Hair styling polymers containing vinyl alkanoate monomers and carboxylic acid or carboxylic acid anhydride-functionalized vinyl ester monomers

Abstract

A hair styling polymer is provided, which, based on the dry polymer, comprises 70-95% by weight of a vinyl alkanoate monomer having 4-13 carbon atoms, 5-30% by weight of a carboxylic acid / carboxylic acid anhydride functionalized vinyl ester monomer having 4-12 carbon atoms, 0-5% by weight of a multiethylene unsaturated crosslinking agent, and 0-20% by weight of other monoethylene unsaturated monomers, wherein the other monoethylene unsaturated monomers are different from the vinyl alkanoate monomer having 4-13 carbon atoms and the carboxylic acid / carboxylic acid anhydride functionalized vinyl ester monomer having 4-12 carbon atoms, and the hair styling polymer comprises less than 15% by weight of monoethylene unsaturated C 4~6 The hair styling polymer contains a dicarboxylic acid monomer and comprises at least two different vinyl alkanoate monomers having 4 to 13 carbon atoms.

Description

[Technical Field]

[0001] The present invention relates to a hair styling polymer. Specifically, the present invention relates to a hair styling polymer, wherein the hair styling polymer comprises, based on the dry weight of the hair styling polymer, 70 to 95% by weight of structural units of vinyl alkanoate monomers having 4 to 13 carbon atoms, 5 to 30% by weight of structural units of carboxylic acid / carboxylic acid anhydride functionalized vinyl ester monomers having 4 to 12 carbon atoms, 0 to 5% by weight of structural units of multiethylene unsaturated crosslinking agents, based on the dry weight of the hair styling polymer, and 0 to 20% by weight of structural units of other monoethylene unsaturated monomers, wherein the other monoethylene unsaturated monomers include structural units of other monoethylene unsaturated monomers different from monoethylene unsaturated vinyl alkanoate having 4 to 13 carbon atoms and monoethylene unsaturated carboxylic acid / carboxylic acid anhydride functionalized vinyl ester monomers having 4 to 12 carbon atoms, and the hair styling polymer comprises less than 15% by weight of monoethylene unsaturated C 4~6 The hair styling polymer contains structural units of dicarboxylic acid monomers, and comprises structural units of at least two different vinyl alkanoate monomers having 4 to 13 carbon atoms each. [Background technology]

[0002] Hair styling polymers or fixatives are designed to set temporary styles or curls in hair. They can be applied to wet hair or after the hair has dried to maintain the shape and style of the hair. Preferably, the hair styling polymer provides hair-holding and curl-holding properties, leaves little flake or powder when combed, hardens or dries quickly on the hair, is non-sticky, and is easily removed with shampoo. Hair styling polymers are often delivered with a solvent, usually an alcohol such as ethanol or a mixture of alcohol and water. In the case of aerosol-type hair care formulations, such as hair sprays and mousses, a propellant (e.g., isobutane, butane, propane, or dimethyl ether) may be added as part of the delivery system.

[0003] Hair-fixing polymers are disclosed in U.S. Patent No. 10,166,179 by Ive et al., in which Ive et al. disclose a hair-fixing polymer comprising 55-60% by weight of ethyl acrylate, 30-50% by weight of (meth)acrylic acid, 1-5% by weight of an associated monomer containing an oxyalkylated ethylenically unsaturated methacrylic acid ester terminated by a hydrophobic non-aromatic branched chain having 12-22 carbon atoms, and 1-4% by weight of a crosslinking agent.

[0004] Nevertheless, there is a growing demand for hair styling polymers that provide hair setting effects while easily meeting sustainability requirements. The use of bio-based materials as raw materials is a desirable sustainability characteristic for new hair styling polymers. It is also desirable for hair styling polymers to be biodegradable.

[0005] Therefore, there is still a need for novel hair styling polymers that are bio-derived and / or biodegradable, while still providing a hair setting effect. [Overview of the project]

[0006] The present invention provides a hair styling polymer comprising, based on the dry weight of the hair styling polymer, 70-95% by weight of structural units of vinyl alkanoate monomers having 4-13 carbon atoms, 5-30% by weight of structural units of carboxylic acid / carboxylic acid anhydride functionalized vinyl ester monomers having 4-12 carbon atoms, 0-5% by weight of structural units of multiethylenically unsaturated crosslinking agents, and 0-20% by weight of structural units of other ethylenically unsaturated monomers, wherein the other monoethylenically unsaturated monomers are different from monoethylenically unsaturated vinyl alkanoates having 4-13 carbon atoms and monoethylenically unsaturated carboxylic acid / carboxylic acid anhydride functionalized vinyl ester monomers having 4-12 carbon atoms, and the hair styling polymer comprises less than 15% by weight of monoethylenically unsaturated C12C 4~6 The hair styling polymer contains structural units of dicarboxylic acid monomers, and comprises structural units of at least two different vinyl alkanoate monomers having 4 to 13 carbon atoms.

[0007] The present invention provides a hair styling polymer comprising, based on the dry weight of the hair styling polymer, 70-95% by weight of structural units of vinyl alkanoate monomers having 4-13 carbon atoms, 5-30% by weight of structural units of carboxylic acid / carboxylic acid anhydride functionalized vinyl ester monomers having 4-12 carbon atoms, 0-5% by weight of structural units of multiethylenically unsaturated crosslinking agents, and 0-20% by weight of structural units of other ethylenically unsaturated monomers, wherein the other monoethylenically unsaturated monomers are different from monoethylenically unsaturated vinyl alkanoates having 4-13 carbon atoms and monoethylenically unsaturated carboxylic acid / carboxylic acid anhydride functionalized vinyl ester monomers having 4-12 carbon atoms, and the hair styling polymer comprises less than 15% by weight of monoethylenically unsaturated C12C 4~6 The hair styling polymer comprises structural units of dicarboxylic acid monomers, and comprises structural units of at least two different vinyl alkanoate monomers having 4 to 13 carbon atoms, and based on the dry weight of the hair styling polymer, at least 80% by weight comprises structural units of monoethylene 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.

