WO2009122845A1

WO2009122845A1 - Hair cosmetic composition

Info

Publication number: WO2009122845A1
Application number: PCT/JP2009/054014
Authority: WO
Inventors: 律子宮川; 恭生永原; 明宏寺口
Original assignee: ライオン株式会社
Priority date: 2008-04-04
Filing date: 2009-03-04
Publication date: 2009-10-08
Also published as: KR20100133452A; CN102046145A; HK1153952A1; MY159866A; CN102046145B; JP5804665B2; JP2009249329A; KR101659634B1

Abstract

Disclosed is a hair cosmetic composition characterized by containing (A) an acrylic polymer described below and (B) a nonionic polymer. The hair cosmetic preparation is also characterized in that the mass ratio (A)/(B) is within the range of 0.1-10.0. (A) an acrylic polymer which contains, as constitutional units, 70-95% by mole of a monomer unit represented by general formula (1) and 5-30% by mole of a monomer unit represented by general formula (2) (In the formulae, R¹ represents a hydrogen atom or a methyl group; R² represents a hydrogen atom or a -CH₂OH group; A represents an oxygen atom or an -NH- group; R³ represents a hydrogen atom or a methyl group; and M represents a hydrogen atom, an alkali metal atom, an ammonium or an amine.)

Description

Hair cosmetics

The present invention relates to a hair cosmetic that imparts volume and gloss to the top of the head.

If a person who wants to give hair a firmness and firmness and wants to have a volume at the top of the head, using a hair conditioner (both flushing type and non-flushing type) will produce a feeling of adhesion with the conditioner component (oil etc.) There is a problem that the rise of the top of the head is crushed and sticky and the volume is reduced. On the other hand, a technique is proposed in which the conditioner component is changed from a general oil component to a polymer compound or solid fat having a low adhesion feeling to impart stickiness and firmness (Patent Document 1: Japanese Patent Laid-Open No. 2000-2000). No. 204024, Patent Document 2: JP-A-10-95714, Patent Document 3: JP-A 2006-199648). However, due to the formation of a film after drying, phenomena such as wobbling, smoothness and glossiness were observed, and it was not possible to reach a level that simultaneously satisfied volume feeling, glossiness and smoothness.

JP 2000-204024 A JP-A-10-95714 JP 2006-199648 A JP 2007-137830 A JP 2007-161986

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a hair cosmetic material that imparts a sense of volume to the top of the head and gloss to the hair.

As a result of intensive studies to achieve the above object, the present inventors have used a specific (A) acrylic acid polymer and (B) nonionic polymer in combination, and a mass ratio represented by (A) / (B) By setting the ratio to 0.1 to 10, the (A) component and the (B) component interact with each other to form a soft and glossy film on the hair, giving a firmness and elasticity that is not stiff, It has been found that the volume at the top of the head can be increased and gloss can be imparted to the hair. Furthermore, it was discovered that blending the cationic surfactant of component (C) with this hair cosmetic can give smoothness to the hair, and the present invention has been made.

Accordingly, the present invention provides the following inventions.
[1]. A hair cosmetic comprising the following (A) acrylic acid polymer and (B) nonionic polymer, wherein the mass ratio represented by (A) / (B) is 0.1 to 10.0 .
(A) As a constituent unit, 70 to 95 mol% of a monomer unit represented by the following general formula (1) and 5 to 30 mol% of a monomer unit represented by the following general formula (2) are included. Acrylic acid polymer

(Wherein R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom or a —CH ₂ OH group, and A represents an oxygen atom or —NH—).

(In the formula, R ³ represents a hydrogen atom or a methyl group, and M represents a hydrogen atom, an alkali metal atom, ammonium or an amine.)
[2]. (B) The hair cosmetic composition according to [1], wherein the component is a vinylpyrrolidone polymer or a cellulose polymer.
[3]. The hair cosmetic according to [1] or [2], further comprising (C) a cationic surfactant. In addition, the subject of said [3] is providing the hair cosmetics which improve the smoothness to hair.

According to the present invention, it is possible to provide a hair cosmetic that imparts a sense of volume at the top of the head and improves the smoothness and gloss of the hair.

According to the present invention, it is possible to provide a hair cosmetic that imparts a sense of volume at the top of the head and a gloss of the hair. Furthermore, the hair cosmetics which give smoothness to hair can be provided by mix | blending (C) component.

(A) Acrylic acid-based polymer 70 to 95 mol% of a monomer unit represented by the following general formula (1) and 5 to 30 mol% of a monomer unit represented by the following general formula (2), It is an acrylic acid polymer comprising a copolymer contained as a structural unit, and can be used alone or in combination of two or more.

