US 20140336308A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2014/0336308 A1 Mateu et al. (43) Pub. Date: NOV. 13, 2014

(54) LOW ENERGY, COLD PROCESS Publication Classi?cation FORMULATION AID (51) 1111.0. (71) Applicants:Juan R. Mateu, Oak Ridge, NJ (US); C08L 91/06 (2006.01) Adam Perle, Fair?eld, NJ (US) (52) U.S.Cl. CPC ...... C08L 91/06 (2013.01) (72) Inventors: Juan R. Mateu, Oak Ridge, NJ (US); USPC ...... 524/27; 524/547; 524/548; 524/612; Adam Perle, Fair?eld, NJ (US) 524/317 (73) Assignee: Jeen International Corporation, Fair?eld, NJ (US) (57) ABSTRACT (21) App1.No.: 14/276,404 Provided are cold process formulation aids (CPFAs), meth ods for their manufacture, and personal care products made (22) Filed: May 13, 2014 using them. CPFAs include (i) a polymer having an aliphatic backbone and a plurality of pendant groups thereon that are Related US. Application Data pendant ionic or ionizable groups, or pendant groups having (63) Continuation-in-part of application No. 13/630,863, at least one permanent dipole that includes an acid, alcohol, ?led on Sep. 28, 2012, which is a continuation of thiol, ester, amine, amide, imide, imine, or nitrile moiety, and (ii) a wax selected from natural waxes and synthetic waxes, application No. 13/082,317, ?led onApr. 7, 2011, now wherein if the wax is not micronized and is not self-emulsi Pat. No. 8,299,162. fying, the ratio, by weight, of the non-micronized wax to the (60) Provisional application No. 61/321,765, ?led on Apr. polymer having an aliphatic backbone is from about 60:40 to 7, 2010, provisional application No. 61/347,664, ?led 80:20, and if the wax is a micronized wax or a self-emulsify on May 24, 2010, provisional application No. 61/435, ing wax, the ratio, by weight, of wax to polymer backbone is 128, ?led on Jan. 21, 2011. 70:30 to 98:2. US 2014/0336308 A1 Nov. 13, 2014

LOW ENERGY, COLD PROCESS occur when manufacturing emulsions (or hydrogels) using FORMULATION AID CPFAs of the present invention. [0006] Importantly, in conventional manufacturing pro CROSS-REFERENCES TO RELATED cesses, the emulsion is not stabilized until the emulsion is APPLICATIONS cooled down. This “cool down” stage is critical. However, the [0001] This application is a continuation-in-part of, and rate and duration of cool down can impact the sensorial prop claims the bene?t of priority to, US. Non-Provisional appli erties of the ?nal ?nished product, often causing batch-to cation Ser. No. 13/630,863, ?led on Sep. 28, 2012. applica batch variation. CPFAs of the present invention solve this tion Ser. No. 13/ 630,863 claims the bene?t of priority to US. problem, providing a streamlined process, with fewer addi Non-Provisional application Ser. No. 13/082,317, ?led on tion steps, using only one vessel, with signi?cantly lower Apr. 7, 2011, and now US. Pat. No. 8,299,162, claims the energy requirements to create reproducible emulsions (and priority bene?t of US. Provisional Application Ser. No. hydrogels). 61/321,765 ?led on Apr. 7, 2010, US. Provisional Applica [0007] Polyacrylic acids, polyacrylates, polycacrylate tion Ser. No. 61/347,664 ?led on May 24, 2010, and US. copolymers, polyacrylate crosspolymers, and their respective Provisional Application Ser. No. 61/435,128 ?led on Jan. 21, salts (collectively referred to in the present application as 2011. The contents of US. Non-Provisional application Ser. “Polyacrylic Acid Derivatives” and abbreviated as “PADs”) Nos. 13/630,863 and 13/082,317, as well as US. Provisional 4components of the CPFAs of the present inventioniare Application Ser. Nos. 61/321,765, 61/347,664, and 61/435, typically provided by suppliers of chemical raw materials in 128 are each incorporated herein by reference in their powder form and serve a number of functions in personal care entirety. formulations (as well as in paints and other surface coatings, adhesives, and textiles), including as aqueous rheology modi STATEMENT REGARDING FEDERALLY ?ers. However, when provided in powder form, PADs are not SPONSORED RESEARCH OR DEVELOPMENT easily or thoroughly dispersed, and often form aggregates. To overcome these limitations, PADs are commonly sold as dis [0002] Not applicable. persions in a solvent also containing an emulsi?er. When provided in the form of a dispersion, the powder is “plasti FIELD OF THE INVENTION cized”, and is thus more easily added to an emulsion to [0003] The present invention is directed to low-energy, low achieve the desired rheology. Typically, the solvent is petro carbon footprint, cold process formulation aids (CPFAs), leum derived (e. g., mineral oil or a hydrogenated alkene, such methods for their manufacture, and methods of using them in as polydecene, polybutylene, or squalene) and the emulsi?er the manufacture of personal care products. When one or a is ethoxylated. There is, however, a growing demand to combination of CPFAs of the present invention is/are com reduce the use of petroleum derived ingredients, especially in bined with an aqueous medium and other ingredients, an personal care formulations. Accordingly, there is a need for emulsion (or hydrogel) can be formed, often at temperatures being able to disperse PADs without petroleum-derived sol not exceeding 30° C. vents and without forming aggregates. This need is met by the inventive compositions of the present invention. In personal BACKGROUND OF THE INVENTION care formulations, esters are among the most common ingre dientsifunctioning as emollients and conditioners (e.g., Iso [0004] CPFAs of the present invention allow the creation of stable emulsions and hydro gels in a manner that is markedly propyl Myristate), as solvents (e.g., Ethyl Acetate), as fra grance components (e.g., Methyl Salicylate), and as more ef?cient than the conventional manufacturing processes in several respects. Conventional emulsion manufacturing preservatives (e.g., Propylparaben). Caprylic/Capric Glycer ides (“CTG”) is also widely used for its emollient properties, processes requires two heated mixing vessels. The aqueous increasing the water content of skin by blocking the evapo phase is weighed, staged and introduced into a ?rst vessel. The oil phase is weighed, staged and introduced into a second rative loss of water. However, PADs are known to have lim ited or no solubility in cosmetically acceptable esters or CTG. vessel. Prior to being combined, the contents of the two To the extent PADs could be mixed into such esters or CTG, separate vessels must each be heated to a temperature greater the resultant sticky paste was very high in viscosity, too high than the melt point of the highest wax in the emulsion, typi cally by 5 degrees Centigrade. If, for example, the aqueous to be used in the manufacture of personal care products. Accordingly, there is a need to be able to render PADs are phase is colder than the oil phase, waxes in the oil phase can directly soluble in cosmetically-acceptable esters and CTG, crystallize. Further, in conventional emulsion manufactur ingiparticularly, complex multi-ingredient formulationsi without a petroleum-derived solvent. That need is met by the ingredients must be carefully weighed, added in speci?c compositions and methods of the present invention whereby order, and mixed for speci?c mixing times. Addition of one PADs (and mixtures thereof) are combined speci?c minimum phase into another phase is often sensitive to the rate of amount of one or a mixture of emulsifying waxes, which, in certain embodiments, are polyglyceryl esters, thereby render addition. If two phases are combined too quickly, increased ing the PADs directly soluble in cosmetically-acceptable mixing time, and energy, is required to stabilize the emulsion. [0005] Using CPFAs of the present invention is simpler and esters and CTG. requires less energy. CPFAs of the present invention allow the SUMMARY OF THE INVENTION two phases of the emulsion, aqueous and oil, to be combined into a single vessel, not two (or more) vessel, and thereafter [0008] The present invention relates to cold process formu mixed and heated to the desired temperature. Only one vessel lation aids (CPFAs), methods for their manufacture, uses of needs to be heated (and cleaned). At low as well as high CPFAs in making cold process emulsions and hydrogels for temperatures, the mixture containing CPFA is emulsi?ed and use in personal care, household and industrial applications. homogenous. Moreover, crystallization of waxes does not The cold processing aids include at least one wax and a US 2014/0336308 A1 Nov. 13, 2014

polymer having a backbone and a plurality of pendant groups wherein R is a straight or branched chain saturated or unsat thereon that are pendant ionic or ionizable groups, or pendant urated alkyl having 2 to 30 carbon atoms, or phenyl; and an groups having at least one permanent dipole that includes an alcohol having the formula R4OH wherein R is a straight or acid, alcohol, thiol, ester, amine, amide, imide, imine, or branched chain saturated or unsaturated alkyl having 2-30 nitrile moiety. The backbone can be an aliphatic backbone or carbon atoms, or phenyl. Either one or both of the acid or a polysaccharide backbone, a siloxane backbone, or a polya alcohol may be a “fatty” acid or alcohol, having from about 6 mide backbone. The present invention is also directed to to 22 carbon atoms. compositions and methods for rendering polyacrylic acids, [0014] As used herein, “cosmetically-acceptable diesters” polyacrylates, polycacrylate copolymers, polyacrylate cros refer to the reaction products of a dicarboxylic acid and an spolymers, and their respective salts directly soluble in cos aliphatic or aromatic alcohol. The dicarboxylic acid may metically-acceptable esters and CTG by combining, in spe contain from 2 to 30 carbon atoms, and may be in the straight ci?c ratios, the PAD with an emulsifying wax, which, in or branched chain, saturated or unsaturated form. The dicar preferred embodiments is a polyglyceryl ester. boxylic acid may be substituted with one or more hydroxyl groups. The aliphatic or aromatic alcohol may also contain 2 DETAILED DESCRIPTION OF THE INVENTION to 30 carbon atoms, and may be in the straight or branched [0009] As used in herein, the term “emulsion” is to be chain, saturated, or unsaturated form. The aliphatic or aro understood as a homogenous mixture of at least two other matic alcohol may be substituted with one or more substi wise immiscible ingredients. Emulsions can be of the oil-in tutents such as hydroxyl. Preferably, one or more of the acid water type or the silicone-in-water type, or, in certain embodi or alcohol is a fatty acid or alcohol containing 14-22 carbon ments, so-called “invert” emulsions, of the water-in-oil type, atoms. The dicarboxylic acid may also be an alpha hydroxy the silicone-in-water type. Additionally, so-called “triple” acid. emulsionsiincluding, for example, water-in-oil-in-water, [0015] “Cosmetically-acceptable triesters” as used in the can be made by combining the cold process aid of the present present application refers to the reaction products of a tricar invention with an aqueous medium as well as other ingredi boxylic acid and an aliphatic or aromatic alcohol The acid and ents. alcohol contain 2 to 30 carbon atoms, and may be saturated or [0010] As used herein, “aqueous medium” refers to a sub unsatured, straight or branched chain, and, may be substituted stance that is preferably liquid at room temperature (22°-27o with one or more hydroxyl groups. Preferably, one or more of C.) but does not exclude the use of said liquid at a temperature the acid or alcohol is a fatty acid or alcohol containing 14 to lower than the melt point of the patentable compositions 22 carbon atoms. described in this invention and that includes at least 50%, [001 6] In describing the weight of ingredients used in form preferably at least 75%, still more preferably at least 90%, by ing the compositions of the present invention, the word weight, water. The remainder of the aqueous medium can be “about” is to be understood to refer to that variation in the compounds that are freely miscible with water, for example measured quantity as would be expected by one skilled in the alcohols such as ethanol and the propanols, and polyalkylene art exercising a level of care commensurate with the objective glycols, to mention just a few. of the measurement and the equipment used, and includes [0011] The adjective “cold” in the term “cold process”i uncertainties that may be introduced by mathematical round used in the present application to describe “cold process ing errors. Unless otherwise expressly noted or required by formulation aid” as well as a method for creating emulsions or the context, all percentages refer to percentages by weight hydrogels using such a formulation aidimeans a tempera (wt-%) and the percentage of an ingredient is the percentage ture below the melting point of the at least one wax that is an by weight of the ingredient by weight of the composition/ integral component of the cold process formulation aid. blend in which the ingredient is a component. For example, in Accordingly, when a formulator adds a cold process formu a blend or mixture described as containing ingredient X at a lation aid of the present invention to an aqueous medium, an concentration of 2%, ingredient X would constitute 2% emulsion or hydrogel is formed without having to heat the weight of the blend. In a ?rst aspect of the present invention, aqueous medium above the melting point of the at least one one or more CPFAs are added to an aqueous medium at wax. This “one wax” will be the wax in the CFPA that has the temperatures greater than the melt point of the CPFA, or in the highest melt point. case of more than one CPFA the highest melt point of the [0012] As used herein, “cosmetically-acceptable ester” CPFAs. refers to a compound formed by the reaction of a mono-, di [0017] In embodiments of this ?rst aspect of the invention, or tri-carboxylic acid with an aliphatic or aromatic alcohol the cold process formulation aid of the present invention, in resulting in, respectively, monoesters, diesters and triesters, certain of its embodiments, includes a polymer having an each as de?ned below. The carboxylic acid may contain from aliphatic backbone and a plurality of pendant groups thereon 2 to 30 carbon atoms, and may be straight-chain or branched that are pendant ionic or ionizable groups, and/or that are chain, saturated or unsaturated. The carboxylic acid may also pendant groups having at least one permanent dipole that be substituted with one or more hydroxyl groups. The ali includes an acid, alcohol, thiol, ester, amines, amide, imide, phatic or aromatic alcohol may contain 2 to 30 carbon atoms, imine, or nitrile moiety. may be straight-chain or branched-chain, saturated or unsat [0018] By aliphatic backbone is meant that the main poly urated. The aliphatic or aromatic alcohol may contain one or mer chain consists of a majority, preferably essentially exclu more substituents including, for example, a hydroxyl group. sively, of carbon-carbon bonds. The ester is “cosmetically-acceptable” such that it is not [0019] Polymers having an aliphatic backbone are well irritating or sensitiZing when applied to the skin known in the polymer arts and can be made by, for example, [0013] As used in the present invention, “cosmetically-ac free-radical initiated polymerization of compounds (mono ceptable monoesters” are esters formed by the reaction of a mers) having a carbon-carbon double bond, colloquially monocarboxylic acid having the formula R4COOH, referred to as “vinyl-type monomers”. Poly(methyl meth US 2014/0336308 A1 Nov. 13, 2014

