Hair styling formulations

Abstract

There is provided a hair styling polymer comprising: a cosmetically acceptable carrier; and a hair styling polymer comprising: 70% to 95% by weight, based on the dry polymer, of a monoethylenically unsaturated vinyl alkanoate monomer having 4 to 13 carbon atoms; from 5% to 30% by weight, based on the dry weight of the hairstyling polymer, of structural units of a monoethylenically unsaturated carboxylic acid / carboxylic acid anhydride functionalized vinyl ester monomer having from 4 to 12 carbon atoms; from 0% to 5% by weight, based on the dry weight of the hair styling polymer, of structural units of a polyethylenically unsaturated crosslinking monomer; and 0% to 20% by weight, based on the dry weight of the hairstyling polymer, of structural units of other monoethylenically unsaturated monomers, wherein the further monoethylenically unsaturated monomer is different from the monoethylenically unsaturated alkanoic acid vinyl ester monomer having from 4 to 13 carbon atoms and the monoethylenically unsaturated carboxylic acid / carboxylic acid anhydride functionalized vinyl ester monomer having from 4 to 12 carbon atoms.

Description

[0001] The present invention relates to a hair styling formulation. In particular, the present invention relates to a hair styling formulation comprising: a cosmetically acceptable carrier; and a hair styling polymer comprising: 70 to 95 weight percent, based on the dry weight of the hair styling polymer, of structural units of a monoethylenically unsaturated alkanoic acid vinyl ester monomer having 4 to 13 carbon atoms; 5 to 30 weight percent, based on the dry weight of the hair styling polymer, of structural units of a monoethylenically unsaturated carboxylic acid / carboxylic acid anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms; 0 to 5 weight percent, based on the dry weight of the hair styling polymer, of structural units of a polyethylenically unsaturated crosslinking monomer; and 0 to 20 weight percent, based on the dry weight of the hair styling polymer, of structural units of other monoethylenically unsaturated monomers, wherein the other monoethylenically unsaturated monomers are different from the monoethylenically unsaturated alkanoic acid vinyl ester monomer having 4 to 13 carbon atoms and the monoethylenically unsaturated carboxylic acid / carboxylic acid anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms.

[0002] Many consumers use some type of hair styling product as part of their daily routine grooming. Styling products are provided in a variety of forms. These forms can include aerosol and non-aerosol sprays, aerosol and non-aerosol mousses, gels, lacquers, styling waters, spray gels, spray mousses, waxes, pastes, pomades, and serums. The overall market for these hair styling products continues to grow.

[0003] An important component in hair styling products is a hair styling polymer or fixative designed to set a temporary hairstyle or curl to the hair. Hair styling formulations can be applied to wet hair or after the hair is dry to hold the shape and style of the hair. Advantageously, the hair styling polymer provides hair fixative properties and curl retention under a variety of humidity conditions, has little to no flaking or hair breakage when combed, cures or dries quickly on the hair, is not tacky, and is easily removed with shampoo.

[0004] Hair fixative polymers are disclosed in U.S. Patent No. 10,166,179 to Ive et al. Ive et al. disclose a hair fixative polymer comprising 55 to 60 weight percent of ethyl acrylate, 30 to 50 weight percent of (meth)acrylic acid; 1 to 5 weight percent of an associative monomer comprising a methacrylic ester having an alkoxylated ethylenically unsaturated group capped with a hydrophobic non-aromatic branched chain having 12 to 22 carbon atoms; and 1 to 4 weight percent of a crosslinker.

[0005] Nonetheless, the demand for hair styling formulations that provide hair styling benefits while also being beneficial to sustainability requirements continues to increase. The use of materials of biological origin as raw materials is a desirable sustainability characteristic of new hair styling polymers designed for use in hair styling formulations. Additionally, it is desirable to have hair styling polymers that exhibit biodegradability.

[0006] Accordingly, there remains a need for new hair styling formulations that include new hair styling polymers that provide hair styling benefits while also being of biological origin and / or biodegradable.

[0007] The present invention provides a hair styling formulation comprising: a cosmetically acceptable carrier; and a hair styling polymer comprising: 70% to 95% by weight of structural units of a monoethylenically unsaturated alkanoic acid vinyl ester monomer having 4 to 13 carbon atoms, based on the dry weight of the hair styling polymer; 5% to 30% by weight of structural units of a monoethylenically unsaturated carboxylic acid / carboxylic acid anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms, based on the dry weight of the hair styling polymer; 0% to 5% by weight of structural units of a polyethylenically unsaturated crosslinking monomer, based on the dry weight of the hair styling polymer; and 0% to 20% by weight of structural units of other monoethylenically unsaturated monomers, based on the dry weight of the hair styling polymer, wherein the other monoethylenically unsaturated monomers are different from the monoethylenically unsaturated alkanoic acid vinyl ester monomer having 4 to 13 carbon atoms and the monoethylenically unsaturated carboxylic acid / carboxylic acid anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms.

[0008] A hair styling formulation comprising: 20% to 99.5% by weight of a cosmetically acceptable carrier based on the weight of the hair styling formulation; and 0.5% to 20% by weight of a hair styling polymer comprising: 70% to 95% by weight of structural units of a monoethylenically unsaturated alkanoic acid vinyl ester monomer having 4 to 13 carbon atoms based on the dry weight of the hair styling polymer; 5% to 30% by weight of structural units of a monoethylenically unsaturated carboxylic acid / carboxylic acid anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms based on the dry weight of the hair styling polymer; 0% to 5% by weight of structural units of a polyethylenically unsaturated crosslinking monomer based on the dry weight of the hair styling polymer; and 0% to 20% by weight of structural units of a further monoethylenically unsaturated monomer based on the dry weight of the hair styling polymer, wherein the further monoethylenically unsaturated monomer is different from the monoethylenically unsaturated alkanoic acid vinyl ester monomer having 4 to 13 carbon atoms and the monoethylenically unsaturated carboxylic acid / carboxylic acid anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms; wherein the hair styling polymer comprises < 5 mole % of monomer residues of a monomer having a six-membered heterocyclic ring; wherein the hair styling polymer comprises < 15% by weight of monoethylenically unsaturated C 4-6 dicarboxylic acid monomer based on the dry weight of the hair styling polymer; and wherein the hair styling polymer comprises structural units of at least two different monoethylenically unsaturated alkanoic acid vinyl ester monomers having 4 to 13 carbons.

[0009] A hair styling formulation comprising: a cosmetically acceptable carrier; a hair care adjuvant; and a hair styling polymer comprising: 70% to 95% by weight of structural units of a monoethylenically unsaturated alkanoic acid vinyl ester monomer having 4 to 13 carbon atoms based on the dry weight of the hair styling polymer; 5% to 30% by weight of structural units of a monoethylenically unsaturated carboxylic acid / carboxylic acid anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms based on the dry weight of the hair styling polymer; 0% to 5% by weight of structural units of a polyethylenically unsaturated crosslinking monomer based on the dry weight of the hair styling polymer; and 0% to 20% by weight of structural units of a further monoethylenically unsaturated monomer based on the dry weight of the hair styling polymer, wherein the further monoethylenically unsaturated monomer is different from the monoethylenically unsaturated alkanoic acid vinyl ester monomer having 4 to 13 carbon atoms and the monoethylenically unsaturated carboxylic acid / carboxylic acid anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms.

