EP4687827A1

EP4687827A1 - Hair styling polymers comprising vinvyl alkanoate monomers and carboxylic acid or carboxylic anhydride functionalised vinyl ester monomers

Info

Publication number: EP4687827A1
Application number: EP24719926.8A
Authority: EP
Inventors: Fanwen Zeng; Inna Shulman; Kinjalbahen JOSHI; Matthew Carter; Ligeng YIN
Original assignee: Rohm and Haas Co; Union Carbide Corp
Current assignee: Rohm and Haas Co; Union Carbide Corp
Priority date: 2023-03-29
Filing date: 2024-03-18
Publication date: 2026-02-11
Also published as: CN121099984A; JP2026510825A; WO2024205964A1; KR20250166270A

Abstract

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

Description

HAIR STYLING POLYMERS COMPRISING VINVYL ALKANOATE MONOMERS AND CARBOXYLIC ACID OR CARBOXYLIC ANHYDRIDE FUNCTIONALISED VINYL ESTER MONOMERS

[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 wt%, based on dry weight of the hair styling polymer, of structural units of vinyl alkanoate monomer having 4 to 13 carbon atoms; 5 to 30 wt%, based on dry weight of the hair styling polymer, of structural units of carboxylic acid/carboxylic anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms; 0 to 5 wt%, based on dry weight of the hair styling polymer, of structural units of a multiethylenically unsaturated crosslinker; 0 to 20 wt%, based on dry weight of the hair styling polymer, of structural units of an other monoethylenically unsaturated monomer, wherein the other monoethylenically unsaturated monomer is different from the monoethylenically unsaturated vinyl alkanoate having 4 to 13 carbon atoms and the monoethylenically unsaturated carboxylic acid/carboxylic anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms; wherein the hair styling polymer comprises < 15 wt%, based on dry weight of the hair styling polymer, of structural units of monoethylenically unsaturated C4-6 dicarboxylic acid monomer; and wherein the hair styling polymer comprises structural units of at least two different vinyl alkanoate monomers having 4 to 13 carbons.

[0002] Hair styling polymers or fixatives are designed for setting a temporary style or curl to hair. The hair styling polymers may be applied to hair wet or after the hair has dried to maintain the shape and style of the hair. Desirably, the hair styling polymer provides hair holding properties and curl retention with little flaking or powder on combing, rapid curing or drying on hair, nonstickiness, and be easily removable using shampooing. Hair styling polymers are frequently delivered with a solvent which is usually an alcohol, such as ethanol, or a mixture of an alcohol and water. In the case of aerosol formulations type hair care formulations, such as hairsprays and mousses, a propellant may be added as part of the delivery system (e.g., isobutane, butane, propane or dimethyl ether).

[0003] A hair fixative polymer is disclosed in United States Patent No. 10,166,179 by Ive et al. Ive et al. disclose a hair fixative polymer comprising 55 to 60 wt% of ethyl acrylate, 30 to 50 wt% of (meth)acrylic acid; 1 to 5 wt% of an associative monomer comprising a methacrylic ester with an oxyalkylated ethylenic unsaturated terminated by a hydrophobic, non-aromatic branched chain with 12 to 22 carbon atoms; and 1 to 4 wt% of a crosslinking agent.

[0004] Notwithstanding, there is an increasing demand for hair styling polymers that provide hair setting benefits while also facilitating sustainability claims. The use of biosourced materials as feedstocks is a desired sustainability property for new hair styling polymers. Also, it would be desirable to have hair styling polymers that exhibit biodegradability. [0005] Accordingly, there remains a need for new hair styling polymers that provide hair setting benefits while also being biosourced and/or biodegradable.

[0006] The present invention provides a hair styling polymer, comprising: 70 to 95 wt%, based on dry weight of the hair styling polymer, of structural units of vinyl alkanoate monomer having 4 to 13 carbon atoms; 5 to 30 wt%, based on dry weight of the hair styling polymer, of structural units of carboxylic acid/carboxylic anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms; 0 to 5 wt%, based on dry weight of the hair styling polymer, of structural units of a multiethylenically unsaturated crosslinker; 0 to 20 wt%, based on dry weight of the hair styling polymer, of structural units of an other ethylenically unsaturated monomer, wherein the other monoethylenically unsaturated monomer is different from the monoethylenically unsaturated vinyl alkanoate having 4 to 13 carbon atoms and the monoethylenically unsaturated carboxylic acid/carboxylic anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms; wherein the hair styling polymer comprises < 15 wt%, based on dry weight of the hair styling polymer, of structural units of monoethylenically unsaturated C4-6 dicarboxylic acid monomer; and wherein the hair styling polymer comprises structural units of 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 wt%, based on dry weight of the hair styling polymer, of structural units of vinyl alkanoate monomer having 4 to 13 carbon atoms; 5 to 30 wt%, based on dry weight of the hair styling polymer, of structural units of carboxylic acid/carboxylic anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms; 0 to 5 wt%, based on dry weight of the hair styling polymer, of structural units of a multiethylenically unsaturated crosslinker; 0 to 20 wt%, based on dry weight of the hair styling polymer, of structural units of an other ethylenically unsaturated monomer, wherein the other monoethylenically unsaturated monomer is different from the monoethylenically unsaturated vinyl alkanoate having 4 to 13 carbon atoms and the monoethylenically unsaturated carboxylic acid/carboxylic anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms; wherein the hair styling polymer comprises < 15 wt%, based on dry weight of the hair styling polymer, of structural units of monoethylenically unsaturated C4-6 dicarboxylic acid monomer; wherein the hair styling polymer comprises structural units of at least two different vinyl alkanoate monomers having 4 to 13 carbons; and wherein at least 80 wt%, based on dry weight of the hair styling polymer, comprises structural units of the monoethylenically unsaturated vinyl alkanoate monomers having 4 to 13 carbon atoms and structural units of carboxylic acid/carboxylic anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms.