[0008] The present invention provides a hair styling polymer comprising, based on the dry weight of the hair styling polymer, 70-95% by weight of structural units of vinyl alkanoate monomers having 4-13 carbon atoms, 5-30% by weight of structural units of carboxylic acid / carboxylic acid anhydride functionalized vinyl ester monomers having 4-12 carbon atoms, 0-5% by weight of structural units of multiethylenically unsaturated crosslinking agents, and 0-20% by weight of structural units of other ethylenically unsaturated monomers, wherein the other monoethylenically unsaturated monomers are different from monoethylenically unsaturated vinyl alkanoates having 4-13 carbon atoms and monoethylenically unsaturated carboxylic acid / carboxylic acid anhydride functionalized vinyl ester monomers having 4-12 carbon atoms, and the hair styling polymer comprises less than 15% by weight of monoethylenically unsaturated C12C 4~6 The hair styling polymer contains structural units of dicarboxylic acid monomers, and comprises structural units of at least two different vinyl alkanoate monomers having 4 to 13 carbon atoms, and based on the dry weight of the hair styling polymer, comprises structural units of monoethylene 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, and the hair styling polymer contains more than 55 mol% of structural units of monoethylene unsaturated vinyl alkanoate monomers having 4 to 13 carbon atoms.

[0009] The present invention provides a hair styling polymer comprising, based on the dry weight of the hair styling polymer, 70-95% by weight of structural units of vinyl alkanoate monomers having 4-13 carbon atoms, 5-30% by weight of structural units of carboxylic acid / carboxylic acid anhydride functionalized vinyl ester monomers having 4-12 carbon atoms, 0-5% by weight of structural units of multiethylenically unsaturated crosslinking agents, and 0-20% by weight of structural units of other ethylenically unsaturated monomers, wherein the other monoethylenically unsaturated monomers are different from monoethylenically unsaturated vinyl alkanoates having 4-13 carbon atoms and monoethylenically unsaturated carboxylic acid / carboxylic acid anhydride functionalized vinyl ester monomers having 4-12 carbon atoms, and the hair styling polymer comprises less than 15% by weight of monoethylenically unsaturated C12C 4~6 The hair styling polymer contains structural units of dicarboxylic acid monomers, and comprises structural units of at least two different vinyl alkanoate monomers having 4 to 13 carbon atoms, and based on the dry weight of the hair styling polymer, comprises at least 80% by weight of monoethylene 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, and comprises more than 55 mol% of monoethylene unsaturated vinyl alkanoate monomers having 4 to 13 carbon atoms, and comprises less than 0.1 mol% of amide-containing monomer structural units, and comprises less than 0.1% by weight of amino-containing monomer structural units based on the dry weight of the hair styling polymer.

[0010] The present invention provides a hair styling polymer comprising, based on the dry weight of the hair styling polymer, 70-95% by weight of structural units of vinyl alkanoate monomers having 4-13 carbon atoms, 5-30% by weight of structural units of carboxylic acid / carboxylic acid anhydride functionalized vinyl ester monomers having 4-12 carbon atoms, 0-5% by weight of structural units of multiethylenically unsaturated crosslinking agents, and 0-20% by weight of structural units of other ethylenically unsaturated monomers, wherein the other monoethylenically unsaturated monomers are different from monoethylenically unsaturated vinyl alkanoates having 4-13 carbon atoms and monoethylenically unsaturated carboxylic acid / carboxylic acid anhydride functionalized vinyl ester monomers having 4-12 carbon atoms, and the hair styling polymer comprises less than 15% by weight of monoethylenically unsaturated C12C 4~6 The hair styling polymer contains structural units of dicarboxylic acid monomers, and contains structural units of at least two different vinyl alkanoate monomers having 4 to 13 carbon atoms, and based on the dry weight of the hair styling polymer, at least 80% by weight contains structural units of monoethylene 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, and the hair styling polymer contains more than 55 mol% of structural units of monoethylene unsaturated vinyl alkanoate monomers having 4 to 13 carbon atoms, and 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.

[0011] [ka] In the formula, the dotted line (------) represents a bond point along the polymer backbone, and in the formula, R 1 and R 2is independently selected from hydrogen and C 1~3 alkyl groups, and the hair styling polymer comprises less than 0.01 mole % of structural units of diether-containing monomers.

[0012] The present invention provides a hair styling polymer, the hair styling polymer comprising, based on the dry weight of the hair styling polymer, 70 to 95 wt % of structural units of vinyl alkanate monomers having 4 to 13 carbon atoms, 5 to 30 wt % of structural units of carboxylic acid / carboxylic acid anhydride-functionalized vinyl ester monomers having 4 to 12 carbon atoms, 0 to 5 wt % of structural units of multiethylenically unsaturated crosslinking agents, based on the dry weight of the hair styling polymer, 0 to 20 wt % of structural units of other ethylenically unsaturated monomers, wherein the other monoethylenically unsaturated monomers are different from monoethylenically unsaturated vinyl alkanates having 4 to 13 carbon atoms and monoethylenically unsaturated carboxylic acid / carboxylic acid anhydride-functionalized vinyl ester monomers having 4 to 12 carbon atoms, the hair styling polymer comprising less than 15 wt % of structural units of monoethylenically unsaturated C 4~6 dicarboxylic acid monomers, the hair styling polymer comprising structural units of at least two different vinyl alkanate monomers having 4 to 13 carbons, at least 80 wt % being, based on the dry weight of the hair styling polymer, structural units of monoethylenically unsaturated vinyl alkanate 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, the hair styling polymer comprising more than 55 mole % of structural units of monoethylenically unsaturated vinyl alkanate monomers having 4 to 13 carbon atoms, the hair styling polymer comprising less than 10 wt % of structural units of alkyl acrylate monomers containing 2 to 10 carbon atoms, based on the dry weight of the hair styling polymer.

