C.sub.30branched alkyl (meth)acrylamides, and combinations thereof; whereinthe polymer has a glass transistion temperature of greater thanabout 45.degree. C.

[0011] In a second aspect, the invention provides a compositioncomprising a polymer comprising repeating units derived from (a)from 16% by weight to about 35% by weight of said polymer of atleast one N-vinyl lactam monomer; (b) at least one monomer selectedfrom the group consisting of functionalized and unfunctionalizedC.sub.1-C.sub.6 alkyl (meth)acrylates, C.sub.1-C.sub.6 alkyl(meth)acrylamides and combinations thereof; and (c) at least onemonomer selected from the group consisting of functionalized andunfunctionalized C.sub.8-C.sub.30 branched alkyl (meth)acrylates,C.sub.8-C.sub.30 branched alkyl (meth)acrylamides, and combinationsthereof; wherein the polymer has a glass transistion temperature ofgreater than about 45.degree. C. Non-limiting examples of suchcompositions include personal care compositions, coatingcompositions, Household, Industrial and Institutional compositions,pharmaceutical compositions, food compositions, cementing fluids,oilfield compositions, construction compositions, servicing fluids,gravel packing muds, fracturing fluids, completion fluids, workoverfluids, spacer fluids, drilling muds, biocides, adhesives, inks,papers, polishes, membranes, metal working fluids, plastics,textiles, printing compositions, lubricants, preservatives,agrochemicals, and wood-care compositions. Particularly, thecomposition is a personal care composition.

[0012] In a third aspect, the invention provides a method forprotecting a keratinous substrate from UV radiation comprisingapplying onto the substrate a composition comprising: (a) a polymercomprising repeating units derived from: from 16% by weight toabout 35% by weight of said polymer of at least one N-vinyl lactammonomer; at least one monomer selected from the group consisting offunctionalized and unfuctionalized C.sub.1-C.sub.6 alkyl(meth)acrylates, C.sub.1-C.sub.6 alkyl (meth)acrylamides andcombinations thereof; and at least one monomer selected from thegroup consisting of functionalized and unfunctionalizedC.sub.8-C.sub.30 branched alkyl (meth)acrylates, C.sub.8-C.sub.30branched alkyl (meth)acrylamides, and combinations thereof, whereinthe polymer has a glass transistion temperature of greater thanabout 45.degree. C.; and (b) at least one UV active.

DESCRIPTION OF THE DRAWINGS

[0013] Each of FIGS. 1 to 4 depict the percent water resistancestudy of sun care formulations comprising polymers according to theinvention in comparison to various commercially availableformulations.

[0014] FIG. 5 depicts the in-vitro water resistance testmethod.

DETAILED DESCRIPTION

[0015] Before explaining at least one aspect of the disclosedand/or claimed inventive concept(s) in detail, it is to beunderstood that the disclosed and/or claimed inventive concept(s)is not limited in its application to the details of constructionand the arrangement of the components or steps or methodologies setforth in the following description or illustrated in the drawings.The disclosed and/or claimed inventive concept(s) is capable ofother aspects or of being practiced or carried out in various ways.Also, it is to be understood that the phraseology and terminologyemployed herein is for the purpose of description and should not beregarded as limiting.

[0016] Unless otherwise defined herein, technical terms used inconnection with the disclosed and/or claimed inventive concept(s)shall have the meanings that are commonly understood by those ofordinary skill in the art. Further, unless otherwise required bycontext, singular terms shall include pluralities and plural termsshall include the singular.

[0017] All patents, published patent applications, and non-patentpublications referenced in any portion of this application areherein expressly incorporated by reference in their entirety to thesame extent as if each individual patent or publication wasspecifically and individually indicated to be incorporated byreference.

[0018] All of the articles and/or methods disclosed herein can bemade and executed without undue experimentation in light of thepresent disclosure. While the articles and methods of the disclosedand/or claimed inventive concept(s) have been described in terms ofparticular aspects, it will be apparent to those of ordinary skillin the art that variations may be applied to the articles and/ormethods and in the steps or in the sequence of steps of the methoddescribed herein without departing from the concept, spirit andscope of the disclosed and/or claimed inventive concept(s). Allsuch similar substitutes and modifications apparent to thoseskilled in the art are deemed to be within the spirit, scope andconcept of the disclosed and/or claimed inventive concept(s).

[0019] As utilized in accordance with the disclosure, the followingterms, unless otherwise indicated, shall be understood to have thefollowing meanings.

[0020] The use of the word "a" or "an" when used in conjunctionwith the term "comprising" may mean "one," but it is alsoconsistent with the meaning of "one or more," "at least one," and"one or more than one." The use of the term "or" is used to mean"and/or" unless explicitly indicated to refer to alternatives onlyif the alternatives are mutually exclusive, although the disclosuresupports a definition that refers to only alternatives and"and/or."

[0021] Throughout this application, the term "about" is used toindicate that a value includes the inherent variation of error forthe quantifying device, the method being employed to determine thevalue, or the variation that exists among the study subjects. Forexample, but not by way of limitation, when the term "about" isutilized, the designated value may vary by plus or minus twelvepercent, or eleven percent, or ten percent, or nine percent, oreight percent, or seven percent, or six percent, or five percent,or four percent, or three percent, or two percent, or onepercent.

[0022] The use of the term "at least one" will be understood toinclude one as well as any quantity more than one, including butnot limited to, 1, 2, 3, 4, 5, 10, 15, 20, 30, 40, 50, 100, etc.The term "at least one" may extend up to 100 or 1000 or moredepending on the term to which it is attached. In addition, thequantities of 100/1000 are not to be considered limiting as loweror higher limits may also produce satisfactory results. Inaddition, the use of the term "at least one of X, Y, and Z" will beunderstood to include X alone, Y alone, and Z alone, as well as anycombination of X, Y, and Z. The use of ordinal number terminology(i.e., "first", "second", "third", "fourth", etc.) is solely forthe purpose of differentiating between two or more items and,unless otherwise stated, is not meant to imply any sequence ororder or importance to one item over another or any order ofaddition.

[0023] As used herein, the words "comprising" (and any form ofcomprising, such as "comprise" and "comprises"), "having" (and anyform of having, such as "have" and "has"), "including" (and anyform of including, such as "includes" and "include") or"containing" (and any form of containing, such as "contains" and"contain") are inclusive or open-ended and do not excludeadditional, unrecited elements or method steps. The term "orcombinations thereof" as used herein refers to all permutations andcombinations of the listed items preceding the term. For example,"A, B, C, or combinations thereof" is intended to include at leastone of: A, B, C, AB, AC, BC, or ABC and, if order is important in aparticular context, also BA, CA, CB, CBA, BCA, ACB, BAC, or CAB.Continuing with this example, expressly included are combinationsthat contain repeats of one or more item or term, such as BB, AAA,MB, BBC, AAABCCCC, CBBAAA, CABABB, and so forth. The skilledartisan will understand that typically there is no limit on thenumber of items or terms in any combination, unless otherwiseapparent from the context.

[0024] The term "each independently selected from the groupconsisting of" means when a group appears more than once in astructure, that group may be selected independently each time itappears.

[0025] The term "hydrocarbyl" includes straight-chain andbranched-chain alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl,aryl groups, and combinations thereof with optional heteroatom(s).A hydrocarbyl group may be mono-, di- or polyvalent.

[0026] The term "alkyl" refers to a functionalized orunfunctionalized monovalent straight-chain or branched-chainC.sub.1-C.sub.60 group optionally having one or more heteroatoms.Particularly, an alkyl is a C.sub.1-C.sub.45 group and moreparticularly, a C.sub.1-C.sub.30 group. Non-limiting examples ofalkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl,isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, n-heptyl,n-octyl, 2-ethylhexyl, tert-octyl, iso-norbornyl, n-dodecyl,tert-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, andn-eicosyl.

[0027] The term "alkylene" refers to a functionalized orunfunctionalized divalent straight-chain or branched-chainC.sub.1-C.sub.40 group optionally having one or more heteroatoms.Particularly, an alkylene is a C.sub.1-C.sub.30 group and moreparticularly, a C.sub.1-C.sub.20 group. Non-limiting examples ofalkylene groups include --CH.sub.2--. --CH.sub.2--CH.sub.2--,--CH(CH.sub.3)--CH.sub.2--, --CH.sub.2--CH(CH.sub.3)--,--C(CH.sub.3).sub.2, --CH.sub.2--, --CH.sub.2--C(CH.sub.3).sub.2--,--CH(CH.sub.3)--CH(CH.sub.3)--,--C(CH.sub.3).sub.2--C(CH.sub.3).sub.2--,--CH.sub.2--CH.sub.2--CH.sub.2--,--CH(CH.sub.3)--CH.sub.2--CH.sub.2--,--CH.sub.2--CH(CH.sub.3)--CH.sub.2--,--CH.sub.2--CH.sub.2--CH(CH.sub.3)--,--CH.sub.2--CH.sub.2--CH.sub.2--CH.sub.2--,--CH.sub.2--CH.sub.2--CH.sub.2--CH.sub.2--CH.sub.2--,--CH.sub.2--CH.sub.2--CH.sub.2--CH.sub.2--CH.sub.2--CH.sub.2--, and--CH.sub.2--CH.sub.2--CH.sub.2--CH.sub.2--CH.sub.2--CH.sub.2--CH.sub.2--.

[0028] The term "heteroatom" refers to oxygen, nitrogen, sulfur,silicon, phosphorous, and/or halogen. The heteroatom(s) may bepresent as a part of one or more heteroatom-containing functionalgroups. Non-limiting examples of heteroatom-containing functionalgroups include ether, hydroxy, epoxy, carbonyl, carboxamide,carboxylic ester, carboxylic acid, imine, imide, amine, sulfonic,sulfonamide, phosphonic, and silane groups.

[0029] The term "halogen" refers to chloro, bromo, iodo and/orfluoro.

[0030] The term "ammonium" includes protonated NH.sub.3 andprotonated primary, secondary, and tertiary organic amines.

[0031] The term "functionalized" refers to the state of a moietythat has one or more functional groups introduced to it by way ofone or more functionalization reactions known to a person havingordinary skill in the art. Non-limiting examples offunctionalization reactions include epoxidation, sulfonation,hydrolysis, amidation, esterification, hydroxylation,dihydroxylation, amination, ammonolysis, acylation, nitration,oxidation, dehydration, elimination, hydration, dehydrogenation,hydrogenation, acetalization, halogenation, dehydrohalogenation,Michael addition, aldol condensation, Canizzaro reaction, Mannichreaction, Clasien condensation, Suzuki coupling, and the like.

[0032] The term "residue of" refers to a fragment of a reactantthat remains after a reaction with another reactant(s). The residuemay be mono-, di- or polyvalent.

[0033] The term "monomer" refers to a small molecule thatchemically bonds during polymerization to one or more monomers ofthe same or different kind to form a polymer.

[0034] The term "polymer" refers to a large molecule comprising oneor more types of monomer residues (repeating units) connected bycovalent chemical bonds. By this definition, polymer encompassescompounds wherein the number of monomer units may range from veryfew, which more commonly may be called as oligomers, to very many.Non-limiting examples of polymers include homopolymers, andnon-homopolymers such as copolymers, terpolymers, tetrapolymers andthe higher analogues. The polymer may have a random, block, and/oralternating architecture.

[0035] The term "homopolymer" refers to a polymer that consistsessentially of a single monomer type.

[0036] The term "non-homopolymer" refers to a polymer thatcomprises more than one monomer types.

[0037] The term "copolymer" refers to a non-homopolymer thatcomprises two different monomer types.

[0038] The term "terpolymer" refers to a non-homopolymer thatcomprises three different monomer types.

[0039] The term "branched" refers to any non-linear molecularstructure. The term includes both branched and hyper-branchedstructures.

[0040] The term "free radical addition polymerization initiator"refers to a compound used in a catalytic amount to initiate a freeradical addition polymerization. The choice of initiator dependsmainly upon its solubility and its decomposition temperature.

[0041] The term "alkyl (meth) acrylate" refers to an alkyl ester ofacrylic and/or methacrylic acid.

[0042] The term "alkyl (meth) acrylamide" refers to an alkyl amideof acrylic and/or methacrylic acid.

[0043] The "glass transition temperature" (Tg) of a polymer ischaracterized by a change from a relatively hard, brittle, glassymaterial to a soft, more flexible, flowable material as thetemperature is raised through the glass transition temperature.

[0044] The terms "personal care composition" and "cosmetics" referto compositions intended for use on or in the human body, such asskin, sun, hair, oral, cosmetic, and preservative compositions,including those to alter the color and appearance of the skin andhair.

[0045] The term "sun care composition" refers to any compositionintended for use on the human body for protection from harmful orundesirable radiation from the sun.

[0046] The term "pharmaceutical composition" refers to anycomposition comprising at least one pharmaceutically activeingredient, as well as any product which results, directly orindirectly, from combination, complexation, or aggregation of anytwo or more of the ingredients, from dissociation of one or more ofthe ingredients, or from other types of reactions or interactionsof one or more of the ingredients.

[0047] The term "pharmaceutically active ingredient" should beconstrued in a broad sense as including any ingredient consideredto have a therapeutic effect when delivered to a subject in needthereof and further being regulated by drug authorities like CDER,EMEA, TAG etc. Pharmaceutically active ingredients may actsystemically upon oral consumption, or locally such as when presentin the buccal cavity, on the skin, etc. They may also be deliveredacross the skin as in transdermal drug delivery systems.

[0048] The term "oilfield composition" refers to a composition thatmay be used in the exploration, extraction, recovery, and/orcompletion of any hydrocarbon. Non-limiting examples of oilfieldcompositions include cement fluids, anti-agglomerants, kinetichydrate inhibitors, shale swelling inhibitors, drilling fluids,drilling muds, servicing fluids, gravel packing muds, frictionreducers, fracturing fluids, completion fluids, and work overfluids.

[0049] The term "servicing fluid" refers to a fluid used to drill,complete, work over, fracture, or in any way prepare a well borefor the recovery of materials residing in a subterranean formationpenetrated by the well bore. It is understood that "subterraneanformation" encompasses both areas below exposed earth or areasbelow earth covered by water such as sea or ocean water. Examplesof servicing fluids include, but are not limited to, a drillingfluid or mud, a cement slurry, a gravel packing fluid, a fracturingfluid, a completion fluid, and a workover fluid, all of which arewell known in the art.

[0050] The term "performance chemicals composition" refers to anynon-personal care composition. Performance chemicals compositionsserve a broad spectrum of arts, and include non-limitingcompositions such as: adhesives, agricultural, biocides, coatings,electronics, household-industrial-institutional (HI&I), inks,membranes, metal fluids, oilfield, paper, paints, plastics,printing, construction, and wood-care compositions.

[0051] The term "coating composition" refers to any compositionsuitable for application on a substrate in order to provide one ormore desired functions, including, but not limited to protecting,smoothing, strengthening, decorating, color enhancing/altering,substrate preparing and/or texturizing. The substrate for a coatingcomposition may include, without limitation, paper, paper board,wood, inorganic substrate, woven and non-woven textiles, metal,leather, powder, plastic, polymer, glass, cement, ceramic, traffic,tile, rubber, sealant, cable, concrete, plasterboard, adhesives,fillers, primers, inks, fertilizers, pharmaceuticals, structuralmaterials, molding, printing, inks, and the like. Examples ofcoating compositions include, without limitation, the following:paints, primers, stains, sealers, varnishes/polyurethanes,adhesives, waterproofers, wood hardeners. Coating compositions maybe applied by brush, dauber, roll, strip/sheet, and/or trowel, ormay be atomized and applied as a spray, mist, or droplet.

[0052] A "paint composition" is a non-limiting, specific type of a"coating composition". Paints may be water based or non-water based(i.e., solvent based). Paint compositions may be designed for anynumber of substrates, including wood, siding, dry wall, plaster,plastics, masonry, brick, tile, particle board, glass, stucco,concrete, and the like. Non-limiting examples of paints includeexterior paints, interior paints, architectural paints, andautomotive paints.

[0053] All percentages, ratio, and proportions used herein arebased on a weight basis unless other specified.

[0054] In a first aspect, the invention provides a polymercomprising repeating units derived from (a) from 16% by weight toabout 35% by weight of said polymer of at least one N-vinyl lactammonomer; (b) at least one monomer selected from the groupconsisting of functionalized and unfunctionalized C.sub.1-C.sub.6alkyl (meth)acrylates, C.sub.1-C.sub.6 alkyl (meth)acrylamides andcombinations thereof; and (c) at least one monomer selected fromthe group consisting of functionalized and unfunctionalizedC.sub.8-C.sub.30 branched alkyl (meth)acrylates, C.sub.8-C.sub.30branched alkyl (meth)acrylamides, and combinations thereof; whereinthe polymer has a glass transistion temperature of greater thanabout 45.degree. C.

[0055] The N-vinyl lactam has a structure:

##STR00002##

wherein Q is a functionalized or unfunctionalized C.sub.1-C.sub.10alkylene and each R.sub.1, R.sub.2, and R.sub.3 is independentlyselected from the group consisting of hydrogen and functionalizedand unfunctionalized C.sub.1-C.sub.4 alkyl groups. Non-limitingexamples of Q include functionalized and unfunctionalized--CH.sub.2--CH.sub.2--, --CH.sub.2--CH.sub.2--CH.sub.2--,--CH.sub.2--CH.sub.2--CH.sub.2--CH.sub.2--, and--CH.sub.2--CH.sub.2--CH.sub.2--CH.sub.2--CH.sub.2-- groups.Particularly, Q is --CH.sub.2--CH.sub.2--CH.sub.2-- or--CH.sub.2--CH.sub.2--CH.sub.2--CH.sub.2--CH.sub.2-- group.Particularly, each R.sub.1, R.sub.2, and R.sub.3 is independentlyselected from the group consisting of hydrogen and methyl groups.More particularly, each R.sub.1, R.sub.2, and R.sub.3 ishydrogen.

[0056] Non-limiting examples of N-vinyl lactams includeN-vinyl-2-pyrrolidone, N-vinyl-2-piperidone, N-vinyl-2-caprolactam,N-vinyl-3-methyl-2-pyrrolidone, N-vinyl-3-methyl-2-piperidone,N-vinyl-3-methyl-2-caprolactam, N-vinyl-4-methyl-2-pyrrolidone,N-vinyl-4-methyl-2-caprolactam, N-vinyl-5-methyl-2-pyrrolidone,N-vinyl-5-methyl-2-piperidone, N-vinyl-5,5-dimethyl-2-pyrrolidone,N-vinyl-3,3,5-trimethyl-2-pyrrolidone,N-vinyl-5-methyl-5-ethyl-2-pyrrolidone,N-vinyl-3,4,5-trimethyl-3-ethyl-2-pyrrolidone,N-vinyl-6-methyl-2-piperidone, N-vinyl-6-ethyl-2-piperidone,N-vinyl-3,5-dimethyl-2-piperidone,N-vinyl-4,4-dimethyl-2-piperidone, N-vinyl-7-methyl-2-caprolactam,N-vinyl-7-ethyl-2-caprolactam, N-vinyl-3,5-dimethyl-2-caprolactam,N-vinyl-4,6-dimethyl-2-caprolactam,N-vinyl-3,5,7-trimethyl-2-caprolactam, and combinations thereof.Particularly, N-vinyl lactam is selected from the group consistingof N-vinyl-2-pyrrolidone, N-vinyl-2-piperidone, andN-vinyl-2-caprolactam. More particularly, N-vinyl lactam isN-vinyl-2-pyrrolidone.

[0057] Non-limiting examples of C.sub.1-C.sub.6 alkyl(meth)acrylates include methyl (meth)acrylate, ethyl(meth)acrylate, propyl (meth)acrylate, iso-butyl (meth)acrylate,sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl(meth)acrylate, iso-amyl (meth)acrylate, n-hexyl (meth)acrylate,and combinations thereof. Particularly, C.sub.1-C.sub.6 alkyl(meth)acrylate is selected from the group consisting of methyl(meth)acrylate, ethyl (meth)acrylate, and combinations thereof.More particularly, C.sub.1-C.sub.6 alkyl (meth)acrylate is methyl(meth)acrylate.

[0058] Non-limiting examples of C.sub.1-C.sub.6 alkyl(meth)acrylamides include methyl (meth)acrylamide, N,N-dimethyl(meth)acrylamide, ethyl (meth)acrylamide, propyl (meth)acrylamide,iso-butyl (meth)acrylamide, sec-butyl (meth)acrylamide, tert-butyl(meth)acrylamide, n-pentyl (meth)acrylamide, iso-amyl(meth)acrylamide, n-hexyl (meth)acrylamide, and combinationsthereof. Particularly, C.sub.1-C.sub.6 alkyl (meth)acrylamide isselected from the group consisting of methyl (meth)acrylamide,ethyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide andcombinations thereof. More particularly, C.sub.1-C.sub.6 alkyl(meth)acrylamide is methyl (meth)acrylamide.