[0008] The present invention provides a hair styling polymer, comprising: 70 to 95 wt%, based on dry weight of the hair styling polymer, of structural units of vinyl alkanoate monomer having 4 to 13 carbon atoms; 5 to 30 wt%, based on dry weight of the hair styling polymer, of structural units of carboxylic acid/carboxylic anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms; 0 to 5 wt%, based on dry weight of the hair styling polymer, of structural units of a multiethylenically unsaturated crosslinker; 0 to 20 wt%, based on dry weight of the hair styling polymer, of structural units of an other ethylenically unsaturated monomer, wherein the other monoethylenically unsaturated monomer is different from the monoethylenically unsaturated vinyl alkanoate having 4 to 13 carbon atoms and the monoethylenically unsaturated carboxylic acid/carboxylic anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms; wherein the hair styling polymer comprises < 15 wt%, based on dry weight of the hair styling polymer, of structural units of monoethylenically unsaturated C4-6 dicarboxylic acid monomer; wherein the hair styling polymer comprises structural units of at least two different vinyl alkanoate monomers having 4 to 13 carbons; wherein at least 80 wt%, based on dry weight of the hair styling polymer, comprises structural units of the monoethylenically unsaturated vinyl alkanoate monomers having 4 to 13 carbon atoms and structural units of carboxylic acid/carboxylic anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms; and wherein the hair styling polymer comprises >55 mol% structural units of monoethylenically unsaturated vinyl alkanoate monomer having 4 to 13 carbon atoms.

[0009] The present invention provides a hair styling polymer, comprising: 70 to 95 wt%, based on dry weight of the hair styling polymer, of structural units of vinyl alkanoate monomer having 4 to 13 carbon atoms; 5 to 30 wt%, based on dry weight of the hair styling polymer, of structural units of carboxylic acid/carboxylic anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms; 0 to 5 wt%, based on dry weight of the hair styling polymer, of structural units of a multiethylenically unsaturated crosslinker; 0 to 20 wt%, based on dry weight of the hair styling polymer, of structural units of an other ethylenically unsaturated monomer, wherein the other monoethylenically unsaturated monomer is different from the monoethylenically unsaturated vinyl alkanoate having 4 to 13 carbon atoms and the monoethylenically unsaturated carboxylic acid/carboxylic anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms; wherein the hair styling polymer comprises < 15 wt%, based on dry weight of the hair styling polymer, of structural units of monoethylenically unsaturated C4-6 dicarboxylic acid monomer; wherein the hair styling polymer comprises structural units of at least two different vinyl alkanoate monomers having 4 to 13 carbons; wherein at least 80 wt%, based on dry weight of the hair styling polymer, comprises structural units of the monoethylenically unsaturated vinyl alkanoate monomers having 4 to 13 carbon atoms and structural units of carboxylic acid/carboxylic anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms; wherein the hair styling polymer comprises >55 mol% structural units of monoethylenically unsaturated vinyl alkanoate monomer having 4 to 13 carbon atoms; wherein the hair styling polymer comprises less than 0.1 mol% structural units of an amide containing monomer; and wherein the hair styling polymer comprises less that 0. 1 wt%, based on dry weight of the hair styling polymer, of structural units of an amino containing monomer.

[0010] The present invention provides a hair styling polymer, comprising: 70 to 95 wt%, based on dry weight of the hair styling polymer, of structural units of vinyl alkanoate monomer having 4 to 13 carbon atoms; 5 to 30 wt%, based on dry weight of the hair styling polymer, of structural units of carboxylic acid/carboxylic anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms; 0 to 5 wt%, based on dry weight of the hair styling polymer, of structural units of a multiethylenically unsaturated crosslinker; 0 to 20 wt%, based on dry weight of the hair styling polymer, of structural units of an other ethylenically unsaturated monomer, wherein the other monoethylenically unsaturated monomer is different from the monoethylenically unsaturated vinyl alkanoate having 4 to 13 carbon atoms and the monoethylenically unsaturated carboxylic acid/carboxylic anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms; wherein the hair styling polymer comprises < 15 wt%, based on dry weight of the hair styling polymer, of structural units of monoethylenically unsaturated C4-6 dicarboxylic acid monomer; wherein the hair styling polymer comprises structural units of at least two different vinyl alkanoate monomers having 4 to 13 carbons; wherein at least 80 wt%, based on dry weight of the hair styling polymer, comprises structural units of the monoethylenically unsaturated vinyl alkanoate monomers having 4 to 13 carbon atoms and structural units of carboxylic acid/carboxylic anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms; wherein the hair styling polymer comprises >55 mol% structural units of monoethylenically unsaturated vinyl alkanoate monomer having 4 to 13 carbon atoms; wherein the hair styling polymer comprises less than 5 wt%, based on dry weight of the hair styling polymer, of structural units of formula I wherein the dotted lines ( - ) represent points of attachment along the polymer backbone; wherein R¹ and R² are independently selected from a hydrogen and a C1-3 alkyl group; and wherein the hair styling polymer comprises less than 0.01 mol% structural units of diether containing monomer.