[0013] The present invention provides a hair styling polymer comprising, based on the dry weight of the hair styling polymer, 70-95% by weight of structural units of vinyl alkanoate monomers having 4-13 carbon atoms, 5-30% by weight of structural units of carboxylic acid / carboxylic acid anhydride functionalized vinyl ester monomers having 4-12 carbon atoms, 0-5% by weight of structural units of multiethylenically unsaturated crosslinking agents, and 0-20% by weight of structural units of other ethylenically unsaturated monomers, wherein the other monoethylenically unsaturated monomers are different from monoethylenically unsaturated vinyl alkanoates having 4-13 carbon atoms and monoethylenically unsaturated carboxylic acid / carboxylic acid anhydride functionalized vinyl ester monomers having 4-12 carbon atoms, and the hair styling polymer comprises less than 15% by weight of monoethylenically unsaturated C12C 4~6 The hair styling polymer contains structural units of dicarboxylic acid monomers, and comprises structural units of at least two different vinyl alkanoate monomers having 4 to 13 carbon atoms, and based on the dry weight of the hair styling polymer, comprises at least 80% by weight of monoethylene unsaturated vinyl alkanoate monomer structural units 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, and comprises more than 55 mol% of monoethylene unsaturated vinyl alkanoate monomer structural units having 4 to 13 carbon atoms, and comprises less than 2% by weight of drying oil based on the dry weight of the hair styling polymer.

[0014] The present invention provides a hair styling polymer comprising, based on the dry weight of the hair styling polymer, 70-95% by weight of structural units of vinyl alkanoate monomers having 4-13 carbon atoms, 5-30% by weight of structural units of carboxylic acid / carboxylic acid anhydride functionalized vinyl ester monomers having 4-12 carbon atoms, 0-5% by weight of structural units of multiethylenically unsaturated crosslinking agents, and 0-20% by weight of structural units of other ethylenically unsaturated monomers, wherein the other monoethylenically unsaturated monomers are different from monoethylenically unsaturated vinyl alkanoates having 4-13 carbon atoms and monoethylenically unsaturated carboxylic acid / carboxylic acid anhydride functionalized vinyl ester monomers having 4-12 carbon atoms, and the hair styling polymer comprises less than 15% by weight of monoethylenically unsaturated C12C 4~6 The hair styling polymer contains structural units of dicarboxylic acid monomers, and comprises structural units of at least two different vinyl alkanoate monomers having 4 to 13 carbon atoms, and based on the dry weight of the hair styling polymer, comprises at least 80% by weight of monoethylene unsaturated vinyl alkanoate monomer structural units 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, and comprises more than 55 mol% of monoethylene unsaturated vinyl alkanoate monomer structural units having 4 to 13 carbon atoms, and comprises less than 5 mol% of monomer residues having a 6-membered heterocycle.

[0015] The present invention provides a hair styling polymer, and the hair styling polymer comprises, based on the dry weight of the hair styling polymer, structural units of vinyl alkanoate monomers having 4 to 13 carbon atoms in an amount of 70 to 95% by weight, structural units of carboxylic acid / carboxylic anhydride-functionalized vinyl ester monomers having 4 to 12 carbon atoms in an amount of 5 to 30% by weight, structural units of a multiethylenically unsaturated crosslinking agent in an amount of 0 to 5% by weight, and structural units of other ethylenically unsaturated monomers in an amount of 0 to 20% by weight, wherein the other monoethylenically unsaturated monomers are different from monoethylenically unsaturated vinyl alkanoates having 4 to 13 carbon atoms and monoethylenically unsaturated carboxylic acid / carboxylic anhydride-functionalized vinyl ester monomers having 4 to 12 carbon atoms, and the hair styling polymer comprises, based on the dry weight of the hair styling polymer, less than 15% by weight of monoethylenically unsaturated C 4~6 structural units of dicarboxylic acid monomers, the hair styling polymer comprises structural units of at least two different vinyl alkanoate monomers having 4 to 13 carbons, at least 80% by weight, based on the dry weight of the hair styling polymer, comprises structural units of monoethylenically unsaturated vinyl alkanoate 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, the hair styling polymer comprises more than 55 mol% of structural units of monoethylenically unsaturated vinyl alkanoate monomers having 4 to 13 carbon atoms, the hair styling polymer comprises less than 0.1 mol% of structural units of amide-containing monomers, the hair styling polymer comprises less than 0.1% by weight of structural units of amino-containing monomers, based on the dry weight of the hair styling polymer, and 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,

[0016] [Chemical formula]

[0017] In the formula, the dotted line (------) represents a bonding point along the polymer backbone. In the formula, R 1 and R 2 are independently selected from hydrogen and C 1~3 alkyl groups. The hair styling polymer contains structural units of a diether-containing monomer of less than 0.01 mol%. The hair styling polymer contains structural units of an alkyl acrylate monomer containing 2 to 10 carbon atoms of less than 10% by weight based on the dry weight of the hair styling polymer. The hair styling polymer contains monomer residues having a 6-membered heterocyclic ring of less than 5 mol%.

[0018] The present invention provides a hair styling polymer, and the hair styling polymer contains structural units of a vinyl alkanoate monomer having 4 to 13 carbon atoms of 70 to 95% by weight based on the dry weight of the hair styling polymer, structural units of a carboxylic acid / carboxylic anhydride-functionalized vinyl ester monomer having 4 to 12 carbon atoms of 5 to 30% by weight based on the dry weight of the hair styling polymer, structural units of a multiethylenically unsaturated crosslinking agent of 0 to 5% by weight based on the dry weight of the hair styling polymer, and structural units of other ethylenically unsaturated monomers of 0 to 20% by weight based on the dry weight of the hair styling polymer, wherein the other monoethylenically unsaturated monomer is different from a monoethylenically unsaturated vinyl alkanoate having 4 to 13 carbon atoms and a monoethylenically unsaturated carboxylic acid / carboxylic anhydride-functionalized vinyl ester monomer having 4 to 12 carbon atoms, and contains structural units of the other ethylenically unsaturated monomer. The hair styling polymer contains less than 15% by weight of monoethylenically unsaturated C 4~6The hair styling polymer contains structural units of dicarboxylic acid monomers, and contains structural units of at least two different vinyl alkanoate monomers having 4 to 13 carbon atoms, and based on the dry weight of the hair styling polymer, at least 80% by weight comprises structural units of monoethylene 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, the hair styling polymer contains more than 55 mol% of structural units of monoethylene unsaturated vinyl alkanoate 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 contains less than 0.1% by weight of amino-containing monomer structural units based on the dry weight of the hair styling polymer, the hair styling polymer contains less than 5% by weight of structural units of formula I,