[0010] This invention provides a hair styling formulation comprising: a cosmetically acceptable carrier; and a hair styling polymer comprising: 70% to 95% by weight, based on the dry weight of the hair styling polymer, structural units of a monoene unsaturated vinyl ester monomer having 4 to 13 carbon atoms; 5% to 30% by weight, based on the dry weight of the hair styling polymer, structural units of a monoene unsaturated carboxylic acid / carboxylic anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms; 0% to 5% by weight, based on the dry weight of the hair styling polymer, structural units of a polyene unsaturated crosslinking monomer; and 0% to 20% by weight, based on the dry weight of the hair styling polymer, structural units of other monoene unsaturated monomers, wherein the other monoene unsaturated monomers are different from monoene unsaturated vinyl esters having 4 to 13 carbon atoms. The hair styling polymer comprises vinyl ester monomers and monoalkenyl unsaturated carboxylic acid / carboxylic anhydride-functionalized vinyl ester monomers having 4 to 12 carbon atoms; wherein, based on the dry weight of the hair styling polymer, at least 80% by weight comprises structural units of monoalkenyl unsaturated alkyl vinyl ester monomers having 4 to 13 carbon atoms and structural units of carboxylic acid-functionalized vinyl ester monomers having 4 to 12 carbon atoms; wherein the hair styling polymer comprises >55 mol% of structural units of monoalkenyl unsaturated alkyl vinyl ester monomers having 4 to 13 carbon atoms; wherein the hair styling polymer comprises less than 0.1 mol% of structural units of amide-containing monomers; wherein the hair styling polymer comprises less than 0.1 mol% of structural units of amino-containing monomers based on the dry weight of the hair styling polymer; and wherein the hair styling polymer comprises less than 5 mol% of structural units of Formula I based on the dry weight of the hair styling polymer. (I); The dashed lines (------) represent attachment points along the polymer backbone; where R 1 and R 2 Independently selected from hydrogen and C 1-3 The hair styling polymer comprises less than 0.01 mol% of a diether-containing monomer structural unit; wherein the hair styling polymer comprises less than 10 wt% of a 2 to 10 carbon atom alkyl acrylate monomer structural unit based on the dry weight of the hair styling polymer; wherein the hair styling polymer comprises <5 mol% of a six-membered heterocyclic monomer residue (e.g., a glucose moiety); and wherein the hair styling polymer comprises <15 wt% of a monoalkenyl unsaturated C group based on the dry weight of the hair styling polymer. 4-6 Structural units of dicarboxylic acid monomers.

[0011] The present invention provides a method for styling hair, comprising: selecting a hair styling preparation; applying the hair styling preparation of the present invention to the hair; and styling the hair to provide a styling state; wherein the hair styling preparation sets the hair in the styling state. Detailed Implementation

[0012] The applicant has been surprised to find that the following hair styling formulations can effectively style hair (even under high humidity conditions, i.e., ≥80% relative humidity) and given the biodegradability of the hair styling polymers (according to the OECD) The 302B procedure also exhibits improved sustainability characteristics, comprising: a cosmetically acceptable carrier; and a hair styling polymer comprising: 70% to 95% by weight, based on the dry weight of the hair styling polymer, structural units of monoene unsaturated vinyl alkanoate monomers having 4 to 13 carbon atoms; 5% to 30% by weight, based on the dry weight of the hair styling polymer, structural units of monoene unsaturated carboxylic acid / carboxylic anhydride functionalized vinyl ester monomers having 4 to 12 carbon atoms; 0% to 5% by weight, based on the dry weight of the hair styling polymer, structural units of polyene unsaturated crosslinking monomers; and 0% to 20% by weight, based on the dry weight of the hair styling polymer, structural units of other monoene unsaturated monomers, wherein these other monoene unsaturated monomers are different from the monoene unsaturated vinyl alkanoate monomers having 4 to 13 carbon atoms and the monoene unsaturated carboxylic acid / carboxylic anhydride functionalized vinyl ester monomers having 4 to 12 carbon atoms.

[0013] Unless otherwise specified, ratios, percentages, parts, etc., are all by weight. Weight percentages (or % by weight) in a composition are percentages of dry weight, i.e., excluding any solvents that may be present in the composition. The percentage of monomer units in a polymer is a percentage of solid weight (i.e., excluding any solvents present in the polymer).

[0014] As used herein, unless otherwise specified, the phrase "molecular weight" or M W This refers to the weight-average molecular weight as measured in a conventional manner using gel permeation chromatography (GPC) and conventional standards, such as narrow molecular weight standards of amylopectin ranging from 180 Daltons to 708,000 Daltons. GPC techniques are discussed in detail in *Modern Size-Exclusion Liquid Chromatography – Practice of Gel Permeation and Gel Filtration Chromatography*, 2nd Edition, AM Striegel, WW Yau, JJ Kirkland, DD Bly; John Wiley & Sons, Inc. 2009. Molecular weights are reported in Daltons or, equivalently, g / mol.

[0015] As used herein and in the appended claims, the term "structural unit" refers to the residue of the indicated monomer as present in the hair styling polymer; thus, for example, the structural unit of vinyl acetate is as follows: where the dotted line ( ) represents the point of attachment along the polymer backbone.

[0016] Preferably, the hair styling preparations of the present application are leave-on conditioners, aerosol hair sprays, pump hair sprays, styling gels, spray gels, and mousses.

[0017] Preferably, the hair styling preparations of the present application comprise: a cosmetically acceptable carrier (preferably, 20% to 99.5% by weight (more preferably, 25% to 98% by weight; still more preferably, 30% to 97% by weight; most preferably, 40% to 96% by weight) of a cosmetically acceptable carrier, based on the weight of the hair styling preparation); optional hair care adjuncts; optional pH adjusting agents; and a hair styling polymer (preferably, 0.5% to 20% by weight (more preferably, 2% to 15% by weight; still more preferably, 3% to 14% by weight; most preferably, 4% to 12% by weight) of a hair styling polymer, based on the weight of the hair styling preparation), comprising: 70% to 95% by weight (preferably, 72% to 90% by weight; more preferably, 75% to 87.5% by weight; most preferably, 77.5% to 85% by weight) of structural units of a monoethylenically unsaturated alkanoic acid vinyl ester monomer having 4 to 13 carbon atoms, based on the dry weight of the hair styling polymer; 5% to 30% by weight (preferably, 10% to 28% by weight; more preferably, 12.5% to 25% by weight; most preferably, 15% to 22.5% by weight) of structural units of a monoethylenically unsaturated carboxylic acid / carboxylic acid anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms, based on the dry weight of the hair styling polymer; 0% to 5% by weight (preferably, 0% to 2.5% by weight; more preferably, 0% to 1% by weight; most preferably, 0% to 0.5% by weight) of structural units of a polyethylenically unsaturated crosslinking monomer, based on the dry weight of the hair styling polymer; and 0% to 20% by weight (preferably, 0% to 5% by weight; more preferably, 0% to 4% by weight; most preferably, 0% to 3% by weight) of structural units of other ethylenically unsaturated monomers, based on the dry weight of the hair styling polymer, wherein the other monoethylenically unsaturated monomers are different from the monoethylenically unsaturated alkanoic acid vinyl ester monomer having 4 to 13 carbon atoms and the monoethylenically unsaturated carboxylic acid / carboxylic acid anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms.

