Hair styling polymers comprising alkanoic acid vinyl ester monomers and carboxylic acid or carboxylic acid anhydride functionalized vinyl ester monomers

Abstract

There is provided a hair styling polymer comprising: from 70% to 95% by weight, based on dry polymer, of a vinyl alkanoate monomer having from 4 to 13 carbons; from 5% to 30% by weight, based on dry polymer, of a carboxylic acid / carboxylic acid anhydride functionalized vinyl ester monomer having from 4 to 12 carbons; from 0% to 5% by weight, based on dry polymer, of a polyethylenically unsaturated crosslinker; from 0% to 20% by weight, based on dry polymer, of a further monoethylenically unsaturated monomer wherein the further monoethylenically unsaturated monomer is different from the alkanoic acid vinyl ester monomer having from 4 to 13 carbon atoms and the carboxylic acid / carboxylic acid anhydride functionalized vinyl ester monomer having from 4 to 12 carbon atoms; wherein the hair styling polymer comprises lt based on dry polymer; 15% by weight of a monoethylenically unsaturated C4-6 dicarboxylic acid monomer; and wherein the hair styling polymer comprises at least two different alkanoic acid vinyl ester monomers having from 4 to 13 carbons.

Description

[0001] The present invention relates to a hair styling polymer. In particular, the present invention relates to a hair styling polymer comprising: 70 to 95 weight % of structural units of a vinyl alkanoate monomer having 4 to 13 carbon atoms, based on the dry weight of the hair styling polymer; 5 to 30 weight % of structural units of a 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 weight % of structural units of a multi-ethylenically unsaturated crosslinker, based on the dry weight of the hair styling polymer; 0 to 20 weight % of structural units of other mono-ethylenically unsaturated monomers, wherein the other mono-ethylenically unsaturated monomers are different from the mono-ethylenically unsaturated vinyl alkanoate having 4 to 13 carbon atoms and the mono-ethylenically 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; wherein the hair styling polymer comprises < 15 weight % of mono-ethylenically unsaturated C 4-6 structural units of a dicarboxylic acid monomer; and wherein the hair styling polymer comprises at least two different vinyl alkanoate monomers having 4 to 13 carbons.

[0002] Hair styling polymers or fixatives are designed to set temporary hair styles or curls. Hair styling polymers can be applied to wet hair or after the hair is dry to hold the shape and style of the hair. Advantageously, hair styling polymers provide hair fixative properties and curl retention, little to no powder or hair strand shedding when combing, fast setting or drying on the hair, no tacky feel, and easy to remove with shampoo. Hair styling polymers are often delivered with the aid of a solvent, which is usually an alcohol such as ethanol, or a mixture of alcohol and water. For hair care formulations of the aerosol formulation type, such as hairsprays and mousses, a propellant can be added as part of the delivery system (e.g. isobutane, butane, propane, or dimethyl ether).

[0003] 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 % of ethyl acrylate, 30 to 50 weight % of (meth)acrylic acid; 1 to 5 weight % of an associative monomer comprising a methacrylate 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 % of a crosslinker.

[0004] Nonetheless, the demand for hair styling polymers 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 for new hair styling polymers. Additionally, it is desirable to have hair styling polymers that exhibit biodegradability.

[0005] Accordingly, there remains a need for new hair styling polymers that provide hair styling benefits while also being of biological origin and / or biodegradable.

[0006] The present invention provides a hair styling polymer comprising: 70 to 95 weight percent of structural units of a vinyl alkanoate monomer having 4 to 13 carbon atoms, based on the dry weight of the hair styling polymer; 5 to 30 weight percent of structural units of a 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 weight percent of structural units of a multi-ethylenically unsaturated crosslinker, based on the dry weight of the hair styling polymer; 0 to 20 weight percent of structural units of other ethylenically unsaturated monomers, based on the dry weight of the hair styling polymer, wherein the other mono-ethylenically unsaturated monomers are different from the mono-ethylenically unsaturated vinyl alkanoate having 4 to 13 carbon atoms and the mono-ethylenically unsaturated carboxylic acid / carboxylic acid anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms; wherein the hair styling polymer comprises < 15 weight percent of mono-ethylenically unsaturated C 4-6 dicarboxylic acid monomer; and wherein the hair styling polymer comprises at least two different vinyl alkanoate monomers having 4 to 13 carbons.