[0059] Non-limiting examples of C.sub.8-C.sub.30 branched alkyl(meth)acrylates include 2-ethylhexyl (meth)acrylate;1,1,3,3-tetramethylbutyl (meth)acrylate; 1,1-dimethylhexyl(meth)acrylate; 6-methylheptyl (meth)acrylate; 7-methyloctyl(meth)acrylate; 2-propylheptyl (meth)acrylate; 8-methylnonyl(meth)acrylate; 9-methyldecyl (meth)acrylate; 10-methylundecyl(meth)acrylate; 11-methyldodecyl (meth)acrylate; 12-methyltridecyl(meth)acrylate; 13-methyltetradecyl (meth)acrylate;14-methylpentadecyl (meth)acrylate; 15-methylhexadecyl(meth)acrylate; 16-methylheptadecyl (meth)acrylate;17-methyloctadecyl (meth)acrylate; and combinations thereof.Particularly, C.sub.8-C.sub.30 branched alkyl (meth)acrylate isselected from the group consisting of 2-ethylhexyl (meth)acrylate;1,1,3,3-tetramethylbutyl (meth)acrylate and combinations thereof.More particularly, C.sub.8-C.sub.30 branched alkyl (meth)acrylateis 2-ethylhexyl (meth)acrylate.

[0060] Non-limiting examples of C.sub.8-C.sub.30 branched alkyl(meth)acrylamides include N-2-ethylhexyl (meth)acrylamide;N-1,1,3,3-tetramethylbutyl (meth)acrylamide; N-1,1-dimethylhexyl(meth)acrylamide; N-6-methylheptyl (meth)acrylamide;N-7-methyloctyl (meth)acrylamide; N-2-propylheptyl(meth)acrylamide; N-8-methylnonyl (meth)acrylamide; N-9-methyldecyl(meth)acrylamide; N-10-methylundecyl (meth)acrylamide;N-11-methyldodecyl (meth)acrylamide; N-12-methyltridecyl(meth)acrylamide; N-13-methyltetradecyl (meth)acrylamide;N-14-methylpentadecyl (meth)acrylamide; N-15-methylhexadecyl(meth)acrylamide; N-16-methylheptadecyl (meth)acrylamide;N-17-methyloctadecyl (meth)acrylamide; and combinations thereof.Particularly, C.sub.8-C.sub.30 branched alkyl (meth)acrylamide isselected from the group consisting of N-2-ethylhexyl(meth)acrylamide; N-1,1,3,3-tetramethylbutyl (meth)acrylamide; andcombinations thereof. More particularly, C.sub.8-C.sub.30 branchedalkyl (meth)acrylamide is N-2-ethylhexyl (meth)acrylamide.

[0061] Particularly, polymers according to the invention compriserepeating units derived from: (a) from 18% by weight to about 25%by weight of said polymer of at least one monomer selected from thegroup consisting of N-vinyl-2-pyrrolidone, N-vinyl-2-caprolactam,and combinations thereof; (b) at least one monomer selected fromthe group consisting of methyl (meth)acrylate, methyl(meth)acrylamide, tert-butyl (meth)acrylate, tert-butyl(meth)acrylamide, N,N-dimethyl (meth)acrylamide, and combinationsthereof; and (c) at least one monomer selected from the groupconsisting of 2-ethylhexyl (meth)acrylate; N-2-ethylhexyl(meth)acrylamide; 1,1,3,3-tetramethylbutyl (meth)acrylate;N-1,1,3,3-tetramethylbutyl (meth)acrylamide; and combinationsthereof.

[0062] More particularly, the polymer comprises repeating unitsderived from: (a) from 18% by weight to about 25% by weight of saidpolymer of at least one monomer selected from the group consistingof N-vinyl-2-pyrrolidone, N-vinyl-2-caprolactam, and combinationsthereof; (b) from about 25% by weight to about 50% by weight ofsaid polymer of at least one monomer selected from the groupconsisting of methyl (meth)acrylate, methyl (meth)acrylamide,tert-butyl (meth)acrylate, tert-butyl (meth)acrylamide,N,N-dimethyl (meth)acrylamide, and combinations thereof; and (c)from about 30% by weight to about 70% by weight of said polymer ofat least one monomer selected from the group consisting of2-ethylhexyl (meth)acrylate; N-2-ethylhexyl (meth)acrylamide;1,1,3,3-tetramethylbutyl (meth)acrylate; N-1,1,3,3-tetramethylbutyl(meth)acrylamide; and combinations thereof.

[0063] Even more particularly, the polymer comprises repeatingunits derived from: (a) from 18% by weight to about 25% by weightof said polymer of N-vinyl-2-pyrrolidone, (b) from about 25% byweight to about 50% by weight of said polymer of methyl(meth)acrylate, and (c) from about 30% by weight to about 70% byweight of said polymer of 2-ethylhexyl (meth)acrylate.

[0064] Particularly, the polymer according to the invention has astructure selected from the group consisting of:

##STR00003## ##STR00004## ##STR00005## ##STR00006## ##STR00007####STR00008##

wherein x has a value ranging from 18% by weight to about 35% byweight of the polymer, and y and z are independently selectednon-zero weight % values such that sum of x, y and z for eachpolymer equals 100. More particularly, the polymer according to theinvention has a structure selected from the group consistingof:

##STR00009## ##STR00010##

wherein x has a value ranging from 18% by weight to about 35% byweight of the polymer, and y and z are independently selectednon-zero weight % values such that sum of x, y and z for eachpolymer equals 100. Even more particularly, the polymer has astructure:

##STR00011##

wherein x has a value ranging from 18% by weight to about 35% byweight of the polymer, and y and z are independently selectednon-zero weight % values such that sum of x, y and z for eachpolymer equals 100.

[0065] Particularly, x has a value ranging from 18% by weight toabout 35% by weight of the polymer; more particularly, from 18% byweight to about 30% by weight of the polymer; and even moreparticularly, from 18% by weight to about 25% by weight of thepolymer.

[0066] Particularly, y has a value ranging from about 15% by weightto about 75% by weight of the polymer; more particularly, fromabout 20% by weight to about 60% by weight of the polymer; and evenmore particularly, from about 25% by weight to about 50% by weightof the polymer.

[0067] Particularly, z has a value ranging from about 20% by weightto about 90% by weight of the polymer; more particularly, fromabout 25% by weight to about 80% by weight of the polymer; and evenmore particularly, from about 30% by weight to about 70% by weightof the polymer.

[0068] The weight % values of constituent monomers for each polymerdisclosed herein are such that their sum for each polymer equals100.

[0069] The polymers according to the invention have a glasstransition temperature ranging from about 45.degree. C. to about85.degree. C. More particularly, the glass transition temperatureranges from about 50.degree. C. to about 75.degree. C. Even moreparticularly, the glass transition temperature ranges from about55.degree. C. to about 70.degree. C.

[0070] The polymers according to the invention may be used alone orin combination with other ingredient(s) in various compositions andproduct forms.

[0071] In a second aspect, the invention provides a compositioncomprising a polymer comprising repeating units derived from (a)from 16% by weight to about 35% by weight of said polymer of atleast one N-vinyl lactam monomer; (b) at least one monomer selectedfrom the group consisting of functionalized and unfunctionalizedC.sub.1-C.sub.6 alkyl (meth)acrylates, C.sub.1-C.sub.6 alkyl(meth)acrylamides and combinations thereof; and (c) at least onemonomer selected from the group consisting of functionalized andunfunctionalized C.sub.8-C.sub.30 branched alkyl (meth)acrylates,C.sub.8-C.sub.30 branched alkyl (meth)acrylamides, and combinationsthereof; wherein the polymer has a glass transistion temperature ofgreater than about 45.degree. C.

[0072] Non-limiting examples of compositions include personal carecompositions, coating compositions, pharmaceutical compositions,coating compositions, household, industrial and institutionalcompositions, cementing fluids, oilfield compositions, constructioncompositions, servicing fluids, gravel packing muds, fracturingfluids, completion fluids, workover fluids, spacer fluids, drillingmuds, food compositions, biocides, adhesives, inks, papers,polishes, membranes, metal working fluids, plastics, textiles,printing compositions, lubricants, preservatives, agriculturalcompositions, and wood-care compositions. Particularly, thecomposition is a personal care composition, coating composition,household, industrial and institutional composition, pharmaceuticalcomposition, or an agricultural composition. More particularly, thecomposition is a personal care composition.

[0073] Non-limiting examples of personal care compositions that maycomprise polymer(s) according to the invention include sun carecompositions, face care compositions, lip care compositions, eyecare compositions, skin care compositions, after-sun compositions,body care compositions, nail care compositions, anti-agingcompositions, insect repellants, oral care compositions, deodorantcompostions, hair care compositions, conditioning compositions,color cosmetic compositions, color-protection compostions,self-tanning compositions, and foot care compositions.

[0074] Particularly, the personal care composition is a sun carecomposition. More particularly, the personal care composition is awater-resistant sun care composition.

[0075] Typically, sun care compositions may also comprise one ormore UV actives. Non-limiting examples of UV actives includeorganic and inorganic materials that scatter, absorb, and/orreflect radiation having a wavelength from about 100 nm to about400 nm.

[0076] In one particular aspect, the sun care composition protectsagainst UV-A, UV-B, and/or UV-C radiation.

[0077] UV-A radiation, from about 320 nm to about 400 nm, has thelongest wavelengths within the UV spectrum, and consequently is theleast energetic. UV-A radiation includes UV-A1 (from about 340 nmto about 400 nm) and UV-A2 (from about 320 nm to about 340 nm).UV-B radiation has shorter wavelengths, from about 290 nm to about320 nm. UV-C radiation has the shortest wavelengths from about 200nm to about 290 nm.

[0078] In another aspect, the sun care compositions may not containUV actives, and may be regarded as tanning oils or tanpromoters.

[0079] Sun care compositions may be formulated, for example, forapplication to the lips, hair, face, cheeks, neck, area around theeyes, full hands, and body area. Self-tanning compositions, whichare products that color skin without requiring full sun exposure,also fit under the sun care umbrella.

[0080] Suitable UV actives (or UV filters) that may be included inthe personal care compositions most likely will depend on localregulations. As the rules governing the names and usage levelsevolve over time, it is impossible to include every UV absorberthat may be used with the invention.

[0081] Non-limiting examples of suitable UV actives include: octylsalicylate; pentyl dimethyl PABA; octyl dimethyl PABA;benzophenone-1; benzophenone-6;2-(2H-benzotriazole-2-yl)-4,6-di-tert-pentylphenol;ethyl-2-cyano-3,3-diphenylacrylate; homomenthyl salicylate;bis-ethylhexyloxyphenol methoxyphenyl triazine;methyl-(1,2,2,6,6-pentamethyl-4-piperidyl)-sebacate;2-(2H-benzotriazole-2-yl)-4-methylphenol; diethylhexyl butamidotriazone; amyl dimethyl PABA; 4,6-bis(octylthiomethyl)-o-cresol;CAS number 65447-77-0; red petroleum; ethylhexyl triazone;octocrylene; isoamyl-p-methoxycinnamate; drometrizole; titaniumdioxide;2,4-di-tert-butyl-6-(5-chloro-2H-benzotriazole-2-yl)-phenol;2-hydroxy-4-octyloxybenzophenone; benzophenone-2; diisopropylmethylcinnamate; PEG-25 PABA;2-(1,1-dimethylethyl)-6-[[3-(1,1-dimethylethyl)-2-hydroxy-5-methylphenyl]-methyl-4-methylphenyl acrylate; drometrizole trisiloxane; menthylanthranilate; butyl methoxydibenzoylmethane; 2-ethoxyethylp-methoxycinnamate; benzylidene camphor sulfonic acid;dimethoxyphenyl-[1-(3,4)]-4,4-dimethyl 1,3-pentanedione; zincoxide;N,N'-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenylpropionamide)-]; pentaerythritoltetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate];2,6-di-tert-butyl-4-[4,6-bis(octylthio)-1,3,5-triazin-2-ylamino]phenol;2-(2H-benzotriazole-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol;trolamine salicylate; diethylanolamine p-methoxycinnamate;polysilicone-15; CAS number 152261-33-1; 4-methylbenzylidenecamphor; bisoctrizole; n-phenyl-benzenamine; reaction products with2,4,4-trimethylpentene; sulisobenzone;(2-ethylhexyl)-2-cyano-3,3-diphenylacrylate; digalloyl trioleate;polyacrylamido methylbenzylidene camphor; glyceryl ethylhexanoatedimethoxycinnamate;1,3-bis-[(2'-cyano-3',3'-diphenylacryloyl)oxy]-2,2-bis-{[(2'-cyano-bis-(2-,2,6,6-tetramethyl-4-piperidyl)-sebacate; benzophenone-5;1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,-5H)-trione; hexamethylenediamine; benzophenone-8;ethyl-4-bis(hydroxypropyl) aminobenzoate;6-tert-butyl-2-(5-chloro-2H-benzotriazole-2-yl)-4-methylphenol;p-aminobenzoic acid;3,3',3'',5,5',5''-hexa-tert-butyl-.alpha.-.alpha.'-.alpha.''-(mesitylene--2,4,6-triyl)tri-p-cresol; lawsone with dihydroxyacetone;benzophenone-9; benzophenone-4; ethylhexyl dimethoxy benzylidenedioxoimidazoline propionate;N,N'-bisformyl-N,N'-bis-(2,2,6,6-tetramethyl-4-piperidinyl)-;3-benzylidene camphor; terephthalylidene dicamphor sulfonic acid;camphor benzalkonium methosulfate; bisdisulizole disodium;etocrylene; ferulic acid;2-(2H-benzotriazole-2-yl)-4-(1,1,3,3-tetramethylbutyl)-phenol;4,6-bis(dodecylthiomethyl)-o-cresol; .beta.-2-glucopyranoxy propylhydroxy benzophenone; phenylbenzimidazole sulfonic acid;benzophenone-3; diethylamine hydroxybenzoyl hexylbenzoate;3',3'-diphenylacryloyl)oxylmethyl}-propane; ethylhexylp-methoxycinnamate, and blends thereof.

[0082] Particularly, the UV filters that may be used in thewater-resistant sun care compositions comprising the polymersaccording to the invention include one or more of: Bemotrizinol(Escalol.TM. S UV filter (Ashland)), Padimate 0 (Escalol.TM. 507 UVfilter (Ashland)), Avobenzone (Escalol.TM. 517 UV filter(Ashland)), Octinoxate (Escalol.TM. 557 UV filter (Ashland)),Oxybenzone (Escalol.TM. 567 UV filter (Ashland)), Sulisobenzone(Escalol.TM. 577 UV filter (Ashland)), Octisalate (Escalol.TM. 587UV filter (Ashland)), Homosalate (Escalol.TM. HMS UV filter(Ashland)), and Octocrylene (Escalol.TM. 597 UV filter(Ashland)).

[0083] The water-resistant sun care compositions according to theinvention may further comprise at least one additive selected fromthe group consisting of secondary polymers for improvingwater-resistance, UV active solubilizers, oils, waxes, solvents,emulsifiers, preservatives, antioxidants, vitamins, perfumes,insect repellants, dyes, pigments, humectants, fillers, thickeners,film formers, stabilizers, buffers, spreading agents, pearlizingagents, electrolytes, acids, bases, pharmaceutically ordermatologically or cosmetically acceptable excipients, andcombinations thereof.

[0084] Non-limiting, yet particular examples of water-resistant suncare compositions according to the invention include anoil-in-water emulsion, a water-in-oil emulsion, an oil-water-oilemulsion, a water-oil-water emulsion, a water-in-silicone emulsion,an oily solution, a lipid fusion, a hydro-alcoholic gel, ananhydrous formulation, an anhydrous gel, an aqueous gel, analcoholic solution or a hydro-alcoholic solution.

[0085] In particular aspects, the polymer according to theinvention is present in an amount from about 0.01% by weight toabout 20% by weight of the sun care compositions described herein.More particularly, the polymer is present from about 0.1% by weightto about 10% by weight of the sun care composition. Even moreparticularly, the polymer is present from about 0.25% by weight toabout 5.0% by weight of the sun care composition.

[0086] Non-limiting examples of suitable antioxidants and/orantiradical protecting agents include: BHA (tert-butyl-4-hydroxyanisole), BHT (2,6-di-tert-butyl-p-cresol), TBHQ (tert-butylhydroquinone), polyphenols such as proanthocyanodic oligomers,flavonoids, hindered amines such as tetra amino piperidine,erythorbic acid, polyamines such as spermine, cysteine,glutathione, superoxide dismutase, lactoferrin, and blendsthereof.

[0087] Non-limiting applications of hair care compositions include:hair styling, hair setting, hair sculpting, hair curling, hairholding, hair waving, hair fixing, hair maintaining, hair shaping,hair straightening, hair volumizing, hair relaxing, shampooing,hair conditioning, hair cleansing, promoting hair style durability,imparting humidity resistance to hair and hair styles, enhancinghair shine, repairing split ends of hair, enhancing hairmanageability such as lightness, smoothness, softness,disentangling and/or suppleness of hair, modulating hairstylability, protecting hair from thermal damage, hair dyeing, haircoloring, hair bleaching, oxidation dyeing of hair, limiting haircolor bleeding, protecting hair color, hair treating (e.g.,anti-dandruff), anti-hair fall, and protecting hair from UVradiation.

[0088] The hair care compositions may further comprise one or moreadditional ingredients. Particularly, the additional ingredientsmay be selected from the group consisting of: skin care or haircare agents, hair styling agents, hair fixative agents, filmformers, structurants, gelling agents, surfactants, thickeners,preservatives, viscosity modifiers, electrolytes, pH adjustingagents, perfumes, dyes, organosilicon compounds, anti-dandruffagents, anti-foaming agents, anti-frizz agents, penetrants,vitamins, conditioning agents, chelating agents, antimicrobialagents, preservatives, UV absorbers, sunscreens, natural extracts,propellants, carriers, diluents, solvents, pharmaceutical actives,lubricants, combing aids, plasticizers, solubilizers, neutralizingagents, vapor pressure suppressants, bleaching agents, hydratingagents, moisturizers, cosmetic adjuvants and/or additives,protectants, and mixtures thereof.

[0089] Non-limiting applications of the oral care compositionsinclude: tooth and/or mouth cleansing, providing denture adhesion,delivering and/or retaining actives to oral cavity, mouth washing,mouth refreshing, mouth rinsing, mouth gargling, providing oralhygiene, preventing, reducing, controlling, and/or removing toothstain, preventing and/or controlling tooth decay, preventing and/orcontrolling tartar, tooth flossing, tooth whitening and/orbleaching, mouth treating, and tooth filling.

[0090] The polymers described herein also may be used alone or incombination with other ingredient(s) in pharmaceutical and/ornutritional compositions.

[0091] Non-limiting applications of the pharmaceutical and/ornutritional compositions include: providing anti-tack, binder,coating, disintegrating, dispersing, encapsulating, filling, filmforming, lubricating, and solubilizing. Additional insight into howthe polymers described herein find application in this art area maybe found in the following publications by Ashland SpecialtyIngredients: Health and nutrition product guide--Performanceenhancing products (08/2008), Plasdone.TM. povidones productoverview (04/2010), Plasdone.TM. K-12 and K-17povidones--Solubilizers for liquid softgel fill compositions(09/2010), Plasdone.TM. K-29/32 povidone--High efficiency binderfor wet granulation (04/2010), Plasdone.TM. S-630copovidone--Product Overview (04/2010), Polyplasdone.TM. Ultra andUltra-10 crospovidones--Product overview (09/2010),Polyplasdone.TM. superdisintegrants--Product overview (07/2010),Polyplasdone.TM. crospovidone--Superdisintegrants for orallydisintegrating and chewable tablets (07/2010), Polyplasdone.TM.crospovidone--Nonionic superdisintegrant for improved dissolutionof cationic drugs (07/2009), Polyplasdone.TM. crospovidone--Thesolution for poorly soluble drugs (07/2009), Polyplasdone.TM.crospovidone--Novel pelletization aid for extrusion spheronization(07/2010), PVP-Iodine povidone iodine antiseptic agent (03/2004),and Pharmaceutical technical bulletin--PVP-Iodine for prophylaxisand treatment of bovine mastitis (12/2003). Each publication ishereby incorporated in its entirety by reference.