acrylate) and poly(acrylic acid) are examples of polymers [0025] Poly(acrylic acid), also referred to in the present having aliphatic backbones that can be obtained by the free application as poly(acrylic) acid, is the polymer of acrylic radical polymerization of, respectively, methyl methacrylate acid (2-propenoic acid) and conforms generally to the for and acrylic acid. mula: [0020] The polymers having an aliphatic backbone and a plurality of pendant groups thereon that are pendant ionic or CHZCH ionizable groups, and/or that are pendant groups having at | least one permanent dipole that includes an acid, alcohol, COOH thiol, ester, amine, amide, imide, imine, or nitrile moiety X useful in making the cold process formulation aid of the present invention can be homopolymers, obtained by poly [0026] Poly(acrylic acid) is soluble in tetrahydrofuran, merizing a single monomer, or they can be co- or ter-poly water, methanol, and ethanol, but precipitates from ether, mers, obtained by polymerizing a mixture of two or three acetone, and hexane, and is commercially available under the monomers. following tradenames: AC-lOHiNihon Junyaku Company, [0021] The polymers having an aliphatic backbone and a Ltd. (Tokyo, Japan); Creagel TN 5004C.I.T. sarl (Dreux, plurality of pendant groups can be, and in certain embodi France); Jurymer AC-lOLHPiNihon Junyaku Company, ments are, crosslinked polymers. Crosslinking can be Ltd. (Tokyo, Japan); Modarez V 1300 PXiSynthron (Leval achieved by methods known in the art, for example by com lois, France); OriStar PALAiOrient Stars LLC (Torrance, bining a compound (“crosslinking agent”) having two or Calif.). more polymerizable carbon-carbon double bonds with the monomer(s) being polymerized. Allyl ether and 0t,u)-diallyl [0027] The term “Polyacrylate” as used in the present ethers and 0t,u)-diacrylate or dimethacrylate esters of poly application refers to a synthetic resins produced by the poly (alkylene glycols) are examples of crosslinking agents that merization of acrylic esters. The term “acrylic ester” is well can be used to prepare crosslinked polymers having an ali known to the person having ordinary skill in the chemical arts. phatic backbone and a plurality of ionic, ionizable, or perma Acrylic acid molecules are esteri?ed by reaction with alco nent dipole-containing pendant groups. Others crosslinking hols, most commonly ethanol or methanol. In the esteri?ca agents are known in the art. tion reaction, the hydrogen atom in the carboxyl group on the acrylic acid molecule is replaced by an organic groupia [0022] The pendant groups, occasionally referred to in the methyl group in reactions with methanol, and an ethyl group art as “side-chains”, useful in the practice of certain embodi in reactions with ethanol. The most common polyacrylates ments of the present invention are groups, or “radicals”, that are polyethyl acrylate and polymethyl acrylate, represented are attached to a carbon atom in the main polymer chain by a chemical bond, but are not part of the main polymer chain. by the formula CH2:CHCOZR, where R is an organic group. The pendant groups attached to the main polymer chain can [0028] The following is a non-limiting list of polyacrylate be present in the monomer(s) at the time of polymerization, or salts and their derivatives, which can be used in forming the they can be formed by post-polymerization reaction, for inventive compositions of the present inventioninamely example post-polymerization sali?cation or hydrolysis of a CPFAs as well as blends with glyceryl esters that can be sali?able or hydrolysable functional group that was present added directly to, and will be directly soluble in, a cosmeti as, or as part of, a substituent on the monomer(s) at the time of cally-acceptable ester or CTG. polymerization. The methoxycarbonyl [4C(O)4OCH3] [0029] Sodium Polyacrylate is the sodium salt of Poly group of poly(methyl methacrylate), obtained by polymeriza acrylic Acid. It is commercially available under the following tion of methyl methacrylate, is an example of a pendant group tradenames: Activsoft MS lOOiInnospec Performance that was present as a substituent on a monomer at the time of polymerization. Chemicals (Salisbury, NC); Acusol AD-7 PolymeriThe Dow Chemical Company (Midland, Mich.);AronvisiNihon [0023] The pendant groups of the polymers having an ali Junyaku Company, Ltd. (Tokyo, Japan); Cosmedia phatic backbone and a plurality of pendant groups that are SPiBASF Personal Care and Nutrition Gmbh (Germany); useful in the practice of certain embodiments of the present Covacryl ACiSensient Cosmetic Technologies (France); invention can be ionic or ionizable, or they can be groups that Covacryl J22iSensient Cosmetic Technologies (France); have at least one permanent dipole due to the presence in the Covacryl MV60—Sensient Cosmetic Technologies (France); pendant group of an acid, alcohol, thiol, ester, amine, amide, Covacryl RHiSensient Cosmetic Technologies (France); imide, imine, or nitrile moiety, or they can be a combination Flocare CGEL lOOiSNF SAS (Andrezieux, France); Flo of any of the foregoing. care DP/PSD lOO—SNF SAS (Andrezieux, France); Flocare [0024] Ionic pendant groups carry permanent ionic G300iSNF SAS (Andrezieux, France); Flocare G800i SNF SAS (Andrezieux, France); RapiThix A- l OOiAshland charges. The carboxylate group, 4C(O)O_M+, where M+ is Inc. (Wilmington, Del.); Rheogic 250HiNihon Junyaku a metal cation, especially a cation of an alkali metal, is an Company, Ltd. (Tokyo, Japan); Rheosol APiRheolabs Inc. example of an ionic pendant group. Sodium polyacrylate (the sodium salt of poly(acrylic acid)) is a preferred polymer (South Holland, Ill.); Rhesperse RMlOOiInnospec Perfor mance Chemicals (Salisbury, NC); Sanfresh ST-500 having an aliphatic backbone and a plurality of pendant ionic groups for use in certain embodiments of the cold process MPSAiRisera Co., Ltd. (Hakodate, Japan); formulation aid of the present invention. Other polycacrylate [0030] Ammonium Polyacrylate is the ammonium salt of copolymers, polyacrylate crosspolymers, and their respective Polyacrylic Acid and is commercially available under the salts may be used in forming CPFAs (as well as in other tradename Covacryl VIP from Sensient Cosmetic Technolo aspects of the present invention as further described below). gies (Saint Ouen L’Aumone, France). US 2014/0336308 A1 Nov. 13, 2014

[0031] Potassium Polyacrylate is the potassium salt of -continued Polyacrylic Acid. O H [0032] Potassium Aluminum Polyacrylate is a mixture of C — O the potassium and aluminum salts of Polyacrylic Acid. [0033] Sodium Polyacrylate Starch is a starch grafted with O the polymer sodium acrylate. This starch is commercially CH3O available under the following tradenames: Makimousse O 12iDaito Kasei Kogyo Co., Ltd. (Osaka, Japan); Makimo C —O usse 25iDaito Kasei Kogyo Co., Ltd. (Osaka, Japan); San H fresh ST-lOOCiSanyo Chemical Industries Ltd. (Kyoto, O O Japan); Sanfresh ST-lOOMCiSanyo Chemical Industries Ltd. (Kyoto, Japan); Sanwet IM-300MCiSanyo Chemical Industries Ltd. (Kyoto, Japan) [0034] The term “Acrylates Copolymer” as used in the [0040] Polyacrylate-5 is a copolymer of styrene, ethylhexyl present application refers to a copolymer of two or more acrylate, hydroxyethyl acrylate, and one or more monomers monomers consisting of acrylic acid, methacrylic acid or one of acrylic acid, methacrylic acid, or one of their simple esters. of their esters (e.g., polyethyl acrylate and polymethyl acry late). According to INCI naming conventions, copolymers [0041] Polyacrylate-6 is a copolymer of methyl methacry consisting of two or more constituent monomers are named late, triethoxysilylpropyl-methacrylate, tris(trimethylsiloxy) by listing the monomers separated by a slash (/) followed by silylpropylmethacrylate and acryloyloxyethyl (trimethyl) the word “Copolymer,” e.g., Acrylates/Acrylamide Copoly ammonium chloride monomers. This copolymer is commercially available under the tradename MK Polymer mer. In the case of INCI names assigned to cross polymers from Shin-Etsu Chemical Co. (Tokyo, Japan). before March 2003, the earlier name is retained without copolymer notation. An arbitrary number may follow the [0042] Polyacrylate-7 is a copolymer of 2-acryloylethyl name. For example, Polyacrylate-l. trimethylammonium chloride, acrylic acid, acrylamide, and [0035] The following is a non-limiting list of Acrylates 2-acrylamido-2-methylpropane sulfonic acid. This copoly mer is commercially available under the tradename OF-420 Copolymers, which can be used to make CPFAs and which, when combined with a glyceryl ester in accordance with the from WSP Chemicals & Technology LLC (Leetsdale, Pa.). present invention, can be added directly to, and will be [0043] Polyacrylate-8 is a copolymer of hydroxypropy directly soluble in, a cosmetically-acceptable ester or CTG. lacrylate, butylaminoethyl methacrylate, and one or more [0036] Polyacrylate-l is a copolymer of vinyl pyrrolidone, monomers of acrylic acid, methacrylic acid, or one of their dimethylaminoethyl methacrylate, stearyl acrylate and simple esters. This copolymer is commercially available under the tradename Balance AM from AkzoNobel Global PPG-3 diacrylate monomers. This copolymer is commer cially available under the tradename Cosquat GA467 from Personal Care (Bridgewater, NJ). Osaka Organic Chemical Ind., LTD. (Osaka, Japan). [0044] Polyacrylate-9 is a copolymer of octylpropenamide, [0037] Polyacrylate-2 is a copolymer of styrene, acryla butylaminoethyl-methacrylate, hydroxypropylmethacrylate, mide, octyl acrylate and methyl methacrylate monomers. and one or more momoners of acrylic acid, methacrylic acid or one of thier simple esters. This copolymer is commercially [0038] Polyacrylate-3 is a copolymer of methacrylic acid, available under the tradename Amphomer 28-4920 from methyl methacrylate, methylstyrene isopropylisocyanate and AkzoNobel Global Personal Care (Bridgewater, NJ). PEG-40 behenate monomers. This copolymer is commeri [0045] Polyacrylate-lO is a copolymer of sodium acry cially available under the tradename Viscophobe DB-lOOO loyldimethyltaurate, sodium acrylate, acrylamide and vinyl from Dow Chemical Company (Midland, Mich.). pyrrolidone monomers. [0039] Polyacrylate-4 is a polymer of the acrylic monomers [0046] Polyacrylate-ll is a copolymer of sodium acry having the empirical formula (C24H34OIO.C24H2209. loyldimethyl taurate, sodium acrylate, hydroxyethyl acrylate, C24H2209)x and is represented by the following structures: lauryl acrylate, butyl acrylate and acrylamide monomers. [0047] Polyacrylate-12 is a copolymer of C3_ll acrylate, 0 styrene, Methacrylic Acid (q.v.) and acetoacetoxyethyl meth acrylate monomers. This copolymer is commercially avail able under the tradename Acudyne NP-l from Dow Chemical 0 Company (Midland, Mich.). M [0048] Polyacrylate-l3 is the copolymer of acrylic acid, acrylamide, sodium acrylate and sodium acryloyldimethyl taurate monomers. [0049] Polyacrylate-l4 is a copolymer of PEG-25 C10_3O alkyl ether methacrylate, PEG-20 PPG-5 allyl ether and one or more monomers consisting of acrylic acid, methacrylic acid or one of their simple esters. This copolymer is commer 0—0 cially available under the tradename Fixate PLUS Polymer H from Lubrizol Advanced Materials, Inc. (Cleveland, Ohio). o o [0050] Polyacrylate-15 is a copolymer of n-butyl acrylate, ethyl acrylate, methyl methacrylate, ethylene, methacrylic acid and styrene monomers. This copolymer is commercially US 2014/0336308 A1 Nov. 13, 2014

available under the tradename Syntran PC 5208 from lnter methacrylate and Methyl Methacrylate (q.v.) monomers polymer Corporation (Canton, Mass.). modi?ed With hydrogen peroxide. [0051] Polyacrylate-l6 is a copolymer of n-butyl acrylate, [0059] Polyacrylate-25 is a copolymer of Dimethylamino diethylaminoethyl methacrylate, ethyl acrylate, methacrylic ethyl Methacrylate (q.v.), Lauryl Methacrylate (q.v.), stearyl acid, hydroxypropyl methacrylate, methyl methacrylate and methacrylate, Methyl Methacrylate (q.v.) and Butyl Meth styrene monomers. This copolymer is commercially avail acrylate (q.v.), modi?ed With hydrogen peroxide. [0060] Polyacrylate-26 is a copolymer of n-butyl acrylate, able under the tradename Syntran PC5 1 12 from lnterpolymer t-butylamino-ethylmethacrylate, methylmethacrylate, dim Corporation (Canton, Mass.). ethylaminoethyl methacrylate and hydroxyethyl methacry [0052] Polyacrylate-l7 is a copolymer of n-butyl acrylate, late monomers. diethylaminoethyl methacrylate, hydroxyethyl methacrylate, [0061] Polyacrylate-27 is a copolymer of vintyl toluene, methyl methacrylate and t-butylaminoethyl methacrylate. 2-ethylhexyl acrylate, 2-hydroxyethyl methacrylate, vinyl [0053] Polyacrylate-l8 is a copolymer of n-butyl acrylate, imidazole, and methoxy PEG-8 methacrylate monomers. ethyl acrylate, methacrylic acid, hydroxypropyl methacrylate This copolymer is commercially available under the trade and styrene monomers. name Tinocare WRP from BASF Corporation (Florham Park, [0054] Polyacrylate-l9 is a copolymer of n-butyl acrylate, N.J.). methacrylic acid, methyl methacrylate, dimethylaminoethyl [0062] Polyacrylate-28 is a copolymer of hydroxyethyl methacrylate and methoxy PEG-8 acrylate. acrylate, sodium acryloyldimethyltaurate, sodium acrylate and tris(hydroxymethyl)-acrylamidomethane. This copoly [0055] Polyacrylate-20 (also known as Acrylates/Methoxy mer is commercially available under the tradename Sepinov PEG-10 Maleate/ Styrene Copolymer) is a copolymer of sty F900 from Seppic (Paris, France). rene, methoxy PEG-10 maleate and one or more monomers [0063] Polyacrylate-29 is a copolymer of stearyl methacry consisting of acrylic acid, methacrylic acid or one of their late, methoxy PEG-9 methacrylate and methacrylic acid. simple esters. Polyacrylate-20 is commercially available as [0064] Polyacrylate-30 is a copolymer of acrylonitrile, Opulyn 305 Opaci?er from The DoW Chemical Company methacrylic acid, octyl acrylate, and styrene. (Midland, Mich). [0065] Polyacrylate-3l is a copolymer of Cl_18 alkyl acry [0056] Polyacrylate-2l is a copolymer of 2-ethylhexyl late, C1_8 alkyl acrylate, methoxymethyl acrylamide and one acrylate, butyl methacrylate, methacrylic acid, methyl meth or more monomers consisting of acrylic acid, methacrylic acrylate, hydroxypropyl methacrylate and styrene. acid or one of their simple esters neutralized With aminom [0057] Polyacrylate-22 is a complex polymer that is pre ethyl-propanol (AMP). This copolymer is commercially pared by ?rst reacting isophorone diisocyanate (lPDl With a available under the tradename Plascize L-9959 from Goo copolymer made from Adipic Acid (q.v.) and Neopentyl Gly Chemical Company, Ltd. (Kyoto, Japan). col (q.v.). The isocyanate groups on the resulting polymer are [0066] Polyacrylate-32 is a copolymer of PEG/PPG-23/6 then reacted With hydroxyethyl methacrylate followed by Dimethicone (q.v.), sodium acryloyldimethyltaurate, citra quenching With ethanol to eliminate residual urethane conic anhydride and one or more monomers of acrylic acid, groups. Finally, the polymer above is copolymerized With methacrylic acid or one of their simple esters. This copolymer acrylic acid, methacrylic acid, and methyl methacrylate, then is commercially available under the tradename Fixate Design partially neutralized With aminomethyl propanol (AMP). Polymer from Lubrizol Advanced Materials, Inc. (Cleveland, This polymer is commercially available under the tradename Ohio). Luviset Shape from BASF Corporation (Florham Park, NI.) [0067] Polyacrylate-33 is a copolymer that conforms gen [0058] Polyacrylate-24 is a copolymer of Dimethylamino erally to the formula (structure beloW) Where R represents a ethyl Methacrylate (q.v.), Lauryl Methacrylate (q.v.), stearyl Cl6-22 alkyl grouP