[0007] The present invention provides a hair styling polymer comprising: 70 to 95 weight percent of structural units of a vinyl alkanoate monomer having 4 to 13 carbon atoms, based on the dry weight of the hair styling polymer; 5 to 30 weight percent of structural units of a 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 weight percent of structural units of a multi-ethylenically unsaturated crosslinker, based on the dry weight of the hair styling polymer; 0 to 20 weight percent of structural units of other ethylenically unsaturated monomers, based on the dry weight of the hair styling polymer, wherein the other mono-ethylenically unsaturated monomers are different from the mono-ethylenically unsaturated vinyl alkanoate having 4 to 13 carbon atoms and the mono-ethylenically unsaturated carboxylic acid / carboxylic acid anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms; wherein the hair styling polymer comprises < 15 weight percent of mono-ethylenically unsaturated C 4-6carboxylic acid / carboxylic acid anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms; and wherein the hair styling polymer comprises > 55 mole % of structural units of the monoethylenically unsaturated alkane acid vinyl ester monomer having 4 to 13 carbon atoms. The present invention provides a hair styling polymer comprising: from 70 wt% to 95 wt% of structural units of a monoethylenically unsaturated alkane acid vinyl ester monomer having 4 to 13 carbon atoms, based on the dry weight of the hair styling polymer; from 5 wt% to 30 wt% of structural units of a 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; from 0 wt% to 5 wt% of structural units of a multiethylenically unsaturated crosslinker, based on the dry weight of the hair styling polymer; from 0 wt% to 20 wt% 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 alkane acid vinyl ester 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 < 15 wt% of structural units of a monoethylenically unsaturated C 4-6 carboxylic acid / carboxylic acid anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms; and wherein the hair styling polymer comprises > 55 mole % of structural units of the monoethylenically unsaturated alkane acid vinyl ester monomer having 4 to 13 carbon atoms.

[0008] A hair styling polymer comprising: 70 to 95 weight percent, based on dry weight of the hair styling polymer, of structural units of a vinyl alkanoate monomer having 4 to 13 carbon atoms; 5 to 30 weight percent, based on dry weight of the hair styling polymer, of structural units of a carboxylic acid / carboxylic acid anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms; 0 to 5 weight percent, based on dry weight of the hair styling polymer, of structural units of a multi-ethylenically unsaturated crosslinking agent; 0 to 20 weight percent, based on dry weight of the hair styling polymer, of structural units of other ethylenically unsaturated monomers, wherein the other mono-ethylenically unsaturated monomers are different than the mono-ethylenically unsaturated vinyl alkanoate having 4 to 13 carbon atoms and the mono-ethylenically unsaturated carboxylic acid / carboxylic acid anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms; wherein the hair styling polymer comprises < 15 weight percent, based on dry weight of the hair styling polymer, of mono-ethylenically unsaturated C 4-6 carboxylic acid monomers; wherein the hair styling polymer comprises at least two different vinyl alkanoate monomers having 4 to 13 carbons; wherein at least 80 weight percent, based on dry weight of the hair styling polymer, comprises structural units of the mono-ethylenically unsaturated vinyl alkanoate monomer having 4 to 13 carbon atoms and the carboxylic acid / carboxylic acid anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms; wherein the hair styling polymer comprises > 55 mole percent of structural units of the mono-ethylenically unsaturated vinyl alkanoate monomer having 4 to 13 carbon atoms; wherein the hair styling polymer comprises less than 0.1 mole percent of structural units of amide containing monomers; and wherein the hair styling polymer comprises less than 0.1 weight percent, based on dry weight of the hair styling polymer, of structural units of amino containing monomers.