[0092] Any range in composition pH may be used. In aspects whereinthe composition may be applied to keratinous material, the pH mayrange from about 2 to 12. pH may be adjusted to a desired value bymeans of adding one or more acidifying or alkalinizing agents thatare well-known in the state of the art. For example, thecomposition can contain at least one alkalizing or acidifying agentin amounts from about 0.01% to about 30% based on the total weightof the composition.

[0093] Non-limiting examples of acidifying or acidic pH adjustingagents include organic acids, such as citric acid, acetic acid,carboxylic acids, .alpha.-hydroxyacids, .beta.-hydroxyacids,.alpha.,.beta.-hydroxyacids, salicylic acid, tartaric acid, lacticacid, glycolic acid, natural fruit acids, and combinations thereof.In addition, inorganic acids, for example hydrochloric acid, nitricacid, sulfuric acid, sulfamic acid, phosphoric acid, andcombinations thereof can be utilized.

[0094] Non-limiting examples of alkalizing or alkaline pH adjustingagents include ammonia, alkali metal hydroxides (such as sodiumhydroxide and potassium hydroxide), ammonium hydroxide,alkanolamines (such as mono-, di- and triethanolamine),diisopropylamine, dodecylamine, diisopropanolamine, aminomethylpropanol, cocamine, oleamine, morpholine, triamylamine,triethylamine, tromethamine(2-amino-2-hydroxymethyl)-1,3-propanediol), andtetrakis(hydroxypropyl)ethylenediamine, hydroxyalkylamines andethoxylated and/or propoxylated ethylenediamines, alkali metalsalts of inorganic acids, such as sodium borate (borax), sodiumphosphate, sodium pyrophosphate, and the like, and mixturesthereof.

[0095] Non-limiting examples of alkalizing agent can be chosen fromammonia, alkali carbonates, alkanolamines, like mono-, di- andtriethanolamines, as well as their derivatives, sodium or potassiumhydroxides and compounds of the following formula:

##STR00012##

wherein R.sub.1 may be a propylene residue that may be optionallysubstituted with an hydroxyl group or a C.sub.1-C.sub.4 alkylradical; R.sub.2, R.sub.3, R.sub.4 and R.sub.5 are identical ordifferent and represent a hydrogen atom, a C.sub.1-C.sub.4 alkylradical or C.sub.1-C.sub.4 hydroxyalkyl radical.

[0096] The composition may comprise one or more buffers. Suitablebuffering agents include but are not limited to alkali or alkaliearth carbonates, phosphates, bicarbonates, citrates, borates,acetates, acid anhydrides, succinates and the like, such as sodiumphosphate, citrate, borate, acetate, bicarbonate, and carbonate.The personal care compositions may be formulated in any of theproduct forms known to a person of ordinary skill in the art.Non-limiting product forms are described below.

Product Forms

[0097] Non-limiting hair care product forms include: shampoos,conditioners, aerosols, mousses, sprays, mists, gels, waxes,creams, lotions, glues, pomades, spritzes, solutions, oils,liquids, solids, W/O emulsions, O/W emulsions, suspensions,multiple emulsions, microemulsions, microencapsulated products,sticks, balms, tonics, pastes, reconstitutable products,nanoemulsions, solid lipid nanoparticles, liposomes, cubosomes,neosomes, putties, lacquers, serums, perms, volumizers, packs,flakes, 2-in-1 shampoo/conditioner products, and 3-in-1shampoo/conditioner/styling products.

[0098] The compositions according to the invention may also takethe form of after-shampoo compositions, to be rinsed off or not,for permanents, straightening, waving, dyeing, or bleaching, or theform of rinse compositions to be applied before or after dyeing,bleaching, permanents, straightening, relaxing, waving or evenbetween the two stages of a permanent or straightening process.

[0099] Non-limiting sun care product forms include: solutions,liquids, creams, powders, lotions, gels, pastes, waxes, aerosols,sprays, mists, roll-ons, sticks, milks, emulsions, and wipes.

[0100] Non-limiting skin care product forms include: solutions,oils, lotions, creams, ointments, liquids, gels, solids, W/Oemulsions, O/W emulsions, milks, suspensions, microemulsions,dispersions, microencapsulated products, sticks, balms, tonics,pastes, mists, reconstitutable products, peels, soaps, aerosols,mousses, waxes, glues, pomades, spritzes, putties, lacquers,serums, perms, powders, pencils, flakes, blush, highlighters,bronzers, concealers, and 2-way cake products.

[0101] The compositions of the invention may also take the form ofskin-washing compositions, and particularly in the form ofsolutions or gels for the bath or shower, or of make-up removalproducts.

[0102] The six skin care product categories that follow next may beconsidered a subset of the skin and sun care products:

[0103] (1) Eye Care

[0104] Non-limiting eye care product forms include: mascaras, eyeliners, eye shadows, curlers of eye lashes, eyebrow pencils, andeye pencils.

[0105] (2) Lip Care

[0106] Non-limiting lip care product forms include: lipsticks, lipbalms, lip pencils, lip glosses, lip sprays, transparent lip bases,tinted lip moisturizers, and multi-functional color sticks that canalso be used for cheeks and eyes.

[0107] (3) Nail Care

[0108] Non-limiting nail care product forms include: nail polishes,nail varnishes, enamels, nail varnish removers, home-manicureproducts such as cuticle softeners and nail strengtheners, andartificial nails.

[0109] (4) Face Care

[0110] Non-limiting face care product forms include: creams,lotions, solutions, oils, liquids, peels, scrubs, emulsions,suspensions, microemulsions, microencapsulated product, pastes,reconstitutable product, aerosols, mousses, gels, waxes, glues,pomades, spritzes, facial wet-wipes, putties, lacquers, serums,perms, powders, blush, highlighters, bronzers, masks, andconcealers.

[0111] (5) Body Care

[0112] Non-limiting body care product forms include: foams, peels,masks, gels, sticks, aerosols, lotions, salts, oils, balls,liquids, powders, peels, pearls, bar soaps, liquid soaps, bodywashes, cleansers, scrubs, creams, flakes, other bath and showerproducts, shaving products, waxing products, and sanitizers.

[0113] (6) Foot Care

[0114] Non-limiting foot care product forms include: mousses,creams, lotions, powders, liquids, sprays, aerosols, gels, flakes,and scrubs.

[0115] Non-limiting oral care product forms include: toothpastes,adhesives, gums, gels, powders, creams, solutions, lotions,liquids, dispersions, suspensions, emulsions, tablets, capsules,rinses, flosses, aerosols, strips, films, pads, bandages,microencapsulated products, syrups, and lozenges.

[0116] Also contemplated are personal care compositions comprisingpolymer(s) described herein complexed with iodine. Thesecompositions may be used in treating skin conditions, non-limitingexamples of which include dermatitis, wounds, bacterial infections,burns, rashes, and herpes. These complexed compositions may bestaining, substantially non-staining, or essentiallynon-staining.

[0117] Examples of related personal care compositions are disclosedin U.S. Pat. Nos. 5,599,800; 5,650,166; 5,916,549; and 6,812,192;U.S. patent application 2009/0317432; EP 556,660; 661,037; 661,038;662,315; 676,194; 796,077; 970,682; 976383; 1,415,654; and2,067,467; and WO 2005/032506; each of which is hereby incorporatedin its entirety by reference.

[0118] It is also contemplated that the personal care compositionsmay be used in products for male and/or female personal groomingand/or toiletry such as: sanitary napkins, baby diapers, adultdiapers, feminine products, products for incontinence, and otherrelated products.

[0119] An array of additional personal care compositions, methods,and uses are contemplated. Disclosure of these compositions may befound in the following brochures by Ashland Specialty Ingredients,each of which is hereby incorporated in its entirety by reference:Plasdone.TM. K-29/32, Advanced non-oxidative, non-abrasive teethwhitening in toothpastes, mouthwashes, and oral rinses (2010),Polymers for oral care, product and applications guide (2002), Acomposition guide for excellent hair styling gels and lotions(4/2003), PVP (polyvinylpyrrolidone) (no date provided), andTextile chemicals, solutions for the most challenging productenvironment (no date provided).

[0120] Also contemplated are additional personal care compositionsthat may comprise the polymers described herein. Disclosures onsuch compositions may be found in the publications listed below,each of which is hereby incorporated in its entirety by reference:(1) Prototype Compositions--Personal Care Products (2009) fromXiameter, Dow Corning. (2) Sun care compositions under the category"Refreshing Sun", "Younger Sun", "Sun for Men", and "Sunny Glow"from Dow Corning. (3) Cosmetic Nanotechnology, Polymers andColloids in Cosmetics, 2007, ACS Symposium Series. (4) ReviewPaper: Lipid nanoparticles (SLN, NLC) in cosmetic andpharmaceutical dermal products, International Journal ofPharmaceutics, Volume 366, 2009.

Optional: Additional Composition Ingredients

[0121] It is also contemplated that the personal care compositionsoptionally may contain one or more additional ingredients.

[0122] Further, it is contemplated that the composition ingredientsmay be formulated in a single container, or the ingredients may beformulated in-part in two or more distinct containers of the sameor different type, the contents of which may require mixing priorto use.

[0123] Furthermore, it also is contemplated that the compositionsmay be prepared in the form of concentrates that may be diluted bya suitable substance(s) prior to use. The concentrate may, in turn,be present in any of the forms as described under `Product Forms`for the personal care compositions of the invention.

[0124] A non-limiting list of classes of additional ingredientsthat may optionally be present in different types of personal carecompositions is provided below: conditioning agents,antimicrobials, protectives (for example, antiradical agents),abrasives, UV absorbers, emulsifiers (including, but not limited toethoxylated fatty acids, ethoxylated glyceryl esters, ethoxylatedoils, ethoxylated sorbitan esters, fatty esters, PEG esters,polyglycerol esters), antiperspirants (including, but not limitedto aluminium chlorohydrates, aluminium zirconium chlorohydrates),antioxidants, vitamins and/or provitamins, botanicals, fixatives,oxidizing agents, reducing agents, dyes, cleansing agents, anionic,cationic, nonionic, and/or amphoteric surfactants, thickenersand/or gelling agents, perfumes, flavors, and/or fragrances,pearlizing agents, stabilizers, pH adjusters, filters,antimicrobial agents, preservatives and/or disinfectants,associative polymers, oils of vegetable, mineral, and/or syntheticorigin, polyols, silicones, colorants, bleaching agents,highlighting agents, propellants (including, but not limited tohydrocarbons, dimethyl ether, fluorocarbons), styling polymers,benefit agents, skin tighteners (including, but not limited toarbutin and kojic acids), tanning agents (including, but notlimited to dihydroxyacetone), solvents and/or cosolvents, diluents,essential oils, sequestrants and/or chelators, carriers, andnatural extracts and/or natural products.

[0125] The amount of each ingredient in the composition variesdepending on the type of composition, the function and/orphysicochemical property of the ingredient, and the amount of otherco-ingredients. The precise amount of each ingredient may be easilydetermined by any person skilled in the related arts.

[0126] It may be desirable to include one or more ingredientsdescribed in the prior art disclosures IPCOM000186541D,IPCOM000128968D, and IPCOM000109682D on www.ip.com, the contents ofeach of these disclosures are hereby incorporated in their entiretyby reference.

[0127] Further reference to formulary co-ingredients and productforms include the disclosures in US 2010/0183532, paragraphs[0096]-[0162], and WO 2010/105050, paragraphs [0053]-[0069], thecontents of which are hereby incorporated in their entirety byreference.

[0128] Non-limiting examples of structurants that may be used inthe hair care compositions according to the invention includedextrin palmitate, trihydroxystearin, hydroxy stearic acid,hydrophilic or hydrophobic silica, hydrophobically modified clayselected from the group consisting of stearalkonium hectorite,quaternium-18 bentonite, quaternium-18 hectorite, disteardimoniumhectorite, derivatives thereof, and mixtures thereof.

[0129] The hair care compositions of the invention may additionallycomprise one or more hair styling agents, hair fixative agents,and/or film formers.

[0130] Particularly useful as styling agents are hair stylingpolymers. The hair styling polymers may be cationic, anionic,amphoteric or nonionic in nature. The polymers may be synthetic ornaturally derived. Non-limiting examples of hair styling polymersinclude the following polymer products available for sale fromAshland Specialty Ingredients: (1) Cationic styling polymers withhair conditioning benefits--Styleze.TM. W Polymer, Styleze.TM.CC-10 (pseudo cationic), Gafquat.TM. 755 NP, and Gafquat.TM. 440;(2) Styling polymers with excellent high humidity curlretention--Styleze.TM. 2000, Allianz.TM. LT 120, Styleze.TM. WPolymer, and Advantage.TM. LCA; (3) Non-ionic styling polymers withbroad ingredient compatibility--Polyvinylpyrrolidones such as PVPK-30, PVP K-60 and PVP K-90, Vinylpyrrolidone/vinyl acetatecopolymers such as PVP/VA (E, I or W) 735, PVP/VA (E or W) 635,PVP/VA (E or I) 535, PVP/VA (E or I) 335 and PVP/VA S-630, andpoly(vinylpyrrolidone/dimethylaminoethylmethacrylate) polymers suchas Copolymer 845/937. Additional details on the aforementionedpolymers and methods of use, or compositions thereof, may be foundin a publication from Ashland Specialty Ingredients titled "AComposition Guide for Excellent Hair Styling Gels and Lotions"(2002) that is hereby incorporated in its entirety byreference.

[0131] A non-limiting example of hair fixative agent that may beused in hair care compositions according to the invention includesa hair fixative polymer available for sale from Ashland SpecialtyIngredients, AquaStyle.TM. 300 (INCI name Polyquaternium-69). Arelated publication from Ashland Specialty Ingredients titled"Aquastyle.RTM. 300, A Fixative Polymer with Enhanced StylingBenefits" (2007) is hereby incorporated in its entirety byreference.

[0132] Non-limiting examples of film formers that may be used inhair care compositions according to the invention include filmforming polymers available for sale from Ashland SpecialtyIngredients such as (1) Aquaflex.TM. FX 64, (2) AquaCat.TM. clearcationic solution, (3) Aqualon.TM. carboxymethylcellulose, (4)Klucel.TM. hydroxypropylcellulose, and (5) Primaflo.TM. HP22polymer solution.

[0133] Further details on hair styling agents, hair fixativeagents, and/or film formers may be found in U.S. Pat. Nos.7,871,600, 7,205,271, 7,122,175, 7,041,281, 6,998,114, 6,749,836,6,689,346, 6,599,999, 6,562,325, 6,413,505, 6,387,351, 6,228,352,5,643,581, 5,922,312, 5,897,870, 5,879,669, 5,709,850, 5,753,216and 5,632,977 each of which is hereby incorporated in its entiretyby reference.

[0134] Non-limiting examples of anti-frizz agents that may be usedin hair care compositions according to the invention includeanti-frizz polymers available for sale from Ashland SpecialtyIngredients such as AquaStyle.TM. 300 and Styleze.TM. XT3.Information on related anti-frizz agents may be found in U.S. Pat.Nos. 7,914,773, 7,785,575, and U.S. published application2010/00093584, the disclosures of each of which is herebyincorporated in its entirety by reference.

[0135] One or more plasticizers or coalescing agents may be addedto modify the film forming characteristics of hair carecompositions according to the invention. Non-limiting examples ofplasticizers include glycols, adipic esters, phthalate esters,isobutyrate esters, terephthalate esters, epoxidized butyl estersor fatty acids, epoxidized vegetable oils, glycerine,di-2-ethylhexyladipate or dioctyladipate (DOA), di-2-ethylhexylphthalate or dioctyl phthalate (DOP), di-2-ethylhexyl terephthalate(DOTP), dicyclohexyl phthalate, diisononyl adipate,diisononylphthalate, n-butyl benzyl phthalate, 1,3-butyleneglycol/adipic acid polyester, dialkyl adipate, dialkyl phthalatederivatives where the alkyl group is a C.sub.1-C.sub.12 alkylgroup, di-n-hexylazelate, diphenylphthalate, tricresol phosphate,benzyl benzoate, dibutyl phosphate, tributyl phosphate,tributoxyethyl phosphate, triphenyl phosphate, butyl acetylricinoleate, glycerol acetyl ricinoleate, dibutyl phthalate,diethyl phthalate, dioctyl phthalate, dimethoxyethyl phthalate,diisobutyl phthalate, diamyl phthalate, dibutyl glycolate, butylstearate, triethyl citrate, tributyl citrate, tributyl acetylcitrate, 2-hexyltriethylacetyl citrate, dibutyl tartarate, camphor,epoxidized butyl esters of linseed oil fatty acids, epoxidizedlinseed oil, epoxidized soya oil, propylene glycol adipate,2,2,4-trimethyl-1,3-pentanediol diisobutyrate (TXIB), methylabietate, cumyl acetate, dibutoxyethyl adipate, di-n-hexylazalate,glyceryl-tri-benzerate, tri-n-butylcitrate, dioctyl fumarate,triisonyl trimellitate, dioctyl isophthalate, butyl oleate,chlorinated paraffin, tricresolphosphate, dibutyl sebacate,dimethicone copolyol (Dow Corning 190), PEG-6 capric/caprylicglyceride (SOFTIGEN 767), DIACETIN, LAURAMIDE DEA (MONAMID 716),phenyl trimethicone (ABIL AV 20-1000), propylene glycol,dipropylene glycol, as well as polymeric plasticizers, and mixturesthereof. Non-limiting examples of coalescing solvents includeacetone, methyl acetate, and di- or tri-propylene glycol methylethers, and mixtures thereof. Further examples of plasticizers maybe found in U.S. Pat. Nos. 5,753,216 and 5,676,935, the disclosuresof each of which are hereby incorporated in its entirety byreference.

[0136] Non-limiting examples of propellants that may be used inhair care compositions of the invention includetrichlorofluoromethane, chlorodifluoromethane, 1,1-difluoroethane,dichlorotetrafluoroethane, monochlorodifluoromethane,trichlorotrifluoroethane, dimethyl ether, C.sub.1-C.sub.4hydrocarbons such as methane, ethane, propane, n-butane, andisobutane, water-soluble gases such as, dimethyl ether, carbondioxide, and/or nitrous oxide, and insoluble, compressed gases suchas nitrogen, helium, and fully-fluorinated oxetanes and oxepanes,and mixtures thereof.

[0137] Non-limiting examples of penetrants that may be used in haircare compositions of the invention include lanolin compounds,protein hydrolysates, protein derivatives, and mixturesthereof.

[0138] Non-limiting examples of anti-foaming agents that may beused in hair care compositions of the invention include carrieroils, silicone oils, silicone foam inhibitors, hydrophobic silica,hydrophobic fat derivatives, waxes, water-insoluble polymers,amphiphilic components, emulsifiers, coupling agents, and mixturesthereof.

[0139] Any known conditioning agent may be used in the personalcare compositions of the invention. An extensive discussion onconditioning agents may be found in the book Conditioning Agentsfor Skin and Hair, Cosmetic Science and Technology Series, Volume21, 1999, Marcel Dekker Publishers. The contents of the book arehereby incorporated in its entirety by reference.

[0140] Conditioning agents may be chosen from synthetic oils,mineral oils, vegetable oils, fluorinated or perfluorinated oils,natural or synthetic waxes, silicones, cationic polymers, proteinsand hydrolyzed proteins, cationic surfactants, ceramide typecompounds, fatty amines, fatty acids and their derivatives, as wellas mixtures of these different types of compounds.

[0141] Non-limiting examples of suitable synthetic oils include:polyolefins, e.g., poly-.alpha.-olefins, such as polybutenes,polyisobutenes, polydecenes, and blends thereof. The polyolefinsmay be hydrogenated.

[0142] Non-limiting examples of suitable mineral oils includehexadecane and oil of paraffin.

[0143] Non-limiting examples of suitable animal and vegetable oilsinclude: sunflower oil, corn oil, soy oil, avocado oil, jojoba oil,squash oil, raisin seed oil, sesame seed oil, walnut oil, fish oil,glycerol tricaprocaprylate, purcellin oil, liquid jojoba, andblends thereof. Also suitable are natural oils such as oils ofeucalyptus, lavender, vetiver, litsea cubeba, lemon, sandalwood,rosemary, chamomile, savory, nutmeg, cinnamon, hyssop, caraway,orange, geranium, cade, bergamot, and blends thereof.

[0144] The conditioning agent may be a fluorinated or aperfluorinated oil. The fluoridated oils may also be fluorocarbonssuch as fluoramines, e.g., perfluorotributylamine, fluoridatedhydrocarbons such as perfluorodecahydronaphthalene, fluoroesters,fluoroethers, and blends thereof.