[0018] Preferably, the hair styling formulation of the present application comprises 20% to 99.5% by weight (preferably, 25% to 98% by weight; more preferably, 30% to 97% by weight; most preferably, 40% to 96% by weight) of a cosmetically acceptable carrier based on the weight of the hair styling formulation. More preferably, the hair styling formulation of the present application comprises 20% to 99.5% by weight (preferably, 25% to 98% by weight; more preferably, 30% to 97% by weight; most preferably, 40% to 96% by weight) of a cosmetically acceptable carrier based on the weight of the hair styling formulation; wherein the cosmetically acceptable carrier is an aqueous carrier. Still more preferably, the hair styling formulation of the present application comprises 20% to 99.5% by weight (preferably, 25% to 98% by weight; more preferably, 30% to 97% by weight; most preferably, 40% to 96% by weight) of a cosmetically acceptable carrier based on the weight of the hair styling formulation; wherein the cosmetically acceptable carrier is water and C 1-4 a mixture of alcohols (preferably, ethanol, propanol, isopropanol; more preferably, ethanol). Still more preferably, the hair styling formulation of the present application comprises 20% to 99.5% by weight (preferably, 25% to 98% by weight; more preferably, 30% to 97% by weight; most preferably, 40% to 96% by weight) of a cosmetically acceptable carrier based on the weight of the hair styling formulation; wherein the cosmetically acceptable carrier is 5% to 45% by weight (preferably, 7.5% to 40% by weight) of water and 55% to 95% by weight (preferably, 60% to 92.5% by weight) of C 1-4 a mixture of alcohols (preferably, ethanol, propanol, isopropanol; more preferably, ethanol). Most preferably, the hair styling formulation of the present application comprises 20% to 99.5% by weight (preferably, 25% to 98% by weight; more preferably, 30% to 97% by weight; most preferably, 40% to 96% by weight) of a cosmetically acceptable carrier based on the weight of the hair styling formulation; wherein the cosmetically acceptable carrier is 5% to 45% by weight (preferably, 7.5% to 40% by weight) of water and 55% to 95% by weight (preferably, 60% to 92.5% by weight) of ethanol based on the weight of the cosmetically acceptable carrier.

[0019] Preferably, the hair styling formulation of the present application comprises 0.5% to 20% by weight (preferably, 2% to 15% by weight; more preferably, 3% to 14% by weight; most preferably, 4% to 12% by weight) of a hair styling polymer based on the weight of the hair styling formulation; wherein the hair styling polymer comprises: 70% to 95% by weight (preferably, 72% to 90% by weight; more preferably, 75% to 87.5% by weight; most preferably, 77.5% to 85% by weight) of structural units of a monoethylenically unsaturated alkanoic acid vinyl ester monomer having 4 to 13 carbon atoms based on the dry weight of the hair styling polymer; 5% to 30% by weight (preferably, 10% to 28% by weight; more preferably, 12.5% to 25% by weight; most preferably, 15% to 22.5% by weight) of structural units of a monoethylenically unsaturated carboxylic acid / carboxylic acid anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms based on the dry weight of the hair styling polymer; 0% to 5% by weight (preferably, 0% to 2.5% by weight; more preferably, 0% to 1% by weight; most preferably, 0% to 0.5% by weight) of structural units of a polyethylenically unsaturated crosslinking monomer based on the dry weight of the hair styling polymer; and 0% to 20% by weight (preferably, 0% to 5% by weight; more preferably, 0% to 4% by weight; most preferably, 0% to 3% by weight) of structural units of other ethylenically unsaturated monomers based on the dry weight of the hair styling polymer, wherein the other monoethylenically unsaturated monomers are different from the monoethylenically unsaturated alkanoic acid vinyl ester monomer having 4 to 13 carbon atoms and the monoethylenically unsaturated carboxylic acid / carboxylic acid anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms.