[0019] [ka] In the formula, the dotted line (------) represents a bond point along the polymer backbone, and in the formula, R 1 and R 2 is hydrogen and C 1~3 Selected independently of alkyl groups, the hair styling polymer contains structural units of diether-containing monomers in amounts less than 0.01 mol%, the hair styling polymer contains structural units of alkyl acrylate monomers containing 2 to 10 carbon atoms in amounts less than 10% by weight based on the dry weight of the hair styling polymer, the hair styling polymer contains monomer residues having 6-membered heterocycles in amounts less than 5 mol%, the hair styling polymer contains drying oil in amounts less than 2% by weight based on the dry weight of the hair styling polymer, the drying oil is selected from the group consisting of safflower oil, linseed oil, castor oil, oyster oil, sunflower oil, soybean oil, perilla oil, tall oil, dehydrated castor oil, poppy oil, tuni oil, very long oil alkyds, long oil alkyds, and mixtures thereof. [Modes for carrying out the invention]

[0020] The applicant surprisingly found that the hair styling polymer contains, based on the dry weight of the hair styling polymer, 70-95% by weight of monoethylene unsaturated vinyl alkanoate monomer structural units having 4-13 carbon atoms, 5-30% by weight of carboxylic acid / carboxylic acid anhydride functionalized vinyl ester monomer structural units having 4-12 carbon atoms, 0-5% by weight of multiethylene unsaturated crosslinking agent structural units, and 0-20% by weight of other monoethylene The structural units of the lenticular unsaturated monomers include other monoethylene unsaturated monomer structural units, which are different from monoethylene unsaturated vinyl alkanoate monomers having 4 to 13 carbon atoms and monoethylene unsaturated carboxylic acid / carboxylic acid anhydride functionalized vinyl ester monomers having 4 to 12 carbon atoms, and the hair styling polymer contains less than 5 mol% monomer residues having 6-membered heterocycles (e.g., glucose moieties), and the hair styling polymer contains less than 15 wt% monoethylene unsaturated C based on the dry weight of the hair styling polymer. 4~6 Containing structural units of dicarboxylic acid monomers, the hair styling polymer contains structural units of at least two different monoethylenically unsaturated vinyl alkanoate monomers having 4 to 13 carbon atoms, and was found to be able to effectively style hair (even under high humidity conditions, i.e., relative humidity of 80% or higher), and to be biodegradable according to the OECD 302B procedure.

[0021] Unless otherwise specified, ratios, percentages, and parts are expressed by weight. Weight percentages (or weight %) in a composition are based on dry weight, i.e., the percentage excluding all solvents that may be present in the composition. Percentages of monomer units in a polymer are based on solid weight, i.e., the percentage excluding all solvents present in the polymer.

[0022] Where used herein, unless otherwise indicated, "molecular weight" or M W The term refers to the weight-average molecular weight measured in the conventional manner using gel permeation chromatography (GPC) and conventional standards such as pullulan narrow molecular weight standards in the molecular weight range of 180 to 708,000 daltons. The GPC technique is discussed in detail in *Modern Size-Exclusion Liquid Chromatography - Practice of Gel Permeation and Gel Filtration Chromatography*, Second Edition, AMStriegel, WWYau, JJKirkland, DDBly; John Wiley & Sons, Inc. 2009. Molecular weight is reported herein in units of daltons or equivalently in g / mol.

[0023] As used herein and in the appended claims, the term “structural unit” refers to the remainder of a specified monomer present in a polymer, and therefore, for example, the structural units of vinyl acetate are exemplified as follows:

[0024] [ka] In the formula, the dotted lines (------) represent bond points along the polymer backbone.

[0025] Preferably, the hair styling polymer of the present invention is a solution polymer (i.e., manufactured using a solution polymerization process). Preferably, the hair styling polymer of the present invention has a turbidity of less than 20 NTU (preferably less than 17 NTU, more preferably less than 10 NTU, most preferably less than 7 NTU) when measured at 25°C in a 1% by weight polymer solution in ethanol / water (63% by weight / 37% by weight) at pH 7.5.

[0026] Preferably, the hair styling polymer of the present invention comprises, based on the dry weight of the hair styling polymer, 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 monoethylene unsaturated vinyl alkanoate monomers 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 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% 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 multiethylene unsaturated crosslinking agent; and based on the dry weight of the hair styling polymer... The hair styling polymer contains 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 monoethylene unsaturated monomers, wherein the other monoethylene unsaturated monomers are different from monoethylene unsaturated vinyl alkanoate monomers having 4 to 13 carbon atoms and monoethylene unsaturated carboxylic acid / carboxylic acid anhydride functionalized vinyl ester monomers having 4 to 12 carbon atoms, and the hair styling polymer contains less than 15% by weight (preferably less than 10% by weight, more preferably less than 5% by weight, even more preferably less than 1% by weight, even more preferably less than 0.1% by weight, even more preferably less than 0.01% by weight, even more preferably less than 0.001% by weight, most preferably less than the detectable limit) of monoethylene unsaturated C12 based on the dry weight of the hair styling polymer. 4~6 The hair styling polymer contains structural units of dicarboxylic acid monomers, and comprises structural units of at least two different monoethylenically unsaturated vinyl alkanoate monomers having 4 to 13 carbon atoms.