cnzcrewrite cnzc cnzc Trcnzc —

CH3 CH3

® indicates text missing or illegible When ?led US 2014/0336308 A1 Nov. 13, 2014

[0068] Polyacrylate-33 is commercially available under the methacrylic acid or one of their simple esters, crosslinked tradename Rheomer 33 from Rhodia Novecare (Bristol, Pa.). with trimethylolpropane PEG-15 triacrylate. This copolymer [0069] Polyacrylate-34 is a copolymer of octoxy PEG-8 is commercially available under the tradename Fixate Super PPG-6 methacrylate, PPG-9 methacrylate, PPG-6 acrylate hold Polymer from Lubrizol Advanced Materials, Inc. and 2-methoxyethylacrylate monomers. (Cleveland, Ohio). [0070] Polyacrylate-35 is formed by reacting Dipen [0080] Polyacrylate Crosspolymer-3 is a copolymer of taerythrityl Pentaacrylate (q.v.) with the cyclic trimer of hex butyl acrylate, PEG-10 acrylate, PPG-6 acrylate and dim amethylene diisocyanate. ethylacrylamide, crosslinked by PEG-23 Diacrylate. This [0071] Polyacrylate-36 is a copolymer of Butyl Methacry copolymer is commercially available under the tradename late (q.v.), HEMA (q.v.), PEG-10 acrylate, PPG-6 acrylate, Plascize L-64S from Goo Chemical Company, Ltd. (Kyoto, and dimethylacrylamide. Japan). [0072] Polyacrylate-37 is a copolymer of per?uorohexyl ethyl acrylate, PEG-5 metha-crylate, acrylic acid and [0081] Polyacrylate Crosspolymer-4 is a copolymer of phosphonoxyethyl methacrylate. This copolymer is commer sodium acryloyldimethyltaurate, dimethyl acrylamide, cially available under the tradename FPL from Daito Kasei sodium acrylate, acrylic acid and hydroxyethylacrylate Kogyo Co., Ltd. (Osaka, Japan). crosslinked with methylene bis-propenamide. This copoly [0073] AMP-Acrylates Polyacrylate Crosspolymer-9 is a mer is commercially available under the tradename Sepinov polymer of hydroxyethylacrylate, methoxyethylacrylate, and P500 from Seppic (Paris, France). one or more monomers of acrylic acid, methacrylic acid or [0082] Polyacrylate Crosspolymer-5 is the crosslinked one of their simple esters neutralized with aminomethylpro copolymer that conforms generally to the formula (structure panol. below) where n has an average value of 7.

—CH2CH CHZCH CHZCH _ CHZCH _ é=0 é=0 i=0 é=0 J) J) J) J) 0 (CH2); (CHZCHZO)nH (CH2)ZOH (CHZCHZO),,C

(01:2)50113 _ CHCHZ

[0074] Dimethicone PEG-8 Polyacrylate is the siloxane [0083] This copolymeris commercially available underthe polymer obtained by free radical polymerization of PEG-8 tradename COSP23 from Miyoshi Kasei, Inc. (Urawa, Dimethicone (q.v.) esteri?ed with acrylic acid. This polymer Japan). is commercially available under the tradename Silsoft Sur [0084] Polyacrylate Crosspolymer-6 is a copolymer of face PF from Momentive Performance Materials (Friendly, ammonium acryloyldimethyl-taurate, dimethylacrylamide, W. Va.). lauryl methacrylate and laureth-4 methacrylate, crosslinked [0075] The term “Acrylates Crosspolymer” as used in the with trimethylolpropane triacrylate. This copolymer is com present application refers to a copolymer of acrylic acid, mercially available under the tradename Sepimax Zen from methacrylic acid or one of its esters, crosslinked with glycol Seppic Affaires Reglementaires (Puteux, France). dimethacrylate. [0085] Polyacrylate Crosspolymer-7 is a copolymer of [0076] Under INCI nomenclature conventions, crosspoly methacrylate PPG-6 phosphate and one or more monomers of mers consisting of two or more constituent monomers are acrylic acid, methacrylic acid or one of their simple esters, named by listing the monomers separated by a slash (/) fol crosslinked with dimethicone PEG/PPG-25/ 29 acrylate. This lowed by the word “Crosspolymer”. In the case of INCI copolymer is commercially available under the tradename names assigned to cross polymers before March 2003, the Y-l7552 from Momentive Performance Materials (Friendly, earlier name is retained without copolymer notation. An arbi W. Va.). trary number may follow the name. For example, Polyacry [0086] Polyacrylate Crosspolymer-8 is a copolymer of late-l Crosspolymer. t-butyl methacrylate, stearyl methacrylate, methoxy PEG-23 [0077] The following is a non-limiting list of Acrylates methacrylate, and dimethylacrylamide, crosslinked with eth Crosspolymers, which can be used to form a CPFA of the ylene glycol dimethacrylate. present invention, and when combined with a glyceryl ester in accordance with the present invention, can be added directly [0087] Polyacrylate Crosspolymer-9 is a copolymer of to, and will be directly soluble in, a cosmetically-acceptable t-butylaminoethyl methacrylate and carboxyethyl acrylate, ester or CTG. crosslinked with a combination of pentaerythritol tetraacry [0078] Polyacrylate-l Crosspolymer is a copolymer of one late and a hexafunctional acrylate formed by reacting pen or more simple esters of acrylic or methacrylic acid, C1_4 taerythritol triacrylate with toluene diisocyanate. dialkylamino C1_6 alkyl methacrylate, PEG/PPG-30/5 allyl [0088] Polyacrylate Crosspolymer-10 is the crosslinked ether, PEG 20-25 Clo_3O alkyl ether methacrylate, hydroxy polymer prepared by polymerizing a mixture of trimethox C2_6 alkyl methacrylate crosslinked with ethylene glycol ysilylpropylmethacrylate with trimethyloylpropane tri dimethacrylate. This copolymer is commercially available methacrylate. under the tradename Carbopol Aqua CC Polymer from Lubri [0089] Polyacrylate Crosspolymer-ll is a polymer of zol Advanced Materials, Inc. (Cleveland, Ohio). methacrylic acid, acryloyl dimethyltaurate and dimethylacry [0079] Polyacrylate-2 Crosspolymer is a copolymer of lamide, crosslinked with PPG-3 glyceryl triacrylate, and par PEG/PPG-23/6 Dimethicone citraconate, Clo_3O alkyl PEG tially neutralized with ammonia. It conforms generally to the 25 methacrylate, and one or more monomers of acrylic acid, structure below. US 2014/0336308 A1 Nov. 13, 2014

erg cm _‘ CHZC '— "HZCH CHZC F "HZCH (I:=O (I:=O (I:=O (I:=O (I... (D [H I... CH3CCH3 y CH3 AH. o=%=o o- .NH4+

®indicates text missing or illegible when filed

[0090] This copolymer is commercially available under the [0097] Ammonium Polyacryloyldimethyl Taurate is a tradename Aristo?ex Velvet from Clariant International Ltd. polymer that conforms generally to the following structure: (MuttenZ, Switzerland). [0091] Polyacrylate Crosspolymer-12 is a copolymer of t-butyl methacrylate, stearyl methacrylate, methoxy PEG-23 methacrylate, and dimethylacrylamide, crosslinked with methylene bis-acrylamide. [0092] Polyacrylate Crosspolymer-14 is a copolymer of acrylic acid, lauryl methacrylate, cetyl methacrylate, stearyl methacrylate, and phosphorylcholine glycol methacrylate, CH3 crosslinked by an allyl ether of pentaerythritol. This copoly mer is commercially available under the tradename Phospho [0098] It is commercially available under the tradenames mer ST610KC from KCl Ltd. (Seoul, South Korea). Gransil APK-l, Gransil ORB-25, Gransil ORB-II-JP from [0093] Sodium Polyacrylate Crosspolymer-l is a complex Grant Industries, Inc. (Elmwood Park, N.J.) and as crosslinked polymer that is made by ?rst preparing a silicone [0099] SilDerm Formulating Base and SilDerm Formulat copolymer by reacting a methacrylate-terminated polydim ing Base IF from Active Concepts LLC (Lincolnton, NC). ethylsiloxane polymer containing silicon hydride groups with [0100] Sodium Polyacryloyldimethyl Taurate is a polymer PEG-18/PPG-17 allyl ether. The silicone copolymer is then that conforms generally to the following structure: dispersed in water that contains sodium hydroxide and reacted with Methacrylic Acid (q.v.) and methacryloyl PPG-6 phosphate. [0094] CPFAs of the present invention may also be formed where the polymer having an aliphatic backbone and a plu NH rality of pendant group is an acryloyl ester of a N-dimethyl derivative of taurine. The organic functional group acryloyl crgocrrzso; 'Na+ (IUPAC prop-2-enoyl) is a univalent radical derived from CH3 acrylic acid having the structure CH2:CH4COi. Taurine (IUPAC 2-aminoethanesulfonic acid) has structural formula NH2CH2CH2SO3H. These compounds are known in the art, [0101] It is commercially available from Seppic (Paris, and referred to in the present application as acryloyldimeth France) under the tradename Simulgel 800 and as Viscolam yltaurates. AT 100 P from Lamberti S.p.A. (Gallarate, Italy). [0 1 02] Acrylamide/ Sodium Acryloyldimethyltaurate/ [0095] Additionally, acryloyldimethyltaurates when com Acrylic Acid Copolymer is a copolymer of acrylamide, bined with a glyceryl ester in accordance with the present sodium acryloyldimethyltaurate and acrylic acid monomers. invention, can be added directly to, and will be directly This copolymer is commercially available under the trade soluble in, a cosmetically-acceptable ester or CTG. names Acudyne SCP and Acudyne SCP Hair Styling Hair [0096] The following is a non-limiting list of salts, cross Fixative Resin from The Dow Chemical Company (Midland, polymers and copolymers of acryloyldimethyltaurate com Mich.). pounds suitable for use in the inventive compositions of the [0 1 03] Acrylamide/ Sodium Acryloyldimethyltaurate present invention. Copolymer is a copolymer of acrylamide and sodium acry US 2014/0336308 A1 Nov. 13, 2014