[0020] Preferably, the hair styling polymer of the present application comprises: 70 to 95 wt% (preferably, 72 to 90 wt%; more preferably, 75 to 87.5 wt%; most preferably, 77.5 to 85 wt%) of structural units of a monoethylenically unsaturated alkanoic acid vinyl ester monomer having 4 to 13 carbon atoms, based on the dry weight of the hair styling polymer; wherein the monoethylenically unsaturated alkanoic acid vinyl ester monomer having 4 to 13 carbon atoms is selected from the group consisting of vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl valerate (also known as vinyl g-valerate), vinyl 3-methylbutyrate, vinyl 2-methylbutyrate, vinyl pivalate, vinyl hexanoate (also known as vinyl n-hexanoate), vinyl 4-methylvalerate, vinyl 2-methylvalerate, vinyl 3,3-dimethylbutyrate, vinyl 2,2-dimethylbutyrate, vinyl heptanoate, vinyl 5-methylhexanoate, vinyl 2-methylhexanoate, vinyl 4,4-dimethylvalerate, vinyl 2,2-dimethylvalerate, vinyl octanoate, vinyl 6-methylheptanoate, vinyl 2-methylheptanoate, vinyl 5,5-dimethylhexanoate, vinyl 2,2-dimethylhexanoate, vinyl nonanoate, vinyl 7-methyloctanoate, vinyl 2-methyloctanoate, vinyl 6,6-dimethylheptanoate, vinyl 2,2-dimethylheptanoate, vinyl decanoate, vinyl 8-methylnonanoate, vinyl 2-methylnonanoate, vinyl 7,7-dimethyloctanoate (also known as vinyl neodecanoate), vinyl 2,2-dimethyloctanoate, vinyl undecanoate, vinyl 9-methyldecanoate, vinyl 2-methyldecanoate, vinyl 2-methyl-2-propylhexanoate, vinyl 2-ethyl-2-methylheptanoate, vinyl 2,2-dimethyloctanoate, vinyl 2,2-dimethylheptanoate, vinyl 2-ethyl-2-methylhexanoate, vinyl 2-methyl-2-propylvalerate, vinyl 2-ethylhexanoate, and mixtures thereof (preferably, wherein the hair styling polymer comprises structural units of at least two different monoethylenically unsaturated alkanoic acid vinyl ester monomers having 4 to 13 carbons).More preferably, the hair styling polymer of the present application comprises: 70 to 95 weight % (preferably, 72 to 90 weight %; more preferably, 75 to 87.5 weight %; most preferably, 77.5 to 85 weight %) of structural units of a monoethylenically unsaturated alkanoic acid vinyl ester monomer having 4 to 13 carbon atoms based on the dry weight of the hair styling polymer; wherein the monoethylenically unsaturated alkanoic acid vinyl ester monomer having 4 to 13 carbon atoms is selected from the group consisting of vinyl acetate, vinyl pentanoate, vinyl 3-methylbutanoate, vinyl 2-methylbutanoate, vinyl pivalate, vinyl decanoate, vinyl 8-methylnonanoate, vinyl 2-methylnonanoate, vinyl 7,7-dimethyloctanoate, vinyl 2,2-dimethyloctanoate, vinyl 2-methyl-2-propylhexanoate, vinyl 2-ethyl-2-methylheptanoate, vinyl 2,2-dimethyloctanoate, and mixtures thereof (preferably wherein the hair styling polymer comprises structural units of at least two different monoethylenically unsaturated alkanoic acid vinyl ester monomers having 4 to 13 carbons). Still more preferably, the hair styling polymer of the present application comprises: 70 to 95 weight % (preferably, 72 to 90 weight %; more preferably, 75 to 87.5 weight %; most preferably, 77.5 to 85 weight %) of structural units of a monoethylenically unsaturated alkanoic acid vinyl ester monomer having 4 to 13 carbon atoms based on the dry weight of the hair styling polymer; and wherein the monoethylenically unsaturated alkanoic acid vinyl ester monomer is selected from the group consisting of vinyl acetate, vinyl pivalate, vinyl 7,7-dimethyloctanoate, vinyl 2,2-dimethyloctanoate, vinyl 2-methyl-2-propylhexanoate, vinyl 2-ethyl-2-methylheptanoate, vinyl 2,2-dimethyloctanoate, and mixtures thereof (preferably wherein the hair styling polymer comprises structural units of at least two different monoethylenically unsaturated alkanoic acid vinyl ester monomers having 4 to 13 carbons). Most preferably, the hair styling polymer of the present application comprises: 70 to 95 weight % (preferably, 72 to 90 weight %; more preferably, 75 to 87.5 weight %; most preferably, 77.5 to 85 weight %) of structural units of a monoethylenically unsaturated alkanoic acid vinyl ester monomer having 4 to 13 carbon atoms based on the dry weight of the hair styling polymer; and wherein the monoethylenically unsaturated alkanoic acid vinyl ester monomer is selected from the group consisting of vinyl acetate, vinyl pivalate, vinyl 2-methyl-2-propylhexanoate, vinyl 2-ethyl-2-methylheptanoate, vinyl 2,2-dimethyloctanoate, and mixtures thereof (preferably wherein the hair styling polymer comprises structural units of at least two different monoethylenically unsaturated alkanoic acid vinyl ester monomers having 4 to 13 carbons).

[0021] Preferably, the hair styling polymer of the present application comprises > 55 mole % (preferably, > 56 mole %; more preferably, > 60 mole %; still more preferably, > 70 mole %; yet more preferably, > 75 mole %; most preferably > 80 mole %) of structural units of monoethylenically unsaturated alkane acid vinyl ester monomers having 4 to 13 carbon atoms.

[0022] Preferably, the hair styling polymer of the present application comprises: 5 to 30 wt% (preferably, 10 to 28 wt%; more preferably, 12.5 to 25 wt%; most preferably, 15 to 22.5 wt%) of structural units of a carboxylic acid / carboxylic anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms based on the dry weight of the hair styling polymer; wherein the carboxylic acid / carboxylic anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms is selected from the group consisting of 2-oxo-2-(vinyloxy)acetic acid, 3-oxo-3-(vinyloxy)propanoic acid, 4-oxo-4-(vinyloxy)butanoic acid (aka vinyl succinic acid hydrogen ester) (aka vinyl succinic acid), 5-oxo-5-(vinyloxy)pentanoic acid, 6-oxo-6-(vinyloxy)hexanoic acid (aka vinyl adipic acid) (aka vinyl adipic acid hydrogen ester) (aka 6-vinyloxy-6-oxohexanoic acid), 2-(2,5-dioxotetrahydrofuran-3-yl)vinyl acetate, 2-(2-oxo-2-(vinyloxy)ethyl)succinic acid, 7-oxo-7-(vinyloxy)heptanoic acid, 8-oxo-8-(vinyloxy)octanoic acid, 9-oxo-9-(vinyloxy)nonanoic acid, 10-oxo-10-(vinyloxy)decanoic acid, and mixtures thereof. More preferably, the hair styling polymer of the present application comprises: 5 to 30 wt% (preferably, 10 to 28 wt%; more preferably, 12.5 to 25 wt%; most preferably, 15 to 22.5 wt%) of structural units of a carboxylic acid / carboxylic anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms based on the dry weight of the hair styling polymer; wherein the carboxylic acid / carboxylic anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms is selected from the group consisting of 4-oxo-4-(vinyloxy)butanoic acid, 5-oxo-5-(vinyloxy)pentanoic acid, 6-oxo-6-(vinyloxy)hexanoic acid, 2-(2,5-dioxotetrahydrofuran-3-yl)vinyl acetate, 2-(2-oxo-2-(vinyloxy)ethyl)succinic acid, 7-oxo-7-(vinyloxy)heptanoic acid, 8-oxo-8-(vinyloxy)octanoic acid, and mixtures thereof.Still more preferably, the hair styling polymer of the present application comprises: 5 to 30 weight % (preferably, 10 to 28 weight %; more preferably, 12.5 to 25 weight %; most preferably, 15 to 22.5 weight %) of structural units of a carboxylic acid / carboxylic anhydride functional vinyl ester monomer having 4 to 12 carbon atoms based on the dry weight of the hair styling polymer; wherein the carboxylic acid / carboxylic anhydride functional vinyl ester monomer having 4 to 12 carbon atoms is selected from the group consisting of 4-oxo-4-(vinyloxy)butanoic acid, 5-oxo-5-(vinyloxy)pentanoic acid, 6-oxo-6-(vinyloxy)hexanoic acid, 2-(2,5-dioxotetrahydrofuran-3-yl)vinyl acetate, 2-(2-oxo-2-(vinyloxy)ethyl)succinic acid, 7-oxo-7-(vinyloxy)heptanoic acid, 8-oxo-8-(vinyloxy)octanoic acid, and mixtures thereof). Most preferably, the hair styling polymer of the present application comprises: 5 to 30 weight % (preferably, 10 to 28 weight %; more preferably, 12.5 to 25 weight %; most preferably, 15 to 22.5 weight %) of structural units of a carboxylic acid / carboxylic anhydride functional vinyl ester monomer having 4 to 12 carbon atoms based on the dry weight of the hair styling polymer; wherein the carboxylic acid / carboxylic anhydride functional vinyl ester monomer having 4 to 12 carbon atoms is selected from the group consisting of 4-oxo-4-(vinyloxy)butanoic acid, 2-(2,5-dioxotetrahydrofuran-3-yl)vinyl acetate, 2-(2-oxo-2-(vinyloxy)ethyl)succinic acid, and mixtures thereof.