[0145] Non-limiting examples of suitable natural and syntheticwaxes include: carnauba wax, candelila wax, alfa wax, paraffin wax,ozokerite wax, vegetable waxes such as olive wax, rice wax,hydrogenated jojoba wax, absolute flower waxes such as blackcurrant flower wax, animal waxes such as bees wax, modified beeswax (cerabellina), marine waxes and polyolefin waxes such aspolyethylene wax, and blends thereof.

[0146] The conditioning agent may be any silicone known by thoseskilled in the art. Silicones include polyorganosiloxanes that areinsoluble in the composition. The silicones may be present in theform of oils, waxes, resins, or gums. They may be volatile ornon-volatile.

[0147] Non-limiting examples of suitable silicones include:polyalkyl siloxanes, polyaryl siloxanes, polyalkyl aryl siloxanes,silicone gums and resins, polyorgano siloxanes modified byorganofunctional groups, and blends thereof.

[0148] Suitable polyalkyl siloxanes include polydimethyl siloxaneswith terminal trimethyl silyl groups or terminal dimethyl silanolgroups (dimethiconol) and polyalkyl (C1-C20) siloxanes. Suitablepolyalkyl aryl siloxanes include polydimethyl methyl phenylsiloxanes and polydimethyl diphenyl siloxanes. The siloxanes canhave a linear or branched structure.

[0149] Suitable silicone gums include polydiorganosiloxanes, suchas those having a number-average molecular weight between 200,000Da and 1,000,000 Da used alone or mixed with a solvent.

[0150] Non-limiting examples of suitable silicone gums include:polymethyl siloxane, polydimethyl siloxane/methyl vinyl siloxanegums, polydimethyl siloxane/diphenyl siloxane, polydimethylsiloxane/phenyl methyl siloxane, polydimethyl siloxane/diphenylsiloxane/methyl vinyl siloxane, and blends thereof.

[0151] Non-limiting examples of suitable silicone resins includesilicones with a dimethyl/trimethyl siloxane structure and resinsof the trimethyl siloxysilicate type.

[0152] The organo-modified silicones suitable for use in theinvention include silicones such as those previously defined andcontaining one or more organofunctional groups attached by means ofa hydrocarbon radical, and grafted silicone polymers. Theorgano-modified silicones may be one from the amino functionalsilicone family.

[0153] The silicones may be used in the form of emulsions,nano-emulsions, or microemulsions.

[0154] The cationic polymers that may be used as conditioningagents according to the invention generally have a molecular weight(average number) from about 500 Da to about 5,000,000 Da, andparticularly from about 1,000 Da to about 3,000,000 Da. Theexpression "cationic polymer" as used herein indicates any polymerhaving at least one cationic group.

[0155] The cationic polymers may be chosen from among polymerscontaining primary, secondary, tertiary amine, and/or quaternaryammonium groups that may form part of the main polymer backboneand/or side chain(s).

[0156] Non-limiting examples of suitable cationic polymers includepolyamines, polyaminoamides, and quaternary polyammonium classes ofpolymers, such as:

[0157] (1) homopolymers and copolymers derived from acrylic ormethacrylic esters or amides. The copolymers may contain one ormore units derived from acrylamides, methacrylamides, diacetoneacrylamides, acrylic or methacrylic acids or their esters,vinyllactams such as vinyl pyrrolidone or vinyl caprolactam, andvinyl esters. Non-limiting, specific examples include: copolymersof acrylamide and dimethyl amino ethyl methacrylate quaternizedwith dimethyl sulfate or with an alkyl halide; copolymers ofacrylamide and methacryloyl oxyethyl trimethyl ammonium chloride;the copolymer of acrylamide and methacryloyl oxyethyl trimethylammonium methosulfate; copolymers of vinyl pyrrolidone anddialkylaminoalkyl acrylate or methacrylate, optionally quaternized,such as the products sold under the name Gafquat.TM. by AshlandSpecialty Ingredients; terpolymers of dimethyl amino ethylmethacrylate, vinyl caprolactam, and vinyl pyrrolidone such as theproduct sold under the name Gaffix.TM. VC 713 by Ashland SpecialtyIngredients; the vinyl pyrrolidone/methacrylamidopropyldimethylamine copolymer, marketed under the name Styleze.TM. CC 10by Ashland Specialty Ingredients; and the vinylpyrrolidone/quaternized dimethyl amino propyl methacrylamidecopolymers such as the product sold under the name Gafquat.TM. HS100 by Ashland Specialty Ingredients (Wayne, N.J.).

[0158] (2) derivatives of cellulose ethers containing quaternaryammonium groups, such as hydroxy ethyl cellulose quaternaryammonium that has reacted with an epoxide substituted by atrimethyl ammonium group.

[0159] (3) derivatives of cationic cellulose such as cellulosecopolymers or derivatives of cellulose grafted with a hydrosolublequaternary ammonium monomer, as described in U.S. Pat. No.4,131,576, such as hydroxy alkyl cellulose, and hydroxymethyl-,hydroxyethyl- or hydroxypropyl-cellulose grafted with a salt ofmethacryloyl ethyl trimethyl ammonium, methacrylamidopropyltrimethyl ammonium, or dimethyl diallyl ammonium.

[0160] (4) cationic polysaccharides such as described in U.S. Pat.Nos. 3,589,578 and 4,031,307, guar gums containing cationictrialkyl ammonium groups, and guar gums modified by a salt, e.g.,chloride of 2,3-epoxy propyl trimethyl ammonium.

[0161] (5) polymers composed of piperazinyl units and alkylene orhydroxy alkylene divalent radicals with straight or branchedchains, possibly interrupted by atoms of oxygen, sulfur, nitrogen,or by aromatic or heterocyclic cycles, as well as the products ofthe oxidation and/or quaternization of such polymers.

[0162] (6) water-soluble polyamino amides prepared bypolycondensation of an acid compound with a polyamine. Thesepolyamino amides may be reticulated.

[0163] (7) derivatives of polyamino amides resulting from thecondensation of polyalkylene polyamines with polycarboxylic acidsfollowed by alkylation by bi-functional agents.

[0164] (8) polymers obtained by reaction of a polyalkylenepolyamine containing two primary amine groups and at least onesecondary amine group with a dioxycarboxylic acid chosen from amongdiglycolic acid and saturated dicarboxylic aliphatic acids having 3to 8 atoms of carbon. Such polymers include those described in U.S.Pat. Nos. 3,227,615 and 2,961,347.

[0165] (9) cyclopolymers of alkyl diallyl amine or dialkyl diallylammonium such as the homopolymer of dimethyl diallyl ammoniumchloride and copolymers of diallyl dimethyl ammonium chloride andacrylamide.

[0166] (10) quaternary diammonium polymers such as hexadimethrinechloride.

[0167] (11) quaternary polyammonium polymers, including, forexample, Mirapol.RTM. A 15, Mirapol.RTM. AD1, Mirapol.RTM. AZ1, andMirapol.RTM. 175 products sold by Miranol.

[0168] (12) quaternary polymers of vinyl pyrrolidone and vinylimidazole such as the products sold under the names Luviquat.RTM.FC 905, FC 550, and FC 370 by BASF Corporation.

[0169] (13) quaternary polyamines.

[0170] (14) reticulated polymers known in the art.

[0171] Other cationic polymers that may be used include cationicproteins or hydrolyzed cationic proteins, polyalkyleneimines suchas polyethyleneimines, polymers containing vinyl pyridine or vinylpyridinium units, condensates of polyamines and epichlorhydrins,quaternary polyurethanes, and derivatives of chitin.

[0172] The conditioning agent may comprise a protein or hydrolyzedcationic or non-cationic protein. Non-limiting examples of suitablecompounds include: hydrolyzed collagens having triethyl ammoniumgroups, hydrolyzed collagens having trimethyl ammonium andtrimethyl stearyl ammonium chloride groups, hydrolyzed animalproteins having trimethyl benzyl ammonium groups (benzyltrimoniumhydrolyzed animal protein), hydrolyzed proteins having groups ofquaternary ammonium on the polypeptide chain, including at leastone C1-C18 alkyl, and blends thereof.

[0173] Non-limiting examples of suitable hydrolyzed cationicproteins include: Croquat.RTM. L, in which the quaternary ammoniumgroups include a C12 alkyl group, Croquat.RTM. M, in which thequaternary ammonium groups include C10-C18 alkyl groups,Croquat.RTM. S in which the quaternary ammonium groups include aC18 alkyl group, Crotein.RTM. Q in which the quaternary ammoniumgroups include at least one C1-C18 alkyl group, and blends thereof.These products are sold by Croda.

[0174] The conditioning agent may also comprise quaternizedvegetable protein(s) such as wheat, corn, or soy proteins,non-limiting examples of which include: cocodimonium hydrolyzedwheat protein, laurdimonium hydrolyzed wheat protein, steardimoniumhydrolyzed wheat protein, 2-N-stearoyl amino-octadecane-1,3-diol,2-N-behenoyl amino-octadecane-1,3-diol,2-N-[2-hydroxy-palmitoyl]-amino-octadecane-1,3-diol, 2-N-stearoylamino-octadecane-1,3,4-triol, n-stearoyl phytosphingosine,2-N-palmitoyl amino-hexadecane-1,3-diol, bis-(N-hydroxy ethyln-cetyl) malonamide, n-(2-hydroxy ethyl)-N-(3-cetoxyl-2-hydroxypropyl) amide of cetylic acid, n-docosanoyl n-methyl-D-glucamine,and blends thereof.

[0175] The conditioning agent may also comprise a cationicsurfactant such as a salt of a primary, secondary, or tertiaryfatty amine, optionally polyoxyalkylenated, a quaternary ammoniumsalt, a derivative of imidazoline, or an amine oxide. Conditioningagents may also be selected from the group consisting of: mono-,di-, and tri-alkyl amines, and quaternary ammonium compounds with acounterion such as a chloride, a methosulfate, a tosylate, etc.Non-limiting examples of suitable amines include: cetrimoniumchloride, dicetyldimonium chloride, behentrimonium methosulfate,and blends thereof.

[0176] The conditioning agent may comprise a fatty amine.Non-limiting examples of suitable fatty amines include: dodecylamines, cetyl amines, stearyl amines such as stearamidopropyldimethylamine, and blends thereof.

[0177] The conditioning agent may comprise a fatty acid orderivative(s) thereof. Non-limiting examples of suitable fattyacids include: myristic acid, palmitic acid, stearic acid, behenicacid, oleic acid, linoleic acid, isostearic acid, and blendsthereof. The derivatives of fatty acids include carboxylic esteracids including mono-, di-, tri- and tetra-carboxylic acids esters,amides, anhydrides, esteramides, imides, and mixtures of thesefunctional groups.

[0178] Also suitable as conditioning agents are the followingcommercial products:

[0179] (1) Aquacat.TM. Clear Cationic Solution (INCI Name: guarhydroxypropyltrimonium Chloride), n-Hance.TM. SP-100 (INCI Name:acrylamidopropyl trimonium chloride/acrylamide copolymer), andn-Hance.TM. cationic guar (INCI Name: guar hydroxypropyltrimoniumchloride) from Ashland Specialty Ingredients

[0180] (2) Salcare.RTM. from BASF Corp.

[0181] (3) Softcat.TM. Polymers from The Dow Chemical Company.

[0182] (4) Jaguar.RTM. C500, Polycare.RTM. Boost,Mackconditioner.TM. Brite, and Mackine.RTM. 301 from Rhodia.

[0183] (5) Stepanquat.RTM. ML, Stepanquat.RTM. GA-90, Ninol.RTM.,and Ammonyx.RTM. from Stepan Company.

[0184] (6) Conditioneze.TM. 7 and Conditioneze.TM. NT-20 fromAshland Specialty Ingredients (Wayne, N.J.).

[0185] Of course, mixtures of two or more conditioning agents maybe used.

[0186] The conditioning agent(s) may be present in an amount fromabout 0.001% to about 20%, particularly from about 0.01% to about10%, and even more particularly from about 0.1% to about 3% byweight of the composition.

[0187] Personal care compositions may optionally compriseantimicrobial agent(s).

[0188] Non-limiting examples of suitable water insoluble,non-cationic antimicrobial agents include: halogenated diphenylethers, phenolic compounds including phenol and its homologs, monoand poly-alkyl and aromatic halophenols, resorcinol and itsderivatives, bisphenolic compounds and halogenated salicylanilides,benzoic esters, halogenated carbanilides, and blends thereof.

[0189] Non-limiting examples of suitable water solubleantimicrobial agents include: quaternary ammonium salts,bis-biquanide salts, triclosan monophosphate, and blendsthereof.

[0190] The quaternary ammonium agents include those in which one ortwo of the substituents on the quaternary nitrogen has a carbonchain length (typically alkyl group) from about 8 to about 20,typically from about 10 to about 18 carbon atoms, while theremaining substituents (typically alkyl or benzyl group) have alower number of carbon atoms, such as from about 1 to about 7carbon atoms, typically methyl or ethyl groups.

[0191] Non-limiting examples of suitable quaternary ammoniumantibacterial agents include: Dodecyl trimethyl ammonium bromide,tetradecylpyridinium chloride, domiphen bromide,n-tetradecyl-4-ethyl pyridinium chloride, dodecyldimethyl(2-phenoxyethyl)ammonium bromide, benzyl dimethylstearylammonium chloride, cetyl pyridinium chloride, quaternized5-amino-1,3-bis(2-ethyl-hexyl)-5-methyl hexahydropyrimidine,benzalkonium chloride, benzethonium chloride, methyl benzethoniumchloride, and blends thereof.

[0192] Other antimicrobial compounds arebis[4-(R-amino)-1-pyridinium]alkanes as disclosed in U.S. Pat. No.4,206,215. Other antimicrobials such as copper salts, zinc saltsand/or stannous salts may also be included. Also useful areenzymes, including endoglycosidase, papain, dextranase, mutanase,and blends thereof. Such antimicrobial agents are disclosed in U.S.Pat. Nos. 2,946,725 and 4,051,234. The antimicrobial agents mayalso comprise chlorhexidine, triclosan, and flavor oils such asthymol. Triclosan and other agents are disclosed in U.S. Pat. Nos.5,015,466 and 4,894,220.

[0193] In particular aspects, one or more preservatives may beincluded.

[0194] Non-limiting examples of suitable preservatives include:benzoic acid, sorbic acid, dehydroacetic acid, diazolidinyl ureas,imidazolidinyl ureas, salicylic acid, piroctone olamine, DMDMhydantoin, IPBC (iodopropynyl butylcarbamate), triclosan, bronopol,formaldehyde, isothiazolinones, nitrates/nitrites, parabens,phenoxyethanol, potassium sorbate, sodium benzoate, sulphites,sulphur dioxide, and blends thereof.

[0195] In particular aspects, preservative boosters/solvents may beincorporated, non-limiting examples of which include: caprylylglycol, hexylene glycol, pentylene glycol, ethylhexylglycerin,caprylhydroxamic acid, caprylohydroxamic acid, glyceryl caprylate,and blends thereof.

[0196] Polysaccharides, such as gum Arabic, may be included aswell.

[0197] Personal care compositions may comprise liquid orliquid-like carrier(s) that help to distribute, disperse, and/ordissolve the ingredients.

[0198] Non-limiting examples of suitable liquid carriers include:water, alcohols, oils, esters, and blends thereof.

[0199] The compositions of the invention may also be in the form ofaqueous or hydro-alcoholic solutions.

[0200] The physiological and cosmetically acceptable medium mayconsist exclusively of water, a cosmetically acceptable solvent, ora blend of water and a cosmetically acceptable solvent, such as alower alcohol composed of C1 to C4, such as ethanol, isopropanol,t-butanol, n-butanol, alkylene glycols such as propylene glycol,and glycol ethers.

[0201] Personal care compositions may comprise vitamin(s),provitamin(s), and/or mineral(s).

[0202] Non-limiting examples of suitable vitamins include: ascorbicacid (vitamin C), vitamin E, vitamin E acetate, vitamin Ephosphate, B vitamins such as B3 and B5, niacin, vitamin A,derivatives thereof, and blends thereof.

[0203] Non-limiting examples of suitable provitamins include:panthenol, retinol, and blends thereof.

[0204] Non-limiting examples of suitable minerals include: talc,clay, calcium carbonate, silica, kaolin, mica, and blends thereof.Further examples of minerals that may be used in the personal carecompositions may be found in a brochure titled Minerals forpersonal care from Imerys Performance Minerals, the disclosure ofwhich is hereby incorporated in its entirety by reference.

[0205] Personal care compositions may comprise one or moresurfactants. Surfactants serve in solubilizing, dispersing,emulsifying and/or reducing the interfacial tension. Surfactantsmay be chosen from anionic, nonionic, amphoteric, zwitterionic, orcationic surfactants, or blends thereof.

[0206] Anionic surfactants useful herein include the water-solublesalts of alkyl sulfates having from 8 to 20 carbon atoms in thealkyl radical (e.g., sodium alkyl sulfate) and the water-solublesalts of sulfonated monoglycerides of fatty acids having from 8 to20 carbon atoms. Sodium lauryl sulfate (SLS) and sodium coconutmonoglyceride sulfonates are non-limiting examples of anionicsurfactants of this type.

[0207] Non-limiting examples of suitable anionic surfactantsinclude: sarcosinates, taurates, isethionates, sodium laurylsulfoacetate, sodium laureth carboxylate, and sodium dodecylbenzenesulfonate. Also suitable are alkali metal or ammonium saltsof surfactants such as the sodium and potassium salts of thefollowing: lauroyl sarcosinate, myristoyl sarcosinate, palmitoylsarcosinate, stearoyl sarcosinate, and oleoyl sarcosinate.

[0208] Non-limiting examples of suitable cationic surfactantsinclude: derivatives of aliphatic quaternary ammonium compoundshaving at least one long alkyl chain containing from about 8 toabout 18 carbon atoms, such as, lauryl trimethylammonium chloride,cetyl pyridinium chloride, cetyl trimethylammonium bromide,di-isobutylphenoxyethyl-dimethylbenzylammonium chloride, coconutalkyltrimethylammonium nitrite, cetyl pyridinium fluoride, andblends thereof. Further suitable are quaternary ammonium fluorideshaving detergent properties such as compounds described in U.S.Pat. No. 3,535,421. Certain cationic surfactants may act asgermicides in the compositions disclosed herein.

[0209] Nonionic surfactants useful herein include compoundsproduced by the condensation of alkylene oxide groups (hydrophilicin nature) with an organic hydrophobic compound which may bealiphatic or alkylaromatic in nature.

[0210] Non-limiting examples of suitable nonionic surfactantsinclude: poloxamers (sold under the trade name Pluronic.RTM. byBASF Corporation), polyethylene oxide condensates of alkyl phenols,products derived from the condensation of ethylene oxide with thereaction product of propylene oxide and ethylene diamine, ethyleneoxide condensates of aliphatic alcohols, long chain tertiary amineoxides, long chain tertiary phosphine oxides, long chain dialkylsulfoxides, and blends thereof.

[0211] Non-limiting examples of suitable zwitterionic surfactantsinclude betaines and derivatives of aliphatic quaternary ammoniumcompounds in which the aliphatic radicals can be straight chain orbranched, and which contain an anionic water-solubilizing group,e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate.

[0212] Non-limiting examples of suitable betaines include: decylbetaine or 2-(N-decyl-N,N-dimethylammonio)acetate, coco betaine or2-(N-coc-N,N-dimethyl ammonio)acetate, myristyl betaine, palmitylbetaine, lauryl betaine, cetyl betaine, stearyl betaine, and blendsthereof. The amidobetaines are exemplified by cocoamidoethylbetaine, cocoamidopropyl betaine, lauramidopropyl betaine, and thelike. The betaines of choice include cocoamidopropyl betaines suchas lauramidopropyl betaine. Suitable betaine surfactants aredisclosed in U.S. Pat. No. 5,180,577.

[0213] Other surfactants such as fluorinated surfactants may alsobe incorporated within the compositions of the invention.

[0214] Also suitable as surfactants are the following commercialproducts:

[0215] (1) Alkanolamides, under the trade names Amidex.TM. andSchercomid.TM.; amido-amines, under the trade names Katemul.TM. andSchercodine.TM.; amine oxides, under the trade names Chemoxide.TM.and Schercamox.TM.; amphoterics, under the trade namesChembetaine.TM., Schercotaine.TM. and Schercoteric.TM.;imidazolines, under the trade name Schercozoline.TM.; pearlizingagents, under the trade name Quickpearl.TM.; performanceconcentrates, under the trade names Sulfochem.TM. and Chemoryl.TM.;soaps (potassium cocoate and potassium soyate); specialtyethoxylates, under the trade name Chemonic.TM.; specialty quatsunder the trade names Quatrex.TM. and Schercoquat.TM.; sulfates,under the trade name Sulfochem.TM.; and sulfosuccinates, under thetrade name Chemccinate.TM. from Lubrizol.