loyldimethyltaurate monomers and is available under the and sodium acryloyldimethyltaurate crosslinked with meth tradename Simulgel 600 from Seppic (Paris, France). ylene bis-acrylamide. This crosspolymer is commercially [0104] Ammonium Acryloyldimethyltaurate/Laureth-7 available under the tradename SUpolymer G-l from Toho Methacrylate Copolymer is a copolymer of ammonium acry Chemical Industry Co., Ltd. (Tokyo, Japan). loyldimethyltaurate and laureth-7 methacrylate monomers. [0118] Melamine/Resorcinol/Acryloyldimethyltaurate/ [0105] Ammonium Acryloyldimethyltaurate/Steareth-8 PEG-6 Methacrylate Crosspolymer is a copolymer of Methacrylate Copolymer is a copolymer of ammonium acry melamine, Resorcinol (q.v.), acryloyldimethyltaurate, and loyldimethyltaurate and steareth-8 methacrylate monomers. PEG-6 methacrylate crosslinked with 1,5-pentanedial. [01 06] Ammonium Acryloyldimethyltaurate/Vinyl Forma [0119] Sodium Acrylate/Acryloyldimethyltaurate/Dim mide Copolymer is a copolymer of ammonium acryloyldim ethylacrylamide Crosspolymer is a crosslinked copolymer of ethyltaurate and vinyl formamide monomers. sodium acrylate, acryloyldimethyltaurate and dimethylacry [0107] Ammonium Acryloyldimethyltaurate/VP Copoly lamide. This crosspolymer is commercially available under mer is a copolymer of ammonium acryloyldimethyltaurate the tradename Sepinov P88 from Seppic (Paris, France). and vinylpyrrolidone monomers. This copolymer is commer [0120] Sodium Acryloyl Dimethyl Taurate/PEG-8 Diacry cially available under the tradename Aristo?ex AVC from late Crosspolymer is a polymer of sodium acryloyl dimethyl Clariant International Ltd. (Muttenz, Switzerland) and also taurate crosslinked by PEG-8 diacrylate. This polymer is under the tradenames Botanimulse PSFiH and Botanimulse commercially available under the tradename FW200 Poly PSF-M from Botanigenics, Inc. (Chatsworth, Calif). mer System from Power Paper Ltd. (Petah Tikva, Israel). [0108] Hydroxyethyl Acrylate/Sodium Acryloyldimethyl [0121] Sodium Acryloyldimethyltaurate/VP Crosspoly Taurate Copolymer is a copolymer of sodium hydroxyethyl mer is a copolymer of sodium acryloyldimethyltaurate and acrylate and acryloyldimethyl taurate monomers and is avail vinylpyrrolidone crosslinked by l,l,l-trimethylolpropane able from Seppic (Paris, France) under the tradenames Sepi triacrylate. This copolymer is commercially available under plus S, Sepiplus VG, Simulgel FL, Simulgel IiNS 100, and the tradename Aristo?ex AVS from Clariant International Simulgel NS. Ltd. (Muttenz, Switzerland). [0109] Sodium Acrylates/Methacryloylethyl Phosphate [0122] Other copolymers of acrylic acid useful in the prac Copolymer is the sodium salt of a copolymer of acrylic acid, tice of the present invention include ammonium VA/acrylates methacrylic acid or one or more of its simple esters and copolymer, sodium acrylates copolymer, ethylene/acrylic methacryloylethyl phosphate. acid copolymer, ethylene/ calcium acrylate copolymer, ethyl [0110] Sodium Acrylate/Sodium Acryloyldimethyl Tau ene/magnesium acrylate copolymer, ethylene/ sodium acry rate/Acrylamide Copolymer is a copolymer of sodium acry late copolymer, ethylene/zinc acrylate copolymer, ethylene/ late, sodium acryloyldimethyltaurate and acrylamide mono acrylic acid/VA copolymer, acrylates/VP copolymer, mers. acrylates/VA copolymer, steareth-lO allyl ether/acrylatesco [01 1 1] SodiumAcrylate/ Sodium Acryloyldimethyl Taurate polymer, acrylates/steareth-50 acrylate copolymer, acrylates/ Copolymer is a copolymer of sodium acrylate and sodium steareth-20 methacrylate copolymer, acrylates/ammonium acryloyldimethyl taurate monomers. This copolymer is com methacrylate copolymer, styrene/acrylates copolymer, sty mercially available under the tradename Flocare PSD 30 from rene/acrylates/ammonium methacrylate copolymer, 10 SNF SAS (Andrezieux, France) and the tradename Sepinov ammonium styrene/acrylates copolymer, sodium styrene/ EG-P from Seppic (Paris, France). acrylates copolymer, acrylates/hydroxyesters acrylates [0112] Sodium Acryloyldimethyl Taurate/Acrylamide/VP copolymer, betaine acrylate copolymers including methacry Copolymer is a copolymer of sodium acryloyldimethyltau loyl ethyl betaine/acrylates copolymer, lauryl acrylate/VA rate, acrylamide and vinylpyrrolidone monomers. copolymer, VA/butyl maleate/isobomyl acrylate copolymer, [0113] Sodium Acryloyldimethyltaurate/Methacrylami ethylene/methacrylate copolymer, vinylcaprolactam/VP/ dolauric Acid Copolymer is a copolymer of sodium acry dimethylaminoethyl methacrylate copolymer, sodium acry loyldimethyltaurate and methyacrylamidolauric acid mono lates/acrolein copolymer, VP/dimethylaminoethylmethacry mers. late copolymer, AMP-acrylates copolymer), where “VA” is [0114] Ammonium Acryloyldimethyltaurate/Beheneth-25 “vinyl acetate” and “VP” is “vinyl polymer”. Methacrylate Crosspolymer is a copolymer of ammonium [0123] Polymers of acrylic acid and its salts (polyacrylic acryloyldimethyltaurate and beheneth-25 methacrylate acid, ammonium polyacrylate, potassium aluminum poly monomers. This copolymer is commercially available under acrylate, potassium polyacrylate, sodium polyacrylate) have the tradenames Aristo?ex BLV and Aristo?ex HMB from similar properties and can be used in the practice of the Clariant International Ltd. (Muttenz, Switzerland). present invention. [0115] Ammonium Acryloyldimethyltaurate/Carboxy [0124] Other copolymers copolymerized with polyacry ethyl Acrylate Crosspolymer is a copolymer of ammonium lates include polyacrylamide and PVA, sodium polyacrylate acryloyl dimethyltaurate and carboxyethyl acrylate starch, acrylamide/ sodium polyacrylate, hydroxyethyl acry crosslinked with trimethylolpropane trimethacrylate. This late/sodium acrylodimethyl taurate copolymer, acrylate copolymer is commercially available under the tradename copolymer, acrylamide/ ammonium acrylate copolymer, Aristo?ex TAC from Clariant International Ltd. (Muttenz, acrylates/beheneth-25 methacrylate/steareth-30 methacry Switzerland). late copolymer, polyvinyl alcohols (and derivatives or [0116] Ammonium Acryloyldimethyltaurate/Steareth-25 blends), PVP (derivatives and blends), sodium/carbomer, car Methacrylate Crosspolymer is a copolymer of ammonium bomer, TEA-carbomer, and acrylates/Cm3O alkyl acrylate acryloyldimethyltaurate and steareth-25 methacrylate mono crosspolymer, to mention just a few. mers. [0125] Examples of commercially available polymers hav [0117] Dimethylacrylamide/Sodium Acryloyldimethyl ing an aliphatic backbone and a plurality of pendant groups taurate Crosspolymer is a copolymer of dimethylacrylamide thereon that are pendant ionic or ionizable groups, and/or that US 2014/0336308 A1 Nov. 13, 2014

are pendant groups having at least one permanent dipole nary ammonium polymers are also known as “polyquats” or include Carbopols® Ultrez-lO, Ultrez-20, Ultrez-21; “polyquaterniums”. Non-limiting examples of “polyquats” Pemulen TR-l and Pemulin TR-2 (all the foregoing available suitable for use in the cold process formulations aids of the from Lubrizol Advanced Materials, Cleveland Ohio, USA); present invention and methods of using the same include: as well as Sepinov EMT-10 (distributed in the United States Polyquat 6iPoly(diallyl-dimethylammonium chloride); by SEPPIC Inc., Fair?eld N.J.), to mention just a few. Polyquat 7, a copolymer of acrylamide and diallyldimethyl [0126] Ionizable pendant groups are or include a functional ammonium chloride; Polyquat 11, a copolymer of vinylpyr group that includes, a labile (“acidic”) hydrogen atom. The rolidone and quarternized dimethylaminoethyl methacrylate; carboxyl group (4CO2H), the sulfate group (iOiSO3H), Polyquat 32iPoly(acrylamide 2-methacryloxyethyltrim and the sul?te group (iSO3H) are examples of functional ethyl ammonium chloride); Polyquat 37iPoly(2-methacry groups that have labile hydrogen atoms and that can be, or be loxyethyltrimethylammonium chloride); Polyquat a constituent of, an ionizable pendant group. Polymers of 67iPolymer of hydroxyethyl cellulose with dimethyldode acrylic acid, commonly referred to as “carbomers”, are pre cylammonium and trimethylammonium. ferred polymers having an aliphatic backbone and a plurality [0130] In certain embodiments of this aspect of the present of ionizable pendant groups that are useful in the cold process inventioniin which the polymer component of the CPFA is formulation aid of the present invention, in certain of its an aliphatic backbone having a plurality of pendant groups embodiments. Carboxyl functionality is found in fatty acids, thereon that are pendant ionic or ionizable group sithe CPFA which can be waxes. is “eutectic”, a term that the person of ordinary skill in the art [0127] Pendant groups having a permanent dipole include will understand to mean a mixture of chemical compounds pendant groups that are or that include one or more of an forming a single chemical composition that solidi?es at a alcoholic hydroxyl group, carboxylic group, thiolic thiol lower temperature than any material in the composition. In group, ester group, amide group, imide group, imine group, or characterizing certain CPFA compositions of the present nitrile group, to mention just a few. Examples of polymers application as “eutectic”, the inventors mean that these having an aliphatic backbone and a plurality of pendant CPFAs solidify at a lower temperature than any material in the groups having a permanent dipole include poly(vinyl pyrroli composition (i.e., its component parts). The eutectic nature of done), poly(vinyl alcohol), poly(methyl methacrylate), and certain CPFAs of the present invention is demonstrated by copolymers of methyl acrylate and/or methyl methacrylate differential scanning calorimetry, which shows the CPFA has with alkyl esters of acrylic acid and/or methacrylic acid hav a single melt/ freeze point. ing about 10 to about 30 carbon atoms in the alkyl group, to [0131] In eutectic embodiments of the present invention, mention just a few. CPFAs are produced by the process of combining at least two [0128] The plurality of pendant groups of the polymers componentsi (i) at least one wax component and (ii) at least having an aliphatic backbone and a plurality of pendant one polymer component having an aliphatic backbone and a groups that are useful in the practice of the present invention, plurality of pendant groups thereon that are pendant ionic or in certain of its embodiments, can include more than one type ionizable groups, or pendant groups having at least one per of pendant group selected, independently, from ionic, ioniz manent dipole that includes an acid, alcohol, thiol, ester, able, and permanent-dipole-including pendant groups. To amine, amide, imide, imine, or nitrile moietyiat a tempera mention just one example, such polymer can have both alkyl ture that is at least about 5° C. above (a) the higher of the ester and carboxyl pendant groups. Such polymer can also melting point of the wax (or in CPFAs containing more than have more than one species of the same type or genus of one wax, the wax with the highest melting point) or (b) the pendant group. For example, such polymer can have both softening point of the polymer component having an aliphatic carboxyl and sulfate ionizable pendant groups, to mention backbone with a plurality of pendant ionic or ionizable just one example. Aminesieither non-neutralized or par groups (or in CPFAs containing more than one polymer com tially or totally neutralized with an inorganic or organic base, ponent having an aliphatic backbone and a plurality of pen or quatemizediare also ionizable. As will be understood by dant ionic or ionizable group groups thereon, the polymer the person having ordinary skill in the art, when ionizable having the highest softening point). For purposes of describ groups, when subjected to the action of a base, give anionic ing eutectic embodiments of the present invention, and the groups (e.g., carboxyl groups) and when subjected to the process for making the same, the term “softening point” is to action of an acid or quaternization, give cationic groups (e. g., be understood to mean a temperature at which a material tertiary amine). Neutralization of the anionizable groups (or softens to a speci?ed extent. Softening point can be deter cationizable groups respectively) with the base (or the acid mined, for example, by the Vicat method (ASTM-D 1525 or respectively) may be carried out partially or completely, ISO 306), Heat De?ection Test (ASTM-D648) or a ring and depending on the amounts of neutralizing agents used. ball method (ISO 4625 or ASTM E28-67/E28-99 or ASTM [0129] The term “quaternary ammonium” is common D36 or ASTM D6493-l l). chemical nomenclature and its meaning will be understood [0132] In certain eutectic embodiments of the present by one skilled in the art. There are two types of ammonium invention, in which the highest melting point of the wax compounds: acidic, and non-acidic. Acidic ammonium com component(s) is a temperature that is higher than the highest pounds are acid salts of amines, and are characterized by softening point of the polymer component(s), the CPFA is having an NiH covalent bond wherein the NiH bond is formed by a process in which the wax component(s) and the reactive with and may protonate bases. Non-acidic, or “qua polymer component(s) are combined at a temperature that is ternary” ammonium compounds do not have this NiH bond, at least about 5° C. higher than the highest melting point of the and are not reactive with bases in the same way. Quaternary wax component(s). ammonium compounds are generally characterized by hav [0133] In other eutectic embodiments of the present inven ing four covalent bonds, usually four carbon-nitrogen bonds tion, in which the highest softening point of the polymer attached to the positively-charged central nitrogen. Quater component(s) of the CPFA is a temperature that is higher than US 2014/0336308 Al Nov. 13, 2014

the highest melting point of the wax(es), the CPFA is formed amount of polymer can be decreased) if an emulsion or hydro by a process in which the wax component(s) and the polymer gel is to be formed at or near the eutectic point of the CPFA. component(s) are combined at a temperature that is at least By way of non-limiting example, if a CPFA can have a wax: about 5° C. higher than the highest softening point of the polymer ratio of 70:30, a CPFA can also be made within the polymer component(s). scope of the present invention with the same wax and polymer [0134] Eutectic CPFA of the present application can, and but at different ratios, for example 80:20, if the emulsion is to preferably are made by a process involving the following be formed at or near the eutectic point. It will also be under sequential steps: stood that a CPFA having a higher polymer contentifor [0135] (i) add wax(es) to a vessel; heat to a temperature of example 60:404could be used to form an emulsion at ambi at least about 5° C. above the melt point of the highest melt ent temperature. point wax; mix until a homogenous batch of molten wax(es) [0143] A second aspect of the present invention is directed is achieved; to cold process formulation aids and methods employing the [0136] (ii) add polymer(s) having an aliphatic backbone same for rendering polyacrylic acids, polyacrylates, poly with a plurality of pendant ionic or ionizable groups to the cacrylate copolymers, polyacrylate crosspolymers, and their batch of molten wax(es) from step (i) while heating to a respective salts (collectively referred to in the present appli temperature of at least about 5° C. above the highest melt cation as “Polyacrylic Acid Derivatives” and abbreviated as point of the wax(es) or the highest softening point of the “PADs”) directly soluble in cosmetically-acceptable esters polymer(s); mix until a homogenous eutectic mixture is and Caprylic/Capric Glycerides (CTG), without using a formed; petroleum-derived solvent. [0137] (iii) cool the eutectic mixture from step (ii) to a [0144] Caprylic/Capric Triglyceride (abbreviated “CTG”) temperature of about 5° C. above the congealing point of the is a medium chain triglyceride esteri?ed from caprylic and mixture; capric acids and glycerine. CTG is an article of commerce [0138] (iv) pour the eutectic mixture from step (iii) onto a available from suppliers of chemical raw materials used in the chilled surface having a temperature from about —10° C. to formulation of personal care and pharmaceutical products, about 10° C., producing a CPFA in the form of a solid wax, or including from Jeen International Corp. (Fairlawn, N.J.) wax-like substance. under the tradename JEECHEM® CTG. [0139] The solid wax (or wax-like substance) produced by [0145] The inventive compositions according to this aspect the above-described process can be poured and cast into a of the present invention are cold process formulation aids block, ?aked, or prilled, and, optionally, ground to smaller comprising (a) at least one PAD and (b) at least one emulsi particle size and/orpassed through a sieve to achieve a desired fying wax. particle size cut-off. [0140] In preferred embodiments of the present invention, [0146] A non-limiting list of emulsifying waxes suitable in step (iii) the polymer(s) having an aliphatic backbone with for use in this aspect of the invention are provided above. a plurality of pendant ionic or ionizable groups start to soften [0147] In certain preferred embodiments of this aspect of at a temperature of about 30° C., with near complete softening the invention, the emulsifying wax is a polyglyceryl ester. achieved at a temperature typically ranging from about 60° C. Polyglyceryl esters are liquid, non-ionic surfactants based on to about 120° C. linear polyglycerol and fatty acids. [0141] In certain embodiments of the ?rst aspect of the [0148] Particularly preferred polyglyceryl esters include invention directed to eutectic CPFAs, where the polymer Polyglyceryl Monostearate, Polyglyceryl-3 Stearate, Polyg having an aliphatic backbone is an acrylic acid that has been lyceryl-6 Distearate Hexaglyceryl Distearate, Decaglyceryl pre-neutralized, a salt of a polyacrylic ester (e. g., sodium Dipalmitate, all commercially available from, Lonza, Inc. polyacrylate), or a salt of an acrylic acid, and the wax is not (Allendale, N.J.; among other suppliers of raw materials used micronized and is not emulsifying, the ratio, by weight, of the in the manufacture of personal care products) under the trade non-micronized/non-emulsifying wax to the polymer having name Polyaldo. an aliphatic backbone is from about 60:40 to 80:20, and if the [0149] Polyglycerol-3 (also known as Polyglycerin-3) is a wax is a micronized wax or a emulsifying wax, the ratio, by clear yellowish viscous liquid with an average molecular weight, of wax to polymer backbone is 70:30 to 98:2. weight of 250 g/mol. Polyglycerin-3 is a glycerin polymer [0142] In other embodiments of the ?rst aspect of the inven containing 3 glycerin units. It is water-soluble and is less tion directed to eutectic CPFAs, where polymer having an hygroscopic than glycerol or diglycerol. aliphatic backbone is an acrylic acid or polyacrylic acid, and [0150] Polyglycerin-6 is a glycerin polymer containing 6 the wax is not micronized and is not self-emulsifying, the glycerin units. ratio, by weight, of the non-micronized/non-emulsifying wax to the polymer having an aliphatic backbone is, in preferred [0151] Polyglyceryl-3 Stearate is an ester of stearic acid embodiments, from about 70:30 to 95:5, and if the wax is a and Polyglycerin-3 and has the empirical formula C27H54OS. micronized wax or a emulsifying wax, the ratio, by weight, of Polyglyceryl-3 Stearate is an article of commerce available wax to polymer backbone is, in preferred embodiments, from from suppliers of chemical raw materials to formulators of about 90: 10 to 99.5 :0.5 . All ratios refer to Wax:Polymer com personal care and pharmaceutical products, including under positions. It will be understood by the skilled artisan that the the tradenames CaprolTM 3GS from Abitec Corporation (Co above preferred embodiments relate to CPFAs which are lumbus, Ohio), AkolineTM PG 7 from AarhusKarlshamn AB, comprised of a high wax content (at least about 70), where the and as PolyaldoTM TGMS KFG (3-1-8) from Lonza (Allen CPFA does not contain an emulsifying wax, and where the dale, NI.) CPFA is to be added to an aqueous medium at room tempera [0152] Polyglyceryl-6 Distearate is a diester of stearic acid ture. As described elsewhere in the present application, the and Polyglycerin-6 and is available under the tradenames amount of wax can be increased (and correspondingly the Caprol 6G2S from Abitec Corporation (Columbus, Ohio), US 2014/0336308 A1 Nov. 13, 2014 11