[0023] Preferably, the hair styling polymer of the present application comprises: 0 wt.% to 5 wt.% (preferably, 0 wt.% to 2.5 wt.%; more preferably, 0 wt.% to 1 wt.%; most preferably, 0 wt.% to 0.5 wt.%) of structural units of a multi-ethylenically unsaturated crosslinking monomer; based on the dry weight of the hair styling polymer; wherein the multi-ethylenically unsaturated crosslinking monomer is selected from the group consisting of multi-ethylenically unsaturated crosslinking monomers having an average of two or three vinyl groups per molecule. More preferably, the hair styling polymer of the present application comprises: 0 wt.% to 5 wt.% (preferably, 0 wt.% to 2.5 wt.%; more preferably, 0 wt.% to 1 wt.%; most preferably, 0 wt.% to 0.5 wt.%) of structural units of a multi-ethylenically unsaturated crosslinking monomer; based on the dry weight of the hair styling polymer; wherein the multi-ethylenically unsaturated crosslinking monomer is selected from the group consisting of: allyl (meth)acrylate, tripropyleneglycol di(meth)acrylate, diethylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, diallyl phthalate, trimethylolpropane tri(meth)acrylate, divinylbenzene, divinyltoluene, trivinylbenzene, divinyl naphthalene, and mixtures thereof. Most preferably, the hair styling polymer of the present application comprises: 0 wt.% to 5 wt.% (preferably, 0 wt.% to 2.5 wt.%; more preferably, 0 wt.% to 1 wt.%; most preferably, 0 wt.% to 0.5 wt.%) of structural units of a multi-ethylenically unsaturated crosslinking monomer; based on the dry weight of the hair styling polymer; wherein the multi-ethylenically unsaturated crosslinking monomer is diallyl phthalate.

[0024] Preferably, the hair styling polymer of the present application comprises: 0% to 20% by weight (preferably, 0% to 5% by weight; more preferably, 0% to 4% by weight; most preferably, 0% to 3% by weight) of structural units of other monoethylenically unsaturated monomers, based on the dry weight of the hair styling polymer, wherein the other monoethylenically unsaturated monomers are different from the monoethylenically unsaturated alkanoic acid vinyl ester monomers having 4 to 13 carbon atoms and the monoethylenically unsaturated carboxylic acid / carboxylic acid anhydride functionalized vinyl ester monomers having 4 to 12 carbon atoms, and wherein the other monoethylenically unsaturated monomers are selected from the group consisting of (meth)acrylic acid alkyl esters, (meth)acrylamide alkyl esters, vinyl ethers, vinyl sulfonic acids, styrene sulfonic acids, acrylamide propyl methanesulfonic acids, (meth)acrylic acid, maleic acid, salts thereof, and mixtures thereof. More preferably, the hair styling polymer of the present application comprises: 0% to 20% by weight (preferably, 0.1% to 5% by weight; more preferably, 0.5% to 4% by weight; most preferably, 1% to 3% by weight) of structural units of other monoethylenically unsaturated monomers, based on the dry weight of the hair styling polymer, wherein the other monoethylenically unsaturated monomers are different from the monoethylenically unsaturated alkanoic acid vinyl ester monomers having 4 to 13 carbon atoms and the monoethylenically unsaturated carboxylic acid / carboxylic acid anhydride functionalized vinyl ester monomers having 4 to 12 carbon atoms, and wherein the other monoethylenically unsaturated monomers are selected from the group consisting of (meth)acrylic acid C 1-4 alkyl esters, (meth)acrylamide C 1-4alkenyl esters, vinyl ethers, vinyl sulfonic acids, styrene sulfonic acids, acrylamidopropyl methanesulfonic acids, (meth)acrylic acids, maleic acids, salts thereof, and mixtures thereof. Still more preferably, the hair styling polymer of the present application comprises: 0% to 20% by weight (preferably, 0.1% to 5% by weight; more preferably, 0.5% to 4% by weight; most preferably, 1% to 3% by weight) of structural units of other monoethylenically unsaturated monomers, based on the dry weight of the hair styling polymer, wherein the other monoethylenically unsaturated monomers are different from the monoethylenically unsaturated vinyl alkanoate monomers having 4 to 13 carbon atoms and the monoethylenically unsaturated carboxylic acid / carboxylic acid anhydride functionalized vinyl ester monomers having 4 to 12 carbon atoms, and wherein the other monoethylenically unsaturated monomers are selected from the group consisting of (meth)acrylate methyl esters, (meth)acrylate ethyl esters, (meth)acrylamide methyl esters, (meth)acrylamide ethyl esters, vinyl ethers, vinyl sulfonic acids, styrene sulfonic acids, (meth)acrylic acids, maleic acids, salts thereof, and mixtures thereof. Most preferably, the hair styling polymer of the present application comprises: 0% to 20% by weight (preferably, 0.1% to 5% by weight; more preferably, 0.5% to 4% by weight; most preferably, 1% to 3% by weight) of structural units of other monoethylenically unsaturated monomers, based on the dry weight of the hair styling polymer, wherein the other monoethylenically unsaturated monomers are different from the monoethylenically unsaturated vinyl alkanoate monomers having 4 to 13 carbon atoms and the monoethylenically unsaturated carboxylic acid / carboxylic acid anhydride functionalized vinyl ester monomers having 4 to 12 carbon atoms, and wherein the other monoethylenically unsaturated monomers are selected from the group consisting of vinyl sulfonic acids, salts of vinyl sulfonic acids, and mixtures thereof.

[0025] Preferably, the hair styling polymer of the present application comprises: at least 80% by weight (preferably, 85% to 99.9% by weight; more preferably, 90% to 99.5% by weight; most preferably, 95% to 99% by weight) of structural units of the monoethylenically unsaturated vinyl alkanoate monomers having 4 to 13 carbon atoms and the carboxylic acid / carboxylic acid anhydride functionalized vinyl ester monomers having 4 to 12 carbon atoms, based on the dry weight of the hair styling polymer.

[0026] Preferably, the hair styling polymer of the present application comprises < 5 mole% (preferably, < 1 mole%; more preferably, < 0.1 mole%; most preferably, less than the limit of detection) of monomer residues having a six-membered heterocyclic ring (e.g., a glucose moiety).

[0027] Preferably, the hair styling polymer of the present application comprises < 15 wt.-% (preferably, < 10 wt.-%; more preferably, < 5 wt.-%; still more preferably, < 1 wt.-%; yet more preferably, < 0.1 wt.-%; yet again more preferably, < 0.01 wt.-%; yet still more preferably, < 0.001 wt.-%; most preferably, less than the limit of detection) of monoethylenically unsaturated C 4-6 structural units of dicarboxylic acid monomers.