[0009] A hair styling polymer comprising: 70 to 95 weight percent, based on dry weight of the hair styling polymer, of structural units of a vinyl alkanoate monomer having 4 to 13 carbon atoms; 5 to 30 weight percent, based on dry weight of the hair styling polymer, of structural units of a carboxylic acid / carboxylic acid anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms; 0 to 5 weight percent, based on dry weight of the hair styling polymer, of structural units of a multi-ethylenically unsaturated crosslinking agent; 0 to 20 weight percent, based on dry weight of the hair styling polymer, of structural units of other ethylenically unsaturated monomers, wherein the other mono-ethylenically unsaturated monomers are different than the mono-ethylenically unsaturated vinyl alkanoate having 4 to 13 carbon atoms and the mono-ethylenically unsaturated carboxylic acid / carboxylic acid anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms; wherein the hair styling polymer comprises < 15 weight percent, based on dry weight of the hair styling polymer, of mono-ethylenically unsaturated C 4-6The hair styling polymer comprises structural units of dicarboxylic acid monomers; wherein the hair styling polymer contains structural units of at least two different vinyl alkyl ester monomers having 4 to 13 carbon atoms; wherein, based on the dry weight of the hair styling polymer, at least 80% by weight comprises structural units of monoalkenyl unsaturated vinyl alkyl ester monomers having 4 to 13 carbon atoms and structural units of carboxylic acid / carboxylic anhydride functionalized vinyl ester monomers having 4 to 12 carbon atoms; wherein the hair styling polymer contains >55 mol% of structural units of monoalkenyl unsaturated vinyl alkyl ester monomers having 4 to 13 carbon atoms; wherein the hair styling polymer contains less than 5% by weight 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 Alkyl groups; and wherein the hair styling polymer contains less than 0.01 mol% of structural units containing diether monomers; This invention provides a hair styling polymer comprising: 70% to 95% by weight, based on the dry weight of the hair styling polymer, structural units of vinyl alkyl ester 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 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 a polyene unsaturated crosslinking agent; 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 the monoene unsaturated vinyl alkyl ester having 4 to 13 carbon atoms and the monoene unsaturated carboxylic acid / carboxylic anhydride-functionalized vinyl ester monomers having 4 to 12 carbon atoms; wherein the hair styling polymer comprises <15% by weight, based on the dry weight of the hair styling polymer, monoene unsaturated C 4-6 The hair styling polymer comprises structural units of dicarboxylic acid monomers; wherein the hair styling polymer contains structural units of at least two different vinyl alkyl ester monomers having 4 to 13 carbon atoms; wherein, based on the dry weight of the hair styling polymer, at least 80% by weight comprises structural units of monoalkenyl unsaturated vinyl alkyl ester monomers having 4 to 13 carbon atoms and structural units of carboxylic acid / carboxylic anhydride functionalized vinyl ester monomers having 4 to 12 carbon atoms; wherein the hair styling polymer contains >55 mol% of structural units of monoalkenyl unsaturated vinyl alkyl ester monomers having 4 to 13 carbon atoms; and wherein the hair styling polymer contains less than 10% by weight of structural units of alkyl acrylate monomers having 2 to 10 carbon atoms based on the dry weight of the hair styling polymer.

[0010] The present invention provides a hair styling polymer comprising: 70 to 95 weight percent of structural units of a vinyl alkanoate monomer having 4 to 13 carbon atoms, based on the dry weight of the hair styling polymer; 5 to 30 weight percent of structural units of a 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 weight percent of structural units of a multi-ethylenically unsaturated crosslinker, based on the dry weight of the hair styling polymer; 0 to 20 weight percent of structural units of other ethylenically unsaturated monomers, based on the dry weight of the hair styling polymer, wherein the other mono-ethylenically unsaturated monomers are different than the mono-ethylenically unsaturated vinyl alkanoate having 4 to 13 carbon atoms and the mono-ethylenically unsaturated carboxylic acid / carboxylic acid anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms; wherein the hair styling polymer comprises < 15 weight percent of mono-ethylenically unsaturated C 4-6 structural units of a dicarboxylic acid monomer; wherein the hair styling polymer comprises at least two different vinyl alkanoate monomers having 4 to 13 carbons; wherein at least 80 weight percent, based on the dry weight of the hair styling polymer, comprises structural units of a mono-ethylenically unsaturated vinyl alkanoate monomer having 4 to 13 carbon atoms and structural units of a carboxylic acid / carboxylic acid anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms; wherein the hair styling polymer comprises > 55 mole percent of structural units of a mono-ethylenically unsaturated vinyl alkanoate monomer having 4 to 13 carbon atoms; and wherein the hair styling polymer comprises less than 2 weight percent, based on the dry weight of the hair styling polymer, of a drying oil.