[0027] Preferably, the hair styling polymer of the present invention 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 monoethylene unsaturated vinyl alkanoate monomers having 4 to 13 carbon atoms, based on the dry weight of the hair styling polymer, wherein the monoethylene unsaturated vinyl alkanoate monomers having 4 to 13 carbon atoms include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, and penetrants. Vinyl tanate (also known as vinyl valerate), vinyl 3-methylbutanoate, vinyl 2-methylbutanoate, vinyl pivalate, vinyl hexanoate (also known as vinyl caproate), vinyl 4-methylpentanoate, vinyl 2-methylpentanoate, vinyl 3,3-dimethylbutanoate, vinyl 2,2-dimethylbutanoate, vinyl heptanoate, vinyl 5-methylhexanoate, vinyl 2-methylhexanoate, vinyl 4,4-dimethylpentanoate, vinyl 2,2-dimethylpentanoate, vinyl octanoate, vinyl 6-methylheptanoate, 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 vinyl (also known as neodecanoate vinyl), 2,2-dimethyloctanoate vinyl, undecanoate vinyl, 9-methyldecanoate vinyl, 2-methyl Selected from the group consisting of vinyl decanoate, 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-propylpentanoate, vinyl 2-ethylhexanoate, and mixtures thereof, the hair styling polymer contains structural units of at least two different monoethylenically unsaturated vinyl alkanoate monomers having 4 to 13 carbon atoms.More preferably, the hair styling polymer of the present invention 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 monoethylene unsaturated vinyl alkanoate monomers having 4 to 13 carbon atoms, based on the dry weight of the hair styling polymer, wherein the monoethylene unsaturated vinyl alkanoate monomers having 4 to 13 carbon atoms include vinyl acetate, vinyl pentanoate, vinyl 3-methylbutanoate, and 2-methylbutanoate. Selected from the group consisting of vinyl butanoate, 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, the hair styling polymer contains structural units of at least two different monoethylenically unsaturated vinyl alkanoate monomers having 4 to 13 carbon atoms. More preferably, the hair styling polymer of the present invention 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 monoethylene unsaturated vinyl alkanoate monomers having 4 to 13 carbon atoms, based on the dry weight of the hair styling polymer, wherein the monoethylene unsaturated vinyl alkanoate monomers are 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 the hair styling polymer comprises at least two different monoethylene unsaturated vinyl alkanoate monomer structural units having 4 to 13 carbon atoms.Most preferably, the hair styling polymer of the present invention 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 a monoethylene unsaturated vinyl alkanoate monomer having 4 to 13 carbon atoms, based on the dry weight of the hair styling polymer, wherein the monoethylene unsaturated vinyl alkanoate 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 the hair styling polymer comprises at least two different monoethylene unsaturated vinyl alkanoate monomer structural units having 4 to 13 carbon atoms.

[0028] Preferably, the hair styling polymer of the present invention contains more than 55 mol% (preferably 56 mol% or more, more preferably 60 mol% or more, even more preferably 70 mol% or more, even more preferably 75 mol% or more, and most preferably 80 mol% or more) of structural units of monoethylenically unsaturated vinyl alkanoate monomers having 4 to 13 carbon atoms.

[0029] Preferably, the hair styling polymer of the present invention comprises 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 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 carboxylic acid / carboxylic acid anhydride-functionalized vinyl ester monomers having 4 to 12 carbon atoms are 2-oxo-2-(vinyloxy)acetic acid, 3-oxo-3-(vinyloxy)propanoic acid, 4-oxo-4-(vinyloxy)butanoic acid (also known as vinyl hydrogen succinate) Selected from the group consisting of (also known as vinyl succinic acid), 5-oxo-5-(vinyloxy)pentanoic acid, 6-oxo-6-(vinyloxy)hexanoic acid (also known as vinyl adipic acid), (also known as vinyl hydrogen adipate), (also known as 6-ethenoxy-6-oxohexanoic acid), vinyl 2-(2,5-dioxotetrahydrofuran-3-yl)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 invention comprises 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 carboxylic acid / carboxylic acid anhydride-functionalized vinyl ester monomers having 4 to 12 carbon atoms, and the carboxylic acid / carboxylic acid anhydride-functionalized vinyl ester monomers having 4 to 12 carbon atoms are selected from the group consisting of 4-oxo-4-(vinyloxy)butanoic acid, 5-oxo-5-(vinyloxy)pentanoic acid, 6-oxo-6-(vinyloxy)hexanoic acid, vinyl 2-(2,5-dioxotetrahydrofuran-3-yl)acetate, 2-(2-oxo-2-(vinyloxy)ethyl)succinic acid, 7-oxo-7-(vinyloxy)heptanoic acid, 8-oxo-8-(vinyloxy)octanoic acid, and mixtures thereof.More preferably, the hair styling polymer of the present invention comprises 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 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, and the carboxylic acid / carboxylic acid anhydride-functionalized vinyl ester monomers having 4 to 12 carbon atoms are selected from the group consisting of 4-oxo-4-(vinyloxy)butanoic acid, 5-oxo-5-(vinyloxy)pentanoic acid, 6-oxo-6-(vinyloxy)hexanoic acid, vinyl 2-(2,5-dioxotetrahydrofuran-3-yl)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 invention comprises 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 carboxylic acid / carboxylic acid anhydride-functionalized vinyl ester monomers having 4 to 12 carbon atoms, the carboxylic acid / carboxylic acid anhydride-functionalized vinyl ester monomers having 4 to 12 carbon atoms are selected from the group consisting of 4-oxo-4-(vinyloxy)butanoic acid, vinyl 2-(2,5-dioxotetrahydrofuran-3-yl)acetate, 2-(2-oxo-2-(vinyloxy)ethyl)succinic acid, and mixtures thereof.

[0030] Preferably, the hair styling polymer of the present invention contains 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 multiethylene unsaturated crosslinking agent based on the dry weight of the hair styling polymer, wherein the multiethylene unsaturated crosslinking agent is selected from the group consisting of multiethylene unsaturated crosslinking agents having an average of 2 or 3 vinyl groups per molecule. More preferably, the hair styling polymer of the present invention comprises 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 multiethylene unsaturated crosslinking agent based on the dry weight of the hair styling polymer, the multiethylene unsaturated crosslinking agent being selected from the group consisting of allyl (meth)acrylate, tripropylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, diallyl phthalate, trimethylolpropane tri(meth)acrylate, divinylbenzene, divinyltoluene, trivinylbenzene, divinylnaphthalene, and mixtures thereof. Most preferably, the hair styling polymer of the present invention contains 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 multiethylenically unsaturated crosslinking agent, based on the dry weight of the hair styling polymer, wherein the multiethylenically unsaturated crosslinking agent is diallyl phthalate.