[0028] Preferably, the hair styling polymer of the present application comprises < 5 wt.-% (preferably, < 1 wt.-%; more preferably, < 0.5 wt.-%; still more preferably, < 0.1 wt.-%; yet more preferably, < 0.01 wt.-%; most preferably, less than the limit of detection) of structural units of Formula I based on the dry weight of the hair styling polymer (I) wherein the dotted line ( ) represents the point of attachment along the polymer backbone; and wherein R 1 and R 2 are independently selected from the group consisting of hydrogen and C 1-3 alkyl groups.

[0029] Preferably, the hair styling polymer of the present application comprises < 0.01 mole-% (preferably, < 0.005 mole-%; more preferably, < 0.001 mole-%; most preferably, less than the limit of detection) of structural units of diether-containing monomers.

[0030] Preferably, the hair styling polymer of the present application comprises < 10 wt.-% (preferably, < 5 wt.-%; more preferably, < 1 wt.-%; still more preferably, < 0.1 wt.-%; yet more preferably, < 0.01 wt.-%; yet still more preferably, < 0.001 wt.-%; most preferably, less than the limit of detection) of structural units of alkyl acrylate monomers containing 2 to 10 carbon atoms based on the dry weight of the hair styling polymer. More preferably, the hair styling polymer of the present application comprises < 10 wt.-% (preferably, < 5 wt.-%; more preferably, < 1 wt.-%; still more preferably, < 0.1 wt.-%; yet more preferably, < 0.01 wt.-%; yet still more preferably, < 0.001 wt.-%; most preferably, less than the limit of detection) of structural units of alkyl acrylate monomers containing 2 to 10 carbon atoms; wherein the alkyl acrylate monomers containing 2 to 10 carbon atoms are selected from the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, and mixtures thereof, based on the dry weight of the hair styling polymer.

[0031] Preferably, the hair styling polymer of the present application comprises < 0.1 mole % (preferably, < 0.01 mole %; more preferably, < 0.001 mole %; most preferably, less than the limit of detection) of structural units of amide-containing monomers. More preferably, the hair styling polymer of the present application comprises < 0.1 mole % (preferably, < 0.01 mole %; more preferably, < 0.001 mole %; most preferably, less than the limit of detection) of structural units of amide-containing monomers; wherein the amide-containing monomers are selected from the group consisting of: N vinyl formamide, (meth)acrylamide, 2-acrylamido-2-methyl-propane sulfonic acid (AMPS), 3-(methacrylamido)propyltrimethylammonium chloride (MAPTAC), and mixtures thereof.

[0032] Preferably, the hair styling polymer of the present application comprises < 0.1 wt % (preferably, < 0.01 wt %; more preferably, < 0.001 wt %; most preferably, less than the limit of detection) of structural units of amino-containing monomers, based on the dry weight of the hair styling polymer.

[0033] Preferably, the hair styling polymer of the present application comprises: 0 wt % to 1.1 wt % (preferably, 0 wt % to 1.0 wt %; more preferably, 0 wt % to 0.5 wt %; still more preferably, 0 wt % to 0.1 wt %; most preferably, 0 wt % to 0.01 wt %) of structural units of 2-acrylamido-2-methylpropane sulfonic acid, based on the dry weight of the hair styling polymer.

[0034] Preferably, the hair styling polymer of the present application is biodegradable, as determined according to the procedure of OECD 302B. More preferably, the hair styling polymer of the present application has inherent ultimate biodegradability, as determined according to the procedure of OECD 302B.

[0035] The hair styling polymer of the present application can be prepared using conventional or otherwise known polymerization techniques. Preferably, the hair styling polymer of the present application can be prepared using conventional solution polymerization techniques.

[0036] Preferably, the hair styling formulation of the present application further comprises a volatile organic compound. More preferably, the hair styling formulation of the present application further comprises a volatile organic compound selected from the group consisting of methane, ethane, propane, isopropane, isobutane, pentane, isopentane, butane, dimethyl ether, diethyl ether, dimethoxymethane, fluorocarbons (e.g., 1,3,3,3-tetrafluoropropene), and mixtures thereof. Still more preferably, the hair styling formulation of the present application further comprises from 0 wt.% to 60 wt.% (preferably, from 0 wt.% to 55 wt.%; more preferably, from 0 wt.% to 53 wt.%; most preferably, from 0 wt.% to 52 wt.%) of a volatile organic compound based on the weight of the hair styling formulation; wherein the volatile organic compound is selected from the group consisting of methane, ethane, propane, isopropane, isobutane, pentane, isopentane, butane, dimethyl ether, diethyl ether, dimethoxymethane, fluorocarbons (e.g., 1,3,3,3-tetrafluoropropene), and mixtures thereof. Yet still more preferably, the hair styling formulation of the present application further comprises from 0 wt.% to 60 wt.% (preferably, from 0 wt.% to 55 wt.%; more preferably, from 0 wt.% to 53 wt.%; most preferably, from 0 wt.% to 52 wt.%) of a volatile organic compound based on the weight of the hair styling formulation; wherein the volatile organic compound is selected from the group consisting of dimethyl ether, diethyl ether, dimethoxymethane, and mixtures thereof. Still yet more preferably, the hair styling formulation of the present application further comprises from 0 wt.% to 60 wt.% (preferably, from 0 wt.% to 55 wt.%; more preferably, from 0 wt.% to 53 wt.%; most preferably, from 0 wt.% to 52 wt.%) of a volatile organic compound based on the weight of the hair styling formulation; wherein the volatile organic compound is selected from dimethyl ether, diethyl ether, and mixtures thereof. Most preferably, the hair styling formulation of the present application further comprises from 0 wt.% to 60 wt.% (preferably, from 0 wt.% to 55 wt.%; more preferably, from 0 wt.% to 53 wt.%; most preferably, from 0 wt.% to 52 wt.%) of a volatile organic compound based on the weight of the hair styling formulation; wherein the volatile organic compound is diethyl ether.

[0037] Preferably, the hair styling formulation of the present application further comprises a hair care adjunct. More preferably, the hair styling formulation of the present application further comprises a hair care adjunct; wherein the hair care adjunct is selected from the group consisting of plasticizers, coalescing agents, silicones, emollients, emulsifiers, surfactants, lubricants, humectants, penetrants (e.g., lanolin compounds, protein hydrolysates, other protein derivatives), thickening agents, viscosity modifiers, ethylene adducts, polyoxyethylene cholesterols, colorants (e.g., dyes, toners, pigments), perfumes, preservatives, conditioning agents, pH adjusting agents, buffering agents, and mixtures thereof.

[0038] Preferably, the hair styling formulation of the present application further comprises a pH adjusting agent. More preferably, the hair styling formulation of the present application further comprises a pH adjusting agent; wherein the adjusted pH of the hair styling formulation is from 4 to 10 (preferably, from 5 to 9; more preferably, from 6 to 8.75; most preferably, from 6.5 to 8.5).