[0011] The present invention provides a hair styling polymer comprising: 70 to 95 weight percent of structural units of a vinyl alkanoate monomer having 4 to 13 carbon atoms, based on the dry weight of the hair styling polymer; 5 to 30 weight percent of structural units of a 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 weight percent of structural units of a multi-ethylenically unsaturated crosslinker, based on the dry weight of the hair styling polymer; 0 to 20 weight percent of structural units of other ethylenically unsaturated monomers, based on the dry weight of the hair styling polymer, wherein the other mono-ethylenically unsaturated monomers are different than the mono-ethylenically unsaturated vinyl alkanoate having 4 to 13 carbon atoms and the mono-ethylenically unsaturated carboxylic acid / carboxylic acid anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms; wherein the hair styling polymer comprises < 15 weight percent of mono-ethylenically unsaturated C 4-6carboxylic acid / carboxylic acid anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms; wherein the hair styling polymer comprises > 55 mole % of structural units of the monoethylenically unsaturated alkanoic acid vinyl ester monomer having 4 to 13 carbon atoms; and wherein the hair styling polymer comprises < 5 mole % of structural units of the monomer residue having a six-membered heterocyclic ring.

[0012] The present invention provides a hair styling polymer comprising: 70 to 95 weight % of structural units of a vinyl alkanoate monomer having 4 to 13 carbon atoms based on the dry weight of the hair styling polymer; 5 to 30 weight % of structural units of a 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 weight % of structural units of a multi-ethylenically unsaturated crosslinker based on the dry weight of the hair styling polymer; 0 to 20 weight % of structural units of other ethylenically unsaturated monomers based on the dry weight of the hair styling polymer, wherein the other mono-ethylenically unsaturated monomers are different from the mono-ethylenically unsaturated vinyl alkanoate having 4 to 13 carbon atoms and the mono-ethylenically unsaturated carboxylic acid / carboxylic acid anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms; wherein the hair styling polymer comprises < 15 weight % of structural units of the mono-ethylenically unsaturated C 4-6 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; wherein the hair styling polymer comprises > 55 mole % of structural units of the monoethylenically unsaturated alkanoic acid vinyl ester monomer having 4 to 13 carbon atoms; wherein the hair styling polymer comprises less than 0.1 mole % of structural units of the amide-containing monomer; wherein the hair styling polymer comprises less than 0.1 weight % of structural units of the amino-containing monomer based on the dry weight of the hair styling polymer; wherein the hair styling polymer comprises less than 5 weight % of structural units of Formula I based on the dry weight of the hair styling polymer (I); wherein the dashed line ( ) represents the point of attachment along the polymer backbone; wherein R 1 and R 2 are independently selected from the group consisting of hydrogen and C​1-3 alkyl groups; wherein the hair styling polymer comprises less than 0.01 mole percent of structural units of diether-containing monomers; wherein the hair styling polymer comprises less than 10 weight percent of structural units of alkyl acrylate monomers having 2 to 10 carbon atoms, based on the dry weight of the hair styling polymer; and wherein the hair styling polymer comprises < 5 mole percent of monomeric residues having a six-membered heterocyclic ring.