Plurol Stearique WL 1009 from Gattefosse s.a.s. (Saint Priest, both cationic and anionic polymer chain(s) may also be used France) and Polyaldo HGDS KFG (6-2-8) from Lonza Inc. in accordance with the compositions and methods of the (Allendale, N.J.). present invention. Non-limiting examples of such polymers [0153] As used herein, by the term “directly soluble” in include carboxymethylchitosan, N-hydroxy-dicarboxyethyl cosmetically-acceptable oil or CTG is meant that the inven chitosan, cetyl hydroxyethylcellulose. Amphoteric polysac tive composition comprising a PAD/emulsifying wax blend charide compounds may also be obtained by grafting and can be added to a cosmetically-acceptable oil or CTG and polymerization monomers corresponding onto anionic does not form aggregates, the PAD is not visually perceptible polysaccharides, and include polymers of the type disclosed with the naked eye as a powder or crystal, and the resulting in PreGrant US Patent Application Publication 2008/ mixture of PAD/emulsifying wax and cosmetically-accept 0260674. Non-limiting examples of cationic polysaccharides able oil or CTG does not leave a gritty hard feel when applied suitable for use in the cold process formulations aids of the to the skin. Non-limiting examples of cosmetically-accept present invention and methods of using the same include: able esters into which the inventive blend of PAD/emulsify guar hydrpropyl trimonium chloride; 2-hydroxy-3-(trimethy ing wax are directly soluble are set out below. lammonio) propyl ether chloride; locust bean hydroxypropyl [0154] Cosmetically-acceptable monoesters into which the trimonium chloride; and Casalpina spinosa hydroxypropyl CPFA of the second aspect of the present inventioniblend of trimonium chloride. PAD(s)/emulsifying wax(es) fare directly soluble include, [0158] The cold process formulation aid of the present but are not limited to, hexyldecyl benzoate, hexyl laurate, invention, in other of its embodiments, includes salts of hexadecyl isostearate, hexydecyl laurate, hexyldecyl esters, have one or a plurality of ionizable groups. Poly(as octanoate, hexyldecyl oleate, hexyldecyl palmitate, hexylde partate) for example, perform the same function as, and are cyl stearate, hexyldodecyl salicylate, hexyl isostearate, butyl claimed to be an even more eco-friendly alternative to, the acetate, butyl isostearate, butyl oleate, butyl octyl oleate, polymers having an aliphatic backbone and a plurality of cetyl palmitate, ceyl octanoate, cetyl laurate, cetyl lactate, pendant groups thereon that are pendant ionic or ionizable isostearyl isononanoate, cetyl isononanoate, cetyl stearate, groups and discussed above. Sodium poly(aspartate), fre stearyl lactate, stearyl octanoate, stearyl heptanoate, and quently referred to in the trade as simply poly(aspartate), is stearyl stearate. As will be understood by the skilled artisan, particularly useful in the practice of the present invention. in the above nomenclature, the ?rst term indicates the alcohol [0159] In still further embodiments, the cold process for and the second term indicates the acid in the reaction. For mulation aid of the present invention includes a combination example, stearyl octanoate is the reaction product of stearyl of one or more polymers having an aliphatic backbone and a alcohol and octanoic acid. plurality of pendant groups thereon that are pendant ionic or [0155] Non-limiting examples of cosmetically-acceptable ionizable groups, one or more a polymer having a polysac diesters into which the CPFA blend of PAD(s)/emulsifying charide backbone and a plurality of pendant ionizable or ionic wax(es) of the present invention are directly soluble include, groups selected from carboxyl groups, carboxylate groups, but are not limited to, diisostearyl malate, neopentyl glycol sulfate groups, and salts thereof, and/ or poly(aspartate). One dioctanoate, dibutyl sebacate, di-C12_l3 alkyl malate, dicet non-limiting example of such a CPFA contains cetyl alcohol, earyl dimer dilinoleate, dicetyl adipate, diusocetyl adipate, glyceryl monostearate, sodium polyacrylate, and xanthan diisononyl adipate, diisostearyl dimer dilinoleate, disostearyl gum. In yet further embodiments, the cold process formula fumarate, diisostearyl malate. tion aid of the present invention includes one or more poly [0156] Cosmetically-acceptable triesters into which the mers having a silicone backbone with pendant ionic or ion CPFA blend of PAD(s)/emulsifying wax(es) of the present izable groups, and/or that are pendant groups having at least invention are directly soluble include, but are not limited to, one permanent dipole that includes an alcohol, thiol, ester, triarachidin, tributyl citrate, triisostearyl citrate, tri-C12_l3 amide, amine, imide, imine, or nitrile moiety. Examples of alkyl citrate, tricaprylin. such polymers include amodimethicone and dimethiconol, to [0157] In accordance with the ?rst aspect of the present mention just two. invention, the cold process formulation aid, in other of its [0160] Polymers having pendant ionic or ionizable groups embodiments, includes a polymer having a polysaccharide can be referred to as polyelectrolytes. backbone and a plurality of pendant ionizable or ionic groups [0161] The cold process formulation aid of the present selected from carboxyl groups, sulfate groups, salts of either, invention according to the ?rst aspect of the invention, in all or combinations thereof. The polysaccharide backbone can of its embodiments, includes at least one wax. Waxes are include either or both of pyranoside and furanoside residues. substances which are solid or semi-solid at room temperature, Important is that the polysaccharide backbone have a plural that undergo a reversible solid-liquid change of state, with a ity of pendant ionizable or ionic groups selected from car melting point of greater than or equal to about 30° C., and up boxyl groups, sulfate groups, salts of either, or combinations to about 150° C., and in some embodiments up to about 170° thereof. Preferred are polysaccharides that swell in water at C., and in still other embodiments up to about 200° C., and room temperature, non-limiting examples of which include have an anisotropic crystal organization in solid form. Pref sodium alginate, carrageenan, carboxymethyl cellulose, xan erably, the wax has a melting point of 35° C. to 100° C. But than, starches, and cationic guar. Anionic and cationic waxes having a melting point >100° C. or waxes having a polysaccharides suitable for use in the present invention melting point at or below room temperature (e. g., cocoa but include, but are not limited to the following: anionic polysac ter) can be used in particular embodiments of the present charidesialginic acid, pectin, xanthan gum, hyaluronic acid, invention. chondroitin sulfate, gum arabic, gum karaya, gum tragacanth, [0162] The skilled artisan knows that waxes of commerce carboxymethyl-chitin, cellulose gum; cationic polysaccha rarely have a sharp melting point such as exhibited by, for rides4chitosan, cationic guar gum, cationic hydroxyethyl example, puri?ed organic compounds, and that the melting cellulose. Amphoteric polysaccharide compounds containing point of a wax may vary depending on the test method used. US 2014/0336308 A1 Nov. 13, 2014

The well-known technique of differential scanning calorim thetic waxes useful in the practice of the present invention etry (DSC) can be used to determine the melting point of a include sub stances that can include components from natural wax. DSC can, for example, be performed using a 5 mg sources. sample and a heating rate of 10° per minute. In this example, [0171] Waxes also include esters of long-chain primary the temperature at which the melting endotherrn shows a alcohols and fatty acids, as well as shea butter and cocoa maximum deviation from baseline (i.e. the “peak tempera butter. Accordingly, certain fats or butters are to be under ture”) is taken as the melting point. stood as waxes within the scope of the present invention, since [0163] Waxes useful in the practice of the present invention these materials require an increase in temperature to cause a can be classi?ed by source or chemical structure. Waxes phase transition from a semi-solid or solid to a liquid. Typi useful in the practice of the present invention can be either cally, the melt point for fats and butters considered as waxes hydrogenated (fully or partially) or non-hydrogenated natural within the scope of the present invention is less than about 50° waxes, such as those obtained from animal, botanical, or C. At that temperature, a fat or butter can be converted to a mineral sources, or they can be synthetic waxes. Some syn wax if the fat or butter is hydrogenated, partially or fully. A thetic waxes are synthesized using one or more components non-limiting example of a fat to be considered a wax for from natural sources. Synthetic waxes can include more than purposes of the present invention is castor oil. one wax, each from a different source or of a different chemi [0172] Self-emulsifying waxes may be obtained commer cal class or structure, or they can be a natural wax that has cially from numerous manufacturers and suppliers. Commer been compounded with other components to obtain a syn cially available self-emulsifying waxes that may be useful in thetic wax. the practice of the present invention include ethoxylated and/ [0164] Natural waxes that are animal waxes include bees or propoxylated waxes as well as the following: PEG-20 wax, lanolin, shellac wax, and whale wax. Natural waxes that sorbitan beeswax (Atlas G-1726, Uniqema; Nikkol GBW are botanical waxes include candelilla wax, castor wax, cot 125, Nikko), PEG-6 beeswax (ESTOL 375, Uniqema), ton wax, soy wax, jojoba wax, olive wax, carnauba wax, sugar PEG-8 beeswax (Api?l, Gattefosse), Olivem 1000 (Cetearyl cane wax, rice bran wax, bayberry wax, sun?ower wax, rose Olivate, Sorbitan Olivate, from B&T SRL), PEG-12 beeswax petal wax, and Japan wax. Sun?ower wax is a preferred and PEG-12 carnauba wax. botanical wax for use in the practice of certain embodiments [0173] In certain embodiments, the waxiregardless of of the cold process formulation aid of the present invention. source or typeiis micronized. That is, the wax is used in the [0165] Mineral waxes include montan wax, ozokerite, and form of particles having an average particles size, as deter ceresin. mined by particle size analyzers known in the art, including [0166] Petroleum-based waxes include paraf?n wax and those available from Malvem, of about 50p or less. When microcrystalline wax. micronized waxes are used, additional options for making the cold process formulation aid of the present invention, dis [0167] Synthetic waxes include polyethylene waxes (e.g. cussed below, can be used. Micronized waxes useful in the Jeenate® waxes available from Jeen International of Fair?eld practice of the present invention include Ceridust® micron N.J., USA), silicone waxes, ?uoro waxes, Fischer-Tropsch ized poly(ethylene) (Clariant), Micropoly® micronized poly waxes, polypropylene waxes, esters of poly(ethylene glycol), (ethylene) wax (Micro Powders, Inc.), Microease® micron and pegylated sorbitans, alone or in combination with, for example, monoalkyl ethers of poly(ethylene glycol) (e.g. cet ized synthetic waxes (MicroPowders, Inc.), and Microcare® waxes (MicroPowders, Inc) that include natural waxes (e.g. eareth-20). Synthetic waxes also include so-called “function carnauba wax), to mention just a few. Anticaking agents, such alized waxes, a non-limiting example of which are pegylated as silicas or a harder wax, can be added to a softer wax. animal waxes (e.g. PEG-8 beeswax) Additionally, plasticizers (e.g., esters or oils) may be added to [0168] In certain embodiments of the cold process formu the wax before micronization. As used in the present inven lation aid of the present invention, the wax is a synthetic tion a “plasticizer” means a compound present in an amount emulsifying wax, for example glyceryl monostearate, to men suf?cient to lower the glass transition temperature of the tion just one. Self-emulsifying wax, as that term is used CPFA. Glass transition is measured using a differential scan herein, refers to a chemically modi?ed wax that contains at ning calorimeter. To evaluate the reduction in the glass tran least one emulsi?er component, e.g., a non-ionic emulsi?er. sition temperature caused by the plasticizer, the glass transi [0169] The wax component of the self-emulsifying wax tion temperature of the CPFA is ?rst measured by a method contains one or more cosmetically or dermatological accept known to the person skilled in the art, and a mixture of the able waxes from among waxes of animal origin, waxes of CPFA and the plasticizer is then prepared and a measurement plant origin, waxes of mineral origin and waxes of synthetic is taken by the same method under the same conditions. origin. Examples of waxes of animal origin include bees [0174] The plasticizing compound may be chosen espe waxes, lanolin waxes and Chinese insect waxes. Examples of cially from aliphatic or aromatic polycarboxylic acid esters of waxes of plant origin include rice waxes, olive wax, carnauba aliphatic or aromatic alcohols comprising from 1 to 10 carbon wax, candellila wax, sugar cane waxes, Japan waxes, and atoms, as well as silicone oils. Non-limiting examples of cotton wax. Examples of waxes of mineral origin include plasiticizers include liquid paraf?n, isoparaf?n, hexyl laurate, paraf?ns, microcrystalline waxes, montan waxes and ozok isopropyl myristate, myristyl myristate, cetyl myristate, 2-oc erites. Examples of waxes of synthetic origin include poly tyldodecyl myristate; isopropyl palmitate, 2-ethylhexyl ole?n waxes, e.g., polyethylene waxes, waxes obtained by palmitate, butyl stearate, decyl oleate, 2-octyldodecyl oleate, Fischer-Tropsch synthesis, waxy copolymers and their esters, myristyl lactate, cetyl lactate, lanolin acetate, stearyl alcohol, and silicone and ?uoro waxes. cetostearyl alcohol, oleyl alcohol, avocado oil, almond oil, [0170] Alternatively, hydrogenated oils of animal or plant olive oil, cocoa oil, jojoba oil, gum oil, sun?ower oil, soybean origin (natural waxes) may be present in the self-emulsifying oil, camellia oil, squalane, castor oil, mink oil, cottonseed oil, wax in combination with synthetic compounds. Thus, syn coconut oil, egg yolk oil, beef tallow, lard, polypropylene US 2014/0336308 A1 Nov. 13, 2014