[0216] (2) Avaniel, Cremaphore.RTM., Jordapan.RTM., andPluracare.RTM. from BASF Corp.

[0217] (3) Miracare.RTM. SLB, Mackam.RTM. Bab, Mackanate.RTM. UltraSI, Miranol.RTM. Ultra, and Miracare.RTM. Plaisant from Rhodia.

[0218] (4) Stepan.RTM. Pearl 2, Stepan.RTM. Pearl 4, Stepan.RTM.Pearl Series, Neobee.RTM. M-20, Stepan.RTM. PTC, Amphosol.RTM.2CSF, Steol.RTM., Stepan-Mild.RTM. GCC, Stepan.RTM. SLL-FB,Stepanol.RTM. AM, Stepanol.RTM. PB, Alpha-Step.RTM. BSS-45,Bio-Terge.RTM. 804, Stepan-Mild.RTM. L3, Stepan.RTM. SLL-FB,Stepan.RTM. SSL-CG, and Stepanol.RTM. CFAS-70 from StepanCompany.

[0219] Also suitable as surfactants are those described in the bookSurfactants in Personal Care Products and Decorative Cosmetics,Third Edition, 2006, CRC Press. The disclosure is incorporatedhereby in its entirety by reference.

[0220] Personal care compositions may be also be formulated asdetergent compositions, such as shampoos, bath gels, and bubblebaths. Such compositions comprise water as a liquid carrier. Thesurfactant or surfactants that form the washing base may be chosenalone or in blends, from known anionic, amphoteric, zwitterionicand/or non-ionic surfactants. The quantity and quality of thewashing base must be sufficient to impart a satisfactory foamingand/or detergent value to the final composition. The washing basemay be present in an amount from about 4% to about 50% by weight,particularly from about 6% to about 35% by weight, and moreparticularly from about 8% to about 25% by weight of the finalcomposition.

[0221] Personal care compositions may comprise one or morethickener(s) and/or viscosifier(s).

[0222] Non-limiting examples of suitable thickeners and/orviscosifiers include: Acetamide MEA; acrylamide/ethalkoniumchloride acrylate copolymer; acrylamide/ethyltrimonium chlorideacrylate/ethalkonium chloride acrylate copolymer; acrylamidescopolymer; acrylamide/sodium acrylate copolymer; acrylamide/sodiumacryloyldimethyltaurate copolymer; acrylates/acetoacetoxyethylmethacrylate copolymer; acrylates/beheneth-25 methacrylatecopolymer; acrylates/C10-C30 alkyl acrylate crosspolymer;acrylates/ceteth-20 itaconate copolymer; acrylates/ceteth-20methacrylate copolymer; acrylates/laureth-25 methacrylatecopolymer; acrylates/palmeth-25 acrylate copolymer;acrylates/palmeth-25 itaconate copolymer; acrylates/steareth-50acrylate copolymer; acrylates/steareth-20 itaconate copolymer;acrylates/steareth-20 methacrylate copolymer; acrylates/stearylmethacrylate copolymer; acrylates/vinyl isodecanoate crosspolymer;acrylic acid/acrylonitrogens copolymer; adipic acid/methyl DEAcrosspolymer; agar; agarose; alcaligenes polysaccharides; algin;alginic acid; almondamide DEA; almondamidopropyl betaine;aluminum/magnesium hydroxide stearate; ammoniumacrylates/acrylonitrogens copolymer; ammonium acrylates copolymer;ammonium acryloyldimethyltaurate/vinyl formamide copolymer;ammonium acryloyldimethyltaurate/VP copolymer; ammonium alginate;ammonium chloride; ammonium polyacryloyldimethyl taurate; ammoniumsulfate; amylopectin; apricotamide DEA; apricotamidopropyl betaine;arachidyl alcohol; arachidyl glycol; arachis hypogaea (peanut)flour; ascorbyl methylsilanol pectinate; astragalus gummifer gum;attapulgite; avena sativa (oat) kernel flour; avocadamide DEA;avocadamidopropyl betaine; azelamide MEA; babassuamide DEA;babassuamide MEA; babassuamidopropyl betaine; behenamide DEA;behenamide MEA; behenamidopropyl betaine; behenyl betaine;bentonite; butoxy chitosan; caesalpinia spinosa gum; calciumalginate; calcium carboxymethyl cellulose; calcium carrageenan;calcium chloride; calcium potassium carbomer; calcium starchoctenylsuccinate; C20-40 alkyl stearate; canolamidopropyl betaine;capramide DEA; capryl/capramidopropyl betaine; carbomer;carboxybutyl chitosan; carboxymethyl cellulose acetate butyrate;carboxymethyl chitin; carboxymethyl chitosan; carboxymethyldextran; carboxymethyl hydroxyethylcellulose; carboxymethylhydroxypropyl guar; carnitine; cellulose acetate propionatecarboxylate; cellulose gum; ceratonia siliqua gum; cetearylalcohol; cetyl alcohol; cetyl babassuate; cetyl betaine; cetylglycol; cetyl hydroxyethylcellulose; chimyl alcohol;cholesterol/HDI/pullulan copolymer; cholesteryl hexyl dicarbamatepullulan; citrus aurantium dulcis (orange) peel extract; cocamideDEA; cocamide MEA; cocamide MIPA; cocamidoethyl betaine;cocamidopropyl betaine; cocamidopropyl hydroxysultaine;coco-betaine; coco-hydroxysultaine; coconut alcohol;coco/oleamidopropyl betaine; coco-Sultaine; cocoyl sarcosinamideDEA; cornamide/cocamide DEA; cornamide DEA; croscarmellose;crosslinked bacillus/glucose/sodium glutamate ferment; cyamopsistetragonoloba (guar) gum; decyl alcohol; decyl betaine;dehydroxanthan gum; dextrin; dibenzylidene sorbitol;diethanolaminooleamide DEA; diglycol/CHDM/isophthalates/SIPcopolymer; dihydroabietyl behenate; dihydrogenated tallowbenzylmonium hectorite; dihydroxyaluminum aminoacetate;dimethicone/PEG-10 crosspolymer; dimethicone/PEG-15 crosspolymer;dimethicone propyl PG-betaine; dimethylacrylamide/acrylicacid/polystyrene ethyl methacrylate copolymer;dimethylacrylamide/sodium acryloyldimethyltaurate crosspolymer;disteareth-100 IPDI; DMAPA acrylates/acrylic acid/acrylonitrogenscopolymer; erucamidopropyl hydroxysultaine; ethylene/sodiumacrylate copolymer; gelatin; gellan gum; glyceryl alginate; glycinesoja (soybean) flour; guar hydroxypropyltrimonium chloride;hectorite; hyaluronic acid; hydrated silica; hydrogenated potatostarch; hydrogenated tallow; hydrogenated tallowamide DEA;hydrogenated tallow betaine; hydroxybutyl methylcellulose;hydroxyethyl acrylate/sodium acryloyldimethyl taurate copolymer;hydroxyethylcellulose; hydroxyethyl chitosan; hydroxyethylethylcellulose; hydroxyethyl stearamide-MIPA;hydroxylauryl/hydroxymyristyl betaine; hydroxypropylcellulose;hydroxypropyl chitosan; hydroxypropyl ethylenediamine carbomer;hydroxypropyl guar; hydroxypropyl methylcellulose; hydroxypropylmethylcellulose stearoxy ether; hydroxypropyl starch; hydroxypropylstarch phosphate; hydroxypropyl xanthan gum; hydroxystearamide MEA;isobutylene/sodium maleate copolymer; isostearamide DEA;isostearamide MEA; isostearamide mIPA; isostearamidopropyl betaine;lactamide MEA; lanolinamide DEA; lauramide DEA; lauramide MEA;lauramide MIPA; lauramide/myristamide DEA; lauramidopropyl betaine;lauramidopropyl hydroxysultaine; laurimino bispropanediol; laurylalcohol; lauryl betaine; lauryl hydroxysultaine; lauryl/myristylglycol hydroxypropyl ether; lauryl sultaine; lecithinamide DEA;linoleamide DEA; linoleamide MEA; linoleamide MIPA; lithiummagnesium silicate; lithium magnesium sodium silicate; macrocystispyrifera (kelp); magnesium alginate;magnesium/aluminum/hydroxide/carbonate; magnesium aluminumsilicate; magnesium silicate; magnesium trisilicate; methoxyPEG-22/dodecyl glycol copolymer; methylcellulose; methylethylcellulose; methyl hydroxyethylcellulose; microcrystallinecellulose; milkamidopropyl betaine; minkamide DEA; minkamidopropylbetaine; MIPA-myristate; montmorillonite; Moroccan lava clay;myristamide DEA; myristamide MEA; myristamide MIPA;myristamidopropyl betaine; myristamidopropyl hydroxysultaine;myristyl alcohol; myristyl betaine; natto gum; nonoxynylhydroxyethylcellulose; oatamide MEA; oatamidopropyl betaine;octacosanyl glycol isostearate; octadecene/MA copolymer; oleamideDEA; oleamide MEA; oleamide MIPA; oleamidopropyl betaine;oleamidopropyl hydroxysultaine; oleyl betaine; olivamide DEA;olivamidopropyl betaine; oliveamide MEA; palmamide DEA; palmamideMEA; palmamide MIPA; palmamidopropyl betaine; palmitamide DEA;palmitamide MEA; palmitamidopropyl betaine; palm kernel alcohol;palm kernelamide DEA; palm kernelamide MEA; palm kernelamide MIPA;palm kernelamidopropyl betaine; peanutamide MEA; peanutamide MIPA;pectin; PEG-800; PEG-crosspolymer; PEG-150/decyl alcohol/SMDIcopolymer; PEG-175 diisostearate; PEG-190 distearate; PEG-15glyceryl tristearate; PEG-140 glyceryl tristearate; PEG-240/HDIcopolymer bis-decyltetradeceth-20 ether; PEG-100/IPDI copolymer;PEG-180/laureth-50/.TM.MG copolymer; PEG-10/lauryl dimethiconecrosspolymer; PEG-15/lauryl dimethicone crosspolymer; PEG-2M;PEG-5M; PEG-7M; PEG-9M; PEG-14M; PEG-20M; PEG-23M; PEG-25M;PEG-45M; PEG-65M; PEG-90M; PEG-115M; PEG-160M; PEG-180M; PEG-120methyl glucose trioleate; PEG-180/octoxynol-40/.TM.MG copolymer;PEG-150 pentaerythrityl tetrastearate; PEG-4 rapeseed amide;PEG-150/stearyl alcohol/SMDI copolymer; phaseolus angularis seedpowder; polianthes tuberosa extract; polyacrylate-3; polyacrylicacid; polycyclopentadiene; polyether-1; polyethylene/isopropylmaleate/MA copolyol; polyglyceryl-3 disiloxane dimethicone;polyglyceryl-3 polydimethylsiloxyethyl dimethicone; polymethacrylicacid; polyquarternium-52; polyvinyl alcohol; potassium alginate;potassium aluminum polyacrylate; potassium carbomer; potassiumcarrageenan; potassium chloride; potassium palmate; potassiumpolyacrylate; potassium sulfate; potato starch modified; PPG-2cocamide; PPG-1 hydroxyethyl caprylamine; PPG-2 hydroxyethylcocamide; PPG-2 hydroxyethyl coco/isostearamide; PPG-3 hydroxyethylsoyamide; PPG-14 laureth-60 hexyl dicarbamate; PPG-14 laureth-60isophoryl dicarbamate; PPG-14 palmeth-60 hexyl dicarbamate;propylene glycol alginate; PVP/decene copolymer; PVPmontmorillonite; pyrus cydonia seed; pyrus malus (apple) fiber;rhizobian gum; ricebranamide DEA; ricinoleamide DEA; ricinoleamideMEA; ricinoleamide MIPA; ricinoleamidopropyl betaine; ricinoleicacid/adipic acid/AEEA copolymer; rosa multiflora flower wax;sclerotium gum; sesamide DEA; sesamidopropyl betaine; sodiumacrylate/acryloyldimethyl taurate copolymer; sodiumacrylates/acrolein copolymer; sodium acrylates/acrylonitrogenscopolymer; sodium acrylates copolymer; sodium acrylatescrosspolymer; sodium acrylate/sodium acrylamidomethylpropanesulfonate copolymer; sodium acrylates/vinyl isodecanoatecrosspolymer; sodium acrylate/vinyl alcohol copolymer; sodiumcarbomer; sodium carboxymethyl chitin; sodium carboxymethyldextran; sodium carboxymethyl beta-glucan; sodium carboxymethylstarch; sodium carrageenan; sodium cellulose sulfate; sodiumchloride; sodium cyclodextrin sulfate; sodium hydroxypropyl starchphosphate; sodium isooctylene/MA copolymer; sodium magnesiumfluorosilicate; sodium oleate; sodium palmitate; sodium palmkernelate; sodium polyacrylate; sodium polyacrylate starch; sodiumpolyacryloyldimethyl taurate; sodium polygamma-glutamate; sodiumpolymethacrylate; sodium polystyrene sulfonate; sodiumsilicoaluminate; sodium starch octenylsuccinate; sodium stearate;sodium stearoxy PG-hydroxyethylcellulose sulfonate; sodiumstyrene/acrylates copolymer; sodium sulfate; sodium tallowate;sodium tauride acrylates/acrylic acid/acrylonitrogens copolymer;sodium tocopheryl phosphate; solanum tuberosum (potato) starch;soyamide DEA; soyamidopropyl betaine; starch/acrylates/acrylamidecopolymer; starch hydroxypropyltrimonium chloride; stearamide AMP;stearamide DEA; stearamide DEA-distearate; stearamideDIBA-stearate; stearamide MEA; stearamide MEA-stearate; stearamideMIPA; stearamidopropyl betaine; steareth-60 cetyl ether;steareth-100/PEG-136/HDI copolymer; stearyl alcohol; stearylbetaine; sterculia urens gum; synthetic fluorphlogopite; tallamideDEA; tallow alcohol; tallowamide DEA; tallowamide MEA;tallowamidopropyl betaine; tallowamidopropyl hydroxysultaine;tallowamine oxide; tallow betaine; tallow dihydroxyethyl betaine;tamarindus indica seed gum; tapioca starch; TEA-alginate;TEA-carbomer; TEA-hydrochloride; trideceth-2 carboxamide MEA;tridecyl alcohol; triethylene glycol dibenzoate; trimethyl pentanolhydroxyethyl ether; triticum vulgare (wheat) germ powder; triticumvulgare (wheat) kernel flour; triticum vulgare (wheat) starch;tromethamine acrylates/acrylonitrogens copolymer; tromethaminemagnesium aluminum silicate; undecyl alcohol; undecylenamide DEA;undecylenamide MEA; undecylenamidopropyl betaine; welan gum; wheatgermamide DEA; wheat germamidopropyl betaine; xanthan gum; yeastbeta-glucan; yeast polysaccharides; zea mays (corn) starch; andblends thereof.

[0223] Also suitable as thickeners and/or viscosifiers are thefollowing commercial products:

[0224] (1) Aqualon.TM. carboxymethylcellulose, Benecel.TM.methylcellulose and hydroxypropyl methylcellulose, Blanose.TM.sodium carboxymethylcellulose, Klucel.TM. hydroxypropylcellulose,Natrosol.TM. hydroxyethylcellulose, Natrosol.TM. Plus andPolySurf.TM. cetyl modified hydroxyethylcellulose, n-Hance.TM.cationic guar, n-Hance.TM. HP Series hydroxypropyl guar,n-Hance.TM. SP-100 conditioning polymer, and Supercol.TM. guar gumfrom Ashland Specialty Ingredients

[0225] (2) Carbopol Polymers, Fixate.TM. PLUS Polymer,Glucamate.TM. Thickeners, Amidex.TM. Surfactants, Chembetaine.TM.Surfactants, Chemoxide.TM. Surfactants, Chemonic.TM. Surfactants,Chemccinate.TM. Surfactants, Amidex.TM. BC-24 Surfactant,Chemoryl.TM. LB-30 Surfactant, Novethix.TM. L-10 Polymer,Ceralan.TM. Lanolin Product, Pemulen.TM. TR-1 Polymeric Emulsifier,Pemulen.TM. TR-2 Polymeric Emulsifier, Hydramol.TM. PGPD Ester,Schercodine.TM. M Amido-Amine, Schercodine.TM. P Amido-Amine,Schercomid.TM. Diethanolamides from The Lubrizol Corporation.

[0226] (3) Salcare.RTM. and Luvigel.RTM. from BASF Corporation.

[0227] (4) Aculyn.TM. 22, Aculyn.TM. 28, Aculyn.TM. 33, Aculyn.TM.38, and Aculyn.TM. 44 from The Dow Chemical Company.

[0228] (5) Ammonyx.RTM. C and Stepan-Mild.RTM. GCC from StepanCompany.

[0229] (6) Stabileze.TM., Rapithix.TM. A-60, Rapithix.TM. A-100,Ultrathix.TM. P-100, Lubrajel.TM. and FlexiThix.TM. from AshlandSpecialty Ingredients (Wayne, N.J.).

[0230] Also suitable as a thickener/rheology modifier are lightly-to moderately-crosslinked polyvinylpyrrolidones. Disclosures ofthese polymers are provided in the following publications, each ofwhich is hereby incorporated in its entirety by reference: U.S.Pat. Nos. 5,073,614; 5,312,619; 5,139,770; 5,716,634; 5,470,884;5,759,524; 5,997,887; 6,024,942; as well as internationalapplication PCT/US10/26973, PCT/US10/26976, PCT/US10/26940,PCT/US11/32993, and PCT/US11/34515.

[0231] Personal care compositions may comprise natural extractsand/or natural products. Extensive details on natural products thatcan be used in personal care compositions is provided in bookchapter "Chemistry of Cosmetics, Comprehensive Natural Products II"in Chemistry and Biology; volume 3, 2010.

Oral Care Composition Ingredients

[0232] Oral care compositions may optionally contain one or moreadditional ingredients. Non-limiting examples of suitableingredients include: carriers, dentifrices, cleaning agents, breathfreshening actives, pain relievers, anesthetics, anti-inflammatoryagents, antimicrobial agents, antibacterial agents, anti-calculusagents, anti-plaque agents, gums, thickeners, gelling agents,surfactants, flavors, warming or tingling agents, tooth bleachingagents, whiteners, stain removers, stain preventers, abrasives,adhesives, colors, emollients, emulsifiers, preservatives,solvents, binders, stimulants, depressants, diet aids, smokingcessation aides, vitamins, minerals, throat-soothing agents,spices, herbs, herbal extracts, alkaloids (such as caffeine andnicotine), and humectants.

[0233] The choice of a carrier to be used is basically determinedby the way the composition is to be introduced into the oralcavity. Carrier materials for toothpaste, tooth gel or the likeinclude abrasive materials, sudsing agents, binders, humectants,flavoring and sweetening agents, as disclosed in e.g., U.S. Pat.No. 3,988,433. Carrier materials for biphasic dentifricecompositions are disclosed in U.S. Pat. Nos. 5,213,790; 5,145,666;5,281,410; 4,849,213; and 4,528,180. Mouthwash, rinse or mouthspray carrier materials typically include water, flavoring andsweetening agents, etc., as disclosed in, e.g., U.S. Pat. No.3,988,433. Lozenge carrier materials typically include a candybase; chewing gum carrier materials include a gum base, flavoringand sweetening agents, as in, e.g., U.S. Pat. No. 4,083,955. Sachetcarrier materials typically include a sachet bag, flavoring andsweetening agents. For sub-gingival gels used for delivery ofactives into the periodontal pockets or around the periodontalpockets, a "sub-gingival gel carrier" is chosen as disclosed in,e.g., U.S. Pat. Nos. 5,198,220 and 5,242,910. The selection of acarrier will depend on secondary considerations like taste, cost,and shelf stability, and other factors.

[0234] Oral care compositions may comprise one or more dentalabrasives. Dental abrasives useful in the compositions include manydifferent materials. The material selected must be one which iscompatible within the composition of interest and does notexcessively abrade dentin.

[0235] Non-limiting examples of suitable abrasives include: silicasincluding gels and precipitates, insoluble sodiumpolymetaphosphate, hydrated alumina, calcium carbonate, dicalciumorthophosphate dihydrate, calcium pyrophosphate, tricalciumphosphate, calcium polymetaphosphate, resinous abrasive materialssuch as particulate condensation products of urea and formaldehyde,and blends thereof.

[0236] Another class of abrasives is the particulate thermo-settingpolymerized resins as described in U.S. Pat. No. 3,070,510.