[0013] The present invention provides a hair styling polymer comprising: 70 to 95 weight percent of structural units of vinyl alkanoate monomers having 4 to 13 carbon atoms, based on the dry weight of the hair styling polymer; 5 to 30 weight percent of structural units of 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; 0 to 5 weight percent of structural units of polyethylenically unsaturated crosslinking agents, based on the dry weight of the hair styling polymer; 0 to 20 weight percent 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 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; wherein the hair styling polymer comprises < 15 weight percent of monoethylenically unsaturated C 4-6 dicarboxylic acid monomers; wherein the hair styling polymer comprises at least two different vinyl alkanoate monomers having 4 to 13 carbons; wherein at least 80 weight percent comprises structural units of monoethylenically unsaturated vinyl alkanoate monomers having 4 to 13 carbon atoms and structural units of 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; wherein the hair styling polymer comprises > 55 mole percent of structural units of monoethylenically unsaturated vinyl alkanoate monomers having 4 to 13 carbon atoms; wherein the hair styling polymer comprises less than 0.1 mole percent of structural units of amide-containing monomers; wherein the hair styling polymer comprises less than 0.1 weight percent of structural units of amino-containing monomers, based on the dry weight of the hair styling polymer; wherein the hair styling polymer comprises less than 5 weight percent of structural units of Formula I (I); wherein the dashed line ( ) represents a point of attachment along the polymer backbone; wherein R 1 and R 2 are independently selected from the group consisting of hydrogen and C 1-3alkyl groups; wherein the hair styling polymer comprises less than 0.01 mole % of structural units of diether-containing monomers; wherein the hair styling polymer comprises less than 10 wt. % of structural units of alkyl acrylate monomers having 2 to 10 carbon atoms, based on the dry weight of the hair styling polymer; wherein the hair styling polymer comprises < 5 mole % of monomer residues having a six-membered heterocyclic ring; and wherein the hair styling polymer comprises less than 2 wt. % of a drying oil, based on the dry weight of the hair styling polymer; wherein the drying oil is selected from the group consisting of safflower seed oil, flaxseed oil, castor seed oil, oiticica oil, sunflower oil, soybean oil, perilla oil, tall oil, dehydrated castor seed oil, tung oil, very long oil alcohol resin, long oil alcohol resin, and mixtures thereof. DETAILED DESCRIPTION

[0014] Applicants have surprisingly found that a hair styling polymer comprising the following can effectively style hair (even under high humidity conditions i.e. > 80% relative humidity) and further exhibit biodegradability according to the procedure of OECD 302B: 70 wt. % to 95 wt. % of structural units of ethylenically unsaturated alkanoic acid vinyl ester monomers having 4 to 13 carbon atoms, based on the dry weight of the hair styling polymer; 5 wt. % to 30 wt. % of structural units of 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; 0 wt. % to 5 wt. % of structural units of polyethylenically unsaturated crosslinking agents, based on the dry weight of the hair styling polymer; 0 wt. % to 20 wt. % of structural units of other ethylenically unsaturated monomers, based on the dry weight of the hair styling polymer, wherein the other ethylenically unsaturated monomers are different from the ethylenically unsaturated alkanoic acid vinyl ester monomers having 4 to 13 carbon atoms and the ethylenically unsaturated carboxylic acid / carboxylic acid anhydride functionalized vinyl ester monomers having 4 to 12 carbon atoms; wherein the hair styling polymer comprises < 5 mole % of monomer residues having a six-membered heterocyclic ring (e.g., a glucose moiety); wherein the hair styling polymer comprises < 15 wt. % of ethylenically unsaturated C 4-6 dicarboxylic acid monomers; and wherein the hair styling polymer comprises at least two different ethylenically unsaturated alkanoic acid vinyl ester monomers having 4 to 13 carbons.

[0015] Unless otherwise indicated, ratios, percentages, parts, and the like are by weight. Weight percentages (or wt. %) in the compositions are percentages of dry weight, i.e., not including any solvents that can be present in the composition. Percentages of monomer units in a polymer are percentages of solid weight, i.e., not including any solvents present in the polymer.

[0016] As used herein, unless otherwise indicated, the phrase “molecular weight” or M WMolecular weight refers to weight average molecular weight as measured in a conventional manner using gel permeation chromatography (GPC) and conventional standards such as amylopectin narrow molecular weight standards having a molecular weight range of 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, Second Edition, A. M. Striegel, W. W. Yau, J. J. Kirkland, D. D. Bly; John Wiley & Sons, Inc. 2009. Molecular weight is reported herein in units of Daltons or equivalently g / mol.

[0017] As used herein and in the appended claims, the term "structural unit" refers to the residue of the indicated monomer as present in a polymer; thus, for example, the structural unit of vinyl acetate is as shown below: where the dotted line ( ) represents the point of attachment along the polymer backbone.

[0018] Preferably, the hair styling polymers of the present application are solution polymers (i.e., produced using a solution polymerization process). Preferably, the hair styling polymers of the present application have a turbidity of < 20 NTU (preferably, < 17; more preferably, < 10; most preferably, < 7) when measured in a 1 wt% polymer solution in ethanol / water (63 wt% / 37 wt%) at 25°C at a pH of 7.5.