[0011] The present invention provides a hair styling polymer, comprising: 70 to 95 wt%, based on dry weight of the hair styling polymer, of structural units of vinyl alkanoate monomer having 4 to 13 carbon atoms; 5 to 30 wt%, based on dry weight of the hair styling polymer, of structural units of carboxylic acid/carboxylic anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms; 0 to 5 wt%, based on dry weight of the hair styling polymer, of structural units of a multiethylenically unsaturated crosslinker; 0 to 20 wt%, based on dry weight of the hair styling polymer, of structural units of an other ethylenically unsaturated monomer, wherein the other monoethylenically unsaturated monomer is different from the monoethylenically unsaturated vinyl alkanoate having 4 to 13 carbon atoms and the monoethylenically unsaturated carboxylic acid/carboxylic anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms; wherein the hair styling polymer comprises < 15 wt%, based on dry weight of the hair styling polymer, of structural units of monoethylenically unsaturated C4-6 dicarboxylic acid monomer; wherein the hair styling polymer comprises structural units of at least two different vinyl alkanoate monomers having 4 to 13 carbons; wherein at least 80 wt%, based on dry weight of the hair styling polymer, comprises structural units of the monoethylenically unsaturated vinyl alkanoate monomers having 4 to 13 carbon atoms and structural units of carboxylic acid/carboxylic anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms; wherein the hair styling polymer comprises >55 mol% structural units of monoethylenically unsaturated vinyl alkanoate monomer having 4 to 13 carbon atoms; and wherein the hair styling polymer comprises less than 10 wt%, based on dry weight of the hair styling polymer, of structural units of an alkyl acrylate monomer containing 2 to 10 carbon atoms. [0012] The present invention provides a hair styling polymer, comprising: 70 to 95 wt%, based on dry weight of the hair styling polymer, of structural units of vinyl alkanoate monomer having 4 to 13 carbon atoms; 5 to 30 wt%, based on dry weight of the hair styling polymer, of structural units of carboxylic acid/carboxylic anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms; 0 to 5 wt%, based on dry weight of the hair styling polymer, of structural units of a multiethylenically unsaturated crosslinker; 0 to 20 wt%, based on dry weight of the hair styling polymer, of structural units of an other ethylenically unsaturated monomer, wherein the other monoethylenically unsaturated monomer is different from the monoethylenically unsaturated vinyl alkanoate having 4 to 13 carbon atoms and the monoethylenically unsaturated carboxylic acid/carboxylic anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms; wherein the hair styling polymer comprises < 15 wt%, based on dry weight of the hair styling polymer, of structural units of monoethylenically unsaturated C4-6 dicarboxylic acid monomer; wherein the hair styling polymer comprises structural units of at least two different vinyl alkanoate monomers having 4 to 13 carbons; wherein at least 80 wt%, based on dry weight of the hair styling polymer, comprises structural units of the monoethylenically unsaturated vinyl alkanoate monomers having 4 to 13 carbon atoms and structural units of carboxylic acid/carboxylic anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms; wherein the hair styling polymer comprises >55 mol% structural units of monoethylenically unsaturated vinyl alkanoate monomer having 4 to 13 carbon atoms; and wherein the hair styling polymer comprises less than 2 wt%, based on dry weight of the hair styling polymer, of a drying oil. [0013] The present invention provides a hair styling polymer, comprising: 70 to 95 wt%, based on dry weight of the hair styling polymer, of structural units of vinyl alkanoate monomer having 4 to 13 carbon atoms; 5 to 30 wt%, based on dry weight of the hair styling polymer, of structural units of carboxylic acid/carboxylic anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms; 0 to 5 wt%, based on dry weight of the hair styling polymer, of structural units of a multiethylenically unsaturated crosslinker; 0 to 20 wt%, based on dry weight of the hair styling polymer, of structural units of an other ethylenically unsaturated monomer, wherein the other monoethylenically unsaturated monomer is different from the monoethylenically unsaturated vinyl alkanoate having 4 to 13 carbon atoms and the monoethylenically unsaturated carboxylic acid/carboxylic anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms; wherein the hair styling polymer comprises < 15 wt%, based on dry weight of the hair styling polymer, of structural units of monoethylenically unsaturated C4-6 dicarboxylic acid monomer; wherein the hair styling polymer comprises structural units of at least two different vinyl alkanoate monomers having 4 to 13 carbons; wherein at least 80 wt%, based on dry weight of the hair styling polymer, comprises structural units of the monoethylenically unsaturated vinyl alkanoate monomers having 4 to 13 carbon atoms and structural units of carboxylic acid/carboxylic anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms; wherein the hair styling polymer comprises >55 mol% structural units of monoethylenically unsaturated vinyl alkanoate monomer having 4 to 13 carbon atoms; and wherein the hair styling polymer comprises < 5 mol% of monomer residues having a six membered heterocyclic ring.

[0014] The present invention provides a hair styling polymer, comprising: 70 to 95 wt%, based on dry weight of the hair styling polymer, of structural units of vinyl alkanoate monomer having 4 to 13 carbon atoms; 5 to 30 wt%, based on dry weight of the hair styling polymer, of structural units of carboxylic acid/carboxylic anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms; 0 to 5 wt%, based on dry weight of the hair styling polymer, of structural units of a multiethylenically unsaturated crosslinker; 0 to 20 wt%, based on dry weight of the hair styling polymer, of structural units of an other ethylenically unsaturated monomer, wherein the other monoethylenically unsaturated monomer is different from the monoethylenically unsaturated vinyl alkanoate having 4 to 13 carbon atoms and the monoethylenically unsaturated carboxylic acid/carboxylic anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms; wherein the hair styling polymer comprises < 15 wt%, based on dry weight of the hair styling polymer, of structural units of monoethylenically unsaturated C4-6 dicarboxylic acid monomer; wherein the hair styling polymer comprises structural units of at least two different vinyl alkanoate monomers having 4 to 13 carbons; wherein at least 80 wt%, based on dry weight of the hair styling polymer, comprises structural units of the monoethylenically unsaturated vinyl alkanoate monomers having 4 to 13 carbon atoms and structural units of carboxylic acid/carboxylic anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms; wherein the hair styling polymer comprises >55 mol% structural units of monoethylenically unsaturated vinyl alkanoate monomer having 4 to 13 carbon atoms; wherein the hair styling polymer comprises less than 0. 1 mol% structural units of an amide containing monomer; wherein the hair styling polymer comprises less that 0.1 wt%, based on dry weight of the hair styling polymer, of structural units of an amino containing monomer; wherein the hair styling polymer comprises less than 5 wt%, based on dry weight of the hair styling polymer, of structural units of formula I wherein the dotted lines ( - ) represent points of attachment along the polymer backbone; wherein R¹ and R² are independently selected from a hydrogen and a C1-3 alkyl group; wherein the hair styling polymer comprises less than 0.01 mol% structural units of diether containing monomer; wherein the hair styling polymer comprises less than 10 wt%, based on dry weight of the hair styling polymer, of structural units of an alkyl acrylate monomer containing 2 to 10 carbon atoms; and wherein the hair styling polymer comprises < 5 mol% of monomer residues having a six membered heterocyclic ring.