[0039] Preferably, the pH adjusting agent is selected from the group consisting of at least one of: citric acid, lactic acid, hydrochloric acid, aminoethylpropanediol, triethanolamine, monoethanolamine, sodium hydroxide, potassium hydroxide, amino-2-methyl-1-propanol. More preferably, the pH adjusting agent is selected from the group consisting of at least one of: triethanolamine and amino-2-methyl-1-propanol. Still more preferably, the pH adjusting agent comprises amino-2-methyl-1-propanol. Most preferably, the pH adjusting agent is amino-2-methyl-1-propanol.

[0040] Preferably, the hair styling formulation of the present application comprises less than 2 wt% (preferably, < 1 wt%; more preferably, < 0.01 wt%; still more preferably, < 0.001 wt%; most preferably, < limit of detection) of a dry oil based on the dry weight of the hair styling formulation. Most preferably, the hair styling formulation of the present application comprises less than 2 wt% (preferably, < 1 wt%; more preferably, < 0.01 wt%; still more preferably, < 0.001 wt%; most preferably, < limit of detection) of a dry oil selected from the group consisting of: safflower seed oil, flaxseed oil, castor seed oil, oleyl oil, sunflower oil, soybean oil, perilla oil, tall oil, dehydrated castor seed oil, tung oil, very long oil alcohol acid resin, long oil alcohol acid resin, and mixtures thereof based on the dry weight of the hair styling formulation.

[0041] Preferably, the hair (preferably, mammalian hair; most preferably, human hair) styling method of the present application comprises: selecting a hair styling formulation of the present application; applying the selected hair styling formulation to the hair; styling the hair to provide a styled state to the hair; wherein the hair styling formulation sets the hair in the styled state. More preferably, the hair styling method of the present application comprises: selecting a hair styling formulation of the present application; applying the hair styling formulation to the hair; styling the hair to provide a styled state to the hair; allowing the hair styling formulation on the hair to dry; wherein the dried hair styling formulation sets the hair in the styled state. Most preferably, the hair styling method of the present application further comprises: selecting a hair styling formulation of the present application; wetting the hair with water to provide a wetted hair; applying the hair styling formulation to the wetted hair; styling the hair to provide a styled state to the hair; allowing the hair styling formulation on the styled hair to dry; wherein the dried hair styling formulation sets the hair in the styled state.

[0042] Some embodiments of the present application will now be described in detail in the following Examples.

[0043] Synthesis S1-S4: hair styling polymers Into a 500 mL four necked round bottom reactor equipped with an overhead stirrer, condenser, nitrogen inlet-outlet and thermocouple, was added ethyl acetate (115.0 g) and a nitrogen sparge was established. The thermocouple was connected to a J-Kem temperature controller which provided input to the heating mantle to achieve the desired temperature control. Stirring was started at a rate of 120 rpm. The amounts of monomer mixtures shown in Table 1 were added sequentially to the reactor and washed into the reactor with ethyl acetate (45 g). Azo-bis- isobutyronitrile (0.32 g) was then added to the reactor as a solid through a port and the temperature controller was set to 60 °C under a nitrogen flow. Upon reaching 60 °C, the reactor temperature was held at 60 °C for six hours. A second addition of azo-bis-isobutyronitrile (0.32 g) was then added to the reactor and the temperature controller was raised to 65 °C. Upon reaching 65 °C, the reactor temperature was held at 65 °C for 30 minutes. A third addition of azo-bis-isobutyronitrile (0.32 g) was then added to the reactor and the temperature controller was raised to 70 °C. Upon reaching 70 °C, the reactor temperature was held at 70 °C for 30 minutes. A fourth addition of azo-bis-isobutyronitrile (0.32 g) was then added to the reactor and the temperature controller was raised to 78 °C. Upon reaching 78 °C, the reactor temperature was held at 78 °C for 30 minutes. The reactor was then cooled to ambient temperature with a continuous nitrogen flow. Once cooled, the reactor contents were poured into 1 L of hexanes. The precipitate was isolated using a Buchner funnel and washed with some additional hexanes. The collected product polymer was dried at room temperature under house vacuum, transferred to a crystallizing dish, and further dried in a vacuum oven at 65 °C overnight. The product polymer was analyzed for residual vinyl acetate (VA) monomer content, weight average molecular weight M w The number average molecular weight M n The number average molecular weight M g The differential scanning calorimetry analysis. The results are provided in Table 2.

[0044] Table 1

[0045] Table 2

[0046] Comparative Examples CF1-CF3 and Examples F1-F4: hair styling formulations A hair styling formulation was prepared in each of Comparative Examples CF1-CF3 and Examples F1-F4 having the formulations shown in Table 3. Preparing the formulation by combining the polymer (2.5 g), water (2.5 g), and ethanol (20 g), and sonicating the resulting mixture for one hour was Step 1. The appearance of the mixture after Step 1 was observed and recorded in Table 3. The pH of the mixture was then adjusted to 7 by adding a 2-amino-2-methyl-1-propanol solution (purchased from ANGUS, 95% AMP-95 ™ ) was Step 2. The appearance of the mixture after the pH adjustment in Step 2 was observed and recorded in Table 3. Then, in Step 3, the final step in preparing the hair styling formulation, diethyl ether (25 g) was added to the mixture and sonicated for 1 hour. The appearance of the resulting hair styling formulation from Step 3 was observed and recorded in Table 3.

[0047] Table 3

[0048] Examples F5-F8: hair styling formulations A hair styling formulation was prepared in each of Examples F5-F8 having the formulations shown in Table 4. Preparing the formulation by combining the polymer (1.49 g) (as shown in Table 4), water (4.89), and ethanol (8.09 g), and sonicating the resulting mixture for one hour was Step 1. Then, adjusting the pH of the mixture by adding a 2-amino-2-methyl-1-propanol solution (purchased from ANGUS, 95% AMP-95 ™ ) was Step 2. The turbidity of the resulting mixture after the pH adjustment was observed and recorded in Table 4.

[0049] Table 4

[0050] curl retention The following hair treatment experiments were performed using 8 inch long virgin dark brown Caucasian hair tresses (3.5 g) purchased from International Hair Importers & Products, Inc. Each tress was first rinsed in tap water for 30 seconds, washed with 9 wt% sodium lauryl sulfate (SLS; 0.2 g / g hair) for 30 seconds, rinsed in tap water for 1 minute, and allowed to air dry in a temperature controlled room.

[0051] In each test, a sample of hair strand was then treated with 0.35 g of the hair styling formulation or a commercial styling gel containing a styling polymer prepared according to one of Comparative Examples CF1-CF2, Examples F1, F5-F8, as follows: The formulation was applied to the hair strand and thoroughly spread onto the hair fibers for 2 minutes until a uniform coating was obtained on the hair strand. The treated hair strand was then wet-rolled in a concentric circle configuration onto a 22mm × 70mm curling iron and held in place with hair clips. The curled hair strand was dried overnight in a room with controlled temperature (25°C) and relative humidity (50%). After drying, the curling iron was gently removed from the hair strand, and the curls were hung with clips in a humidity-controlled room at 25°C and 80% relative humidity RH. The length of the curled hair strand was then recorded at intervals during a 24-hour period, i.e., at t=0 hours, 0.5 hours, 1 hour, 2 hours, 6 hours, and 24 hours. The curl retention CR was defined using the following equation. CR = [{L(0)-L(t)} / {L(0)-L(i)}] × 100% Where L(0) is the full extension length of the hair strand, L(i) is the initial curl length, and L(t) is the curl length at a specific time. Higher values ​​correspond to better moisture resistance. Three copies of each hair styling product were tested for curl retention. The average results are reported in Table 5.