[0031] Preferably, the hair styling polymer of the present invention 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 monoethylene unsaturated monomers, based on the dry weight of the hair styling polymer, wherein the other monoethylene unsaturated monomers differ from monoethylene unsaturated vinyl alkanoate monomers having 4 to 13 carbon atoms and monoethylene unsaturated carboxylic acid / carboxylic acid anhydride functionalized vinyl ester monomers having 4 to 12 carbon atoms, and are selected from the group consisting of alkyl (meth)acrylates, alkyl (meth)acrylamides, vinyl ethers, vinyl sulfonic acid, styrene sulfonic acid, acrylamidopropyl methanesulfonic acid, (meth)acrylic acid, maleic acid, salts thereof, and mixtures thereof. More preferably, the hair styling polymer of the present invention 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 monoethylene unsaturated monomers, based on the dry weight of the hair styling polymer, wherein the other monoethylene unsaturated monomers differ from monoethylene unsaturated vinyl alkanoate monomers having 4 to 13 carbon atoms and monoethylene unsaturated carboxylic acid / carboxylic acid anhydride functionalized vinyl ester monomers having 4 to 12 carbon atoms, where the other monoethylene unsaturated monomers are C 1~4 Alkyl (meth)acrylate, C 1~4The other monoethylene unsaturated monomers are selected from the group consisting of alkyl(meth)acrylamide, vinyl ether, vinyl sulfonic acid, styrene sulfonic acid, acrylamidopropylmethanesulfonic acid, (meth)acrylic acid, maleic acid, salts thereof, and mixtures thereof. More preferably, the hair styling polymer of the present invention contains 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 monoethylene unsaturated monomers, based on the dry weight of the hair styling polymer, and unlike monoethylene unsaturated vinyl alkanoate monomers having 4 to 13 carbon atoms and monoethylene unsaturated carboxylic acid / carboxylic acid anhydride functionalized vinyl ester monomers having 4 to 12 carbon atoms, the other monoethylene unsaturated monomers are selected from the group consisting of methyl(meth)acrylate, ethyl(meth)acrylate, methyl(meth)acrylamide, ethyl(meth)acrylamide, vinyl ether, vinyl sulfonic acid, styrene sulfonic acid, (meth)acrylic acid, maleic acid, salts thereof, and mixtures thereof. Most preferably, the hair styling polymer of the present invention 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 monoethylene unsaturated monomers, based on the dry weight of the hair styling polymer, wherein the other monoethylene unsaturated monomers are different from monoethylene unsaturated vinyl alkanoate monomers having 4 to 13 carbon atoms and monoethylene unsaturated carboxylic acid / carboxylic acid anhydride functionalized vinyl ester monomers having 4 to 12 carbon atoms, and the other monoethylene unsaturated monomers are selected from the group consisting of vinyl sulfonic acid, salts of vinyl sulfonic acid, and mixtures thereof.

[0032] Preferably, the hair styling polymer of the present invention comprises, based on the dry weight of the hair styling polymer, at least 80% by weight (preferably 85-99.9% by weight, more preferably 90-99.5% by weight, most preferably 95-99% by weight) of structural units of monoethylene unsaturated vinyl alkanoate monomers having 4-13 carbon atoms, and structural units of carboxylic acid / carboxylic acid anhydride functionalized vinyl ester monomers having 4-12 carbon atoms.

[0033] Preferably, the hair styling polymer of the present invention contains less than 5 mol% (preferably less than 1 mol%, more preferably less than 0.1 mol%, and most preferably less than the undetectable limit) of a monomer residue having a six-membered heterocycle (e.g., a glucose moiety).

[0034] Preferably, the hair styling polymer of the present invention contains less than 15% by weight (preferably less than 10% by weight, more preferably less than 5% by weight, even more preferably less than 1% by weight, even more preferably less than 0.1% by weight, even more preferably less than 0.01% by weight, even more preferably less than 0.001% by weight, most preferably less than the detectable limit) of monoethylene unsaturated C, based on the dry weight of the hair styling polymer. 4~6 It contains structural units of dicarboxylic acid monomers.

[0035] Preferably, the hair styling polymer of the present invention contains less than 5% by weight (preferably less than 1% by weight, more preferably less than 0.5% by weight, even more preferably less than 0.1% by weight, even more preferably less than 0.01% by weight, most preferably less than the detectable limit) of structural units of formula I, based on the dry weight of the hair styling polymer.

[0036] [ka] In the formula, the dotted line (------) represents a point, R 1 and R 2 is hydrogen and C 1~3It is selected independently of alkyl groups.

[0037] Preferably, the hair styling polymer of the present invention contains less than 0.01 mol% (preferably less than 0.005 mol%, more preferably less than 0.001 mol%, and most preferably less than the detectable limit) of structural units of diether-containing monomers.

[0038] Preferably, the hair styling polymer of the present invention contains structural units of an alkyl acrylate monomer containing 2 to 10 carbon atoms in less than 10% by weight (preferably less than 5% by weight, more preferably less than 1% by weight, even more preferably less than 0.1% by weight, even more preferably less than 0.01% by weight, even more preferably less than 0.001% by weight, most preferably less than the detectable limit) based on the dry weight of the hair styling polymer. More preferably, the hair styling polymer of the present invention comprises structural units of an alkyl acrylate monomer containing 2 to 10 carbon atoms in less than 10% by weight (preferably less than 5% by weight, more preferably less than 1% by weight, even more preferably less than 0.1% by weight, even more preferably less than 0.01% by weight, even more preferably less than 0.001% by weight, most preferably less than the detectable limit) based on the dry weight of the hair styling polymer, wherein the alkyl acrylate monomer containing 2 to 10 carbon atoms is 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.

[0039] Preferably, the hair styling polymer of the present invention contains less than 0.1 mol% (preferably less than 0.01 mol%, more preferably less than 0.001 mol%, most preferably less than the detectable limit) of structural units of an amide-containing monomer. More preferably, the hair styling polymer of the present invention contains less than 0.1 mol% (preferably less than 0.01 mol%, more preferably less than 0.001 mol%, most preferably less than the detectable limit) of structural units of an amide-containing monomer, the amide-containing monomer being selected from the group consisting of N-vinylformamide, (meth)acrylamide, 2-acrylamide-2-methylpropanesulfonic acid (AMPS), 3-(methacrylamide)propyltrimethylammonium chloride (MAPTAC), and mixtures thereof.