[0019] 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; 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 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 wt% (preferably, 0 to 2.5 wt%; more preferably, 0 to 1 wt%; most preferably, 0 to 0.5 wt%) of structural units of a polyethylenically unsaturated crosslinking agent, based on the dry weight of the hair styling polymer; 0 to 20 wt% (preferably, 0 to 5 wt%; more preferably, 0 to 4 wt%; most preferably, 0 to 3 wt%) 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; wherein the hair styling polymer comprises < 15 wt% (preferably, < 10 wt%; more preferably, < 5 wt%; still more preferably, < 1 wt%; yet more preferably, < 0.1 wt%; still yet 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 a dicarboxylic acid monomer; 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.

[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 valerianate), 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; 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.More 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 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; 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. Still more 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 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; 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. Most 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 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; 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.

[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 to 5 wt.-% (preferably, 0 to 2.5 wt.-%; more preferably, 0 to 1 wt.-%; most preferably, 0 to 0.5 wt.-%), based on the dry weight of the hair styling polymer, of structural units of a multi-ethylenically unsaturated crosslinker; wherein the multi-ethylenically unsaturated crosslinker is selected from the group consisting of multi-ethylenically unsaturated crosslinkers having on average two or three vinyl groups per molecule. More preferably, the hair styling polymer of the present application comprises: 0 to 5 wt.-% (preferably, 0 to 2.5 wt.-%; more preferably, 0 to 1 wt.-%; most preferably, 0 to 0.5 wt.-%), based on the dry weight of the hair styling polymer, of structural units of a multi-ethylenically unsaturated crosslinker; wherein the multi-ethylenically unsaturated crosslinker is selected from the group consisting of allyl (meth)acrylate, tripropyleneglycol di(meth)acrylate, diethyleneglycol di(meth)acrylate, ethyleneglycol 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, trivinyltoluene, trivinylbenzene, divinyl naphthalene and mixtures thereof. Most preferably, the hair styling polymer of the present application comprises: 0 to 5 wt.-% (preferably, 0 to 2.5 wt.-%; more preferably, 0 to 1 wt.-%; most preferably, 0 to 0.5 wt.-%), based on the dry weight of the hair styling polymer, of structural units of a multi-ethylenically unsaturated crosslinker; wherein the multi-ethylenically unsaturated crosslinker 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.

[0029] (I) wherein the dotted line ( ) represents the point R 1 and R 2 are independently selected from the group consisting of hydrogen and C 1-3 alkyl groups.

[0030] Preferably, the hair styling polymer of the present application comprises < 0.01 mol-% (preferably, < 0.005 mol-%; more preferably, < 0.001 mol-%; most preferably, less than the limit of detection) of structural units of diether-containing monomers.

[0031] 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 again 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 again 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.

[0032] 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)propyl trimethylammonium chloride (MAPTAC), and mixtures thereof.

[0033] 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.

[0034] Preferably, the hair styling polymer 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, < the limit of detection) of a dry oil based on the dry weight of the hair styling polymer. Most preferably, the hair styling polymer 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, < the 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 alkyd resins, long oil alkyd resins, and mixtures thereof.

[0035] 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.

[0036] 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.

[0037] The hair styling polymers of the present application can be prepared using conventional or otherwise known polymerization techniques. Preferably, the hair styling polymers of the present application can be prepared using conventional solution polymerization techniques.

[0038] The hair styling polymers of the present application are suitable for use in hair styling formulations. In particular, the hair styling polymers of the present application provide hair styling performance, including curl retention and hair stiffness.

[0039] Some embodiments of the present application will now be described in detail in the following Examples.

[0040] Synthesis of 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 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). Then azobisisobutyronitrile (0.32 g) was 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. Then a second addition of azobisisobutyronitrile (0.32 g) was 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. Then a third addition of azobisisobutyronitrile (0.32 g) was 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. Then a fourth addition of azobisisobutyronitrile (0.32 g) was 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 hexane. The precipitate was isolated using a Buchner funnel, and washed with some additional hexane. The collected product polymer was dried at room temperature under house vacuum, transferred to a watch glass, 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 Mw, and number average molecular weight Mn, by gel permeation chromatography analysis. w The number average molecular weight Mnwas analyzed by gel permeation chromatography analysis. n The number average molecular weight Mnwas analyzed by gel permeation chromatography analysis, and the glass transition temperature Tgwas analyzed by differential scanning calorimetry. g The results are provided in Table 2.