[0052] Table 5

[0053] curl compression The following hair treatment experiment was conducted using an 8-inch-long strand (3.5g) of native dark brown Caucasian hair purchased from International Hair Importers & Products, Inc. Each strand was first rinsed in tap water for 30 seconds, then washed with 9% sodium lauryl sulfate (SLS; 0.2g / g hair) for 30 seconds, rinsed in tap water for 1 minute, and then air-dried in a temperature-controlled room.

[0054] In each test, a sample of the indicated hair styling formulation or commercial styling gel containing a styling polymer prepared according to one of Comparative Examples CF1-CF2, Examples Fl, F5-F8 was then used to treat a hair tress by applying the formulation to the hair tress and rubbing it thoroughly onto the hair fibers for 2 minutes until a uniform coating was obtained on the hair tress. The treated hair tress was then curled in a concentric circle configuration onto a 22 mm x 70 mm curling iron and held in place with a hair clip. The curled hair tress was dried overnight in a room with controlled temperature (25 °C) and relative humidity (50%). After drying, the curling iron was gently removed from the hair tress and a curl compression test was performed using a Dia-Stron UV 1000 control unit. The individual curling clip was clamped on a stand. A curl compression displacement of 25% was then applied to the curl at a rate of 200 mm / min and the compression force as a function of curl displacement was recorded by the sensor. The test was performed on three curls for each hair styling formulation. The average peak compression force of the treated curls is provided in Table 6 for each hair styling formulation.

[0055] Table 6

Claims

1. A hair styling preparation, said hair styling preparation comprising: A cosmetically acceptable carrier; and Hair styling polymers containing the following: Based on the dry weight of the hair styling polymer, 70% to 95% by weight of structural units of monoolefinic unsaturated vinyl alkyl ester monomers having 4 to 13 carbon atoms. Based on the dry weight of the hair styling polymer, 5% to 30% by weight of structural units of mono-olefinic unsaturated carboxylic acid / carboxylic anhydride functionalized vinyl ester monomers having 4 to 12 carbon atoms. Based on the dry weight of the hair styling polymer, 0% to 5% by weight of the structural units of the polyene unsaturated crosslinked monomer; and Based on the dry weight of the hair styling polymer, 0% to 20% by weight of other monoene unsaturated monomers, wherein the other monoene unsaturated monomers are different from the monoene unsaturated alkyl vinyl ester monomers having 4 to 13 carbon atoms and the monoene unsaturated carboxylic acid / carboxylic anhydride functionalized vinyl ester monomers having 4 to 12 carbon atoms.

2. The hair styling formulation according to claim 1, wherein the hair styling formulation comprises: Based on the weight of the hair styling formulation, 20% to 99.5% by weight of the cosmetically acceptable carrier; and Based on the weight of the hair styling formulation, 0.5% to 20% by weight of the hair styling polymer; The hair styling polymer contains <5 mol% of monomer residues having a six-membered heterocyclic ring (e.g., glucose moiety); The hair styling polymer comprises <15% by weight of monoolefinic unsaturated C based on the dry weight of the hair styling polymer. 4-6 The structural unit of a dicarboxylic acid monomer; and The hair styling polymer comprises at least two different structural units of monoolefinic unsaturated vinyl alkyl ester monomers having 4 to 13 carbon atoms.

3. The hair styling formulation according to claim 2, wherein the cosmetically acceptable carrier is an aqueous carrier; and wherein the aqueous carrier comprises water and C 1-4 A mixture of alcohols.

4. The hair styling formulation of claim 3, wherein the aqueous carrier comprises 5% to 45% by weight of water and 55% to 95% by weight of C 1-4 alcohol.

5. The hair styling formulation according to claim 4, wherein C 1-4 The alcohol is ethanol.

6. The hair styling formulation according to claim 5, wherein the hair styling formulation further comprises a volatile organic compound selected from the group consisting of methane, ethane, propane, isopropane, isobutane, pentane, isopentane, butane, dimethyl ether, diethyl ether, dimethoxymethane, fluorocarbons, and mixtures thereof.

7. The hair styling formulation according to claim 1, wherein the hair styling formulation is selected from the group consisting of: leave-in conditioners, aerosol hair sprays, pump-type hair sprays, styling gels, spray gels, and mousses.

8. The hair styling formulation according to claim 1, further comprising a hair care adjuvant; wherein the hair care adjuvant is selected from the group consisting of: plasticizers, coalescing agents, silicones, emollients, emulsifiers, surfactants, lubricants, humectants, penetrants, thickeners, viscosity modifiers, ethylene adducts, polyoxyethylene cholesterol, colorants, fragrances, preservatives, conditioning agents, pH adjusters, buffers, and mixtures thereof.

9. The hair styling formulation according to claim 1, Based on the dry weight of the hair styling polymer, at least 80% by weight comprises the structural units of the monoalkenyl unsaturated alkyl vinyl ester monomer having 4 to 13 carbon atoms and the structural units of the monoalkenyl unsaturated carboxylic acid / carboxylic anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms. The hair styling polymer comprises >55 mol% of structural units of monoolefinic unsaturated vinyl alkyl ester monomers having 4 to 13 carbon atoms. The hair styling polymer contains less than 0.1 mol% of amide-containing monomer structural units; The hair styling polymer comprises structural units containing amino-containing monomers at a dry weight basis of less than 0.1% by weight of the hair styling polymer. The hair styling polymer comprises less than 5% by weight of a structural unit of Formula I based on the dry weight of the hair styling polymer. The dashed lines (------) represent attachment points along the polymer backbone; where R 1 and R 2 Independently selected from hydrogen and C 1-3 alkyl groups; and The hair styling polymer contains less than 0.01 mol% of structural units containing diether monomers; The hair styling polymer comprises structural units of alkyl acrylate monomers containing 2 to 10 carbon atoms, based on less than 10% by weight of the dry weight of the hair styling polymer. The hair styling polymer contains <5 mol% of monomer residues having a six-membered heterocyclic ring; and The hair styling polymer comprises <15% by weight of monoolefinic unsaturated C based on the dry weight of the hair styling polymer. 4-6 Structural units of dicarboxylic acid monomers.

10. A hair styling method, the hair styling method comprising: Choose hair styling products; Apply the hair styling preparation according to claim 1 to the hair; as well as Styling the hair to provide a styling state; The hair styling agent sets the hair in the styling state.

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