glycol monooleate, neopentyl glycol 2-ethylhexanoate or a [0180] The technique of spray-drying is well known in similar glycol ester oil; triglyceryl isostearate, the triglycer chemical engineering and is summarized, for example, in R. ide of a fatty acid of coconut oil, or a similar oil of a polyhy P. Patel et al., 2 Indian Journal ofScience and Technology, dric alcohol ester; polyoxyethylene lauryl ether, polyoxypro Vol. No. 2, 44-48 (2009). The skilled artisan knows to adjust pylene cetyl ether or a similar polyoxyalkylene ether. the temperature of the molten wax, the nozzle ori?ce size, and [0175] In certain embodiments, the plasticizer may be a the atomizing pres sure to obtain the desired particle size in the silicone oil, non-limiting examples of which include a dim ?nal powder product. Preferred particle sizes are in the range ethylpolysiloxane with the two molecular ends capped with of Sp. to 5 mm, more preferably Sp. to 50p. trimethylsiloxy groups, a copolymer of methylphenylsilox [0181] Prilling is likewise a technique for forming particu ane and of dimethylsiloxane having the two molecular ends late or granular solid particles and is well known in chemical capped with trimethylsiloxy groups, a copolymer of methyl engineering. Prilling is accomplished in a prilling tower in 3,3,3-tri?uoropropylsiloxane and of dimethylsiloxane hav which droplets of a molten combination of one or more waxes ing the two molecular ends capped with trimethylsiloxy with polymers having an aliphatic backbone and a plurality of groups, or similar unreactive linear silicone oils, and also pendant groups thereon that are pendant ionic or ionizable hexamethyl-cyclotrisiloxane, octamethylcyclo-tetrasilox groups, one or more polymers having a polysaccharide back ane, decamethylcyclopentasiloxane, dodecamethylcyclo bone and a plurality of pendant ionizable or ionic groups hexasiloxane or a similar cyclic compound. In addition to the selected from carboxyl groups, carboxylate groups, sulfate unreactive silicone oils, modi?ed polysiloxanes containing groups, and salts thereof, poly(aspartate), or a combination of functional groups such as silanol groups, amino groups and the foregoing, are allowed to fall under the action of gravity polyether groups on the ends or within the side molecular through the tower against a static or dynamic column of gas, chains may be used. for example air or nitrogen. The height of the prilling tower, [0176] Powders such as mica, calcium carbonate, silica, the temperature of the gas, and the size of the droplets are can be used as plasticizers. adjusted, by routine experimentation, according to the melt [0177] Differential scanning calorimetry demonstrates that ing point of the wax and the desired size of the ?nal prill. the heat of disassociation of the wax component of the cold [0182] The cold process formulating aids of the present process formulation aid is different than the heat of disasso invention may vary in physical forms ranging from coarse ciation of the cold process formulation aid itself, the latter powder to ?ake and pastille, which, in turn, can be further being lower. This difference is important both in terms of reduced in size using a jet mill. sensorial properties and rheological pro?les of the ?nal com [0183] When the wax is not a micronized wax and the cold mercial product (i.e., the emulsion or hydrogel). By way of process formulation aid of the present invention is made by non-limiting example, the viscosity of an emulsion contain spray drying or prilling, the ratio, by weight, of the one or ing a wax (W) and polymeric thickener (P) formed by con more waxes to the one or more polymers (i.e. the one or more ventional processes (i.e., heating) is lower than the viscosity polymers having an aliphatic backbone and a plurality of of an emulsion formed without heat (i.e., at room tempera pendant groups thereon that are pendant ionic or ionizable ture) by adding a cold process formulating aid (WP) consist groups, the one or more polymers having a polysaccharide ing essentially of the same wax and same polymeric thickener backbone and a plurality of pendant ionizable or ionic groups at the same concentrations as used in the conventional (i.e., selected from carboxyl groups, carboxylate groups, sulfate heated) emulsion. groups, and salts thereof, the poly(aspartate), or a combina [0178] The cold process formulation aid of the present tion of the foregoing) is preferably from about 60:40 to 80:20. invention can be obtained in powder form, a preferred physi [0184] When a micronized wax having an average particle cal form, by combining one or more polymers having an size not exceeding about 50p, is used, the cold process for aliphatic backbone and a plurality of pendant groups thereon mulation of the present invention can be made by a dry blend that are pendant ionic or ionizable groups, one or more poly ing process. In this case, the ratio, by weight, of one or more mers having a polysaccharide backbone and a plurality of waxes to the one or more polymers is from about 85:15 to pendant ionizable or ionic groups selected from carboxyl about 98:2. The dry blending can be accomplished using a groups, carboxylate groups, sulfate groups, and salts thereof, ribbon mixer, a twin-shell mixer or a high intensity mixer. or poly(aspartate), or a combination of the foregoing, with at Micronized waxes can be used when the polymer is be sen least one wax in a spray drying (also known as spray congeal sitive to higher temperatures since these can be destroyed by ing when heat, rather than a solvent, is being removed), jet high temps.) milling or prilling process. If the wax is a micronized wax [0185] The cold process formulation aid made by any of the micronized to an average particle size of about 5p, a dry above-described methods is preferably in the form of an blending process can su?ice. easily-handled powder. However, the cold process formula [0179] In the spray drying process, the one or more poly tion aid of the present invention, in certain embodiments, can mers having an aliphatic backbone and a plurality of pendant also be provided in the form of a paste or a semi-solid having groups thereon that are pendant ionic or ionizable groups, the a butter-like consistency. When a paste form is desired, waxes one or more polymers having a polysaccharide backbone and or fats having a melting point near or below room tempera a plurality of pendant ionizable or ionic groups selected from ture, e. g. shea butter or especially cocoa butter, are included in carboxyl groups, carboxylate groups, sulfate groups, and the formulation, especially in combination with other waxes salts thereof, the poly(aspartate), or a combination of the (e.g. beeswax). The cold process formulation aid of the foregoing are combined with one or more molten waxes at present invention in paste form can be made using conven about 30° C. to about 150° C., and in in some embodiments up tional compounding equipment, for example a Banbury to about 170° C., and in still other embodiments up to about mixer. 200° C. and the combination converted to a powder by spray [0186] In still further embodiments, the present invention congealing. provides a cold process for making personal care products US 2014/0336308 A1 Nov. 13, 2014

that includes the step of combining the cold process formu weight of the combination. The combination is then cooled to lation aid of the present invention with an aqueous medium a continuous solid mass and comminuted to the desired par and other ingredients. ticle size. [0187] Additional ingredients that may be added to emul [0193] In a modi?cation of the ?rst process, the molten sions formed with the cold process formulation aids of the combination of wax and polyelectrolyte polymer is not present invention include, but are not limited to, oils and cooled to a continuous solid mass. Instead, the molten com esters (as plasticizers); iron oxides; capric caprylic triglycer bination is passed through a spray drying apparatus to cool ide; glycerine; emulsi?ers (polysorbate); silicone com and spray congeal the combination to a powder. pounds, including volatile silicones, elastomers and resins [0194] In another modi?cation of the ?rst process, the mol silicone cross-polymer (Dow Corning 9506).A paste can also ten combination is passed through a prilling tower to cool the be made that contains a level of aqueous medium at levels combination and obtain a prin. lower than those of the intended ?nished formula. All of the aforementioned embodiments can be manufactured to a thick Example 2 paste or cream that can contain 0.1 to 70% of an aqueous medium or water. This can be considered to be a “concen Second Process for Making a Cold Process trate” that can be let down or diluted to a higher level of Formulation Aid with a Micronized Wax and a aqueous medium or water. Said concentrate can be used to Polyelectrolyte Polymer make emulsions. [0195] Wax is micronized by jet mill pulverization to an [0188] In another embodiment, the present invention pro average particle size of about 5 u. The micronized wax is dry vides a method of making a personal care product, without blended with a polyelectrolyte polymer having an aliphatic heating, that includes the steps of (i) combining with an backbone and a plurality of pendant groups thereon that are aqueous medium, in certain, but not all embodiments, at a pendant ionic or ionizable groups, or pendant groups having temperature not exceeding 30° C., a polymer having an ali at least one permanent dipole that includes an alcohol, thiol, phatic backbone and a plurality of pendant groups thereon ester, amide, imide, imine, or nitrile moiety to obtain the cold that are pendant ionic or ionizable groups, or pendant groups processing aid. The polymer having an aliphatic backbone having at least one permanent dipole that includes an acid, and a plurality of pendant groups thereon that are pendant alcohol, thiol, ester, amines, amide, imide, imine, or nitrile ionic or ionizable groups, or pendant groups having at least moiety, thereby forming a hydrogel and (ii) adding a micron one permanent dipole that includes an acid, alcohol, thiol, ized wax, having a mean particle size from 5 to 50 microns, to ester, amine, amide, imide, imine, or nitrile moiety consti the hydrogel of step (i). tutes about 5% by weight of the dry-blended combination. [0189] Polymers having a polysaccharide backbone and a plurality of pendant ionizable or ionic groups selected from Example 3 carboxyl groups, carboxylate groups, sulfate groups, and salts thereof, or polyaspartate can be substituted for the poly Third Process for Making a Cold Process mer having an aliphatic backbone in the above process. Non Formulation Aid Using a Non-Micronized Wax, a limiting examples of polysaccharides having a pendant ion Polyelectrolyte Polymer, and a Silicone izable or ionic groups include dehydroxanthan sold as Amaze Crosspolymer XT from AkzoNobel. [0196] Wax and a polyelectrolyte polymer (described in the [0190] As is known in the dermatologic arts, surfactants previous examples) are melted together. Dow DC 9506 (a can be irritating or negatively impact active ingredients (e.g., silicone cross polymer) is combined with the molten wax and by denaturing proteins). In a still further embodiment, the the polyelectrolyte polymer. The molten combination is cold process formulation aid of the present invention provides cooled to obtain a continuous solid mass that is comminuted a method of making a personal care product that is essentially to the desired particle size. free of ethoxylated surfactants, and in certain embodiments [0197] In a modi?cation of the third process, the molten essentially of free of surfactants. By “essentially surfactant combination of wax, polyelectrolyte, polymer and silicone free” is meant that no surfactant is added to the emulsion, crosspolymer is not cooled to a continuous solid mass. other than surfactant(s), if any, present in the CPFA itself. Instead, the molten combination is passed through a spray [0191] The present invention, in certain of its embodi drying apparatus to cool and spray congeal the combination ments, is illustrated by the following non-limiting examples. to a powder. [0198] In another modi?cation of the third process, the Example 1 molten combination is passed through a prilling tower to cool the combination and obtain a prin. First Process for Making a Cold Process Formulation Example 4 Aid with Non-Micronized Wax and a Polyelectrolyte Polymer Fourth Process for Making a Cold Process Formulation Aid [0192] Non-micronized wax and an oil are melted together. A polyelectrolyte polymer having an aliphatic backbone and [0199] In a fourth process, a molten combination of poly a plurality of pendant groups thereon that are pendant ionic or electrolyte and wax is further combined with oil phase ingre ionizable groups, or pendant groups having at least one per dients (esters, natural oils, synthetic oils, butters (e.g., par manent dipole that includes an alcohol, thiol, ester, amide, tially hydrogenated vegetable oils), silicone compounds) and/ imide, imine, or nitrile moiety is combined with the molten or hydrophilic ingredients (e.g., glycols) to make a paste or wax. The polyelectrolyte polymer constitutes about 30% by slurry, optionally with a surfactant. Two non-limiting US 2014/0336308 A1 Nov. 13, 2014