[0237] Non-limiting examples of suitable resins include: melamines,phenolics, ureas, melamine-ureas, melamine-formaldehydes,urea-formaldehyde, melamine-urea-formaldehydes, cross-linkedepoxides, cross-linked polyesters, and blends thereof.

[0238] Silica dental abrasives of various types may be employedbecause of their unique benefits of exceptional dental cleaning andpolishing performance without unduly abrading tooth enamel ordentine. The silica abrasive polishing materials herein, as well asother abrasives, generally have an average particle size rangingfrom about 0.1 to about 30 microns, and particularly from about 5to about 15 microns. The abrasive can be precipitated silica orsilica gels such as the silica xerogels described in U.S. Pat. No.3,538,230, and U.S. Pat. No. 3,862,307.

[0239] Non-limiting examples of suitable silica abrasives include:silica xerogels marketed under the trade name "Syloid" by the W.R.Grace & Company, Davison Chemical Division and precipitatedsilica materials such as those marketed by the J.M. HuberCorporation under the trade name, Zeodent.RTM., particularly thesilicas carrying the designation Zeodent.RTM. 119, Zeodent.RTM.118, Zeodent.RTM. 109 and Zeodent.RTM. 129. The types of silicadental abrasives useful in the toothpastes of the invention aredescribed in more detail in U.S. Pat. Nos. 4,340,583; 5,603,920;5,589,160; 5,658,553; 5,651,958; and 6,740,311. Each of thesedisclosures is hereby incorporated in its entirety byreference.

[0240] Mixtures of abrasives can be used such as mixtures of thevarious grades of Zeodent.RTM. silica abrasives listed above.

[0241] The total amount of abrasive(s) in the oral carecompositions typically range from about 6% to about 70% by weight;toothpastes may contain from about 10% to about 50% of abrasives byweight of the composition. Dental solution, mouth spray, mouthwashand non-abrasive gel compositions typically contain little or noabrasives.

[0242] Oral care compositions may comprise polymeric mineralsurface active agent(s) (PMSAs). PMSAs include any agent which willhave a strong affinity for the tooth surface, deposit a polymerlayer or coating on the tooth surface and produce the desiredsurface modification effects. The "mineral" descriptor is intendedto convey that the surface activity or substantivity of the polymeris toward mineral surfaces such as calcium phosphate minerals orteeth.

[0243] Non-limiting examples of suitable PMSAs include:polyelectrolytes such as condensed phosphorylated polymers;polyphosphonates; copolymers of phosphate- orphosphonate-containing monomers or polymers with other monomerssuch as ethylenically unsaturated monomers and amino acids or withother polymers such as proteins, polypeptides, polysaccharides,poly(acrylate), poly(acrylamide), poly(methacrylate),poly(ethacrylate), poly(hydroxyalkylmethacrylate), poly(vinylalcohol), poly(maleic anhydride), poly(maleate) poly(amide),poly(ethylene amine), poly(ethylene glycol), poly(propyleneglycol), poly(vinyl acetate), poly(vinyl benzyl chloride),polycarboxylates, carboxy-substituted polymers, and blends thereof.Also suitable as polymeric mineral surface active agents are thecarboxy-substituted alcohol polymers described in U.S. Pat. Nos.5,292,501; 5,213,789, 5,093,170; 5,009,882; and 4,939,284; and thediphosphonate-derivatized polymers in U.S. Pat. No. 5,011,913; thesynthetic anionic polymers including polyacrylates and copolymersof maleic anhydride or acid and methyl vinyl ether (e.g.,Gantrez.RTM.), as described, for example, in U.S. Pat. No.4,627,977. Another example of a polymeric mineral surface activeagent is a diphosphonate modified polyacrylic acid.

[0244] Polymers with activity must have sufficient surface bindingpropensity to desorb pellicle proteins and remain affixed to enamelsurfaces. For tooth surfaces, polymers with end or side chainphosphate or phosphonate functions may be used, although otherpolymers with mineral binding activity may prove effectivedepending upon adsorption affinity.

[0245] PMSAs are useful in the compositions because of their stainprevention benefit. It is believed the PMSAs provide a stainprevention benefit because of their reactivity or substantivity tomineral surfaces, resulting in desorption of portions ofundesirable adsorbed pellicle proteins, in particular thoseassociated with binding color bodies that stain teeth, calculusdevelopment and attraction of undesirable microbial species. Theretention of these PMSAs on teeth can also prevent stains fromaccruing due to disruption of binding sites of color bodies ontooth surfaces.

[0246] The ability of PMSA to bind stain promoting ingredients oforal care products such as stannous ions and cationicantimicrobials is also believed to be helpful. The PMSA will alsoprovide tooth surface conditioning effects which produce desirableeffects on surface thermodynamic properties and surface filmproperties, which impart improved clean feel aesthetics both duringand most importantly, following rinsing or brushing. Many of thesepolymeric agents are also known or expected to provide tartarcontrol benefits when applied in oral compositions, hence providingimprovement in both the appearance of teeth and their tactileimpression to consumers. The desired surface effects may include:1) creating a hydrophilic tooth surface immediately aftertreatment; and 2) maintaining surface conditioning effects andcontrol of pellicle film for extended periods following productuse, including post brushing or rinsing and throughout moreextended periods. The effect of creating an increased hydrophilicsurface can be measured in terms of a relative decrease in watercontact angles. The hydrophilic surface, importantly, is maintainedon the tooth surface for an extended period after using theproduct.

[0247] Oral care compositions may comprise additional anticalculusagent(s), such as a pyrophosphate salt as a source of pyrophosphateion.

[0248] Non-limiting examples of suitable pyrophosphate saltsinclude: dialkali metal pyrophosphate salts, tetraalkali metalpyrophosphate salts, and mixtures thereof. Particularly, disodiumdihydrogen pyrophosphate (Na.sub.2H.sub.2P.sub.2O.sub.7),tetrasodium pyrophosphate (Na.sub.4P.sub.2O.sub.7), andtetrapotassium pyrophosphate (K.sub.4P.sub.2O.sub.7) in theirunhydrated as well as hydrated forms may find utility.

[0249] In compositions of the invention, the pyrophosphate salt maybe present in one of three ways: predominately dissolved,predominately undissolved, or a mixture of dissolved andundissolved pyrophosphate.

[0250] Compositions comprising predominately dissolvedpyrophosphate refer to compositions where at least onepyrophosphate ion source is in an amount sufficient to provide atleast about 1.0% free pyrophosphate ions. The amount of freepyrophosphate ions may be from about 1% to about 15%, particularlyfrom about 1.5% to about 10%, and more particularly from about 2%to about 6%. Free pyrophosphate ions may be present in a variety ofprotonated states depending on the pH of the composition.

[0251] Compositions comprising predominately undissolvedpyrophosphate refer to compositions containing no more than about20% of the total pyrophosphate salt dissolved in the composition,particularly less than about 10% of the total pyrophosphatedissolved in the composition. Tetrasodium pyrophosphate salt may beone such pyrophosphate salt in these compositions. Tetrasodiumpyrophosphate may be the anhydrous salt form or the decahydrateform, or any other species stable in solid form in the oral carecompositions. The salt is in its solid particle form, which may beits crystalline and/or amorphous state, with the particle size ofthe salt being small enough to be aesthetically acceptable andreadily soluble during use. The amount of pyrophosphate salt usefulin making these compositions is any tartar control effectiveamount, generally from about 1.5% to about 15%, particularly fromabout 2% to about 10%, and more particularly from about 3% to about8% by weight of the oral care composition.

[0252] The pyrophosphate salts are described in more detail inKirk-Othmer Encyclopedia of Chemical Technology, third edition,volume 17, Wiley-Interscience Publishers (1982).

[0253] Oral care compositions may comprise peroxide compounds.

[0254] Non-limiting examples of suitable peroxide compoundsinclude: hydrogen peroxide and organic peroxides including ureaperoxide, carbamide peroxide, glyceryl peroxide, benzoyl peroxide,derivatives thereof, and blends thereof.

[0255] Typically, the peroxide compound can be employed in amountsso that at least about 1% by weight of the composition comprisesperoxide. The peroxide compound may comprise from about 2% to about30% by weight of the composition. More particularly, the peroxidecomprises from about 3% to about 15% by weight of the composition.A typical peroxide concentration in the composition is generallyfrom about 2% to about 7% by weight for home use products, and fromabout 15% to about 20% by weight for dental professional use.

[0256] Thickening or gelling agents used in dentifrice compositionsmay include nonionic polyoxyethylene polyoxypropylene blockcopolymers. Illustrative of polyoxyethylene polyoxypropylene blockcopolymers useful in the practice include block copolymers havingthe formulaHO(C.sub.2H.sub.4O).sub.b(C.sub.3H.sub.6O.sub.6).sub.a(C.sub.2H.sub.4O).s-ub.bH wherein a is an integer such that the hydrophobic baserepresented by (C.sub.3H.sub.6O.sub.6) has a molecular weight ofabout 2,750 Da to 4000 Da, b is an integer such that thehydrophilic portion (moiety) represented by (C.sub.2H.sub.4O)constitutes from about 70% to about 80% by weight of the copolymer.Block copolymers of this composition are available commerciallyunder the trademark Pluronic.RTM. F type.

[0257] Pluronic.RTM. F127 has a molecular weight of 4,000 Da andcontains 70% of the hydrophilic polyoxyethylene moiety.

[0258] Also suitable as a thickening agent is lightly- tomoderately-crosslinked PVP, described in international applicationPCT/US11/30642.

[0259] The thickening agents may be present in an amount from about15% to about 50% by weight, particularly from about 25% to about45% by weight of the composition.

[0260] Surfactants may also be included in the oral carecompositions of the invention, where they may serve insolubilizing, dispersing, emulsifying and/or reducing the surfacetension of the teeth in order to increase the contact between thetooth and the peroxide. The compositions may also comprisesurfactants, also commonly referred to as sudsing agents. Suitablesurfactants are those which are reasonably stable and foamthroughout a wide pH range. Surfactants may be chosen from anionic,nonionic, amphoteric, zwitterionic, or cationic surfactants, orblends thereof.

[0261] Anionic surfactants useful herein include the water-solublesalts of alkyl sulfates having from 8 to 20 carbon atoms in thealkyl radical (e.g., sodium alkyl sulfate) and the water-solublesalts of sulfonated monoglycerides of fatty acids having from 8 to20 carbon atoms. Sodium lauryl sulfate (SLS) and sodium coconutmonoglyceride sulfonates are non-limiting examples of anionicsurfactants of this type. Many suitable anionic surfactants aredisclosed in U.S. Pat. No. 3,959,458. The compositions may comprisean anionic surfactant in an amount from about 0.025% to about 9% byweight, particularly from about 0.05% to about 5% by weight, andmore particularly from about 0.1% to about 1% by weight of thecomposition.

[0262] Non-limiting examples of suitable anionic surfactantsinclude: sarcosinates, taurates, isethionates, sodium laurylsulfoacetate, sodium laureth carboxylate, and sodium dodecylbenzenesulfonate. Also suitable are alkali metal or ammonium saltsof surfactants such as the sodium and potassium salts of thefollowing: lauroyl sarcosinate, myristoyl sarcosinate, palmitoylsarcosinate, stearoyl sarcosinate, and oleoyl sarcosinate. Thesarcosinate surfactant may be present in the compositions fromabout 0.1% to about 2.5%, particularly from about 0.5% to about2.0% by weight of the total composition.

[0263] Non-limiting examples of suitable cationic surfactantsinclude: derivatives of aliphatic quaternary ammonium compoundshaving at least one long alkyl chain containing from about 8 toabout 18 carbon atoms such as lauryl trimethylammonium chloride,cetyl pyridinium chloride, cetyl trimethylammonium bromide,di-isobutylphenoxyethyl-dimethylbenzylammonium chloride, coconutalkyltrimethylammonium nitrite, cetyl pyridinium fluoride, andblends thereof. Also suitable are the quaternary ammonium fluoridesdescribed in U.S. Pat. No. 3,535,421, where the quaternary ammoniumfluorides have detergent properties. Certain cationic surfactantscan also act as germicides in the compositions disclosedherein.

[0264] Nonionic surfactants that may be used in the compositions ofthe invention include compounds produced by the condensation ofalkylene oxide groups (hydrophilic in nature) with an organichydrophobic compound which may be aliphatic or alkylaromatic innature.

[0265] Non-limiting examples of suitable nonionic surfactantsinclude: poloxamers (sold under the trade name Pluronic.RTM. byBASF Corporation), polyethylene oxide condensates of alkyl phenols,products derived from the condensation of ethylene oxide with thereaction product of propylene oxide and ethylene diamine, ethyleneoxide condensates of aliphatic alcohols, long chain tertiary amineoxides, long chain tertiary phosphine oxides, long chain dialkylsulfoxides and blends thereof.

[0266] Non-limiting examples of suitable zwitterionic surfactantsinclude betaines and derivatives of aliphatic quaternary ammoniumcompounds in which the aliphatic radicals can be straight chain orbranched, and which contain an anionic water-solubilizing group,e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate.

[0267] Non-limiting examples of suitable betaines include: decylbetaine or 2-(N-decyl-N,N-dimethylammonio)acetate, coco betaine or2-(N-coc-N,N-dimethyl ammonio)acetate, myristyl betaine, palmitylbetaine, lauryl betaine, cetyl betaine, stearyl betaine, and blendsthereof. The amidobetaines are exemplified by cocoamidoethylbetaine, cocoamidopropyl betaine, lauramidopropyl betaine, and thelike. The betaines of choice include cocoamidopropyl betaines suchas lauramidopropyl betaine. Suitable betaine surfactants aredisclosed in U.S. Pat. No. 5,180,577.

[0268] Other surfactants such as fluorinated surfactants may alsobe incorporated within the compositions of the invention.

[0269] Oral care compositions may comprise flavor(s).

[0270] Non-limiting examples of suitable flavors include: methylsalicylate, ethyl salicylate, methyl cinnamate, ethyl cinnamate,butyl cinnamate, ethyl butyrate, ethyl acetate, methylanthranilate, iso-amyl acetate, iso-armyl butyrate, allyl caproate,eugenol, eucalyptol, thymol, cinnamic alcohol, cinnamic aldehyde,octanol, octanal, decanol, decanal, phenylethyl alcohol, benzylalcohol, benzaldehyde, .alpha.-terpineol, linalool, limonene,citral, vanillin, ethyl vanillin, propenyl guaethol, maltol, ethylmaltol, heliotropin, anethole, dihydroanethole, carvone, oxanone,menthone, .beta.-damascenone, ionone, gamma decalactone, gammanonalactone, gamma undecalactone,4-hydroxy-2,5-dimethyl-3(2H)-furanone, and blends thereof.

[0271] Generally suitable flavoring agents are those containingstructural features and functional groups that are less prone tooxidation by peroxide. These include derivatives of flavorchemicals that are saturated or contain stable aromatic rings orester groups.

[0272] Also suitable are flavor chemicals that may undergo someoxidation or degradation without resulting in a significant changein the flavor character or profile. The flavor chemicals, includingmenthol, may be provided as single or purified chemicals ratherthan supplied in the composition by addition of natural oils orextracts such as peppermint, spearmint, or wintergreen oils asthese sources may contain other components that are relativelyunstable and may degrade in the presence of peroxide. Flavoringagents are generally used in the compositions at levels of fromabout 0.001% to about 5% by weight of the composition.

[0273] The flavor system may typically include sweetening agent(s).Sweeteners include compounds of natural and artificial origin.

[0274] Non-limiting examples of suitable water-soluble naturalsweeteners include: monosaccharides, disaccharides andpolysaccharides, such as xylose, ribose, glucose (dextrose),mannose, galactose, fructose (levulose), sucrose (sugar), maltose,invert sugar (a mixture of fructose and glucose derived fromsucrose), partially hydrolyzed starch, corn syrup solids,dihydrochalcones, monellin, steviosides, glycyrrhizin, and blendsthereof.

[0275] Non-limiting examples of suitable water-soluble artificialsweeteners include: soluble saccharin salts, i.e., sodium orcalcium saccharin salts, cyclamate salts, the sodium, ammonium orcalcium salt of3,4-dihydro-6-methyl-1,2,3-oxathiazine-4-one-2,2-dioxide, thepotassium salt of3,4-dihydro-6-methyl-1,2,3-oxathiazine-4-one-2,2-dioxide(acesulfame-K), the free acid form of saccharin, and the like.Other suitable sweeteners include dipeptide based sweeteners, suchas L-aspartic acid derived sweeteners, such asL-aspartyl-L-phenylalanine methyl ester (aspartame) and materialsdescribed in U.S. Pat. No. 3,492,131,L-.alpha.-aspartyl-N-(2,2,4,4-tetramethyl-3-thietanyl)-D-alaninamidehydrate, methyl esters of L-aspartyl-L-phenylglycerin andL-aspartyl-L-2,5,dihydrophenyl-glycine,L-aspartyl-2,5-dihydro-L-phenylalanine,L-aspartyl-L-(1-cyclohexyen)-alanine, derivatives thereof, andblends thereof. Water-soluble sweeteners derived from naturallyoccurring water-soluble sweeteners, such as a chlorinatedderivative of ordinary sugar (sucrose), known, for example, underthe product description of sucralose as well as protein basedsweeteners such as thaumatoccous danielli (Thaumatin I and II) maybe used. The compositions may contain sweetener(s) in an amountfrom about 0.1% to about 10% by weight, in particular from about0.1% to about 1% by weight of the composition.

[0276] In addition, the flavor system may include salivatingagents, warming agents, and numbing agents. These agents arepresent in the compositions in an amount from about 0.001% to about10% by weight, particularly from about 0.1% to about 1% by weightof the composition.

[0277] A non-limiting example of suitable salivating agent includesJambus.RTM. manufactured by Takasago. Non-limiting examples ofsuitable warming agents include capsicum and nicotinate esters suchas benzyl nicotinate. Non-limiting examples of suitable numbingagents include benzocaine, lidocaine, clove bud oil, ethanol, andblends thereof.

[0278] Oral care compositions may comprise chelating agent(s).

[0279] The chelating agents may include metal solubilizing agentsand metal precipitating agents. The metal solubilizing agentsinclude a condensed pyrophosphate compound. For purposes of thisinvention "condensed phosphate" relates to an inorganic phosphatecomposition containing two or more phosphate species in a linear orcyclic pyrophosphate form. The condensed phosphate may be sodiumpyrophosphate, but may also include tripolyphosphate,hexametaphosphate, cyclic condensed phosphate or other similarphosphates well known in the field. The blend may also include anorganic chelating agent. The term "organic phosphate" includesphosphonic acid, di and tri phosphonoc acid compound or its salts.An example of phosphonic acid is1-hydroxyethylidene-1,1-diphosphonic acid that is sold under thetrade name of Dequest.RTM.. The blend may also include a metalprecipitating chelating agent. The term "metal precipitatingchelating agent" is an agent that binds to metals and causes themetal to precipitate and includes halogens such as fluoride. Thechelating agents are incorporated in the oral care compositions ofthe invention in an amount from about 0.1% to about 8.0% by weight,and particularly from about 0.5% to about 3.0% by weight of thecomposition, in a ratio of about 3:1:1 w/w organic chelating agent:condensed phosphate chelating agent: metal precipitating agent.

[0280] Another optional ingredient that may be used in oral carecompositions is a humectant. For example, a humectant may be addedto keep toothpaste compositions from hardening upon exposure toair, to give compositions a moist feel to the mouth, and, forparticular humectants, to impart desirable sweetness of flavor totoothpaste compositions. The humectant, on a pure humectant basis,is generally present from about 0% to about 70%, particularly fromabout 5% to about 25% by weight of the composition.

[0281] Non-limiting examples of suitable humectants include: ediblepolyhydric alcohols such as glycerin, sorbitol, xylitol, butyleneglycol, polyethylene glycol, propylene glycol, trimethyl glycine,and blends thereof.

[0282] The invention also contemplates oral care compositionscomprising polymer(s) described herein complexed with hydrogenperoxide. A description of such complexes is present ininternational application WO 91/07184, the contents of which arehereby incorporated in their entirety by reference.

[0283] Also contemplated are oral care compositions such as thosedescribed in the following patents and patent applications, thecontents of each are hereby incorporated in their entirety byreference: WO 2011/068514, WO 2011/053877, US 2010/0275394, US2011/0076090, US 2008/091935, US 2008/0181716, US 2008/0014224, WO2007/066837, US 2008/0292669, US 2007/0071696, US 2007/0154863, US2008/0317797, US 2005/0249678, US 2007/0178055, US 2007/0189983, WO2005/041910, U.S. Pat. No. 7,785,572, WO 1998/005749, WO1997/022651, and U.S. Pat. No. 5,310,563.

