Hair styling setting polymer

Abstract

JPEG2023552512000022.jpg114170 Monoethylenically unsaturated C 1~12 Structural units of alkyl (meth)acrylate monomers and monoethylenically unsaturated carboxylic acid-containing monomers and monoethylenically unsaturated hydroxy-functionalized C 1~16 and a structural unit of an alkyl (meth)acrylate monomer, wherein α is 0 to 3, d is 0 or 1, and R 1 is hydrogen, C 1~10 Alkyl, aryl, -OSi(R 9 )3 or -X-SiOSi(R 9 )3 and R 2 and R 9 is hydrogen or C 1~10 alkyl, and R 8 is —OSi(CH3)2OSi(CH3)3, and Y is of formula (II), (III), (IV) or (V), where R 4 , R 6 and R 10 is hydrogen or C 1-4 alkyl, and X, R 3 and R 5 is a divalent linking group, and R 7 is C 1~10 is an alkyl group; b is 0-4; and c is 0 or 1. Fixative polymers are provided.

Description

Technical Field

[0001] The present invention relates to a fixing agent polymer. In particular, the present invention relates to a monomeric ethylenically unsaturated C 1~10 , 5 , 1~4 , , 6 , , , 7 ,

[0004] , 3 , , 10 structural unit of an alkyl (meth) acrylate monomer, a structural unit of a monoethylenically unsaturated carboxylic acid-containing monomer, and a monoethylenically unsaturated hydroxy-functionalized C 1~16 structural unit of an alkyl (meth) acrylate monomer and a structural unit of a carbosiloxane monomer of formula (I), and

[0002]

Chemical Formula

[0003]

Chemical Formula

Background Art

[0004] Hair styling compositions, such as hairsprays, styling gels, spray gels, and mousses, are used on hair to hold it in a specific shape or structure. Such compositions typically contain polymer resins, gums, or adhesives designed to ultimately impart desired properties to the hair to which the composition is applied. Polymers are used for a variety of purposes, including, for example, hair retention, volume enhancement, and imparting desirable tactile properties. Much of the ability of hair styling compositions to hold hair in a specific shape is due to the fixing polymers used in the composition. When applied, fixing polymers form thin films and / or welds on the hair at the joints between adjacent hair fibers or at points where fibers intersect, thereby holding the hair in a specific shape or structure.

[0005] For a polymer to be suitable for a hair styling composition, it should exhibit a desirable combination of performance attributes, including, for example, compatibility with other components of the composition, sufficient high-humidity curl retention, sufficient rigidity on the hair, and easy sprayability that results in a uniform mist of spray delivered to the hair.

[0006] An example of a hair fixing agent formulation is disclosed by Chang et al. in U.S. Patent No. 6,214,328. Chang et al. disclose (a) at least one acrylic hair fixing agent resin in a total weight of 1 to 15 weight percent, wherein (i) at least one (C) in a total weight of 5 to 95 weight percent as polymerization units. 1~10 (ii) alkyl (meth)acrylate, (ii) at least one hydroxyalkyl (meth)acrylate in 2 to 26 weight percent, (iii) at least one C in 0 to 50 weight percent 3~8 Monoethylenically unsaturated monocarboxylic acid monomers, and (iv) 2 to 10 weight percent of at least one C 4~8 The present invention provides an aqueous hair styling composition comprising (b) an acrylic hair fixing resin which is a polymer containing a monoethylenically unsaturated dicarboxylic acid monomer, and (b) at least one neutralizing agent.

[0007] Nevertheless, there is still a need for hair-fixing polymers and hair styling formulations containing hair-fixing polymers that promote effective high-humidity curl retention with a flexible hair feel and facilitate shampooing of the fixing polymers from the hair. [Overview of the Initiative]

[0008] This invention relates to a fixative polymer, based on its weight, containing 40-80% by weight of monoethylene unsaturated C 1~12 Based on the structural units of alkyl (meth)acrylate monomers and the weight of the fixing polymer, 10-30% by weight of monoethylene unsaturated carboxylic acid-containing monomer structural units and, based on the weight of the fixing polymer, >0-20% by weight of monoethylene unsaturated hydroxyfunctionalized C 1~16 It comprises structural units of alkyl (meth)acrylate monomers and structural units of carbosiloxane monomer of formula (I) in an amount of 5 to <30% by weight, based on the weight of the fixing agent polymer.

[0009] [ka] In the formula, a is between 0 and 3, d is 0 or 1, and each R 1 is hydrogen, C 1~10 Alkyl group, aryl group, -OSi(R 9 )3 units and -X-SiOSi(R 9 )Independently selected from a group consisting of 3 units, each R 2 and R 9 is hydrogen and C 1~10 Independently selected from the group consisting of alkyl groups, each R 8 It is a -OSi(CH3)2OSi(CH3)3 group, and Y is selected from the group consisting of formulas (II), (III), (IV), and (V).