[0015] The present invention provides a hair styling polymer, comprising: 70 to 95 wt%, based on dry weight of the hair styling polymer, of structural units of vinyl alkanoate monomer having 4 to 13 carbon atoms; 5 to 30 wt%, based on dry weight of the hair styling polymer, of structural units of carboxylic acid/carboxylic anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms; 0 to 5 wt%, based on dry weight of the hair styling polymer, of structural units of a multiethylenically unsaturated crosslinker; 0 to 20 wt%, based on dry weight of the hair styling polymer, of structural units of an other ethylenically unsaturated monomer, wherein the other monoethylenically unsaturated monomer is different from the monoethylenically unsaturated vinyl alkanoate having 4 to 13 carbon atoms and the monoethylenically unsaturated carboxylic acid/carboxylic anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms; wherein the hair styling polymer comprises < 15 wt%, based on dry weight of the hair styling polymer, of structural units of monoethylenically unsaturated C4-6 dicarboxylic acid monomer; wherein the hair styling polymer comprises structural units of at least two different vinyl alkanoate monomers having 4 to 13 carbons; wherein at least 80 wt%, based on dry weight of the hair styling polymer, comprises structural units of the monoethylenically unsaturated vinyl alkanoate monomers having 4 to 13 carbon atoms and structural units of carboxylic acid/carboxylic anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms; wherein the hair styling polymer comprises >55 mol% structural units of monoethylenically unsaturated vinyl alkanoate monomer having 4 to 13 carbon atoms; wherein the hair styling polymer comprises less than 0.1 mol% structural units of an amide containing monomer; wherein the hair styling polymer comprises less that 0.1 wt%, based on dry weight of the hair styling polymer, of structural units of an amino containing monomer; wherein the hair styling polymer comprises less than 5 wt%, based on dry weight of the hair styling polymer, of structural units of formula I wherein the dotted lines ( - ) represent points of attachment along the polymer backbone; wherein R¹ and R² are independently selected from a hydrogen and a C1-3 alkyl group; wherein the hair styling polymer comprises less than 0.01 mol% structural units of diether containing monomer; wherein the hair styling polymer comprises less than 10 wt%, based on dry weight of the hair styling polymer, of structural units of an alkyl acrylate monomer containing 2 to 10 carbon atoms; wherein the hair styling polymer comprises < 5 mol% of monomer residues having a six membered heterocyclic ring; and wherein the hair styling polymer comprises less than 2 wt%, based on dry weight of the hair styling polymer, of a drying oil; wherein the drying oil is selected from the group consisting of safflower oil, linseed oil, castor oil, oiticica oil, sunflower oil, soybean oil, perilla oil, tall oil, dehydrated castor oil, poppy oil, tung oil, very long oil alkyds, long oil alkyds and mixtures thereof.

DETAILED DESCRIPTION

[0016] Applicants have surprisingly found that hair styling polymer, comprising 70 to 95 wt%, based on dry weight of the hair styling polymer, of structural units of monoethylenically unsaturated vinyl alkanoate monomer having 4 to 13 carbon atoms; 5 to 30 wt%, based on dry weight of the hair styling polymer, of structural units of carboxylic acid/carboxylic anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms; 0 to 5 wt%, based on dry weight of the hair styling polymer, of structural units of a multiethylenically unsaturated crosslinker; 0 to 20 wt%, based on dry weight of the hair styling polymer, of structural units of an other monoethylenically unsaturated monomer, wherein the other monoethylenically unsaturated monomer is different from the monoethylenically unsaturated vinyl alkanoate monomer having 4 to 13 carbon atoms and the monoethylenically unsaturated carboxylic acid/carboxylic anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms; wherein the hair styling polymer comprises < 5 mol% of monomer residues having a six membered heterocyclic ring (e.g., a glucose moiety); wherein the hair styling polymer comprises < 15 wt%, based on dry weight of the hair styling polymer, of structural units of monoethylenically unsaturated C4-6 dicarboxylic acid monomer; and wherein the hair styling polymer comprises structural units of at least two different monoethylenically unsaturated vinyl alkanoate monomers having 4 to 13 carbons; can effectively style hair (even under high humidity conditions, i.e., > 80% relative humidity) and also exhibit biodegradability following the procedure of OECD 302B.

[0017] Unless otherwise indicated, ratios, percentages, parts, and the like are by weight. Weight percentages (or wt%) in the composition are percentages of dry weight, i.e., excluding any solven that may be present in the composition. Percentages of monomer units in the polymer are percentages of solids weight, i.e., excluding any solvent present in a polymer.

[0018] As used herein, unless otherwise indicated, the phrase "molecular weight" or Mw refers to the weight average molecular weight as measured in a conventional manner with gel permeation chromatography (GPC) and conventional standards, such as pullulan narrow molecular weight standards with molecular weight range of 180 to 708,000 Daltons. GPC techniques are discussed in detail in Modem 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 weights are reported herein in units of Daltons, or equivalently, g/mol.

[0019] The term "structural units" as used herein and in the appended claims refers to the remnant of the indicated monomer present in the polymer; thus, for example, a structural unit of vinyl acetate is illustrated: wherein the dotted lines ( - ) represent the points of attachment along the polymer backbone.

[0020] Preferably, the hair styling polymer of the present invention is a solution polymer (i.e., produced using a solution polymerization process). Preferably, the hair styling polymer of the present invention has a turbidy of < 20 NTU (preferably, < 17; more preferably, < 10; most preferably, < 7) when measured at 25 °C in a 1 wt% polymer solution in ethanol/water (63wt%/37wt%) with a pH of 7.5.

[0021] Preferably, the hair styling polymer of the present invention comprises: 70 to 95 wt% (preferably, 72 to 90 wt%; more preferably, 75 to 87.5 wt%; most preferably, 77.5 to 85 wt%), based on dry weight of the hair styling polymer, of structural units of monoethylenically unsaturated vinyl alkanoate monomer having 4 to 13 carbon atoms; 5 to 30 wt% (preferably, 10 to 28 wt%; more preferably, 12.5 to 25 wt%; most preferably, 15 to 22.5 wt%), based on dry weight of the hair styling polymer, of structural units of carboxylic acid/carboxylic anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms; 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 dry weight of the hair styling polymer, of structural units of a multiethylenically unsaturated crosslinker; 0 to 20 wt% (preferably, 0 to 5 wt%; more preferably, 0 to 4 wt%; most preferably, 0 to 3 wt%), based on dry weight of the hair styling polymer, of structural units of an other monoethylenically unsaturated monomer, wherein the other monoethylenically unsaturated monomer is different from the monoethylenically unsaturated vinyl alkanoate monomer having 4 to 13 carbon atoms and the monoethylenically unsaturated carboxylic acid/carboxylic 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 detectable limit), based on dry weight of the hair styling polymer, of structural units of monoethylenically unsaturated C4-6 dicarboxylic acid monomer; and wherein the hair styling polymer comprises structural units of at least two different monoethylenically unsaturated vinyl alkanoate monomers having 4 to 13 carbons.