examples of this process are as follows: (1) combine Beewax depending on the type of wax and the manufacturing process with Sodium Acrylate/ Sodium Acryloyldimethyl Taurate (e.g., jet milling). Dry blended CPFAs, irrespective of Copolymer, lsohexdecane and Polysorbate 80; (2) combine whether the wax is functionalized, can have ratios of as low as Sun?ower wax with Hydroxyethylacrylate/ Sodium Acry 0.5% polymer. Molten CPFAs containing emulsifying waxes loyldimethyl Taurate Copolymer. (e.g., fatty acids, fatty alcohols) can also have as low as 0.5% [0200] Any of the above-mentioned processes may com polymer content. Molten CPFAs containing non-emulsifying prise the further step of pre-hydrating the cold process for waxes can, preferably have 20% or higher polymer content, mulation aid of the present invention (i.e., by adding water). although Molten CPFAs having a lower polymer content can CPFAs of this type are available under the tradename CPW be used in accordance with the cold process methods of the JAW, “just add water”, from Jeen lntemational Corp. (Fair present invention. ?eld, N.J.). CPFAs of this type would form a concentrate and, in preferred embodiments, would include one or more pre Example 22 servatives known to the skilled artisan. In addition to water, a ?nal product (e. g., lotion, cream) can be made by adding other Swollen Silicone Oil Gel ingredients, including, for example, anti-aging skin care active ingredient as described below. [0203] The cold process formulation aid of Example 3 is Cold Process Formulation Aids (Examples 5-21) dispersed in water in a suitable vessel at a temperature not above about 30° C. When the processing aid is dispersed, the Example 5iPolyethylene (70%); Sodium Polyacrylate desired amount of silicone oil is added at a temperature not (30%) exceeding about 300 C. to obtain a gel swollen with the Example 6iSun?ower Wax (70%); Sodium Polyacrylate silicone oil. (30%) [0204] Examples of CPFAs in accordance with the second aspect of the invention, in which a blend of PAD(s)/emulsi Example 7iYellow Beeswax (70%); Sodium Polyacrylate fying wax(es) is directly soluble in cosmetically-acceptable (30%) ester(s) or CTG include the following: Example 8iCocoa Butter PPP (35%); Yellow Beeswax (35%); Sodium Polyacrylate (30%) Example 23 Example 9iPolyethylene (45%); Polyvinylpyrrolidone [0205] A CPFA consisting essentially of 10% Polyglyc (25%); Sodium Polyacrylate (30%) eryl-3 Stearate, 30% lsostearyl Neopentanoate, and 60% Example 10—Stearic Acid (30%); Ceteareth-20 (7%); Sodium Polyacrylate Cetearyl Alcohol (62%); Sodium Polyacrylate (1%) Example lliStearic Acid, (32%); Cetearyl Alcohol (32%); Example 24 Glyceryl Stearate (21%); Peg-100 Stearate (10%); Sodium [0206] A CPFA consisting essentially of 10% Polyglyc Polyacrylate (5%) eryl-3 Stearate, 30% lsostearyl Neopentanoate, and 60% Example 124Cetearyl Alcohol (70%); Polysorbate 60 Polyquarternium 37. (25%); Sodium Polyacrylate (5%) Example 13iCetyl Alcohol (50%); Sodium Acrylate Example 25 Acryloyl Dimethyl Taurate Copolymer (30%); Glyceryl Monostearate (15%); Caprylic/Capric Triglyceride (5%) [0207] A CPFA consisting essentially of 20% Sorbitan Stearate, 30% lsopropyl lsostearate, and 50% Polyquater Example 14iStearicAcid (99%); Sodium Acrylate Acryloyl nium 10. Dimethyl Taurate Copolymer (1%) [0201] Example 15iSun?ower wax (35%); Shea butter Example 26 (35%); Sodium Polyacylate (30%) [0208] A CPFA consisting essentially of 15% Polyglyc Example 16iPolyethylene (35%); Sodium Polyacrylate eryl-6 Distearate, 25% C12_C15 Alkyl Benzoate, and 60% (30%); Iron Oxides (15%); Titanium Dioxide (20%) Sodium Alginate. Example 17iPolyethylene (50%); Sodium Polyacrylate (30%); Dimethicone/Vinyl Dimethicone Crosspolymer Example 27 (20%) Example 18iSun?ower Wax (70%);Acrylates/C10_3O Alkyl [0209] CPFAs in accordance with the second aspect of the Acrylate Crosspolymer (30%) invention (Examples 23-26) are generally made by adding the cosmetically-acceptable ester (or CTG) to a vessel; adding Example 19iSun?ower wax (50%); Caprylic/Capric and emulsifying wax to the vessel and mixing the ester, while Triglyceride (20%); Guar Gum (30%) heating to 70-750 C.; adding one or more polymers, where the Example 20iSun?ower wax (50%); Caprylic/Capric polymer(s) have an aliphatic backbone and a plurality of Triglyceride (20%); Carrageenan (30%) pendant groups thereon that are pendant ionic or ionizable groups, or pendant groups having at least one permanent Example 21iSun?ower wax (50%); Caprylic/Capric dipole that includes an acid, alcohol, thiol, ester, amine, Triglyceride (20%); Sodium Alginate (30%). amide, imide, imine, or nitrile moiety, or a polysachharide; [0202] The ratios of the component parts of the CPFAs (i.e., reducing the temperature to 45-35 ° C.; pouring the ?nal blend polymeric backbone, synthetic or natural, and wax) vary into a container. US 2014/0336308 A1 Nov. 13, 2014

Applications Examples acryloyldimethyltaurate copolymer/isohexadecane/polysor bate 80); polyvinylpyrrolidone (PVP); polyvinyl alcohol; [0210] When mixed with an aqueous medium at a tempera crosslinked acrylates, such as crosslinked poly (2-ethylhexyl ture not exceeding 30° C., the cold process formulation aid of acrylate), and hydrophobically-modi?ed acrylates; cellulose the present invention forms a hydrogel or an emulsion. It is derivatives (illustrated above), polysaccharides and gums; also possible to form an emulsion or hydrogel by adding the and crosslinked methacryloyloxyethyl-trimethylammonium cold process formulation aid of the present invention at tem chloride homopolymers sold under the name Salcare SC95. peratures that do not exceed the melt point of the wax com [0216] In preferred embodiments, the mascara contains ponent of the cold process formulation aid or the melt point of both a water-soluble, ?lm-forming polymer and an oil the cold process formulation aid itself. soluble, ?lm-forming polymer, where the water-soluble, ?lm-forming polymer is present at a concentration of from Mascaras 0.5% to 25%, preferably from 1% to 15%, still more prefer [0211] Certain embodiments of the present invention are ably from 1% to 10%, and where the oil-soluble, ?lm-form directed to mascaras that enhance the volume or thickness of ing polymer is present at a concentration of from 1% to 45%, eyelashes. In particularly preferred embodiments, mascara preferably from 3% to 20%. compositions comprising the cold formulation processing aid [0217] In mascara embodiments containing ?bers, the of the present invention not only have long wear and curl, but ?bers may be of natural origin (cotton, silk, wool) or synthetic also exhibit less clumping (i.e., on application and over time) (polyester, rayon, nylon or other polyamides). Fibers typi and are easily removed (i.e., with water). cally have an average length ranging from 0.5 mm to 4.0 mm, [0212] In addition to the cold process formulation aid of the and preferably have an average length ranging from 1.5 mm present invention, the mascara compositions may contain one to 2.5 mm. When present, ?bers may comprise from 0.5% to or more of (i) a self-emulsifying wax, (ii) a latex polymer, 10% wt/wt, preferably from 1% to 5% wt/wt. preferably copolymers of a (meth)acrylic acid and its esters or [0218] In other embodiments directed to volumiZing hair acrylates copolymers, (iii) ?lm-forming polymers, water ?bers, in particular eyelashes, the composition may include soluble and/or oil-soluble, (iv) water-soluble thickening or particles, including powders of the present invention, that are gelling agents, and ?bers. initially at least about 5 microns in equivalent diameter or that [0213] Non-limiting examples of water-soluble, ?lm-form prior to upon application to the lashes swell to a size of at least ing polymers include: polyacrylates and polymethacrylates; about 5 microns in equivalent diameter by any chemical or acrylates copolymers such as those sold by The Lubrizol physical means. Corp. under the tradename Avalure® AC and by Interpolymer [0219] One embodiment of the present invention is directed under the Syntran® PC tradename (Syntran® PC 5208* to volumiZing eyelashes in a two-step process, ?rst by apply Polyacrylate-15; Syntran® PC 5205/5227iPolyacrylate-15 ing a basecoat mascara followed by separate application of a (and) Polyacrylate-17; 3; Syntran® PC 5117iPolyacrylate topcoat mascara. The basecoat contains CPFAs of the present 18 (and) Polyacrylate-19; Syntran® PC 5100 Polyacrylate 21 invention and is exempli?ed by the following formula: (and) Acrylates/Dimethylaminoethyl Methacrylate Copoly CPW-2 (Polyethylene, Sodium Polyacrylate) i10%; mer; Syntran® PC 5400 Ammonium Acrylates); polyvinyl CPW-S (Sun?ower wax, Sodium polyacrylate) i5%; Isod acetates; polyvinyl alcohols; cellulose derivatives (e.g., odecane (40%); Mica 5%; CPW-5 (Polyethylene, Sodium hydroxymethyl cellulose, sodium carboxymethylcellulose, Polyacrylate) i12%); Black Iron Oxide (8%); Jeelux VHIPP ethyl cellulose, hydroxyethyl-cellulose, hydroxypropyl cel (Isopropyl Palmitate, Bis-vinyl Dimethicone/Dimethicone lulose, and hydroxypropyl methylcellulose); cellulose Copolymer) i25%. The topcoat is exempli?ed by the fol acetate phthalate aqueous dispersion; polymers of chitin or lowing formulation: Wateri60%; PEG 150—5%; DC 200 chitosan; vinyl polymers, including vinyl pyrrolidone, poly 1.5 cst (Dimethicone) 25%; Avalure® UR 450 (PPG-17/ vinylpyrrolidone (PVP) and copolymers of vinyl pyrrolidone IPDI/DMPA copolymer) i10%. and PVP (e.g., vinylpyrrolidone/acrylates/lauryl methacry late copolymer, acrylates/Cl_2 succinates/hydroxyacrylates Self-Tanners/Autobronzers copolymer; PVP/DMAPA acrylates copolymer; copolymers [0220] Self-tanning formulations containing cold process of vinylpyrrolidone and caprolactam; polyurethanes (e.g., formulation aids of the present invention include dihydroxy Polyurethane-1, a mixture of 30% polyurethane, 10% etha acetone and at least one reducing sugar, preferably and pref nol, and 60% water, sold under the tradename Luviset® P.U. erably also include a high molecular weight cationic polymer, R. by BASF, Aktiengesellschaft); polyester-polyurethane preferred examples of the latter being described in the fol aqueous dispersions, such as those sold by The Lubrizol lowing U.S. patents, the disclosures of which are incorpo Corp. under the trade names Avalure® UR® and Sancure®; rated, in pertinent part, by reference: US. Pat. Nos. 4,599, and quaternized polymers (e.g., Syntran® PC 5320* 379; 4,628,078; 4,835,206; 4,849,484; and 5,100,660. Polyquatemium sold by Interpolymer). Erythrulose a C4-keto sugar (1,3,4-trihydroxy-butan-2-one) is [0214] Non-limiting examples of oil-soluble, ?lm-forming a preferred reducing sugar and can be used in D- or L-form or polymers include hydrogenated polyisobutenes, poly also as the racemate. Other reducing sugars having self-tan decenes, adipic acid/diethylene glycol/ glycerin crosspoly ning properties that can be used in combination with eryth mer, polyethylene, polyvinyl laurate, dienes (in particular, rulose include glucose, xylose, fructose, reose, ribose, arabi polybutadiene and cylopentadiene), and synthetic-terpene nose, allose, tallose, altrose, mannose, galactose, lactose, based resins. sucrose, erythrose and glyceraldehyde. [0215] Water-soluble thickening or gelling agents may be ?lm-forming polymers and include: polyacrylamides such as Topical Anti-Aging and Dermatologic Compositions Sepigel 305 (INCI name: polyacrylamide/Cl3_l4 isoparaf?n/ [0221] Emulsions made with CPFAs of the present inven Laureth 7) or Simulgel 600 (CTFA name: acrylamide/ sodium tion provide advantages over conventional emulsions made US 2014/0336308 A1 Nov. 13, 2014

by heating two discontinuous phases and then mixing the two may be straight, branched or cyclic. R1 and R2 may be further phases at elevated temperature until homogenous. Notably, substituted with OH, CHO, COOH or a Cl_9 alkoxy group. temperature-sensitive active ingredients (those whose activ Additionally, beta hydroxyacids and polyhydroxyacids may ity is negatively impacted, i.e., diminished, at elevated tem also be added to topical compositions according to the present perature and fragrances can be added directly to the cold invention. process emulsion. [0222] Emulsions containing CPFAs of the present inven Hair Care Products tion can include a multitude of anti-aging skin care active [0226] Cold process emulsions or hydrogels formulated in ingredient. By “anti-aging skin care active ingredient” is accordance with the present invention include hair care meant an ingredient that helps to reduce the appearance of actives known to those of skill in the art that moisturize, and/ or prevent the formation of ?ne lines, wrinkles, age spots, condition, improve bending modulus, increase tensile sallowness, blotchiness, redness, dark circles (i.e., under the strength, increase sheen/shine, improve touchability, reduce eyes). Anti-aging skin care active ingredients are also under split ends, volumize, reduce ?y-away, and/ or increase longev stood as helping to reduce skin oiliness, reduce transepider ity of color treatment. Such materials include proteins and mal water loss, improve skin retention of moisture and/or polypeptides and derivatives thereof, antioxidants, humec improve skin elasticity. Non-limiting examples of skin care tants and moisturizing and conditioning agents actives include: anti-in?ammatory agents (e.g., 1,3 1,6 beta glucan; polyglutamic acid (and) polyfructose); humectants; skin bleaching/lightening agents (e.g., hydroquinone, kojic Antiperspirant/ Deodorants; Wet Wipes acid, ascorbic acid, magnesium ascorbyl phosphate, ascorbyl [0227] In another embodiment, the CPFA of the present 3 aminopropyl phosphate, ascorbyl 3 aminopropyl dihydro invention is advantageously employed in a process for mak gen phosphate); skin soothing agents (e.g., panthenol and ing an extrudable antiperspirant/ solid stick at temperatures derivatives, aloe vera, pantothenic acid and its derivatives, below the melting point of the formula. In this process, a allantoin, bisabolol, and dipotassium glycyrrhizinate); anti homogenized mixture of CPFA, an antiperspirant and/or oxidants; vitamins and derivatives thereof; exfoliants (e.g., deodorant (“AP/Deo”) active ingredient (for example, a salt abrasive particles, hydroxy-acids); anti-aging ingredients, or complex of aluminum and/or zirconium), a structurant including short-chainpeptides (e.g., having less than about 12 (e.g., fatty alcohols and other waxes), absorbent/drying amino acids); and self-tanning agents (e.g., dihydroxyac agents (especially, talc, clay, starches), volatile silicone(s), etone). and, optionally, one or more of suspending agents, emol [0223] Reduction in the appearance of ?ne lines and lients, and fragrance are mixed and homogenized to achieve a wrinkles can be measured by a number of techniques known desired consistency and feel. The resulting mixture is to those of skill in the art and including clinical assessment by extruded to obtain a uniform, solid, cohesive extrudate that is a trained observer (e.g., doctor, nurse, technician) instrumen cut to a desired length. tally (e.g., by use of Sil?o replica masks or an imaging system [0228] The above process is further illustrated by the fol such as VISIA from Can?eld Scienti?c.) Improvements in lowing non-limiting example formulation. The AP/Deo elasticity are measurable, for example, with a Twistometer. active ingredient is incorporated by premixing the active with Reduction in the rate of transepidermal water loss and water and possibly a small amount of propylene glycol. improvement in skin moisture content are measurable, Absorbent/drying agents are particles 10 microns or less and respectively, with an evaporimeter and comeometer. are present in amount of from about 8 to 20% wt/wt. The [0224] In embodiments of the present invention where the volatile silicone(s) are present at a least 15% wt/wt. Trans cold process formulating aid is used to form a topical com parentAP/Deo sticks canbe achieved by forming an emulsion position applied to skin exhibiting visible signs of aging incorporating CPFAs of the present invention, particularly (including ?ne lines, wrinkles, skin laxity, uneven pigmenta self-emulsifying CPFAs (e.g., those including one or more tion), acne lesions, psoriasis, rosacea or an in?ammatory emulsi?ers such as PEG-100 Stearate, Polysorbate-60, Glyc dermatosis, the composition may also contain a natural or eryl Stearate), and oil phase ingredients where the refractive synthetic analog of vitamin A (i.e., a “retinoid”) including indices of the oil and water phase are adjusted to within geometric isomers and stereoisomers, and includes the fol 0.0005 to 0.001 units at room temperature. PEG-400 glycol lowing compounds: retinol; retinal; C2-C22 alkyl esters of and PEGs having a molecular weight of greater than 400 can retinol; including retinyl palmitate, retinyl acetate, retinyl be used to make transparent/translucent gels, some of which propionate; retinoic acid (including all-trans retinoic acid are referred to in the art as “ringing” gels. Such PEGs can be and/ or 13-cis-retinoic acid); as well as compounds described used to make CPFAs of the present invention. For example, as retinoids in US. Pat. Nos. 4,677,120; 4,885,311; 5,049, combining a PAD with PEG 400 Glycol will produce a clear 584; and 5,124,356. transparent/translucent emulsion. [0225] In addition to the cold process formulation aids of [0229] A natural deodorizing powder may be prepared by the present invention, cosmeceutical compositions that mixing alum, sodium bicarbonate, waxes of essential oil and reduce the appearance of the visible signs of aging, topical CPFAs formed from natural waxes and sodium polyacrylate compositions applied in the treatment of acne and other (or one or more salts of sodium polyacrylate or both). in?ammatory dermatoses, as well as self-tanning composi [0230] Low-viscosity AP/Deo roll-ons or sprays (viscosity tions (described above), may contain hydroxy acids, alpha of less than about 2,500 mPas) can be formulated with self hydroxy acids (AHAs). As used in the present application, emulsifying CPFAs of the present invention as de?ned in the AHAs conform to the formula (R1)(R2)C(OH)COOH where preceding paragraph. A non-limiting example of such a low R1 and R2 may be the same or different, and are selected from viscosity AP/Deo composition contains CPFAs of the present the group consisting of H, F, C, Br, alkyl, aralkyl, or aryl invention at a concentration of from 1% to 10% wt/wt, two having 1-29 carbon atoms. The alkyl, aryl or aralkyl groups glucosides in a concentration of from 2% to 10% wt/wt, US 2014/0336308 A1 Nov. 13, 2014