[0010] [ka] In the formula, each R 4 , R6 , and R 10 is hydrogen, and C 1~4 Independently selected from the group consisting of alkyl groups, each X, R 3 and R 5 These are independently divalent linking groups, and each R 7 C 1~10 The present invention provides a fixing polymer that is an alkyl group, where b is 0 to 4 and c is 0 or 1.

[0011] The present invention provides a hair styling formulation containing the fixing polymer of the present invention.

[0012] The present invention provides a method for styling hair, comprising providing a hair styling compound of the present invention, styling the hair, and applying the hair styling compound to the hair. [Modes for carrying out the invention]

[0013] The inventors have identified a unique fixing polymer that exhibits excellent water and sebum resistance, while also possessing high washability (i.e., ease of removal from hair with shampoo), effective high-humidity curl retention, and a soft hair feel (i.e., low curl compression).

[0014] Unless otherwise specified, ratios, percentages, and parts are expressed by weight.

[0015] As used herein and in the appended claims, the term “structural unit” refers to the remainder of the specified monomer in the polymer described in the claims, and therefore the structural unit of n-butyl acrylate is

[0016] [ka]

[0017] This is shown, with the dotted lines representing the bonding points to the polymer backbone.

[0018] As used herein and in the appended claims, the term "(meth)acrylic acid" is intended to function as a general expression encompassing both acrylic acid and methacrylic acid.

[0019] As used herein and in the appended claims, the term "(meth)acrylate" is intended to function as a general expression encompassing both acrylate and methacrylate.

[0020] As used herein and in the appended claims, the term “cosmetic acceptable” refers to an ingredient typically used for topical application to the skin, and is intended to emphasize that materials that are toxic when present in amounts typically found in skincare compositions are not intended as part of the present invention.

[0021] Preferably, the fixing polymer of the present invention contains 40-80% by weight (preferably 45-75% by weight, more preferably 47.5-70% by weight, most preferably 49-65% by weight) of monoethylene unsaturated C, based on the weight of the fixing polymer. 1~12 Based on the structural units of the alkyl (meth)acrylate monomer and the weight of the fixing polymer, 10 to 30% by weight (preferably 12 to 28% by weight, more preferably 15 to 25% by weight, most preferably 16 to 20% by weight) of the structural units of the monoethylenically unsaturated carboxylic acid-containing monomer and, based on the weight of the fixing polymer, >0 to 20% by weight (preferably 1 to 17.5% by weight, more preferably 5 to 15% by weight, most preferably 8 to 12% by weight) of the monoethylenically unsaturated hydroxy-functionalized C 1~16 It comprises structural units of alkyl (meth)acrylate monomers and structural units of carbosiloxane monomers of formula (I) in amounts of 5 to <30% by weight (preferably 6 to 27.5% by weight, more preferably 7 to 25% by weight, most preferably 8 to 22% by weight) based on the weight of the fixing agent polymer,

[0022] [ka] In the formula, a is between 0 and 3, d is 0 or 1, and each R 1 is hydrogen, C 1~10 Alkyl group, aryl group, -OSi(R 9 )3 units and -X-SiOSi(R 9 )Independently selected from a group consisting of 3 units, each R 2 and R 9 is hydrogen and C 1~10 Independently selected from the group consisting of alkyl groups, each R 8 is a -OSi(CH3)2OSi(CH3)3 group, and Y is selected from the group consisting of formulas (II), (III), (IV) and (V) (preferably (II), (III) and (IV), more preferably (II) and (IV), most preferably (IV)),

[0023] [ka] In the formula, each R 4 , R 6 , and R 10 is hydrogen, and C 1~4 Independently selected from the group consisting of alkyl groups, each X, R 3 and R 5 These are independently divalent linking groups, and each R 7 C 1~10 It is an alkyl group, where b is between 0 and 4, and c is 0 or 1.

[0024] Preferably, the fixing polymer of the present invention contains 40-80% by weight (preferably 45-75% by weight, more preferably 47.5-70% by weight, most preferably 49-65% by weight) of monoethylene unsaturated C, based on the weight of the fixing polymer. 1~12 It contains structural units of alkyl (meth)acrylate monomers. More preferably, the fixing polymer of the present invention contains 40 to 80% by weight (preferably 45 to 75% by weight, more preferably 47.5 to 70% by weight, most preferably 49 to 65% by weight) of monoethylene unsaturated C, based on the weight of the fixing polymer. 1~12 It contains the structural units of alkyl (meth)acrylate monomers and is monoethylenically unsaturated C1~12 Alkyl (meth)acrylate monomers are C 1~8 It is an alkyl (meth)acrylate monomer. More preferably, the fixing polymer of the present invention contains 40 to 80% by weight (preferably 45 to 75% by weight, more preferably 47.5 to 70% by weight, most preferably 49 to 65% by weight) of monoethylene unsaturated C, based on the weight of the fixing polymer. 1~12 It contains the structural units of alkyl (meth)acrylate monomers and is monoethylenically unsaturated C 1~12 Alkyl (meth)acrylate monomers are C 1~5 It is an alkyl (meth)acrylate monomer. More preferably, the fixing polymer of the present invention contains 40 to 80% by weight (preferably 45 to 75% by weight, more preferably 47.5 to 70% by weight, most preferably 49 to 65% by weight) of monoethylene unsaturated C, based on the weight of the fixing polymer. 1~12 It contains the structural units of alkyl (meth)acrylate monomers and is monoethylenically unsaturated C 1~12 Alkyl (meth)acrylate monomers are C 1~4 It is an alkyl (meth)acrylate monomer. Most preferably, the fixing polymer of the present invention contains 40-80% by weight (preferably 45-75% by weight, more preferably 47.5-70% by weight, most preferably 49-65% by weight) of monoethylene unsaturated C, based on the weight of the fixing polymer. 1~12 It contains the structural units of alkyl (meth)acrylate monomers and is monoethylenically unsaturated C 1~12 Alkyl (meth)acrylate monomers are mixtures of butyl acrylate and methyl methacrylate.