[0022] Preferably, the hair styling polymer of the present invention comprises: 70 to 95 wt% (preferably, 72 to 90 wt%; more preferably, 75 to 87.5 wt%; most preferably, 77.5 to 85 wt%), based on dry weight of the hair styling polymer, of structural units of monoethylenically unsaturated vinyl alkanoate monomer having 4 to 13 carbon atoms; wherein the monoethylenically unsaturated vinyl alkanoate monomer having 4 to 13 carbon atoms is selected from the group consisting of vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pentanoate (aka vinyl valerate), vinyl 3-methyl butanoate, vinyl 2-methyl butanoate, vinyl pivalate, vinyl hexanoate (aka vinyl caproate), vinyl 4-methyl pentanoate, vinyl 2-methyl pentanoate, vinyl 3,3-dimethyl butanoate, vinyl 2,2-dimethyl butanoate, vinyl heptanoate, vinyl 5-methyl hexanoate, vinyl 2-methyl hexanoate, vinyl 4,4-dimethyl pentanoate, vinyl 2,2-dimethyl pentanoate, vinyl octanoate, vinyl 6-methyl heptanoate, vinyl 2-methyl heptanoate, vinyl 5,5-dimethyl hexanoate, vinyl 2,2-dimethyl hexanoate, vinyl nonanoate, vinyl 7-methyl octanoate, vinyl 2-methyl octanoate, vinyl

6.6-dimethyl heptanoate, vinyl 2,2-dimethyl heptanoate, vinyl decanoate, vinyl 8-methyl nonanoate, vinyl 2-methyl nonanoate, vinyl 7,7-dimethyl octanoate (aka vinyl neodecanoate), vinyl 2,2-dimethyl octanoate, vinyl undecanoate, vinyl 9-methyl decanoate, vinyl 2-methyl 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; and wherein the hair styling polymer comprises structural units of at least two different monoethylenically unsaturated vinyl alkanoate monomers having 4 to 13 carbons. More preferably, the hair styling polymer of the present invention comprises: 70 to 95 wt% (preferably, 72 to 90 wt%; more preferably, 75 to 87.5 wt%; most preferably, 77.5 to 85 wt%), based on dry weight of the hair styling polymer, of structural units of monoethylenically unsaturated vinyl alkanoate monomer having 4 to 13 carbon atoms; wherein the monoethylenically unsaturated vinyl alkanoate monomer having 4 to 13 carbon atoms is selected from the group consisting of vinyl acetate, vinyl pentanoate, vinyl 3-methyl butanoate, vinyl 2-methyl butanoate, vinyl pivalate, vinyl decanoate, vinyl 8-methyl nonanoate, vinyl 2-methyl nonanoate, vinyl

7.7-dimethyl octanoate, vinyl 2,2-dimethyl octanoate, 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 vinyl alkanoate monomers having 4 to 13 carbons. Still more preferably, the hair styling polymer of the present invention comprises: 70 to 95 wt% (preferably, 72 to 90 wt%; more preferably, 75 to 87.5 wt%; most preferably, 77.5 to 85 wt%), based on dry weight of the hair styling polymer, of structural units of monoethylenically unsaturated vinyl alkanoate monomer having 4 to 13 carbon atoms; wherein the monoethylenically unsaturated vinyl alkanoate monomer is selected from the group consisting of vinyl acetate, vinyl pivalate, vinyl 7,7-dimethyl octanoate, vinyl

2.2-dimethyl octanoate, 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 vinyl alkanoate monomers having 4 to 13 carbons. Most preferably, the hair styling polymer of the present invention comprises: 70 to 95 wt% (preferably, 72 to 90 wt%; more preferably, 75 to 87.5 wt%; most preferably, 77.5 to 85 wt%), based on dry weight of the hair styling polymer, of structural units of monoethylenically unsaturated vinyl alkanoate monomer having 4 to 13 carbon atoms; wherein the monoethylenically 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 wherein the hair styling polymer comprises structural units of at least two different monoethylenically unsaturated vinyl alkanoate monomers having 4 to 13 carbons.

[0023] Preferably, the hair styling polymer of the present invention comprises > 55 mol% (preferably, > 56 mol%; more preferably, > 60 mol%; still more preferably, > 70 mol%; yet more preferably, > 75 mol%; most preferably, > 80 mol%) structural units of monoethylenically unsaturated vinyl alkanoate monomer having 4 to 13 carbon atoms.

[0024] Preferably, the hair styling polymer of the present invention comprises: 5 to 30 wt% (preferably, 10 to 28 wt%; more preferably, 12.5 to 25 wt%; most preferably, 15 to 22.5 wt%), based on dry weight of the hair styling polymer, of structural units of carboxylic acid/carboxylic anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms; 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 hydrogen succinate) (aka vinyl succinic acid), 5-oxo-5-(vinyloxy)pentanoic acid, 6-oxo-6-(vinyloxy)hexanoic acid (aka vinyl adipic acid)(aka vinyl hydrogen adipate)(aka 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 wt% (preferably, 10 to 28 wt%; more preferably, 12.5 to 25 wt%; most preferably, 15 to 22.5 wt%), based on dry weight of the hair styling polymer, of structural units of carboxylic acid/carboxylic anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms; 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, 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. Still more preferably, the hair styling polymer of the present invention comprises: 5 to 30 wt% (preferably, 10 to 28 wt%; more preferably, 12.5 to 25 wt%; most preferably, 15 to 22.5 wt%), based on dry weight of the hair styling polymer, of structural units of carboxylic acid/carboxylic anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms; 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, 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 wt% (preferably, 10 to 28 wt%; more preferably, 12.5 to 25 wt%; most preferably, 15 to 22.5 wt%), based on dry weight of the hair styling polymer, of structural units of carboxylic acid/carboxylic anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms; 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, vinyl 2-(2,5-dioxotetrahydrofuran-3-yl)acetate, 2-(2-oxo-2-(vinyloxy)ethyl)succinic acid and mixtures thereof.