[0284] Oral care compositions may comprise one or more dentureadhesives.

[0285] Synthetic materials presently dominate the denture adhesivemarket. Such materials may consist of mixtures of the salts ofshort-acting polymers (e.g., carboxymethylcellulose or "CMC") andlong-acting polymers (e.g., poly[vinyl methyl ether maleate], or"Gantrez" and its salts). Polyvinylpyrrolidone (povidone) may alsobe used.

[0286] Other components of denture adhesive products impartparticular physical attributes to the compositions. Petrolatum,mineral oil, and polyethylene oxide may be included in creams tobind the materials and to make their placement easier. Silicondioxide and calcium stearate may be used in powders to minimizeclumping. Menthol and peppermint oils may be used for flavoring,red dye for color, and sodium borate and methyl- or poly-paraben aspreservatives.

[0287] It is also contemplated that the composition ingredients maybe formulated in a single container, or the ingredients may beformulated in-part in two or more distinct containers of the sameor different type, the contents of which may require mixing priorto use.

[0288] In a third aspect, the invention provides a method forprotecting a keratinous substrate from UV radiation comprisingapplying onto the substrate a water-resistant sun care compositioncomprising: (a) a polymer comprising repeating units derived from:from 16% by weight to about 35% by weight of said polymer of atleast one N-vinyl lactam monomer; at least one monomer selectedfrom the group consisting of functionalized and unfuctionalizedC.sub.1-C.sub.6 alkyl (meth)acrylates, C.sub.1-C.sub.6 alkyl(meth)acrylamides and combinations thereof; and at least onemonomer selected from the group consisting of functionalized andunfunctionalized C.sub.8-C.sub.30 branched alkyl (meth)acrylates,C.sub.8-C.sub.30 branched alkyl (meth)acrylamides, and combinationsthereof, wherein the polymer has a glass transistion temperature ofgreater than about 45.degree. C.; and (b) at least one UVactive.

Methods of Synthesis

[0289] The polymers according to the invention may be readilysynthesized by procedures known by those skilled in the art,non-limiting examples of which include free radical solutionpolymerization, dispersion polymerization, emulsion polymerization,ionic chain polymerization, living polymerization, andprecipitation polymerization.

[0290] Free radical polymerization may be used, especially whenusing water-dispersible and/or water-soluble reaction solvent(s).This type of polymerization method is described in "DecompositionRate of Organic Free Radical Polymerization" by K. W. Dixon(section II in Polymer Handbook, volume 1, 4th edition,Wiley-Interscience, 1999), which is herein incorporated in itsentirety by reference.

[0291] Compounds capable of initiating the free-radicalpolymerization include those materials known to function in theprescribed manner, and include the peroxo and azo classes ofmaterials. Peroxo and azo compounds include, but are not limitedto: acetyl peroxide; azo bis-(2-amidinopropane) dihydrochloride;azo bis-isobutyronitrile; 2,2'-azo bis-(2-methylbutyronitrile);benzoyl peroxide; di-tert-amyl peroxide; di-tert-butyldiperphthalate; butyl peroctoate; tert-butyl dicumyl peroxide;tert-butyl hydroperoxide; tert-butyl perbenzoate; tert-butylpermaleate; tert-butyl perisobutylrate; tert-butyl peracetate;tert-butyl perpivalate; para-chlorobenzoyl peroxide; cumenehydroperoxide; diacetyl peroxide; dibenzoyl peroxide; dicumylperoxide; didecanoyl peroxide; dilauroyl peroxide; diisopropylperoxodicarbamate; dioctanoyl peroxide; lauroyl peroxide; octanoylperoxide; succinyl peroxide; and bis-(ortho-toluoyl) peroxide. Alsosuitable to initiate the free-radical polymerization are initiatormixtures or redox initiator systems, including: ascorbic acid/iron(II) sulfate/sodium peroxodisulfate, tert-butylhydroperoxide/sodium disulfite, and tert-butyl hydroperoxide/sodiumhydroxymethanesulfinate.

[0292] The polymerization reactions may be carried out in thepresence of one or more solvents. Non-limiting examples of solventsthat may be employed include ethanol, isopropanol, tert-butanol,n-hexane, and Ceraphyl.RTM. 230. The polymers may be synthesized ina solvent or a blend of one or more solvents and maintainedtherein, or the synthesis solvent(s) separated from the polymer bymethods known in the art and replaced by a solvent beneficial forformulary development and/or end-use. The polymerizationtemperature may vary from about 5.degree. C. to about 200.degree.C. The polymerization reaction may be carried out at ambientpressure, sub-atmospheric pressure, or super-atmospheric pressure.The polymerization reaction may be carried out in a batch,continuous and/or semi-continuous manner.

[0293] The polymers according to the invention may have aweight-average molecular weight ranging from about 10,000 Da toabout 1,000,000 Da, more particularly from about 25,000 Da to about500,000 Da, and even more particularly from about 50,000 Da toabout 250,000 Da.

[0294] The molecular weight may be controlled using methods knownin the art, including strategies to control the reactiontemperature and time, as well as the use of chain-transfer agentssuch as thiols (e.g., dodecyl mercaptan), and halocarbons (e.g.,chlorinated compounds like carbon tetrachloride).

Characterization of Polymers

[0295] The polymers and compositions comprising the polymersaccording to the invention may be analyzed by known techniques.Especially preferred are the techniques of .sup.13C nuclearmagnetic resonance (NMR) spectroscopy, gas chromatography (GC), andgel permeation chromatography (GPC) in order to decipher polymeridentity, residual monomer concentrations, polymer molecularweight, and polymer molecular weight distribution.

[0296] Nuclear magnetic resonance (NMR) spectroscopy is anespecially preferred method to probe the polymerization product interms of chemical properties such as monomeric composition,sequencing and tacticity. Analytical equipment suitable for theseanalyses includes the Inova 400-MR NMR System by Varian Inc. (PaloAlto, Calif.). References broadly describing NMR include: Yoder, C.H. and Schaeffer Jr., C. D., Introduction to Multinuclear NMR, TheBenjamin/Cummings Publishing Company, Inc., 1987; and Silverstein,R. M., et al., Spectrometric Identification of Organic Compounds,John Wiley & Sons, 1981, which are incorporated in theirentirety by reference.

[0297] Residual monomer levels can be measured by GC, which can beused to indicate the extent of reactant conversion by thepolymerization process. GC analytical equipment to perform thesetests are commercially available, and include the following units:Series 5880, 5890, and 6890 GC-FID and GC-TCD by AgilentTechnologies, Inc. (Santa Clara, Calif.). GC principles aredescribed in Modern Practice of Gas Chromatography, third edition(John Wiley & Sons, 1995) by Robert L. Grob and Eugene F.Barry, which is hereby incorporated in its entirety byreference.

[0298] GPC is an analytical method that separates molecules basedon their hydrodynamic volume (or size) in solution of the mobilephase, such as hydroalcoholic solutions with surfactants. GPC is apreferred method for measuring polymer molecular weightdistributions. This technique can be performed on known analyticalequipment sold for this purpose, and include the TDAmax.TM.Elevated Temperature GPC System and the RImax.TM. ConventionalCalibration System by Viscotek.TM. Corp. (Houston, Tex.). Inaddition, GPC employs analytical standards as a reference, of whicha plurality of narrow-distribution polyethylene glycol andpolyethylene oxide standards representing a wide range in molecularweight is the preferred. These analytical standards are availablefor purchase from Rohm & Haas Company (Philadelphia, Pa.) andVarian Inc. (Palo Alto, Calif.). GPC is described in the followingtexts, which are hereby incorporated in their entirety byreference: Schroder, E., et al., Polymer Characterization, HanserPublishers, 1989; Billingham, N. C., Molar Mass Measurements inPolymer Science, Halsted Press, 1979; and Billmeyer, F., Textbookof Polymer Science, Wiley Interscience, 1984.

[0299] The polymers according to the invention may be preparedaccording to the examples set out below. The examples are presentedfor purposes of demonstrating, but not limiting, the preparation ofthe polymers. Therein, the following abbreviations are used:

UV: Ultra violet VP: N-vinyl-2-pyrrolidone

HPVP: High Purity Vinyl Pyrrolidone

[0300] VCap: N-vinyl-2-caprolactam EHMA: 2-ethylhexyl(meth)acrylate MMA: Methyl (meth)acrylate TBA: tert-butylacrylate

EXAMPLES

Example 1: Synthesis of Poly(VP-Co-MMA-Co-EHMA) with VP/MMA/EHMAWeight Ratio of 20:30:50. Four Hour Feed Reaction in Tert-ButanolSolvent

##STR00013##

[0302] An amount of 36 g of HPVP and 75 g tert-butanol was added tothe reaction vessel as a heel charge. The reaction mixture waspurged three times with nitrogen while stirring and then heated to75.degree. C. to 85.degree. C. A pre-mixed feed charge comprising90 g of EHMA, 54 g of MMA, and tert-butanol was fed in the pump.The feed was started at 70.degree. C. to 80.degree. C. andcontinued for four hours. The jacket temperature was adjusted tomaintain the internal temperature between 80 to 85.degree. C.during the feed. A total amount of 0.9 g of the initial initiatorLuperox.RTM. 11 was charged in six portions during the feed. Afterthe feed was completed, tert-butanol was used to rinse the feedingline, pump and charge line, and discharged into the reactionvessel. The reaction mixture was maintained on hold for one hour at80.degree. C. to 85.degree. C. An amount of 2.0% by weight of totalamount of monomers of chaser initiator Luperox.RTM. 11 was chargedin 12 portions and the reaction sampled for analysis by HPLC. Themixture was maintained on hold for 10 hours at 80.degree. C. to85.degree. C. The sample was dried under high vacuum at 50.degree.C. to 55.degree. C. In the polymer structure shown, x=20 weight %,y=30 weight % and z=50 weight %.

Example 2: Synthesis of Poly(VP-Co-MMA-Co-EHMA) with VP/MMA/EHMAWeight Ratio of 20:30:50. Two Hour Feed Reaction in Tert-ButanolSolvent

##STR00014##

[0304] An amount of 36 g of HPVP and 75 g tert-butanol was added tothe reaction vessel as a heel charge. The reaction mixture waspurged three times with nitrogen while stirring and then heated to80.degree. C. to 85.degree. C. A pre-mixed feed charge comprising90 g of EHMA, 54 g of MMA, and 150 g of tert-butanol was fed in thepump. The feed was started at 70.degree. C. to 80.degree. C. andcontinued for two hours. The jacket temperature was adjusted tomaintain the internal temperature between 80 to 85.degree. C.during the feed. A total amount of 0.9 g of the initial initiatorVazo.RTM. 67 was charged in two portions during the feed. After thefeed was completed, tert-butanol was used to rinse the feedingline, pump and charge line, and discharged into the reactionvessel. The reaction mixture was maintained on hold for one hour at80.degree. C. to 85.degree. C. An amount of 2.0% by weight of totalamount of monomers of chaser initiator Luperox.RTM. 121 was chargedafter every hour after the temperature increased to 90.degree. C.to 91.degree. C. and the reaction sampled for analysis by HPLC. Themixture was maintained on hold for 10 hours at 90.degree. C. to95.degree. C. The sample was dried under high vacuum at 50.degree.C. to 55.degree. C. In the polymer structure shown, x=20 weight %,y=30 weight % and z=50 weight %.

Example 3: Synthesis of Poly(VP-Co-MMA-Co-EHMA) with VP/MMA/EHMAWeight Ratio of 20:30:50. One Hour Feed Reaction in Tert-ButanolSolvent

##STR00015##

[0306] An amount of 36 g of HPVP and 75 g tert-butanol was added tothe reaction vessel as a heel charge. The reaction mixture waspurged three times with nitrogen while stirring and then heated to70.degree. C. to 75.degree. C. A pre-mixed feed charge comprising90 g of EHMA, 54 g of MMA, and tert-butanol was fed in the pump.The feed was started at 70.degree. C. to 75.degree. C. andcontinued for one hour. The jacket temperature was adjusted tomaintain the internal temperature between 70 to 75.degree. C.during the feed. A total amount of 0.9 g of the initial initiatorLuperox.RTM. 11 was charged in one portion during the feed. Afterthe feed was completed, tert-butanol was used to rinse the feedingline, pump and charge line, and discharged into the reactionvessel. The reaction mixture was maintained on hold for one hour at85.degree. C. to 90.degree. C. An amount of 2.0% by weight of totalamount of monomers of chaser initiator Luperox.RTM. 121 was chargedin four portions after every hour. The reaction mixture wasmaintained on hold for 10 hours at 85.degree. C. to 90.degree. C.The sample was dried under high vacuum at 50.degree. C. to55.degree. C. In the polymer structure shown, x=20 weight %, y=30weight % and z=50 weight %.

Example 4: Synthesis of Poly(VP-Co-MMA-Co-EHMA) with VP/MMA/EHMAWeight Ratio of 30:30:40. Three Hour Feed Reaction in Tert-ButanolSolvent

##STR00016##

[0308] An amount of 54 g of HPVP and 75 g tert-butanol was added tothe reaction vessel as a heel charge. The reaction mixture waspurged three times with nitrogen while stirring and then heated to80.degree. C. to 85.degree. C. A pre-mixed feed charge comprising72 g of EHMA, 54 g of MMA, and tert-butanol was fed in the pump.The feed was started at 70.degree. C. to 80.degree. C. andcontinued for three hours. The jacket temperature was adjusted tomaintain the internal temperature between 80 to 85.degree. C.during the feed. A total amount of 0.9 g of the initial initiatorVazo.RTM. 67 was charged in six portions during the feed. After thefeed was completed, tert-butanol was used to rinse the feedingline, pump and charge line, and discharged into the reactionvessel. The reaction mixture was maintained on hold for one hour at85.degree. C. to 85.degree. C. and sampled for analysis by HPLC. Anamount of 2.5% by weight of total amount of monomers of chaserinitiator Vazo.RTM. 67 was charged in six portions. The reactionmixture was maintained on hold for 10 hours at 80.degree. C. to85.degree. C. The sample was dried under high vacuum at 50.degree.C. to 55.degree. C. In the polymer structure shown, x=30 weight %,y=30 weight % and z=40 weight %.

Example 5: Synthesis of Poly(VP-Co-TBA-Co-EHMA) with VP/TBA/EHMAWeight Ratio of 20:30:50. Four Hour Feed Reaction in Tert-ButanolSolvent

##STR00017##

[0310] An amount of 36 g of HPVP and 75 g tert-butanol was added tothe reaction vessel as a heel charge. The reaction mixture waspurged three times with nitrogen while stirring and then heated to70.degree. C. to 75.degree. C. A pre-mixed feed charge comprising90 g of EHMA, 54 g of TBA, and tert-butanol was fed in the pump.The feed was started at 70.degree. C. to 80.degree. C. andcontinued for four hours. The jacket temperature was adjusted tomaintain the internal temperature between 70 to 75.degree. C.during the feed. A total amount of 0.9 g of the initial initiatorLuperox.RTM. 11 was charged in six portions during the feed. Afterthe feed was completed, tert-butanol was used to rinse the feedingline, pump and charge line, and discharged into the reactionvessel. The reaction mixture was maintained on hold for one hour at70.degree. C. to 75.degree. C. and sampled for analysis. Thetemperature was raised to 80.degree. C.-85.degree. C. An amount of2.5% by weight of total amount of monomers of chaser initiatorLuperox.RTM. 11 was charged in six portions every hour. Thereaction mixture was maintained on hold for 10 hours at 80.degree.C. to 85.degree. C. and sampled for analysis by HPLC. The samplewas dried under high vacuum at 50.degree. C. to 55.degree. C. Inthe polymer structure shown, x=20 weight %, y=30 weight % and z=50weight %.

Example 6: Synthesis of Poly(VP-Co-MMA-Co-EHMA) with VP/MMA/EHMAWeight Ratio of 20:30:50. Four Hour Feed Reaction in IsopropanolSolvent

##STR00018##

[0312] An amount of 36 g of HPVP and 75 g tert-butanol was added tothe reaction vessel as a heel charge. The reaction mixture waspurged three times with nitrogen while stirring and then heated to70.degree. C. to 80.degree. C. A pre-mixed feed charge comprising90 g of EHMA, 54 g of MMA, tert-butanol and 30 g of isopropanol wasfed in the pump. The feed was started at 70.degree. C. to80.degree. C. and continued for four hours. The jacket temperaturewas adjusted to maintain the internal temperature between 70 to75.degree. C. during the feed. A total amount of 1.35 g of theinitial initiator Luperox.RTM. 11 was charged in six portionsduring the feed. After the feed was completed, tert-butanol wasused to rinse the feeding line, pump and charge line, anddischarged into the reaction vessel. The reaction mixture wasmaintained on hold for one hour at 70.degree. C. to 75.degree. C.and sampled for analysis. The temperature was raised to 80.degree.C.-85.degree. C. An amount of 2.5% by weight of total amount ofmonomers of chaser initiator Luperox.RTM. 11 was charged in sixportions every hour. The reaction mixture was maintained on holdfor 10 hours at 80.degree. C. to 85.degree. C. and sampled foranalysis by HPLC. The sample was dried under high vacuum at50.degree. C. to 55.degree. C. In the polymer structure shown, x=20weight %, y=30 weight % and z=50 weight %.

Example 7: Synthesis of Poly(VP-Co-MMA-Co-EHMA) with VP/MMA/EHMAWeight Ratio of 20:50:30. Three Hour Feed Reaction in Tert-ButanolSolvent

##STR00019##

[0314] An amount of 36 g of HPVP and 75 g tert-butanol was added tothe reaction vessel as a heel charge. The reaction mixture waspurged three times with nitrogen while stirring and then heated to80.degree. C. to 85.degree. C. A pre-mixed feed charge comprising54 g of EHMA, 90 g of MMA, and tert-butanol was fed in the pump.The feed was started at 70.degree. C. to 80.degree. C. andcontinued for three hours. The jacket temperature was adjusted tomaintain the internal temperature between 80 to 85.degree. C.during the feed. A total amount of 0.9 g of the initial initiatorLuperox.RTM. 11 was charged in six portions during the feed. Afterthe feed was completed, tert-butanol was used to rinse the feedingline, pump and charge line, and discharged into the reactionvessel. The reaction mixture was maintained on hold for one hour at80.degree. C. to 85.degree. C. and sampled for analysis. An amountof 2.5% by weight of total amount of monomers of chaser initiatorLuperox.RTM. 11 was charged in six portions every hour. Thereaction mixture was maintained on hold for 10 hours at 80.degree.C. to 85.degree. C. and sampled for analysis by HPLC. The samplewas dried under high vacuum at 50.degree. C. to 55.degree. C. Inthe polymer structure shown, x=20 weight %, y=50 weight % and z=30weight %.

Example 8: Synthesis of Poly(VP-Co-MMA-Co-EHMA) with VP/MMA/EHMAWeight Ratio of 20:30:50. Four Hour Feed Reaction in Isopropanoland Tert-Butanol Solvent Combination. 30% Solids Process

##STR00020##

[0316] An amount of 36 g of HPVP and 75 g tert-butanol was added tothe reaction vessel as a heel charge. The reaction mixture waspurged three times with nitrogen while stirring and then heated to75.degree. C. to 80.degree. C. A pre-mixed feed charge comprising90 g of EHMA, 54 g of MMA, tert-butanol and 15 g of isopropanol wasfed in the pump. The feed was started at 70.degree. C. to80.degree. C. and continued for four hours. The jacket temperaturewas adjusted to maintain the internal temperature between 75 to80.degree. C. during the feed. A total amount of 1.35 g of theinitial initiator Luperox.RTM. 11 was charged in six portionsduring the feed. After the feed was completed, tert-butanol wasused to rinse the feeding line, pump and charge line, anddischarged into the reaction vessel. The reaction mixture wasmaintained on hold for one hour at 80.degree. C. to 85.degree. C.and sampled for analysis by HPLC. The temperature was raised to80.degree. C.-85.degree. C. An amount of 2.5% by weight of totalamount of monomers of chaser initiator Luperox.RTM. 11 was chargedin six portions every hour. The reaction mixture was maintained onhold for 10 hours at 80.degree. C. to 85.degree. C. The sample wasdried under high vacuum at 50.degree. C. to 55.degree. C. In thepolymer structure shown, x=20 weight %, y=30 weight % and z=50weight %.