polyglycerol-2-dipolyhydroxystearate at a concentration of Polyderm PPIiCO-40 (PEG-40 Hydrogenated Castor Oil/ from 5% to 8% wt/wt, about 5% wt/wt of a polyol, with the IPDI Copolymer) and Polyderm PPI-SI (Dimethiconol/IPDI balance of the composition being oil components selected Copolymer). from the group of linear hydrocarbons with a chain length of [0235] By structuring agent is meant an ingredient that 8 to 40 carbon atoms, esters, particularly esters formed by the improves or increases the hardness of an oil as measured by reaction of C6-C24 fatty acids with C6-C24fatty alcohols, test methods well-known to those of skill in the art including Guerbet alcohols based on C6-C18 fatty alcohols, and silicone drop point and penetration. compounds. The esters and linear hydrocarbons may be [0236] One or more plasticizers may be added to composi branched or unbranched, saturated or unsaturated. In addition tions of the present invention to further modify spreadability to use as roll-ons, sprays, the above-described composition and other application characteristics of the composition. Plas may be used as an impregnating liquid for wet wipes. ticizers may be present at concentrations of from about 0.01 % to about 20%, preferably about 0.05% to about 15%, and Transfer-Resistant Colored Makeup Compositions more preferably from about 0.1% to about 10%. [0237] Cold process emulsions according to the present [0231] In one embodiment, the present invention is directed invention may contain one or more surfactants at a concen to a process for limiting and/ or preventing the transfer of a colored make-up composition from the lips or the skin, where tration of from about 0.01% to about 20%, preferably from the colored make-up composition is comprised of a CPFA of about 0.1% to about 15%, and more preferably from about the present invention, at least partially crosslinked, elasto 0.5% to about 10% by weight of the total composition. The meric organopolysiloxane, a fatty phase containing at least surfactants may be amphoteric, anionic, cationic, or non ionic. one oil that is volatile at room temperature. Transfer resistant lipsticks preferably include a siloxysilicate polymer, prefer [0238] Amphoteric surfactants suitable for use in compo ably trimethylsiloxy silicate. The colored make-up composi sitions of the present invention include propionates, alky tion may be in the form of a foundation, a blush, an eye ldimethyl betaines, alkylamido betaines, sulfobetaines, imi shadow, a concealer, a lipstick, a lipstick topcoat (i.e., applied dazoline. over a base lipstick), and a tinted moisturizer, preferably [0239] Anionic surfactants suitable for use in compositions containing UV radiation absorbers or blocks. Tests for trans of the present invention include fatty alcohol sulfates, alpha fer-resistance are known to those of skill in the art and include ole?n sulfonates, sulfosuccinates, phosphate esters, carboxy the “Kiss Test” described in Example 4 of Us. Pat. No. lates and sarcosinates. 5,505,937. [0240] Cationic surfactants suitable foruse in compositions of the present invention include alkyl quatemaries, alylamido Additional Cosmetic Ingredients quatemaries, imidazoline quatemaries. [0241] Nonionic ionic surfactants suitable for use in com [0232] As will be appreciated by persons skill in the art, a positions of the present invention include alkanolamides, wide-range of water-immiscible materials may be added to ethoxylated amides, esters, alkoxylated alcohols, alkoxylated the cold process emulsions of the present invention, non triglycerides, alkylpolyglucosides, amine oxides, sorbitan limiting examples of which include (i) non-volatile silicone esters and ethoxylates. ?uids, preferably have a viscosity ranging of from about 20 to [0242] Surfactants may also be silicone surfactants includ 100,000 centistokes at 25° C.; (ii) nonvolatile hydrocarbon ing, but not limited, dimethicone copolyols, alkyl dimethi oils including, but not limited to, isoparaf?ns and ole?ns cone copolyols, silicone quaternary compounds, silicone having greater than 20 carbon atoms; (iii) cosmetically-ac phosphate esters and silicone esters. ceptable esters (as de?nedbelow); (iv) lanolin and derivatives thereof; (v) glyceryl esters of fatty acids or triglycerides, Encapsulates derived from animal or vegetable sources; (vi) ?uorinated oils including, but not limited to, ?uorinated silicones, ?uorinated [0243] The cold processing formulation aids of the present esters and per?uoropolyethers; and (vii) Guerbet esters invention may contain other materials embedded therein. formed by the reaction of a carboxylic acid with a Guerbet Encapsulation may be achieved by mixing other materials alcohol. with the required components of the cold processing aid of the [0233] As used herein, “cosmetically-acceptable ester” present invention as taught herein. In one example, the other refers to compounds formed by the reaction of a mono-, di- or material(s) are mixed with the cold processing aid of the tri-carboxylic acid with an aliphatic or aromatic alcohol that present invention in a molten state, before it is atomized and cooled to create a solid wax particle. Non-limiting examples are not irritating or sensitizing when applied to the skin. The of materials that can be embedded inside the cold processing carboxylic acid may contain from 2 to 30 carbon atoms, and formulation aids of the present invention include, but are not may be straight-chain or branched-chain, saturated or unsat urated. The carboxylic acid may also be substituted with one limited to, pigments, preservatives, ?llers, active ingredients or more hydroxyl groups. The aliphatic or aromatic alcohol (either hydrophilic or lipophilic), polymers, fragrance ingre dients (e.g., essential oils and aroma-producing chemicals of may contain 2 to 30 carbon atoms, may be straight-chain or natural or synthetic origin), and mixtures thereof. branched-chain, saturated or unsaturated. The aliphatic or aromatic alcohol may contain one or more substituents Oil-in-Water Emulsions Containing High Molecular Weight including, for example, a hydroxyl group. Polysaccharides [0234] Among other things, the above-listed water-immis cible materials may provide emolliency. Other emollients [0244] In another embodiment, the CPFA described herein known in the art may be used, including urethane emollients is used in oil-in-water emulsions that are stabilized with and conditioners sold under the tradename Polyderm by Alzo polysaccharides, especially xanthan, a poly(glucomannan), International, non-limiting examples of the latter including or both. US 2014/0336308 A1 Nov. 13, 2014

[0245] US. Pat. No. 6,831,107 discloses that high molecu applied to mammalian hair or skin, compositions containing lar weight polysaccharides stabilize oil-in-water emulsions CPFAs of the present invention may be applied as a pro (O/W), without increasing the low-shear viscosity of the tectant, moisturizer, sealer, to household, industrial, hospital emulsion, and allows lower levels of emulsi?ers to be used. and commercial hard surfaces as well as to the exterior sur However, this patent also discloses that use of anionic mate faces of automotive and marine vehicles, including tires and rials, e.g. anionic surfactants, in combination with high wheels, recreational sports equipment, woven and non-wo molecular weight polysaccharides is highly disfavored ven fabrics. Protectant, moisturizer and/or sealer formula because, among other reasons, the ionic material impairs the tions within the scope of the present invention may be applied ability of the polysaccharide to stabilize the emulsion. Appli for example, to rubber, vinyl, plastic, leather, fabric, carpet cants have surprisingly discovered that, despite the fact that ing. the CPFAs of the present invention include polymers having [0251] As used in the present application, by “protectant” is ionic or ionizable groups, the CPFAs are useful in oil-in meant a consumer or industrial product, preferably a spray, water emulsions that are stabilized with high molecular that coats the surface to minimize the degradation of the weight polysaccharides. When a CPFA of the type described coated material due to environmental factors and provide a herein is used, high temperature is not required to form the durable and shiny appearance. The protectant spray may, and emulsion, provided that suf?cient shear energy is supplied. in certain embodiments does contain, either or both of (i) a [0246] For example the CPFA can be incorporated at low UV absorbing or re?ecting/ scattering compound known in temperature to provide rheology modi?cation when higher the art and/or (ii) a cleansing agent (e.g., a surfactant). In viscosity products are desired. Emulsions made with CPFAs embodiments directed to cleansing agents, positively charged can be used as such in a personal care product, or they can be “dirt particles” are entrained in the aqueous phase of an emul used to make articles, e.g. pads impregnated with such a sion containing the CPFA of the present invention. Dirt is product. repelled from the surface while the wax within the emulsion [0247] Non-limiting examples of rheology modi?ers that attaches to the “uncharged”, now clean surface. can be incorporated in CPFAs of the present invention [0252] CPFAs of the present invention may also be used in include: polyurethanes, acrylic polymers (as described furniture restoration, i.e., to ?ll cracks. above), latex, styrene/butadiene; polyvinyl alcohol; clays, including attapulgite, bentonite (both ?occulating and non Topical Hydro-Alcoholic Antiseptic ?occulating), and other montmorillonite clays; cellulosic [0253] A topically-applied, hydro-alcoholic antiseptic polymers as mentioned above, including carboxymethylcel product, meeting the criteria of the Tentative Final Mono lulose, hydroxymethylcellulose, hydroxypropylmethylcellu graph for OTC Healthcare Antiseptic Drug Products (Jun. 17, lose; sulfonates and salts thereof; gums (as described above), 1994), is illustrated below: including but not limited to, guar, xanthan, cellulose, locust bean, and acacia; saccharides (as described above); proteins, OTC Antiseptic Example 1 including cassein, collagen, and albumin. All of the above rheology modi?ers are preferably incorporated in the CPFAs [0254] Phase AiDistilled Water (24%); Ethanol (70%) of the present invention at concentrations of from about 0.2% [0255] Phase B4Cold Processing Aid of Present Invention to 2.0%. (6%) (Sun?ower Wax, Polyacrylate Crosspolymer-6, sold [0248] In preferred embodiments of this aspect of the under the tradename CPW S-ZEN by Jeen International) invention, a CPFA, an emulsi?er, and emulsion stabilizer (polysachamide) are blended to provide a dry product that can OTC Antiseptic Example 2 be dispersed in water and readily then made into emulsions at [0256] Phase AiDistilled Water (26%); Ethanol (65%); low temperature. In these embodiments, it can be useful to use Amino Methyl Propanediol (1.0%); Glycerin 99.7% USP both high HLB and low HLB emulsi?ers and optionally to (3.0%) include materials such as milling aids. Products according to [0257] Phase B4Cold Processing Aid of Present Invention this embodiment can be made by dry blending xanthan and (5%)(Sun?ower Wax, Acrylates/C 1060 Alkyl Acrylate Cros polyglucomannan, emulsi?ers and the CPFA and consolidat spolymer, sold under the tradename CPW-SUN21 by Jeen ing the blend, e.g. by extrusion, desirably at a temperature, International) suf?cient that one or more of the components (typically one [0258] The above OTC antiseptic product is prepared using or more of the emulsi?ers are at least partly melted and can so a cold process formulation aid of the present invention by coat and/or bind the powder components especially the mixing at room temperature the ingredients of Phase A and polysaccharides), to form pellets and then milling the pellets Phase B separately, and then adding Phase B to Phase A. to a desired particle size. While less preferable with respect to Consistent with the above Tentative Final OTC Monograph, energy/heat consumption, the use of CPFAs to thicken an the level of alcohol in this product may be adjusted to between O/ W emulsion as described in this embodiment may also be 60 and 95%. Each of the above formulation are non-drying useful in conventional heated emulsion processes. and leave a silky after feel. [0249] A typical composition for such a dry blend, in parts by weight, is as follows: xanthan (3 to 8% wt/wt); polyglu Biomaterials comannan (3 to % 8 wt/wt); olive wax 84 to 94% wt/wt. The [0259] Cold process formulation aids of the present inven ratio of xanthan to polyglucomannan can be between 1:2 to tion may be used in the manufacture of biocompatible mate 2:1. rials, including, but not limited to, ?llings, coatings, implants Surface Coatings/Protectants and “scaffolding” (i.e., to provide temporary support and stability for damaged tissue and/or to provide a substrate for [0250] In addition to personal care applications, where growth of bone or tissue). The CPFA may include one or more compositions of the present invention containing CPFAs are crosslinked or photocurable (e.g., by ultraviolet light) func