[0025] Preferably, the hair styling polymer of the present invention 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 dry weight of the hair styling polymer, of structural units of a multiethylenically unsaturated crosslinker; wherein the multiethylenically unsaturated crosslinker is selected from the group consisting of multiethylenically unsaturated crosslinkers having an average of two or three vinyl groups per molecule. More preferably, the hair styling polymer of the present invention 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 dry weight of the hair styling polymer, of structural units of a multiethylenically unsaturated crosslinker; wherein the multiethylenically unsaturated crosslinker is 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, divinyl toluene, trivinyl benzene, divinyl naphthalene and mixtures thereof. Most preferably, the hair styling polymer of the present invention 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 dry weight of the hair styling polymer, of structural units of a multiethylenically unsaturated crosslinker; wherein the multiethylenically unsaturated crosslinker is diallyl phthalate.

[0026] Preferably, the hair styling polymer of the present invention comprises: 0 to 20 wt% (preferably, 0 to 5 wt%; more preferably, 0 to 4 wt%; most preferably, 0 to 3 wt%), based on dry weight of the hair styling polymer, of structural units of an other monoethylenically unsaturated monomer, wherein the other monoethylenically unsaturated monomer is different from the monoethylenically unsaturated vinyl alkanoate monomer having 4 to 13 carbon atoms and the monoethylenically unsaturated carboxylic acid/carboxylic anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms and wherein the other monoethylenically unsaturated monomer is selected from the group consisting of alkyl (meth)acrylate, alkyl (meth)acrylamide, vinyl ether, vinyl sulfonic acid, styrene sulfonic acid, acrylamidopropylmethane sulfonic 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 wt% (preferably, 0.1 to 5 wt%; more preferably, 0.5 to 4 wt%; most preferably, 1 to 3 wt%), based on dry weight of the hair styling polymer, of structural units of an other monoethylenically unsaturated monomer, wherein the other monoethylenically unsaturated monomer is different from the monoethylenically unsaturated vinyl alkanoate monomer having 4 to 13 carbon atoms and the monoethylenically unsaturated carboxylic acid/carboxylic anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms and wherein the other monoethylenically unsaturated monomer is selected from the group consisting of CM alkyl (meth)acrylate, Ci-4 alkyl (meth)acrylamide, vinyl ether, vinyl sulfonic acid, styrene sulfonic acid, acrylamidopropylmethane sulfonic acid, (meth)acrylic acid, maleic acid, salts thereof and mixtures thereof. Still more preferably, the hair styling polymer of the present invention comprises: 0 to 20 wt% (preferably, 0.1 to 5 wt%; more preferably, 0.5 to 4 wt%; most preferably, 1 to 3 wt%), based on dry weight of the hair styling polymer, of structural units of an other monoethylenically unsaturated monomer, wherein the other monoethylenically unsaturated monomer is different from the monoethylenically unsaturated vinyl alkanoate monomer having 4 to 13 carbon atoms and the monoethylenically unsaturated carboxylic acid/carboxylic anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms and wherein the other monoethylenically unsaturated monomer is 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 wt% (preferably, 0.1 to 5 wt%; more preferably, 0.5 to 4 wt%; most preferably, 1 to 3 wt%), based on dry weight of the hair styling polymer, of structural units of an other monoethylenically unsaturated monomer, wherein the other monoethylenically unsaturated monomer is different from the monoethylenically unsaturated vinyl alkanoate monomer having 4 to 13 carbon atoms and the monoethylenically unsaturated carboxylic acid/carboxylic anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms and wherein the other monoethylenically unsaturated monomer is selected from the group consisting of vinyl sulfonic acid, salts of vinyl sulfonic acid and mixtures thereof.

[0027] Preferably, the hair styling polymer of the present invention comprises at least 80 wt% (preferably, 85 to 99.9 wt%; more preferably, 90 to 99.5 wt%; most preferably, 95 to 99 wt%), based on dry weight of the hair styling polymer, comprises structural units of the monoethylenically unsaturated vinyl alkanoate monomer having 4 to 13 carbon atoms and structural units of carboxylic acid/carboxylic anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms.

[0028] Preferably, the hair styling polymer of the present invention comprises < 5 mol% (preferably, < 1 mol%; more preferably, < 0.1 mol%; most preferably, less than detectable limit) of monomer residues having a six membered heterocyclic ring (e.g., a glucose moiety). [0029] Preferably, the hair styling polymer of the present invention 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 detectable limit), based on dry weight of the hair styling polymer, of structural units of monoethylenically unsaturated C4-6 dicarboxylic acid monomer.

[0030] Preferably, the hair styling polymer of the present invention 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 detectable limit), based on dry weight of the hair styling polymer, of structural units of formula I

wherein the dotted lines ( - ) represent points of R¹ and R² are independently selected from a hydrogen and a C1-3 alkyl group.

[0031] Preferably, the hair styling polymer of the present invention comprises < 0.01 mol% (preferably, < 0.005 mol%; more preferably, < 0.001 mol%; most preferably, less than detectible limit) structural units of diether containing monomer.

[0032] Preferably, the hair styling polymer of the present invention comprises < 10 wt% (preferably, < 5 wt%; more preferably, < 1 wt%; still more preferably, < 0.1 wt%; yet more preferably, < 0.01 wt%; still yet more preferably, < 0.001 wt%; most preferably, less than detectable limit), based on dry weight of the hair styling polymer, of structural units of an alkyl acrylate monomer containing 2 to 10 carbon atoms. More preferably, the hair styling polymer of the present invention comprises < 10 wt% (preferably, < 5 wt%; more preferably, < 1 wt%; still more preferably, < 0.1 wt%; yet more preferably, < 0.01 wt%; still yet more preferably, < 0.001 wt%; most preferably, less than detectable limit), based on dry weight of the hair styling polymer, of structural units of an alkyl acrylate monomer containing 2 to 10 carbon atoms; wherien 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-ethyl hexyl methacrylate and mixtures thereof.