(In the formula, R ³ represents a hydrogen atom or a methyl group, and M represents a hydrogen atom, an alkali metal atom, ammonium or an amine.)

Examples of the alkali metal atom include sodium atom, potassium atom, and amine include monoethanolamine, diethanolamine, triethanolamine and the like. When M is an alkali metal atom, ammonium or amine, -COOM forms a salt. To do.

As the monomer unit represented by the general formula (1), those in which R ¹ is a hydrogen atom, R ² is a hydrogen atom, and A is —NH— are preferable. The monomer unit represented by the following general formula (2) As the monomer unit, R ³ is preferably a hydrogen atom, and M is preferably a hydrogen atom or a sodium atom.

The ratio of the monomer unit represented by the general formula (1) is 70 to 95 mol% in the acrylic acid polymer (100 mol% of all monomer units), preferably 75 to 90 mol%. The proportion of the monomer unit represented by the formula (2) is 5 to 30 mol% in the acrylic acid polymer (in 100 mol% of all monomer units), and preferably 10 to 25 mol%. When the ratio of the monomer unit represented by the general formula (1) exceeds 95 mol%, the fingering becomes worse, the smoothness is lowered, and the ratio of the monomer unit represented by the general formula (2) If it is less than 5 mol%, it will become wrinkled.

The acrylic acid-based polymer can contain a monomer unit other than the monomer unit represented by the general formula (1) or (2) as long as the effects of the present invention are not impaired. Examples of other monomer units include nonionic monomers, amphoteric monomers, semipolar monomers, and cationic monomers other than the monomer units represented by the general formula (1) or (2). And monomer units corresponding to monomers and polysiloxane group-containing monomers. The proportion of monomer units other than the monomer unit represented by the general formula (1) or (2) is preferably 0 to 25 mol% in the acrylic acid polymer. The acrylic acid polymer of the present invention may be a random copolymer or a block copolymer, and the acrylic acid polymer of the present invention comprises monomer units represented by the general formulas (1) and (2). An acrylic acid polymer composed of a copolymer as a unit is preferred.

Examples of nonionic monomers include esters of alcohols having 1 to 22 carbon atoms and (meth) acrylic acid, amides of alkylamines having 1 to 22 carbon atoms and (meth) acrylic acid, ethylene glycol, 1 1,3-propylene glycol and the like (meth) acrylic acid monoesters, esters obtained by etherifying the hydroxyl groups of these monoesters with methanol, ethanol, etc., (meth) acryloylmorpholine, etc. Examples of the body include betaine group-containing (meth) acrylic esters, betaine group-containing (meth) acrylamides, etc., and examples of semipolar monomers include amine oxide group-containing (meth) acrylic esters and amine oxide groups (Meth) acrylamide and the like. Examples of the cationic monomer include a quaternary amine. Sulfonium group-containing (meth) acrylic esters, quaternary ammonium group-containing (meth) acrylamide and the like.

The polysiloxane group-containing monomer is a compound having a polysiloxane structure and a structure capable of being covalently linked to an acrylic acid polymer. Such a structural unit has a high affinity with the silicone oil usually used together in the cosmetic composition, and serves to bind the silicone oil with other structural units in the acrylic acid-based polymer. In particular, it is considered that there is a function to increase the adsorption power of silicone oil to damaged hair and the like.

In addition, the ratio of each monomer unit in the acrylic acid polymer is the carbonyl group, amide bond, IR absorption of polysiloxane structure and various functional groups, and the methyl group or amide bond site of polydimethylsiloxane and adjacent to them. It can be measured by ¹ H-NMR of a methyl group, methylene group or the like, or ¹³ C-NMR thereof.

The weight average molecular weight of the acrylic acid polymer is usually 3,000 to 100,000. If it is less than 3,000, the volume at the top of the head may be inferior, and if it exceeds 100,000, the hair and skin may be irritated. The weight average molecular weight is preferably 10,000 to 30,000, more preferably 10,000 to 20,000, and further preferably 12,000 to 17,000 from the viewpoint of further increasing the volume feeling and gloss at the top of the head. preferable.

The weight average molecular weight can be measured by gel permeation chromatography. Specifically, the device: manufactured by Tosoh Corporation, SC8010, SD8022, RI8020, CO8011, PS8010, column: Wakopaku (Wakobeads) G-50), developing solvent: water / methanol / acetic acid / sodium acetate = 6/4 / 0.3 / 0.41), and polyethylene glycol can be obtained as a standard substance.