[0040] Preferably, the hair styling polymer of the present invention contains less than 0.1% by weight (preferably less than 0.01% by weight, more preferably less than 0.001% by weight, and most preferably less than the detectable limit) of amino-containing monomer structural units based on the dry weight of the hair styling polymer.

[0041] Preferably, the hair styling polymer of the present invention contains less than 2% by weight (preferably less than 1% by weight, more preferably less than 0.01% by weight, even more preferably less than 0.001% by weight, most preferably less than the detectable limit) of a drying oil based on the dry weight of the hair styling polymer. Most preferably, the hair styling polymer of the present invention contains less than 2% by weight (preferably less than 1% by weight, more preferably less than 0.01% by weight, even more preferably less than 0.001% by weight, most preferably less than the detectable limit) of a drying oil selected from the group consisting of safflower oil, linseed oil, castor oil, oyster oil, sunflower oil, soybean oil, perilla oil, tall oil, dehydrated castor oil, poppy oil, tuni oil, very long-oil alkyd, long-oil alkyd, and mixtures thereof, based on the dry weight of the hair styling polymer.

[0042] Preferably, the hair styling polymer of the present invention contains 0 to 1.1% by weight (preferably 0 to 1.0% by weight, more preferably 0 to 0.5% by weight, even more preferably 0 to 0.1% by weight, most preferably 0 to 0.01% by weight) of structural units of 2-acrylamido-2-methyl-propanesulfonic acid, based on the dry weight of the hair styling polymer.

[0043] Preferably, the hair styling polymer of the present invention is determined to be biodegradable according to the procedure of OECD 302B. More preferably, the hair styling polymer of the present invention is determined to have intrinsic extremophilicity according to the procedure of OECD 302B.

[0044] The hair styling polymer of the present invention can be produced using conventional or otherwise known polymerization techniques. Preferably, the hair styling polymer of the present invention can be produced using conventional solution polymerization techniques.

[0045] The hair styling polymer of the present invention is suitable for use in hair styling formulations. In particular, the hair styling polymer of the present invention provides hair styling performance that retains curls and gives rigidity to the hair.

[0046] Herein, several embodiments of the present invention will be described in detail in the following examples.

[0047] Synthetic S1-S4: Hair Styling Polymers Ethyl acetate (115.0 g) was added to a 500 mL four-neck round-bottom reactor equipped with an overhead stirrer, condenser, nitrogen inlet / outlet, and thermocouple, and nitrogen spraying was established. The thermocouple was connected to a J-Kem temperature controller and an input was provided to the heating mantle to achieve the desired temperature control. Stirring was started at a speed of 120 rpm. The monomer mixtures in the amounts listed in Table 1 were added to the reactor one by one and washed into the reactor with ethyl acetate (45 g). Next, azobisisobutyronitrile (0.32 g) was added to the reactor as a solid through the port, and the temperature controller was set to 60°C under nitrogen flow. Once 60°C was reached, the reactor temperature was maintained at 60°C for 6 hours. Next, a second addition of azobisisobutyronitrile (0.32 g) was made to the reactor, and the temperature controller setting was increased to 65°C. Once 65°C was reached, the reactor temperature was maintained at 65°C for 30 minutes. Next, a third addition of azobisisobutyronitrile (0.32 g) was made to the reactor, and the temperature controller was raised to 70°C. Once 70°C was reached, the reactor temperature was maintained at 70°C for 30 minutes. Next, a fourth addition of azobisisobutyronitrile (0.32 g) was made to the reactor, and the temperature controller was raised to 78°C. Once 78°C was reached, the reactor temperature was maintained at 78°C for 30 minutes. The reactor was then cooled to ambient temperature with a continuous stream of nitrogen. After cooling, the contents of the reactor were poured into 1 L of hexane. The precipitate was isolated using a Buchner funnel and washed with additional hexane. The recovered product polymer was dried at room temperature under house vacuum, transferred to a crystallization dish, and further dried overnight in a vacuum oven at 65°C. The product polymer was analyzed for residual vinyl acetate (VA) monomer content and weight-average molecular weight M by gel permeation chromatography. w Number average molecular weight M by gel permeation chromatography n , and the glass transition temperature T determined by differential scanning calorimetry. g We analyzed this. The results are shown in Table 2.

[0048] [Table 1]

[0049] [Table 2]

[0050] Comparative Examples CF1-CF3 and Examples F1-F4: Hair Styling Formulations Hair styling formulations according to the recipes listed in Table 3 were prepared in Comparative Examples CF1-CF3 and Examples F1-F4, respectively. In Step 1, polymer (2.5 g), water (2.5 g), and ethanol (20 g) were combined, and the resulting mixture was sonicated for 1 hour to prepare the formulation. The appearance of the mixture obtained after Step 1 was observed and recorded in Table 3. Next, in Step 2, the pH of this mixture was adjusted to 7 by adding a 2-amino-2-methyl-1-propanol solution (available from ANGUS, 95% AMP-95™). The appearance of the mixture obtained after pH adjustment in Step 2 was observed and recorded in Table 3. Next, in Step 3, the final step in the preparation of the hair styling formulation, diethyl ether (25 g) was added to this mixture and sonicated for 1 hour. The appearance of the hair styling formulation obtained from Step 3 was observed and recorded in Table 3.

[0051] [Table 3]

[0052] Examples F5-F8: Hair styling formulations Hair styling formulations according to the recipes listed in Table 4 were prepared in each of Examples F5 to F8. In Step 1, the formulation was prepared by combining polymer (1.49 g) (as listed in Table 4), water (4.89 g), and ethanol (8.09 g), and sonicating the resulting mixture for 1 hour. Then, in Step 2, the pH of the mixture was adjusted by adding a 2-amino-2-methyl-1-propanol solution (available from ANGUS, 95% AMP-95™). The turbidity of the resulting mixture after pH adjustment was observed and recorded in Table 4.

[0053] [Table 4]

[0054] Curl retention rate The following hair treatment experiments were conducted using 8-inch long, undyed dark brown Caucasian hair bundles (3.5g) purchased from International Hair Importers & Products, Inc. Each bundle was first rinsed with tap water for 30 seconds, washed with 9% by weight sodium lauryl sulfate (SLS, 0.2g per gram of hair) for 30 seconds, rinsed with tap water for 1 minute, and air-dried in a controlled temperature room.