Example 9: Synthesis of Poly(VP-Co-MMA-Co-EHMA) with VP/MMA/EHMAWeight Ratio of 20:30:50. Four Hour Feed Reaction in Isopropanoland Tert-Butanol Solvent Combination. 40% Solids Process

##STR00021##

[0318] An amount of 36 g of HPVP and 75 g tert-butanol was added tothe reaction vessel as a heel charge. The reaction mixture waspurged three times with nitrogen while stirring and then heated to75.degree. C. to 80.degree. C. A pre-mixed feed charge comprising90 g of EHMA, 54 g of MMA, tert-butanol and 6.5 g of isopropanolwas fed in the pump. The feed was started at 70.degree. C. to80.degree. C. and continued for four hours. The jacket temperaturewas adjusted to maintain the internal temperature between 75 to80.degree. C. during the feed. A total amount of 1.35 g of theinitial initiator Luperox.RTM. 11 was charged in six portionsduring the feed. After the feed was completed, tert-butanol wasused to rinse the feeding line, pump and charge line, anddischarged into the reaction vessel. The reaction mixture wasmaintained on hold for one hour at 75.degree. C. to 80.degree. C.and sampled for analysis by HPLC. The temperature was raised to80.degree. C.-85.degree. C. An amount of 2.5% by weight of totalamount of monomers of chaser initiator Luperox.RTM. 11 was chargedin six portions every hour. The reaction mixture was maintained onhold for 10 hours at 80.degree. C. to 85.degree. C. The sample wasdried under high vacuum at 50.degree. C. to 55.degree. C. In thepolymer structure shown, x=20 weight %, y=30 weight % and z=50weight %.

Example 10: Synthesis of Poly(VP-Co-MMA-Co-EHMA) with VP/MMA/EHMAWeight Ratio of 20:30:50. Four Hour Feed Reaction in Isopropanoland Tert-Butanol Solvent Combination. 40% Solids Process.Isopropanol Distilled Off at the End

##STR00022##

[0320] An amount of 36 g of HPVP, 75 g tert-butanol, and 6.5 g ofisopropanol was added to the reaction vessel as a heel charge. Thereaction mixture was purged three times with nitrogen whilestirring and then heated to 75.degree. C. to 80.degree. C. Apre-mixed feed charge comprising 90 g of EHMA, 54 g of MMA, andtert-butanol was fed in the pump. The feed was started at70.degree. C. to 80.degree. C. and continued for four hours. Thejacket temperature was adjusted to maintain the internaltemperature between 75 to 80.degree. C. during the feed. A totalamount of 1.35 g of the initial initiator Luperox.RTM. 11 wascharged in six portions during the feed. After the feed wascompleted, tert-butanol was used to rinse the feeding line, pumpand charge line, and discharged into the reaction vessel. Thereaction mixture was maintained on hold for one hour at 75.degree.C. to 80.degree. C. and sampled for analysis by HPLC. Thetemperature was raised to 80.degree. C.-85.degree. C. andisopropanol removed by atmospheric distillation. An amount of 2.5%by weight of total amount of monomers of chaser initiatorLuperox.RTM. 11 was charged in six portions. The reaction mixturewas maintained on hold for 10 hours at 80.degree. C. to 85.degree.C. The sample was dried under high vacuum at 50.degree. C. to55.degree. C. In the polymer structure shown, x=20 weight %, y=30weight % and z=50 weight %.

Example 11: Synthesis of Poly(VP-Co-MMA-Co-EHMA) with VP/MMA/EHMAWeight Ratio of 20:30:50. Peroxide/Cu Catalyst Process

##STR00023##

[0322] An amount of 36 g of HPVP, 75 g tert-butanol, 23 g of EHMAand 30 g of isopropanol was added to the reaction vessel as a heelcharge. The reaction mixture was purged three times with nitrogenwhile stirring and then heated to 75.degree. C. to 80.degree. C. Apre-mixed feed charge comprising 67 g of EHMA, 54 g of MMA,tert-butanol and isopropanol was fed in the pump. The feed wasstarted at 70.degree. C. to 80.degree. C. and continued for twohours. The jacket temperature was adjusted to maintain the internaltemperature between 75 to 80.degree. C. during the feed.H.sub.2O.sub.2/Cu catalyst was used as the initial initiator whichwas charged in six portions during the feed. After the feed wascompleted, tert-butanol was used to rinse the feeding line, pumpand charge line, and discharged into the reaction vessel. Thereaction mixture was maintained on hold for one hour at 75.degree.C. to 80.degree. C. and sampled for analysis by HPLC. Thetemperature was raised to 80.degree. C.-85.degree. C. An amount of2.5% by weight of total amount of monomers of chaser initiatorH.sub.2O.sub.2/Cu catalyst was charged in six portions. Thereaction mixture was maintained on hold for 10 hours at 80.degree.C. to 85.degree. C. The sample was dried under high vacuum at50.degree. C. to 55.degree. C. In the polymer structure shown, x=20weight %, y=30 weight % and z=50 weight %.

Example 12: Synthesis of Poly(VP-Co-MMA-Co-EHMA) with VP/MMA/EHMAWeight Ratio of 20:30:50. EHMA Added Partly in Heel in Tert-ButanolSolvent

##STR00024##

[0324] An amount of 36 g of HPVP, 75 g tert-butanol, and 23 g ofEHMA was added to the reaction vessel as a heel charge. Thereaction mixture was purged three times with nitrogen whilestirring and then heated to 75.degree. C. to 80.degree. C. Apre-mixed feed charge comprising 67 g of EHMA, 54 g of MMA, andtert-butanol was fed in the pump. The feed was started at70.degree. C. to 80.degree. C. and continued for two hours. Thejacket temperature was adjusted to maintain the internaltemperature between 80 to 85.degree. C. during the feed. A totalamount of 1.35 g of the initial initiator Luperox.RTM. 11 wascharged in six portions during the feed. After the feed wascompleted, tert-butanol was used to rinse the feeding line, pumpand charge line, and discharged into the reaction vessel. Thereaction mixture was maintained on hold for one hour at 80.degree.C. to 85.degree. C. and sampled for analysis by HPLC. An amount of1.5% by weight of total amount of monomers of chaser initiatorLuperox.RTM. 11 was charged in three portions in three hours. Thereaction mixture was maintained on hold for 10 hours at 80.degree.C. to 85.degree. C. The sample was dried under high vacuum at50.degree. C. to 55.degree. C. In the polymer structure shown, x=20weight %, y=30 weight % and z=50 weight %.

Example 13: Synthesis of Poly(VP-Co-MMA-Co-EHMA) with VP/MMA/EHMAWeight Ratio of 20:30:50. EHMA Added Partly in Heel in Tert-Butanoland Isopropanol Solvent Combination

##STR00025##

[0326] An amount of 36 g of HPVP, 77 g tert-butanol, 45 g of EHMA,and 33 g of isopropanol was added to the reaction vessel as a heelcharge. The reaction mixture was purged three times with nitrogenwhile stirring and then heated to 70.degree. C. to 75.degree. C. Apre-mixed feed charge comprising 45 g of EHMA, 54 g of MMA,tert-butanol, and isopropanol was fed in the pump. The feed wasstarted at 70.degree. C. to 75.degree. C. and continued for twohours. The jacket temperature was adjusted to maintain the internaltemperature between 75 to 80.degree. C. during the feed. A totalamount of 1.35 g of the initial initiator Luperox.RTM. 11 wascharged in three portions during the feed. After the feed wascompleted, tert-butanol was used to rinse the feeding line, pumpand charge line, and discharged into the reaction vessel. Thereaction mixture was maintained on hold for one hour at 75.degree.C. to 80.degree. C. and sampled for analysis by HPLC. Thetemperature was raised to 120.degree. C.-130.degree. C. An amountof 1.5% by weight of total amount of monomers of chaser initiatorLuperox.RTM. 101 was charged in six portions. The reaction mixturewas maintained on hold for six hours at 120.degree. C. to130.degree. C. The sample was dried under high vacuum at 50.degree.C. to 55.degree. C. In the polymer structure shown, x=20 weight %,y=30 weight % and z=50 weight %.

Example 14: Synthesis of Poly(VP-Co-MMA-Co-EHMA) with VP/MMA/EHMAWeight Ratio of 20:30:50. EHMA Added Partly in Heel in n-HeptaneSolvent

##STR00026##

[0328] An amount of 36 g of HPVP, 38 g n-heptane, 36 g of EHMA, and0.5 g of Vazo.RTM. 67 was added to the reaction vessel as a heelcharge. The reaction mixture was purged three times with nitrogenwhile stirring and then heated to 80.degree. C. to 85.degree. C. Apre-mixed feed charge comprising 54 g of EHMA, 54 g of MMA, andn-heptane was fed in the pump. The feed was started at 70.degree.C. to 75.degree. C. and continued for two hours. The jackettemperature was adjusted to maintain the internal temperaturebetween 75 to 80.degree. C. during the feed. After the feed wascompleted, n-heptane was used to rinse the feeding line, pump andcharge line, and discharged into the reaction vessel. The reactionmixture was maintained on hold for one hour at 75.degree. C. to80.degree. C. and sampled for analysis by HPLC. The temperature wasraised to 85.degree. C.-90.degree. C. An amount of 2.0% by weightof total amount of monomers of chaser initiator Luperox.RTM. 121was charged in four portions. The reaction mixture was maintainedon hold for 10 hours at 90.degree. C. The sample was dried underhigh vacuum at 50.degree. C. to 55.degree. C. In the polymerstructure shown, x=20 weight %, y=30 weight % and z=50 weight%.

Example 15: Synthesis of Poly(VP-Co-MMA-Co-EHMA) with VP/MMA/EHMAWeight Ratio of 20:30:50. EHMA Added Partly in Heel inCeraphyl.RTM. 230

##STR00027##

[0330] An amount of 36 g of HPVP, 39 g Ceraphyl.RTM. 230, 36 g ofEHMA, and 0.9 g of Luperox.RTM. 11 was added to the reaction vesselas a heel charge. The reaction mixture was purged three times withnitrogen while stirring and then heated to 80.degree. C. to85.degree. C. A pre-mixed feed charge comprising 54 g of EHMA, 54 gof MMA, and Ceraphyl.RTM. 230 was fed in the pump. The feed wasstarted at 70.degree. C. to 75.degree. C. and continued for twohours. The jacket temperature was adjusted to maintain the internaltemperature between 75 to 80.degree. C. during the feed. After thefeed was completed, Ceraphyl.RTM. 230 was used to rinse the feedingline, pump and charge line, and discharged into the reactionvessel. The reaction mixture was maintained on hold for one hourand sampled for analysis by HPLC. An amount of 2.0% by weight oftotal amount of monomers of chaser initiator Luperox.RTM. 11 wascharged in four portions. The reaction mixture was maintained onhold for 10 hours at 80.degree. C. to 85.degree. C. The sample wasdried under high vacuum at 50.degree. C. to 55.degree. C. In thepolymer structure shown, x=20 weight %, y=30 weight % and z=50weight %.

Example 16: Synthesis of Poly(VP-Co-MMA-Co-EHMA) with VP/MMA/EHMAWeight Ratio of 20:30:50. EHMA not Added in Heel. Ceraphyl.RTM. 230Solvent

##STR00028##

[0332] An amount of 36 g of HPVP, 75 g Ceraphyl.RTM. 230 and 0.9 gof Luperox.RTM. 11 was added to the reaction vessel as a heelcharge. The reaction mixture was purged three times with nitrogenwhile stirring and then heated to 80.degree. C. to 85.degree. C. Apre-mixed feed charge comprising 90 g of EHMA, 54 g of MMA, andCeraphyl.RTM. 230 was fed in the pump. The feed was started at70.degree. C. to 75.degree. C. and continued for two hours. Thejacket temperature was adjusted to maintain the internaltemperature between 75 to 80.degree. C. during the feed. After thefeed was completed, Ceraphyl.RTM. 230 was used to rinse the feedingline, pump and charge line, and discharged into the reactionvessel. The reaction mixture was maintained on hold for one hourand sampled for analysis by HPLC. An amount of 2.0% by weight oftotal amount of monomers of chaser initiator Luperox.RTM. 11 wascharged in four portions. The reaction mixture was maintained onhold for 10 hours at 80.degree. C. to 85.degree. C. The sample wasdried under high vacuum at 50.degree. C. to 55.degree. C. In thepolymer structure shown, x=20 weight %, y=30 weight % and z=50weight %.

Sun Care Application Data

[0333] The sun care formulations comprising polymers according tothe invention were tested for water resistance using an in-vitromethod, the procedure of which is provided below:

In-Vitro Water Resistance

[0334] (1) VITRO-SKIN.RTM. (VS) was cut into 3.0 cm.times.4.0 cmstrips and mounted in place in a 35 mm slide holder. [0335] (2)Four slides were made for each test product. [0336] (3) One slidewas made for the blank, to obtain the baseline and zero readings.[0337] (4) The slides were then placed into a hydration chamber for12-14 hours to allow the VS to hydrate. The relative humidity ofthe chamber was maintained by an 18% w/w glycerin solution. [0338](5) An amount of 6 to 7 mg of the test product was applied to eachstrip of VS. The slide was then placed back in the humidity chamberfor 20 minutes to allow for coalescence of the test product. [0339](6) The initial UV absorbance of each slide was measured with aUV-Visible spectrophotometer (Cary 300 Series) in the wavelengthrange of 290-400 nm. [0340] (7) Two readings were taken for eachslide--one from each end. [0341] (8) The slides were then immersedin a 25.degree. C. water bath, with circulation of 90 rpm for 80minutes. The slides were then removed and allowed to air dry for 15minutes. [0342] (9) The slides were equilibrated in the humiditychamber for 120 minutes, and the absorbance post immersion wascalculated. [0343] (10) The initial and post absorbance data wassaved as a spreadsheet and exported to an Excel spreadsheet. [0344](11) Area under the curve (sum of the y value) from 290-400 nm wascalculated for each reading. This was done for both initialreadings and post immersion readings. [0345] (12) The percent waterresistance was calculated from the following equation:

[0345] Percent Water Resistance=(Absorbance post immersion/InitialAbsorbance).times.100. [0346] (13) The average value of four slidesgave the final percent water resistance.

Sun Care Emulsion I

TABLE-US-00001 [0347] TABLE 1 List of components of Sun CareEmulsion I Trade Name Composition, Phase Ingredient (manufacturer)% w/w A Water 52.65 Phenoxyethanol (and) Rokonsal .TM./ 1.00Methylparaben (and) LiquaPar .TM. MEP Ethylparaben (and)preservative Propylparaben (Ashland Inc.) TriethanolamineTriethanolamine (Dow) 0.15 Acrylic Acid/VP UltraThix .TM. P-1000.40 Crosspolymer polymer (Ashland) B Avobenzone Escalol .TM. 517UV 3.00 filter (Ashland) Octisalate Escalol .TM. 587 UV 5.00 filter(Ashland) Homosalate Escalol .TM. HMS UV 8.00 filter (Ashland)Octocrylene Escalol .TM. 597 UV 5.00 filter (Ashland) Benzopheneone-3 Escalol .TM. 567 UV 6.00 filter (Ashland) Glyceryl StearateArlacel .TM. 165 4.00 (and) PEG- (Croda) 100 Stearate DiisopropylAdipate Ceraphyl .TM. 230 5.50 ester (Ashland) C12-15 Alkyl LactateCeraphyl .TM. 41 2.50 ester (Ashland) Glyceryl Dilaurate Emulsynt.TM. GDL 0.50 emulsifier (Ashland) Stearyl Alcohol 1.00 C Glycerin(and) Lubrajel .TM. II-XD 1.00 Glyceryl (Ashland) PolyacrylateCyclopentasiloxane Si-Tec CM040 3.00 D Phenoxyethanol (and)Optiphen .TM. MIT 0.30 Methyl- Ultra (Ashland) isothiozolinoneTotal 99.0

[0348] An amount of 1.0 g of the polymer prepared according toExample 1 was added to Phase B of Sun Care Emulsion I and theresulting emulsion was tested for water resistance. FIG. 1 showsthe percent water resistance value of the emulsion comprisingpolymer of Example 1 in comparison with various commerciallyavailable sun care products.

Sun Care Emulsion II

TABLE-US-00002 [0349] TABLE 2 List of components of Sun CareEmulsion II Trade Name Composition, Phase Ingredient (manufacturer)% w/w A Water 51.60 Glycerin Glycerin (Ruger) 1.00 Phenoxyethanol(and) LiquaPar .TM. MEP 1.00 Methylparaben (and) preservativeEthylparaben (and) (Ashland) Propylparaben Carbomer Carbomer .TM.980 0.30 (Ashland) B Avobenzone Escalol .TM. 517 UV 3.00 filter(Ashland) Octisalate Escalol .TM. 587 UV 5.00 filter (Ashland)Homosalate Escalol .TM. HMS UV 8.00 filter (Ashland) OctocryleneEscalol .TM. 597 UV 5.00 filter (Ashland) Benzopheneone -3 Escalol.TM. 567 UV 6.00 filter (Ashland) Glyceryl Stearate Arlacel .TM.165 4.00 (and) PEG- (Croda) 100 Stearate Diisopropyl AdipateCeraphyl .TM. 230 5.50 ester (Ashland) C12-15 Alkyl LactateCeraphyl .TM. 41 2.50 ester (Ashland) Glyceryl Dilaurate Emulsynt.TM. GDL 0.50 emulsifier (Ashland) Stearyl Alcohol 1.00Triethanolamine Triethanolamine (Dow) 0.30 C Glycerin (and)Lubrajel .TM. II-XD 1.00 Glyceryl (Ashland) PolyacrylateCyclopentasiloxane Si-Tec CM040 3.00 D Phenoxyethanol (and)Optiphen .TM. MIT 0.30 Methyl- Ultra (Ashland) isothiozolinoneTotal 99.0

[0350] An amount of 1.0 g of the polymer prepared according toExample 1 was added to Phase B of Sun Care Emulsion II and theresulting emulsion was tested for water resistance. FIG. 2 showsthe percent water resistance of the emulsion comprising polymer ofExample 1 in comparison with various commercially available suncare products.

Sun Care Emulsion III

TABLE-US-00003 [0351] TABLE 3 List of components of Sun CareEmulsion III Trade Name Composition, Phase Ingredient(manufacturer) % w/w A Water 55.70 Glycerin Glycerin (Ruger) 2.00Xanthan Gum 0.50 B Avobenzone Escalol .TM. 517 UV 3.00 filter(Ashland) Octisalate Escalol .TM. 587 UV 5.00 filter (Ashland)Homosalate Escalol .TM. HMS UV 8.00 filter (Ashland) OctocryleneEscalol .TM. 597 UV 5.00 filter (Ashland) Benzopheneone -3 Escalol.TM. 567 UV 6.00 filter (Ashland) Glyceryl Stearate Arlacel .TM.165 4.00 (and) PEG- (Croda) 100 Stearate Diisopropyl AdipateCeraphyl .TM. 230 5.50 ester (Ashland) C12-15 Alkyl LactateCeraphyl .TM. 41 2.50 ester (Ashland) Glyceryl Dilaurate Emulsynt.TM. GDL 0.50 emulsifier (Ashland) Stearyl Alcohol 1.00 CPhenoxyethanol (and) Optiphen .TM. MIT 0.30 Methyl- Ultra (Ashland)isothiozolinone Total 99.0

[0352] An amount of 1.0 g of the polymer prepared according toExample 1 was added to Phase B of Sun Care Emulsion III and theresulting emulsion was tested for water resistance. FIG. 3 showsthe percent water resistance of the emulsion comprising polymer ofExample 1 in comparison with various commercially available suncare products.

Anhydrous Formulation

TABLE-US-00004 [0353] TABLE 4 List of components of AnhydrousFormulation Trade Name Composition, Phase Ingredient (manufacturer)% w/w A Ethanol 66.00 B Avobenzone Escalol .TM. 517 UV 3.00 filter(Ashland) Octisalate Escalol .TM. 587 UV 5.00 filter (Ashland)Homosalate Escalol .TM. HMS UV 10.00 filter (Ashland) OctocryleneEscalol .TM. 597 UV 10.00 filter (Ashland) Benzopheneone -3 Escalol.TM. 567 UV 5.00 filter (Ashland) Total 99.0

[0354] An amount of 1.0 g of the polymer prepared according toExample 1 was added to Phase B of the Anhydrous Formulation and theresulting formulation was tested for water resistance. FIG. 4 showsthe percent water resistance of the Anhydrous Formulationcomprising polymer of Example 1 in comparison with variouscommercially available sun care products.

[0355] All references including patent applications and publicationcited herein are incorporated herein by reference in their entiretyand for all purpose to the same extent as if each individualpublication or patent or patent application was specifically andindividually indicated to be incorporated by reference in itsentirety for all purposes. Many modifications and variations of thepresently disclosed and claimed inventive concept(s) can be madewithout departing from its spirit and scope, as will be apparent tothose skilled in the art.

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References

• ip.com