[0041] Table 1 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 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). Then azobisisobutyronitrile (0.32 g) was 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. Then a second addition of azobisisobutyronitrile (0.32 g) was 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. Then a third addition of azobisisobutyronitrile (0.32 g) was 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. Then a fourth addition of azobisisobutyronitrile (0.32 g) was 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 hexane. The precipitate was isolated using a Buchner funnel, and washed with some additional hexane. The collected product polymer was dried at room temperature under house vacuum, transferred to a watch glass, 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 Mw, and number average molecular weight Mn, by gel permeation chromatography analysis.

[0042] Table 2

[0043] Comparative Examples CF1-CF3 and Examples F1-F4: hair styling preparations 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 resulting 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 resulting 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.

[0044] Table 3

[0045] Examples F5-F8: hair styling preparations 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 TM ) was Step 2. The turbidity of the resulting mixture after the pH adjustment was observed and recorded in Table 4.

[0046] Table 4

[0047] curl retention The following hair treatment experiment was performed using 8 inch long virgin dark brown Caucasian hair tresses (3.5 g) purchased from International Hair Importers & Products, Inc. First, each tress was 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.

[0048] 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 with 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.

[0049] Table 5

[0050] 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.

[0051] 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 placed on a stand. A curl compression displacement of 25% was applied to the curl at a rate of 200 mm / min and the compression force as a function of curl displacement was recorded by a 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.

[0052] Table 6

Claims

1. A hair styling polymer, said hair styling polymer comprising: Based on the dry weight of the hair styling polymer, 70% to 95% by weight of the structural unit of a monoolefinic unsaturated vinyl alkyl 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 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 polyene unsaturated crosslinking agent is a structural unit. 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. The hair styling polymer comprises <15% by weight of mono-olefinic unsaturated C based on the dry weight of the hair styling polymer. 4-6 The structural unit of the dicarboxylic acid monomer; and the hair styling polymer therein comprises at least two different structural units of monoolefinic unsaturated vinyl ester monomers having 4 to 13 carbon atoms.

2. The hair styling polymer according to claim 1, wherein, based on the dry weight of the hair styling polymer, at least 80% by weight comprises structural units of a monoolefinic unsaturated vinyl ester monomer having 4 to 13 carbon atoms and structural units of a carboxylic acid / carboxylic anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms.

3. The hair styling polymer according to claim 2, wherein the hair styling polymer comprises >55 mol% of structural units of monoolefinic unsaturated vinyl ester monomers having 4 to 13 carbon atoms.

4. The hair styling polymer according to claim 3, The hair styling polymer comprises structural units containing less than 0.1 mol% of amide monomers; and The hair styling polymer comprises structural units containing amino-containing monomers at less than 0.1% by weight of the dry weight of the hair styling polymer.

5. The hair styling polymer according to claim 3, The hair styling polymer comprises less than 5% by weight 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 alkyl groups; and The hair styling polymer contains less than 0.01 mol% of diether-containing structural units.

6. The hair styling polymer of claim 3, wherein 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.

7. The hair styling polymer of claim 3, wherein the hair styling polymer comprises less than 2% by weight of drying oil based on the dry weight of the hair styling polymer.

8. The hair styling polymer of claim 3, wherein the hair styling polymer comprises <5 mol% of monomer residues having a six-membered heterocyclic ring.

9. The hair styling polymer of claim 4, wherein 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. (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 alkyl groups; 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, at a dry weight percentage of less than 10% based on the dry weight of the hair styling polymer; and The hair styling polymer contains <5 mol% of monomer residues having a six-membered heterocyclic ring.

10. The hair styling polymer of claim 9, wherein the hair styling polymer comprises less than 2% by weight of a drying oil based on the dry weight of the hair styling polymer; wherein the drying oil is selected from the group consisting of: safflower oil, linseed oil, castor oil, sesame oil, sunflower oil, soybean oil, perilla oil, tall oil, dehydrated castor oil, tung oil, very long oil alkyd resin, long oil alkyd resin, and mixtures thereof.

Images