[0055] Next, in each test, a 0.35 g sample of the above hair styling formulation prepared according to one of Comparative Examples CF1-CF2, Examples F1, F5-F8, or a commercially available styling gel containing a styling polymer was applied to a hair bundle, and the hair bundle was treated by rubbing it thoroughly into the hair fibers for 2 minutes until a uniform coating was obtained. The treated hair bundle was then wound wet onto a 22 mm x 70 mm curler with a concentric coil configuration and held in place with bobby pins. The curled hair bundle was dried overnight in a room with controlled temperature (25°C) and relative humidity (50%). After drying, the curler was gently removed from the bundle, and the curl was suspended with clips in a humidity-controlled chamber at 25°C and relative humidity RH80%. The length of the curled bundle was then recorded at intervals over 24 hours, i.e., at t=0, 0.5, 1, 2, 6, and 24 hours. The curl retention rate CR is defined using the following formula. CR=[{L(0)-L(t)} / {L(0)-L(i)}]×100% In the formula, L(0) is the fully extended length of the hair bundle, L(i) is the initial curl length, and L(t) is the curl length at a specific point in time. A higher value corresponds to better moisture resistance. The curl retention test was performed three times for each hair styling compound. The average results are reported in Table 5.

[0056] [Table 5]

[0057] Curl compression The following hair treatment experiments were conducted using 8-inch long, undyed dark brown Caucasian hair bundles (3.5g) purchased from International Hair Importers & Products, Inc. Each bundle was first rinsed with tap water for 30 seconds, washed with 9% by weight sodium lauryl sulfate (SLS, 0.2g per gram of hair) for 30 seconds, rinsed with tap water for 1 minute, and air-dried in a controlled temperature room.

[0058] Next, in each test, a 0.35 g sample of the above hair styling formulation prepared according to one of Comparative Examples CF1-CF2, Examples F1, F5-F8, or a commercially available styling gel containing a styling polymer was applied to a hair bundle. The hair bundle was then treated by rubbing it thoroughly into the hair fibers for 2 minutes until a uniform coating was obtained. The treated hair bundle was then wound wet onto a 22 mm x 70 mm curler with a concentric coil configuration and held in place with bobby pins. The curled hair bundle was dried overnight in a room with controlled temperature (25°C) and relative humidity (50%). After drying, the curler was gently removed from the bundle, and a curl compression test was performed using a Dia-Stron UV 1000 control unit. Individual hair curls were clamped in a holder. A 25% curl compression displacement was applied to the hair curl at a speed of 200 mm / min, and the compression force was recorded by a transducer as a function of curl displacement. Each hair styling formulation was tested on three hair curls. The average peak compression force of the treated hair curls for each hair styling formulation is shown in Table 6.

[0059] [Table 6]

Claims

1. It is a hair styling polymer, Based on the dry weight of the hair styling polymer, 70 to 95% by weight of structural units of monoethylene unsaturated vinyl alkanoate 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 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% by weight of structural units of a multi-ethylenically unsaturated crosslinking agent, Based on the dry weight of the hair styling polymer, 0 to 20% by weight of structural units of other monoethylene unsaturated monomers, wherein the other monoethylene unsaturated monomers include structural units of other monoethylene unsaturated monomers that are different from the monoethylene unsaturated vinyl alkanoate monomers having 4 to 13 carbon atoms and the monoethylene unsaturated carboxylic acid / carboxylic acid anhydride functionalized vinyl ester monomers having 4 to 12 carbon atoms. The hair styling polymer contains less than 15% by weight of monoethylene unsaturated C based on the dry weight of the hair styling polymer. ４～６ A hair styling polymer comprising structural units of a dicarboxylic acid monomer, wherein the hair styling polymer comprises structural units of at least two different monoethylenically unsaturated vinyl alkanoate 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 monoethylene 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.

3. The hair styling polymer according to claim 2, wherein the hair styling polymer comprises structural units of a monoethylenically unsaturated vinyl alkanoate monomer having 4 to 13 carbon atoms in an amount of more than 55 mol%.

4. The hair styling polymer contains structural units of amide-containing monomers in an amount of less than 0.1 mol%, The hair styling polymer according to claim 3, wherein the hair styling polymer contains less than 0.1% by weight of amino-containing monomer structural units based on the dry weight of the hair styling polymer.

5. 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. 【Chemistry 1】 In the formula, the dotted line (--------) represents a bond point along the polymer backbone, and in the formula, R １ and R ２ is hydrogen and C １～３ Selected independently of alkyl groups, The hair styling polymer according to claim 3, wherein the hair styling polymer contains structural units of a diether-containing monomer in an amount of less than 0.01 mol%.

6. The hair styling polymer according to claim 3, wherein the hair styling polymer comprises structural units of an alkyl acrylate monomer containing 2 to 10 carbon atoms in less than 10% by weight, based on the dry weight of the hair styling polymer.

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

8. The hair styling polymer according to claim 3, wherein the hair styling polymer contains a monomer residue having a six-membered heterocycle in an amount of less than 5 mol%.

9. 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. 【Chemistry 2】 In the formula, the dotted line (------) represents a bond point along the polymer backbone. In the formula, R １ and R ２ is hydrogen and C １～３ Selected independently of alkyl groups, The hair styling polymer contains structural units of diether-containing monomers in an amount of less than 0.01 mol%, The hair styling polymer comprises structural units of an alkyl acrylate monomer containing 2 to 10 carbon atoms in less than 10% by weight, based on the dry weight of the hair styling polymer. The hair styling polymer according to claim 4, wherein the hair styling polymer contains a monomer residue having a six-membered heterocycle in an amount of less than 5 mol%.

10. The hair styling polymer according to claim 9, wherein the hair styling polymer contains less than 2% by weight of a drying oil based on the dry weight of the hair styling polymer, and the drying oil is selected from the group consisting of safflower oil, linseed oil, castor oil, oyster oil, sunflower oil, soybean oil, perilla oil, tall oil, dehydrated castor oil, poppy oil, tuni oil, very long oil alkyd, long oil alkyd, and mixtures thereof.

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