The molecular weight of the acrylic acid polymer can be adjusted, for example, by controlling the degree of polymerization of the polymer. The molecular weight and viscosity can also be controlled by increasing or decreasing the addition amount of a crosslinking agent such as a polyfunctional acrylate. However, if a crosslinking agent is added as much as possible, the molecular weight and the viscosity are rapidly increased, and thus there are aspects that are difficult to control in industrial production. For this reason, it is preferable not to contain a crosslinking agent.

The acrylic acid-based polymer can be obtained in accordance with the method described in JP-A-2007-137830. For example, it can be obtained by mixing monomers that give respective structural units or precursors thereof and copolymerizing them by a method such as solution polymerization, suspension polymerization, emulsion polymerization or the like. In addition, the counter ion in the general formula (2) can be subjected to polymerization by substituting a part or all of it for other than hydrogen ion by a neutralization reaction before polymerization, and neutralized after polymerization or other reaction. A part or all of the reaction can be replaced with other than hydrogen ions. These can be appropriately selected depending on the ease of synthesis. The polymerization reaction is preferably performed in a hydrophilic solvent such as ethanol. As the polymerization initiator, a known polymerization initiator such as dimethyl 2,2'-azobis (2-methylpropionate) can be used. In addition, each monomer is mix | blended so that each monomer may become specific mole with respect to the total amount (100 mol%) of all the monomers. The proportion of the structural unit composed of each monomer in the copolymer of the present invention is the same as the blending amount of each monomer at the time of copolymerization.

The polymerization reaction is preferably performed in a hydrophilic solvent. Examples of hydrophilic solvents include ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, alcohol solvents such as methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, and sec-butanol, water, and the like Is mentioned. These may be used alone or in combination of two or more. Among these, it is preferable to use an alcohol solvent.

As polymerization initiators, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2,4-dimethyl) Valeronitrile), dimethyl-2,2′-azobisisobutyrate, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (1-cyclohexanecarbonitrile), 2,2 ′ -Azobis (2-methyl-N- (2-hydroxyethyl) -propionamide), 2,2'-azobis (2-amidinopropane) dihydrochloride, dimethyl 2,2'-azobis (2-methylpropionate) ), Etc., peroxides such as benzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, lauroyl peroxide, persulfates, or redo thereof Hex system or the like, can be used without particular limitation. The polymerization initiator is preferably used in the range of 0.01 to 5% by mass relative to the total monomers.

The polymerization reaction can be performed, for example, in an inert gas atmosphere such as nitrogen or argon, preferably at 30 to 120 ° C., more preferably at 40 to 100 ° C., usually for 1 to 30 hours. After completion of the polymerization, the produced copolymer may be isolated from the reaction solution by an appropriate means such as solvent distillation or addition of a poor solvent. This copolymer can be used as it is or after further purification, for example, in the production of cosmetics. Purification can be carried out by combining appropriate means such as reprecipitation, solvent washing, membrane separation and the like as necessary.

(A) The blending amount of the acrylic acid polymer is preferably 0.05 to 2.0% by mass, more preferably 0.1 to 1.0% by mass in the hair cosmetic. If the blending amount is less than 0.05% by mass, the effect of the present invention may be insufficient. If it exceeds 2.0% by mass, stickiness may occur and the volume may decrease.

(B) Nonionic polymer Nonionic polymers include homopolymers obtained by homopolymerization of the following nonionic monomers, copolymers (copolymers) obtained by copolymerizing a plurality of types, water-soluble polysaccharides (cellulose-based, gum-based). And non-ionic polymers such as starch-based polymers, and the like, can be used singly or in appropriate combination of two or more.

Nonionic monomers include vinyl pyrrolidone, vinyl acetate, (meth) acrylic acid and alcohols having 1 to 22 carbon atoms, polyhydric alcohols, or hydroxy group-containing alkyl groups, (meth) acrylamides and amines thereof. Amide, dialkyl (1 to 22 carbon atoms) aminoethyl (meth) acrylate, vinylimidazole, vinylcaprolactam, polyalkylene (carbon number) in which the hydrogen atom is substituted with an alkyl group having 1 to 22 carbon atoms or a hydroxy group-containing alkyl. 2-3) glycol and the like. In the present invention, (meth) acrylic acid refers to acrylic acid and / or methacrylic acid.

As the nonionic polymer, a vinylpyrrolidone polymer and a cellulose polymer are preferable. In the present invention, the vinyl pyrrolidone-based polymer refers to polyvinyl pyrrolidone which is a homopolymer of vinyl pyrrolidone, or a copolymer (copolymer) of vinyl pyrrolidone and another nonionic monomer.