[0025] Preferably, the fixing polymer of the present invention contains 10 to 30% by weight (preferably 12 to 28% by weight, more preferably 15 to 25% by weight, most preferably 16 to 20% by weight) of monoethylenically unsaturated carboxylic acid-containing monomer structural units, based on the weight of the fixing polymer. More preferably, the fixing polymer of the present invention contains 10 to 30% by weight (preferably 12 to 28% by weight, more preferably 15 to 25% by weight, most preferably 16 to 20% by weight) of monoethylenically unsaturated carboxylic acid-containing monomer structural units, based on the weight of the fixing polymer, and the monoethylenically unsaturated carboxylic acid-containing monomer is selected from the group consisting of (meth)acrylic acid, (meth)acrylooxypropionic acid, itaconic acid, aconitic acid, maleic acid, maleic anhydride, fumaric acid, crotonic acid, citraconic acid, maleic anhydride, monomethyl maleate, monomethyl fumarate, monomethyl itaconic acid, other derivatives (such as the corresponding anhydrides, amides and esters), and mixtures thereof. More preferably, the fixing polymer of the present invention contains 10 to 30% by weight (preferably 12 to 28% by weight, more preferably 15 to 25% by weight, most preferably 16 to 20% by weight) of monoethylenically unsaturated carboxylic acid-containing monomer structural units based on the weight of the fixing polymer, and the monoethylenically unsaturated carboxylic acid-containing monomer is selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, crotonic acid, and mixtures thereof. Most preferably, the fixing polymer of the present invention contains 10 to 30% by weight (preferably 12 to 28% by weight, more preferably 15 to 25% by weight, most preferably 16 to 20% by weight) of structural units of a monoethylenically unsaturated carboxylic acid-containing monomer, based on the weight of the fixing polymer, wherein the monoethylenically unsaturated carboxylic acid-containing monomer is methacrylic acid.

[0026] Preferably, the fixing polymer of the present invention contains, based on the weight of the fixing polymer, >0 to 20% by weight (preferably 1 to 17.5% by weight, more preferably 5 to 15% by weight, most preferably 8 to 12% by weight) of monoethylene unsaturated hydroxyfunctionalized C 1~16 It contains structural units of alkyl (meth)acrylate monomers. More preferably, the fixing polymer of the present invention contains, based on the weight of the fixing polymer, >0 to 20% by weight (preferably 1 to 17.5% by weight, more preferably 5 to 15% by weight, most preferably 8 to 12% by weight) of monoethylenically unsaturated hydroxyfunctionalized C 1~16 Containing the structural unit of alkyl (meth)acrylate monomer, monoethylenically unsaturated hydroxy functionalized C 1~16 Alkyl (meth)acrylate monomers are hydroxy-functionalized C 1~12 It is an alkyl (meth)acrylate monomer. More preferably, the fixing polymer of the present invention contains, based on the weight of the fixing polymer, >0 to 20% by weight (preferably 1 to 17.5% by weight, more preferably 5 to 15% by weight, most preferably 8 to 12% by weight) of monoethylenically unsaturated hydroxyfunctionalized C 1~16 Containing the structural unit of alkyl (meth)acrylate monomer, monoethylenically unsaturated hydroxy functionalized C 1-16 Alkyl (meth)acrylate monomers are hydroxy-functionalized C 1-8 It is an alkyl (meth)acrylate monomer. More preferably, the fixing polymer of the present invention contains >0 to 20% by weight (preferably 1 to 17.5% by weight, more preferably 5 to 15% by weight, most preferably 8 to 12% by weight) of monoethylenically unsaturated hydroxyfunctionalized C based on the weight of the fixing polymer. 1~16 Containing the structural unit of alkyl (meth)acrylate monomer, monoethylenically unsaturated hydroxy functionalized C 1~16 Alkyl (meth)acrylate monomers are hydroxy-functionalized C 1~4It is an alkyl (meth)acrylate monomer. More preferably, the fixing polymer of the present invention contains, based on the weight of the fixing polymer, >0 to 20% by weight (preferably 1 to 17.5% by weight, more preferably 5 to 15% by weight, most preferably 8 to 12% by weight) of monoethylenically unsaturated hydroxyfunctionalized C 1~16 Containing the structural unit of alkyl (meth)acrylate monomer, monoethylenically unsaturated hydroxy functionalized C 1~16 The alkyl (meth)acrylate monomer is selected from the group consisting of hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate, hydroxybutyl methacrylate, hydroxybutyl acrylate, glycerol monomethacrylate, glycerol monoacrylate, and mixtures thereof. More preferably, the fixing polymer of the present invention contains, based on the weight of the fixing polymer, >0 to 20% by weight (preferably 1 to 17.5% by weight, more preferably 5 to 15% by weight, most preferably 8 to 12% by weight) of monoethylenically unsaturated hydroxy-functionalized C 1~16 Containing the structural unit of alkyl (meth)acrylate monomer, monoethylenically unsaturated hydroxy functionalized C 1~16 The alkyl (meth)acrylate monomer is selected from the group consisting of hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate, and mixtures thereof. Most preferably, the fixing polymer of the present invention contains, based on the weight of the fixing polymer, >0 to 20% by weight (preferably 1 to 17.5% by weight, more preferably 5 to 15% by weight, most preferably 8 to 12% by weight) of monoethylenically unsaturated hydroxy-functionalized C 1~16 Containing the structural unit of alkyl (meth)acrylate monomer, monoethylenically unsaturated hydroxy functionalized C 1~16 The alkyl (meth)acrylate monomer is hydroxyethyl methacrylate.