[0033] Preferably, the hair styling polymer of the present invention comprises < 0.1 mol% (preferably, < 0.01 mol%; more preferably, < 0.001 mol%; most preferably, less than detectable limit) of structural units of an amide containing monomer. More preferably, the hair styling polymer of the present invention comprises < 0.1 mol% (preferably, < 0.01 mol%; more preferably, < 0.001 mol%; most preferably, less than detectable limit) of structural units of an amide containing monomer; wherein the amide containing monomer is selected from the group consisting of Mviny I formamide, (meth)acrylamide, 2-acrylamide-2- methyl-propanesulfonic acid (AMPS), 3-(methacrylamide)propyl trimethylammonium chloride (MAPTAC) and mixtures thereof.

[0034] Preferably, the hair styling polymer of the present invention comprises < 0. 1 wt% (preferably, < 0.01 wt%; more preferably, < 0.001 wt%; most preferably, less than detectable limit), based on dry weight of the hair styling polymer, of structural units of an amino containing monomer.

[0035] Preferably, the hair styling polymer of the present invention comprises less than 2 wt% (preferably, < 1 wt%; more preferably, < 0.01 wt%; still more preferably, < 0.001 wt%; most preferably, < detectable limit), based on dry weight of the hair styling polymer, of a drying oil. Most preferably, the hair styling polymer of the present invention comprises less than 2 wt% (preferably, < 1 wt%; more preferably, < 0.01 wt%; still more preferably, < 0.001 wt%; most preferably, < detectable limit), based on dry weight of the hair styling polymer, of a drying oil selected from the group consisting of safflower oil, linseed oil, castor oil, oiticica oil, sunflower oil, soybean oil, perilla oil, tall oil, dehydrated castor oil, poppy oil, tung oil, very long oil alkyds, long oil alkyds and mixtures thereof.

[0036] Preferably, the hair styling polymer of the present invention comprises 0 to 1.1 wt% (preferably, 0 to 1.0 wt%; more preferably, 0 to 0.5 wt%; still more preferably, 0 to 0.1 wt%; most preferably, 0 to 0.01 wt%), based on dry weight of the hair styling polymer, of structural units of 2-acrylamido-2-methyl-propanesulfonic acid.

[0037] Preferably, the hair styling polymer of the present invention is biodegradable as determined following the procedure of OECD 302B. More preferably, the hair styling polymer of the present invention has inherent, ultimate biodegradability as determined following the procedure of OECD 302B.

[0038] The hair styling polymer of the present invention can be made using conventional or otherwise known polymerization techniques. Preferably, the hair styling polymer of the present invention can be made using conventional solution polymerization techniques.

[0039] 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 including curl retention and hair stiffness.

[0040] Some embodiments of the present invention will now be described in detail in the following Examples.

Synthesis S1-S4: Hair styling polymer

[0041] To 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 a heating mantel to achieve desired temperature control. Agitation was started at a rate of 120 rpm. A mixture of the monomers in the amounts noted in TABLE 1 were added to the reactor one by one and washed into the reactor with ethyl acetate (45 g). Then azobisisobutyronitrile (0.32g) was added to the reactor as a solid through the port and the temperature controller was set to 60 °C under nitrogen flow. Upon reaching 60 °C, the reactor temperature was maintained at 60 °C for six hours. An second addition of azobisisobutyronitrile (0.32 g) was then added to the reactor and the temperature controller was raised to 65 °C. Upon reaching 65 °C, the reactor temperature was maintained at 65 °C for 30 minutes. A third addition of azobisisobutyronitrile (0.32 g) was then added to the reactor and the temperature controller was raised to 70 °C. Upon reaching 70 °C, the reactor temperature was maintained at 70 °C for 30 minutes. A fourth addition of azobisisobutyronitrile (0.32 g) was then added to the reactor and the temperature controller was raised to 78 °C. Upon reaching 78 °C, the reactor temperature was maintained at 78 °C for 30 minutes. The reactor was then cooled to ambient temperature with continuous nitrogen flow. Once cooled, the reactor contents were poured into 1 L of hexane. The precipitant was isolated using a Buchner funnel and washed with some additional hexane. The product polymer collected was dried under house vacuum at room temperature, transferred into a crystallization dish and further dried in a vacuum oven at 65 °C overnight. The product polymers were analyzed for residual vinyl acetate (VA) monomer content, weight average molecular weight, M_w, by gel permeation chromatography, number average molecular weight, M_n, by gel permeation chromatography and glass transition temperature, T_g, by differential scanning calorimetry. The results are provided in TABLE 2.

TABLE 2

Comparative Examples CF1-CF3 and Examples F1-F4: Hair styling formulation [0042] A hair styling formulation was prepared in each of Comparative Examples CF1-CF3 and Examples F1-F4 having the recipe noted in TABLE 3. The formulations were prepared by combining the polymer (2.5 g), water (2.5) and ethanol (20 g) and sonicating the resulting mixture for an hour is 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 2-amino-2-methyl- 1 -propanol solution (available from ANGUS, 95% AMP-95™) is step 2. The appearance of the resulting mixture after pH adjustment in step 2 was observed and recorded in TABLE 3. Then diethyl ether (25 g) was added to the mixture and sonicated for 1 hour in step 3, the final step in preparation of the hair styling formulation. The appearance of the resulting hair styling formulation from step 3 was observed and recorded in TABLE 3.

Examples F5-F8; Hair styling formulation

[0043] A hair styling formulation was prepared in each of Examples F5-F8 having the recipe noted in TABLE 4. The formulations were prepared by combining the polymer (1.49 g)(as noted in T BLE 4), water (4.89) and ethanol (8.09 g) and sonicating the resulting mixture for an hour is step 1. The pH of the mixture was then adjusted by adding

2-amino-2-methyl- 1 -propanol solution (available from ANGUS, 95% AMP-95™) is step 2. The turbidity of the resulting mixture after pH adjustment was observed and recorded in TABLE 4.