[0027] Preferably, the fixing agent polymer of the present invention contains, based on the weight of the fixing agent polymer, 5 to <30% by weight (preferably 6 to 27.5% by weight, more preferably 7 to 25% by weight, most preferably 8 to 22% by weight) of the structural unit of the carbosiloxane monomer of formula (I), wherein a is 0 to 3 (preferably 0 to 2, more preferably 0 to 1, most preferably 0), d is 0 or 1 (preferably 0), and each R 1 is hydrogen, C 1~10 alkyl group, aryl group, -OSi(R 9 )3 group and -X-SiOSi(R 9 )3 group (preferably hydrogen, C 1~10 alkyl group, -OSi(R 9 )3 group and -X-SiOSi(R 9 )3 group, more preferably hydrogen, C 1~4 alkyl group, -OSi(R 9 )3 group and -X-SiOSi(R 9 )3 group, most preferably methyl group, -OSi(CH3)3 group and -CH2CH2SiOSi(CH3)3 group) independently selected from the group consisting of, each R 2 and R 9 are hydrogen, and C 1~10 alkyl group (preferably hydrogen, and C 1~5 alkyl group, more preferably hydrogen and C 1~4 alkyl group, even more preferably hydrogen and methyl group, most preferably methyl group) independently selected from the group consisting of, each R 8 is -OSi(CH3)2OSi(CH3)3 group, Y is selected from the group consisting of formula (II), (III), (IV) and (V) (preferably (II), (III), and (IV), more preferably (II) and (IV), most preferably (IV)), wherein each R 4 , R 6 , and R 10 are hydrogen, and C 1~4 alkyl group (preferably hydrogen and C 1~3 group, more preferably hydrogen and C 1~2 alkyl group, most preferably methyl group) independently selected from the group consisting of, each X, R 3 and R5 These are independently divalent linking groups (preferably C 1~10 Alkylene group, more preferably C 2~7 Alkylene group, more more, C 2~5 Alkylene group, most preferably -CH2CH2- or -CH2CH2CH2- group), each R 7 C 1~10 It is an alkyl group, where b is between 0 and 4, and c is 0 or 1.

[0028] Preferably, the fixing polymer of the present invention has a weight-average molecular weight of 5,000 to 250,000 daltons (preferably ≥5,000 daltons, more preferably ≥10,000 daltons, even more preferably ≥20,000 daltons, even more preferably ≥25,000 daltons, most preferably ≥30,000 daltons) (preferably ≤200,000 daltons, more preferably ≤150,000 daltons, even more preferably ≤100,000 daltons, even more preferably ≤75,000 daltons, most preferably ≤60,000 daltons).

[0029] Preferably, the fixing polymer of the present invention is partially neutralized, with 50 to 90 mol% (preferably >50 to 80 mol%, more preferably 51 to 75 mol%, most preferably 55 to 65 mol%) of the carboxylic acid-containing structural units contained in the fixing polymer being neutralized. More preferably, the fixing polymer of the present invention is partially neutralized, with 50 to 90 mol% (preferably >50 to 80 mol%, more preferably 51 to 75 mol%, most preferably 55 to 65 mol%) of the carboxylic acid-containing structural units contained in the fixing polymer being neutralized by a neutralizing agent. Most preferably, the fixing polymer of the present invention is partially neutralized, and 50 to 90 mol% (preferably >50 to 80 mol%, more preferably 51 to 75 mol%, most preferably 55 to 65 mol%) of the carboxylic acid-containing structural units contained in the fixing polymer are neutralized with a neutralizing agent, the neutralizing agent being an amine-containing neutralizing agent (preferably a primary amine-containing neutralizing agent) (e.g., aminomethylpropanol).

[0030] Preferably, the fixing polymer of the present invention contains <1000 ppm by mass of the residual carbosiloxane monomer of formula (I) based on the weight of the fixing polymer. More preferably, the fixing polymer of the present invention contains <500 ppm by mass of the residual carbosiloxane monomer of formula (I) based on the weight of the fixing polymer. Even more preferably, the fixing polymer of the present invention contains <100 ppm by mass of the residual carbosiloxane monomer of formula (I) based on the weight of the fixing polymer. Most preferably, the fixing polymer of the present invention contains <50 ppm by mass of the residual carbosiloxane monomer of formula (I) based on the weight of the fixing polymer.

[0031] Preferably, the fixing polymer of the present invention is a free radical polymer prepared in an organic solvent (preferably ethanol). More preferably, the fixing polymer of the present invention is a free radical polymer prepared in an organic solvent (preferably ethanol), and the fixing polymer (preferably polymerized in an organic solvent and unpurified) contains <500 ppm by mass of residual carbosiloxane monomer of formula (I) based on the weight of the fixing polymer. Most preferably, the fixing polymer of the present invention is a free radical polymer prepared in an organic solvent (preferably ethanol), and the fixing polymer (preferably polymerized in an organic solvent and unpurified) contains <100 ppm by mass (preferably <50 ppm by mass) of residual carbosiloxane monomer of formula (I) based on the weight of the fixing polymer.

[0032] Preferably, the fixative polymer of the present invention has an acid value of 56 to 225 mg KOH / g when measured according to ASTM D664-18 using deionized water as the polymer solvent before any neutralization of the fixative polymer.

[0033] Preferably, the fixing polymer of the present invention has a glass transition temperature T when measured by differential scanning calorimetry. g However, the temperature is ≥25°C (preferably 25-140°C, more preferably 50-140°C).

[0034] Preferably, the hair styling formulation of the present invention is selected from the group consisting of hair spray, hair fixative, hair mousse, hair gel / cream, hair volumizing composition, hair smoothing cream, hair lotion, hair serum, hair oil, and hair clay. Preferably, the hair styling formulation of the present invention is formulated to facilitate hair styling in order to hold or fix the hair in a specific shape.

[0035] Preferably, the hair styling formulation of the present invention comprises the fixing polymer of the present invention. More preferably, the hair styling formulation of the present invention comprises the fixing polymer and a carrier of the present invention. Even more preferably, the hair styling formulation of the present invention comprises the fixing polymer and a carrier of the present invention, the carrier comprising water and monohydric alcohols (e.g., ethanol, isopropyl alcohol, t-butanol and sec-butanol), polyhydric alcohols (e.g., 1,3-propanediol, 1,3-butylene glycol, 1,2-butylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, 2,3-butylene glycol, pentamethylene glycol, 2-butene-1,4-diol, dibutylene glycol, pentyl glycol, hexylene glycol, octylene glycol, glycerin The present invention provides a miscible mixture with a solvent selected from the group consisting of phosphorus, trimethylolpropane, 1,2,6-hexanetriol, pentaerythritol, xylitol, sorbitol, mannitol, maltitol, maltotriose, sucrose, erythritol, glucose, fructose, maltose, xylitolose, diethylene glycol, dipropylene glycol, triethylene glycol, polypropylene glycol, tetraethylene glycol, diglycerin, polyethylene glycol, triglycerin, tetraglycerin, polyglycerin), ketones, ethers, and mixtures thereof. More preferably, the hair styling formulation of the present invention comprises the fixing agent polymer and carrier of the present invention, the carrier being a miscible mixture with water and a solvent selected from the group consisting of ethanol, 1,3-propanediol, 1,3-butylene glycol, sorbitol, dipropylene glycol, glycerin, polyethylene glycol, and mixtures thereof. More preferably, the hair styling formulation of the present invention comprises the fixing polymer and carrier of the present invention, wherein the carrier is a miscible mixture of water and ethanol.Most preferably, the hair styling formulation of the present invention comprises the fixing polymer and carrier of the present invention, wherein the carrier is a miscible mixture of water and ethanol, and the carrier comprises 50-70% by weight (preferably 50-60% by weight) of ethanol and 30-50% by weight (preferably 40-50% by weight) of water based on the weight of the carrier.

[0036] The hair styling formulation of the present invention optionally further comprises additional components selected from the group consisting of emulsifiers, conditioning compounds, oils, aerosol propellants (e.g., liquefied lower hydrocarbons with 3-4 carbon atoms such as propane, butane, and isobutane), softeners, lubricants, penetrating agents (e.g., lanolin compounds), protein hydrolysates, protein derivatives, ethylene adducts, polyoxyethylene cholesterol, colorants (e.g., dyes, hair dyes, bleaches, reducing agents, pH adjusters, sunscreens, preservatives, thickeners (e.g., xanthan gum), and fragrances).