TABLE 4

Curl Retention

[0044] The following hair treatment experiments were performed using 8 inch long, virgin dark brown Caucasian hair tresses (3.5 g) purchased from International Hair Importers & Products, Inc. Each tress was first rinsed in tap water for 30 seconds, washed with a 9 wt. % sodium lauryl sulfate (SLS; 0.2 g/g of hair) for 30 seconds, rinsed with tap water for 1 minute and allowed to air dry in a controlled temperature room.

[0045] In each test, the hair tresses were then treated with a 0.35 g sample of the noted hair styling formulation prepared according to one of Comparative Example CF1-CF2, Example Fl, F5-F8 or a commercial styling gel containing a styling polymer by applying the formulation onto a hair tress and thoroughly rubbing onto the hair fibers for 2 minutes until a uniform coating over the tress was obtained. The treated hair tresses were then curled wet onto a 22 mm x 70 mm curler in a concentric coil configuration and held in place with a bobby pin. The curled hair tresses were dried in a controlled temperature (25 °C) and relative humidity (50%) room overnight. After drying, the curlers were gently removed from the tresses and the curls were suspended by clips in a humidity controlled chamber at 25 °C and 80% relative humidity, RH. The lengths of the curled tresses were then recorded at intervals over a 24 hour period, namely at t=0, 0.5, 1 , 2, 6 and 24 hours. Curl retention, CR, was defined as using the following equation

CR = [{L(0)-L(t)]/{L(0)-L(i)]] x 100% wherein L(0) is the fully extended length of the hair tress, L(i) is the initial curl length and L(t) is the curl length at a specific time. Higher values correspond to better humidity resistance. The curl retention tests were performed for each hair styling formulation in triplicate. The average results are reported in T BLE 5.

TABLE 5

Curl Compression

[0046] The following hair treatment experiments were performed using 8 inch long, virgin dark brown caucasion hair tresses (3.5 g) purchased from International Hair Importers & Products, Inc. Each tress was first rinsed in tap water for 30 seconds, washed with a 9 wt. % sodium lauryl sulfate (SLS; 0.2 g/g of hair) for 30 seconds, rinsed with tap water for 1 minute and allowed to air dry in a controlled temperature room.

[0047] In each test, the hair tresses were then treated with a 0.35 g sample of the noted hair styling formulation prepared according to one of Comparative Example CF1-CF2, Eample Fl, F5-F8 or a commercial styling gel containing a styling polymer by applying the formulation onto a hair tress and thoroughly rubbing onto the hair fibers for 2 minutes until a uniform coating over the tress was obtained. The treated hair tresses were then curled wet onto a 22 mm x 70 mm curler in a concentric coil configuration and held in place with a bobby pin. The curled hair tresses were dried in a controlled temperature (25 °C) and relative humidity (50%) room overnight. After drying, the curlers were gently removed from the tresses and curl compression tests were conducted using Dia-Stron UV 1000 control Unit. The individual hair curls were clamped to a holder. 25% curl compression displacement was applied to the hair curl at a 200 mm/min rate, and the compression force was recorded by a transducer as a function of curl displacement. For each hair styling formulation, the test was conducted on three hair curls. The average peak compression force for the treated hair curls is provided in TABLE 6 for each hair styling formulation.

T BLE 6

Claims

We claim:

1. A hair styling polymer, comprising:

70 to 95 wt%, based on dry weight of the hair styling polymer, of structural units of monoethylenically unsaturated vinyl alkanoate monomer having 4 to 13 carbon atoms;

5 to 30 wt%, based on dry weight of the hair styling polymer, of structural units of carboxylic acid/carboxylic anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms;

0 to 5 wt%, based on dry weight of the hair styling polymer, of structural units of a multiethylenically unsaturated crosslinker;

0 to 20 wt%, based on dry weight of the hair styling polymer, of structural units of an other monoethylenically unsaturated monomer, wherein the other monoethylenically unsaturated monomer is different from the monoethylenically unsaturated vinyl alkanoate monomer having 4 to 13 carbon atoms and the monoethylenically unsaturated carboxylic acid/carboxylic anhydride functionalized vinyl ester monomer having 4 to 12 carbon atoms; wherein the hair styling polymer comprises < 15 wt%, based on dry weight of the hair styling polymer, of structural units of monoethylenically unsaturated C4-6 dicarboxylic acid monomer; and wherein the hair styling polymer comprises structural units of at least two different monoethylenically unsaturated vinyl alkanoate monomers having 4 to 13 carbons.

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

3. The hair styling polymer of claim 2, wherein the hair styling polymer comprises >55 mol% structural units of monoethylenically unsaturated vinyl alkanoate monomer having 4 to 13 carbon atoms.

4. The hair styling polymer of claim 3, wherein the hair styling polymer comprises less than 0.1 mol% structural units of an amide containing monomer; and wherein the hair styling polymer comprises less that 0.1 wt%, based on dry weight of the hair styling polymer, of structural units of an amino containing monomer.

5. The hair styling polymer of claim 3, wherein the hair styling polymer comprises less than 5 wt%, based on dry weight of the hair styling polymer, of structural units of formula I wherein the dotted lines ( - ) represent points of attachment along the polymer backbone; wherein R¹ and R² are independently selected from a hydrogen and a C1-3 alkyl group; and wherein the hair styling polymer comprises less than 0.01 mol% structural units of diether containing monomer.

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

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

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 wt%, based on dry weight of the hair styling polymer, of structural units of formula I wherein the dotted lines ( - ) represent points of attachment along the polymer backbone; wherein R¹ and R² are independently selected from a hydrogen and a C1-3 alkyl group; wherein the hair styling polymer comprises less than 0.01 mol% structural units of diether containing monomer; wherein the hair styling polymer comprises less than 10 wt%, based on dry weight of the hair styling polymer, of structural units of an alkyl acrylate monomer containing 2 to 10 carbon atoms; and wherein the hair styling polymer comprises < 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 wt%, based on dry weight of the hair styling polymer, of a drying oil; wherein the drying oil is selected from the group consisting of safflower oil, linseed oil, castor oil, oiticica oil, sunflower oil, soybean oil, perilla oil, tall oil, dehydrated castor oil, poppy oil, tung oil, very long oil alkyds, long oil alkyds and mixtures thereof.