[0037] Preferably, the hair styling formulation of the present invention contains <0.5% by weight (preferably <0.1% by weight, more preferably <0.01% by weight, most preferably less than the detection limit) of C based on the weight of the hair styling formulation. 10~14 It contains a branched-chain hydrocarbon solvent. More preferably, the hair styling formulation of the present invention contains <0.5% by weight (preferably <0.1% by weight, more preferably <0.01% by weight, most preferably less than the detection limit) of C based on the weight of the hair styling formulation. 10~14 Contains branched-chain hydrocarbon solvents, C 10~14 Branched-chain hydrocarbon solvents have boiling points ranging from 105 to 260°C.

[0038] Preferably, the hair styling formulation of the present invention is an unemulsified hair styling formulation.

[0039] Preferably, the method for styling hair according to the present invention comprises providing the hair styling compound of the present invention, styling the hair (for example, by placing the hair on a roller, curling the hair with an iron, or flattening the hair with an iron), and applying the hair styling compound to the hair. More preferably, the method for styling hair according to the present invention comprises providing the hair styling compound of the present invention, styling the hair (for example, by placing the hair on a roller, curling the hair with an iron, or flattening the hair with an iron), and maintaining the styling while applying the hair styling compound to the hair (for example, by keeping the hair on a roller).

[0040] Herein, several embodiments of the present invention will be described in detail by the following examples.

[0041] Table 1 lists the abbreviations for the monomers used in the examples.

[0042] [Table 1]

[0043] Synthesis of carbosiloxane monomer (M3) The initial organosilicon compound (A1) (657.13 g) was packed into a vacuum-connected reactor, and two top-of-column receptors, a distillation column, a reboiler, and a cooling trap (dry ice) were fixed in place. The reactor contents were then heated to 129°C to strip off volatile substances (29.15 g: hexane / water). Next, the reactor was vacuumed (to 10 mmHg), and the reactor contents were heated to 135°C to remove further volatile substances (26.91 g from the top of the column and 21.56 g from the cooling trap). The inhibitor (D1) was then packed into the reactor contents, forming four sections: two top-of-column receptors (0.410 g each), a cooling trap (0.3 g), and the top of the distillation column (0.50 g). Purge (7% O2 / N2, 40 sccm) was then initiated in the reboiler fluid. Next, catalyst (C1) (2.9g) and MMA (298.77g) were packed into the reactor. The reactor was heated to its set point and refluxed at a top temperature of 64°C or lower to remove volatile substances. The reaction was held for 6 hours, during which time the reactor contents were kept under vacuum, reflux and a pot temperature of 103°C were maintained, and volatile substances were recovered (35.4g). The reactor contents were tested (GC) to determine the conversion rate (GC; conversion rate 96.3%). Next, the vacuum was reduced to 535 mmHg, the reactor contents were heated to 103°C, and the top removal was set to a reflux ratio of 40 and held for 2.5 hours. Next, the vacuum was reduced to 10 mmHg, and the reactor contents were heated to 118°C and maintained for 1 hour while volatile substances were removed (204.31 g, 19.03 g in the cooling trap). The product containing the methacryloxy-functional organosilicon compound (544.02 g, 100% conversion rate to methacryloxy ester (GC), mass balance 97.2%) was obtained as a yellowish, turbid material with a white powder precipitate. The acryloxy-functional organosilicon product has the following structure:

[0044] [ka] It has the properties of a carbosiloxane monomer (M3), which may be referred to herein as such.

[0045] Example 1: Polymer Synthesis A 1-liter round-bottom flask equipped with a glass rod propeller connected to a crescent-shaped Teflon® blade, a condenser, and a thermocouple was used for polymer synthesis. The propeller was driven by an overhead mechanical stirrer. The thermocouple was connected to a J-KEM temperature controller and supplied input to a pneumatic potlifter to achieve the desired temperature. Ethanol (132.39 g of SDA 3-C grade containing 4.76% isopropanol in 200 proof ethanol) was first added to the flask, and the temperature controller was set to 80°C. A nitrogen atmosphere generator was applied to remove entrained air, and the propeller was set to 100 rpm. In a separate 2-liter glass jar, a monomer mixture was prepared containing n-butyl acrylate (10 g), carbosiloxane monomer (M2) (40 g), methyl methacrylate (94 g), glacial methacrylic acid (36 g), and hydroxyethyl methacrylate (20 g, ROCRYL 400LI, available from The Dow Chemical Company). A co-fed initiator solution was prepared by diluting tert-amyl peroxypivalate (3.43 g, Trigonox 125-C75, 75% active in mineral spirits) with ethanol (86.99 g of SDA 3-C grade). When the temperature of the flask contents reached 50°C, the monomer mixture (10 g) was supplied into the flask. When the temperature of the flask contents reached 78°C, the remaining monomer mixture and the co-fed initiator solution were metered and supplied into the flask at rates of 1.06 g / min and 0.50 g / min, respectively. The target feeding time was 180 minutes. Moderate heat was continuously applied to maintain reflux conditions. The temperature gradually increased from 77.8°C to 80.6°C, and the reaction mixture became slightly foamy. The viscosity appeared to have increased slightly, and the stirring speed was increased to 120 rpm at 50% of the feed and remained the same until the end of the batch. Once the monomer feed was complete, ethanol (23.68 g, SDA 3-C grade) was added to the monomer mixture vessel and rinsed into the flask. The contents of the flask were held at 80°C for 30 minutes.Next, trigonox 125-C75 (5.08 g) in ethanol (17.14 g, SDA 3-C grade) was metered and supplied to the flask at a rate of 0.74 g / min over 30 minutes for two chemical traces, with a 30-minute hold between the two traces. The batch was then held for a further 90 minutes and then quenched by air cooling. Ethanol (132.70 g, SDA 3-C grade) was added to the flask contents during cooling as the final dilution. The residual content of monomer (I) in the product polymer was measured by liquid chromatography, and the results are shown in Table 2.

[0046] Comparative Example C1 and Examples 2-6: Polymer Synthesis The polymers of Comparative Example C1 and Examples 2-6 were prepared substantially as described in Example 1, but appropriate modifications were made to reflect the monomer mixtures used, as shown in Table 2. The residual content of monomer (I) in the product polymers was measured by liquid chromatography, and the results are shown in Table 2.

[0047] [Table 2]

[0048] Polymer properties The polymers prepared according to Comparative Example C1 and Examples 1-6 were measured for solids content by weight, Brookfield viscosity using a #2 spindle at 12 rpm under laboratory conditions, and glass transition temperature T as determined by differential scanning calorimetry (DSC). g , weight average molecular weight M w and number-average molecular weight M n We analyzed this. The results are shown in Table 3.

[0049] [Table 3]

[0050] Comparative Examples CF1-CF2 and Examples F1-F6: Hair Styling Formulations In Comparative Examples CF1-CF2 and Examples F1-F6, hair styling formulations were prepared by combining the amounts of components listed in Table 4. The components of Phase A were added to the container one by one while mixing. Next, the components of Phase C were added to the container. Then, the components of Phase B were slowly added to the container, with the contents made clear between additions. The formulations were placed in separate bottles equipped with spray nozzles.

[0051] [Table 4]

[0052] Example S: Hair Styling Process Each strand of hair (8 inches long, 3g, Virgin Brown, available from International Hair Importers) was wet for 30 seconds with 40°C tap water at a flow rate of 5.5 L / min, then massaged into the hair for 30 seconds using gentle vertical strokes with 0.6g of Suave Clarifying Shampoo per gram of hair, then rinsed for 1 minute under 40°C tap water at a flow rate of approximately 5.5 L / min, removing excess water from each strand by pulling twice with the index and middle fingers, detangling with a comb, and then wrapped around a 0.22mm magnetic hard plastic roller. The wrapped strands were then hung overnight in a temperature-controlled room to dry. The next day, each strand was individually sprayed with hair styling compound three times on each side of the curl from a distance of 8 inches and air-dried for 1 hour before testing.

[0053] Water absorption test Hair strands treated and styled with the hair styling formulations of Comparative Examples CF1-CF2 and Examples F1-F3 according to the process of Example S were tested for water absorption three times by placing five drops of water (20 μL each) on each strand and observing the time it took for two drops of water to be absorbed into the hair. The average results are shown in Table 5.

[0054] [Table 5]

[0055] High humidity curl retention Following the process of Example S, hair strands treated and styled with the hair styling formulations of Comparative Examples CF1-CF2 and Examples F1-F3 were removed from the roller and suspended in a humidity chamber at 25°C and 70-80% relative humidity. The curl retention rate (%) relative to the original length of the curls in the roller was measured at multiple checkpoints at the start and over 24 hours. The curl lengths measured at various checkpoints are shown in Table 6. The high-humidity curl retention test showed that, assuming the initial curl length was the same across all samples, the fixing polymers of the present invention in Examples 1 and 3 showed statistically equivalent performance to the comparative polymers after several hours, while the fixing polymer of the present invention in Example 2 showed superior performance.

[0056] [Table 6]

[0057] Curl compression Hair strands treated and styled with the hair styling formulations of Comparative Examples CF1-CF2 and Examples F1-F3 according to the process of Example S were removed from the roller, and curl compression was evaluated for a total of 5 cycles per strand with 6 duplicate strands per hair styling formulation. Peak force was compared across all strands for compression in cycle 1 and cycle 5. The average peak force of each hair styling formulation for compression in cycle 1 and cycle 5, along with stiffness retention, is reported in Table 7. The data from compression in cycles 1 and 5 showed that the fixing polymers of the present invention in Examples 1-3 exhibited more flexible retention than those shown by the commercially available polymer in Comparative Example CF1, meaning that the stiffness of strands treated with the fixing polymers of the present invention was generally lower than that of the comparative polymers. Less stiffness retention may be considered by consumers to provide a more natural feel and style to the hair. Stiffness retention rates were also observed for all samples. Although the fixing polymers of the present invention showed more flexible retention, the level of stiffness retention shown by the formulations of the present invention was better than that of the comparative polymers.

[0058] [Table 7] Water-repellent and sebum-repellent properties The water-repellent and sebum-repellent properties of polymer films are strongly influenced by surface energy. High water-repellent and sebum-repellent properties are desirable for hair styling applications. The water-repellent and sebum-repellent properties of fixative polymers can be evaluated by measuring the water contact angle and sebum contact angle from the surface of the fixative polymer film. Specifically, films were coated from the as-received polymer solution onto black plastic chart (available from Leneta) using a doctor blade film applicator with a gap set to 6 mil (0.1524 mm), and the films were air-dried in an environmentally controlled chamber (72°F and 50% RH) for at least 72 hours. After depositing droplets of water or sebum onto the substrate using a droplet shape analyzer (Kruss DSA100), both the water contact angle and sebum contact angle were measured at approximately 4 seconds and 200 seconds (degrees). For the measurement of the sebum contact angle, artificial sebum solutions with the compositions listed in Table 9 were prepared. The results of the water contact angle and sebum contact angle measurements are shown in Table 8. The contact angle retention rates reported in Table 8 follow the following formula. Retention rate (%) = [(Contact angle at time = 200 seconds) / (Contact angle at time = 4 seconds)] * 100

[0059] [Table 8]

[0060] [Table 9]

Claims

1. A fixing polymer, Based on the weight of the aforementioned fixing polymer, 40 to 80% by weight of monoethylene unsaturated C １～１２ Structural units of alkyl (meth)acrylate monomers, Based on the weight of the aforementioned fixing polymer, 10 to 30% by weight of a monoethylene unsaturated carboxylic acid-containing monomer is used as structural units, Based on the weight of the aforementioned fixing polymer, >0 to 20% by weight of monoethylene unsaturated hydroxyfunctionalized C １～１６ Structural units of alkyl (meth)acrylate monomers, Based on the weight of the fixing polymer, it comprises 5 to <30% by weight of structural units of the carbosiloxane monomer of formula (I), 【Chemistry 1】 During the ceremony, Each R １ is hydrogen, C １～１０ Alkyl group, aryl group, -OSi(R ９ ) ３ A group consisting of three groups, -C2H4-Si(OSi(CH3)3), is independently selected. Each R ２ and R ９ is independently selected from the group consisting of hydrogen and a C １～１０ alkyl group Each R ８ is -OSi(CH ３ ) ２ OSi(CH ３ ) ３ It is the basis, Y is selected from the group consisting of equations (II), (III), (IV), and (V), 【Chemistry 2】 During the ceremony, Each R ４ , R ６ , and R １０ is hydrogen, and C １～４ Independently selected from the group consisting of alkyl groups, Each X, R ３ and R ５ It is independently a divalent linking group, Each R ７ C is independent １～１０ It is an alkyl group, b is between 0 and 4. c is either 0 or 1, In equation (I), (i) If Y is equation (II), then a is 0 and d is 0, (ii) A fixing polymer in which, when Y is selected from the group consisting of formulas (III), (IV), and (V), a is 0 to 3 and d is 0 or 1.

2. The fixative polymer according to claim 1, wherein the fixative polymer has an acid value of 56 to 225 mg KOH / g.

3. The aforementioned fixing polymer has a glass transition temperature T of ≥25°C, as measured by DSC. ｇ The fixing polymer according to claim 1, wherein the fixing polymer has a weight-average molecular weight of ≥ 10,000 Daltons.

4. The fixing polymer according to claim 1, wherein the fixing polymer is a free radical polymer prepared in an organic solvent, and the fixing polymer contains a residual carbosiloxane monomer of formula (I) at a concentration of <500 ppm by mass based on the weight of the fixing polymer.

5. A hair styling compound comprising the fixing polymer described in claim 1.

6. The hair styling compound according to claim 5, further comprising a carrier, wherein the carrier is a miscible mixture of water and a solvent selected from the group consisting of monohydric alcohols, polyhydric alcohols, ketones, ethers and mixtures thereof.

7. The hair styling compound according to claim 6, wherein the carrier is a miscible mixture of 50 to 70% by weight of ethanol and 30 to 50% by weight of water based on the weight of the carrier.

8. The carbosiloxane monomer of formula (I) above is 【Transformation 3】 A hair styling compound according to claim 7, selected from the group consisting of and mixtures thereof.

9. The hair styling compound contains <0.5% by weight of C based on the weight of the hair styling compound. １０～１４ The hair styling compound according to claim 5, comprising a branched-chain hydrocarbon solvent.

10. A method for styling hair and imparting hydrophobicity, To provide the hair styling compound described in claim 9, Styling the aforementioned hair, A method comprising applying the hair styling compound to the hair.

Images