As the polyvinylpyrrolidone, those having a K value of 10 to 100 are preferable. Specific examples thereof include Rubiscol K17, 30, 90 / BASF, polyvinylpyrrolidone K-30, 85, 90, 30W, 85W / manufactured by Nippon Shokubai. It is done. If the K value is less than 10, the effect may be insufficient, and if it exceeds 100, the handling property may be deteriorated.

The K value is a viscosity characteristic value that correlates with the molecular weight, and is calculated by applying a relative viscosity value (25 ° C.) measured by a capillary viscometer to the following Fikentscher equation.
K = (1.5logη _rel −1) / (0.15 + 0.003c) + (300 clogη _rel + (c + 1.5 clogη _rel ) ² ) ^1/2 /(0.15c+0.003c ² )
η _rel : relative viscosity of polyvinyl pyrrolidone aqueous solution with respect to water c: concentration of polyvinyl pyrrolidone in aqueous polyvinyl pyrrolidone solution

As a copolymer (copolymer) of vinyl pyrrolidone and other nonionic monomer, vinyl pyrrolidone / vinyl acetate copolymer (specifically, PVP / VA W-735, S-630, E-535 / ISP, Rubiscol VA55I, VA73E / BASF), vinylpyrrolidone / dimethylaminoethyl methacrylate copolymer (copolymers 845, 937, 958 / ISP), N-vinylpyrrolidone / methacrylamide / N-vinylimidazole copolymer (Rubiset Clear BASF) and the like, and particularly preferred among these is a vinylpyrrolidone / vinyl acetate copolymer, and the molar ratio represented by vinylpyrrolidone VP (mol) / vinyl acetate VA (mol) is VP (mol) / VA (mol) = 50/50 to 99/1 Preferably, more preferably in the range of 60 / 40-99 / 1. This ratio is within the range where the copolymer is completely water-soluble (1 g of this product is added to 1000 mL of water and completely dissolved when left for 30 minutes after infiltration (measurement temperature 25 ° C.). According to the above). Further, 60/40 to 80/20 is preferable from the viewpoint of the effect of giving firmness and firmness. Specific examples that fall within this range include PVP / VA W-735, manufactured by S-630 / ISP, manufactured by Rubiscor VA73E / BASF, and the like. The molar ratio of vinylpyrrolidone (VP) and vinyl acetate (VA) can be determined, for example, by dissolving the copolymer in deuterium and measuring ¹ H-NMR.

Examples of the cellulose polymer include hydroxyethyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl methyl cellulose and the like. When the viscosity of a 2% by weight aqueous solution is 1,000 to 50,000 mPa · s, and when it is difficult to prepare a 2% by weight uniform solution, a 1% by weight aqueous solution is obtained. Those of ˜6,000 mPa · s are preferred. Specifically, hydroxyethylcellulose (Sumitomo Seika HEC SY-25F, SW-25F, SZ-25Y / manufactured by Sumitomo Seika), (Cellosize QP-4400, QP-15000, QP-52000) satisfying the above conditions. / Dow Chemical), hydroxypropyl methylcellulose (Metroise 60SH-4000, 65SH-15000, 90SH-30000 / Shin-Etsu Chemical Co., Ltd.), hydroxyethyl methylcellulose (Metroses SEB-15000, SNB-30000 / Shin-Etsu Chemical Co., Ltd.), etc. It is done. If the viscosity of the 2% by weight aqueous solution is less than 1,000 mPa · s or the viscosity of the 1% by weight aqueous solution is less than 100 mPa · s, the effect of the present invention may be insufficient, and the viscosity of the 2% by weight aqueous solution may be 50,000 mPa · s. If the viscosity of s or a 1% by mass aqueous solution exceeds 6,000 mPa · s, there is a risk of wrinkling. In addition, the said viscosity is BM type | mold viscosity meter, No. 3 rotor or no. It is a value measured under the conditions of 4 rotors, 30, 12 or 6 rpm, 60 seconds, and 25 ° C.

The weight average molecular weight of the nonionic polymer is not particularly limited, but is preferably 10,000 to 1,000,000, more preferably 10,000 to 500,000. The weight average molecular weight can be determined by a light scattering method.

The compounding amount of the nonionic polymer is preferably 0.05 to 2.0% by mass, more preferably 0.1 to 1.0% by mass in the hair cosmetic. If the blending amount is less than 0.05% by mass, the effect of increasing the volume may be insufficient.

The mass ratio of the component (A) and the component (B) represented by (A) / (B) is 0.1 to 10.0, preferably 0.5 to 7.0, 0.8 to 4.0 is more preferable. By setting the mass ratio of the component (A) and the component (B) to 0.1 to 10.0, it is possible to impart a volume feeling at the top of the head and a gloss of the hair. If it is less than 0.1, the effect is insufficient, and if it exceeds 10.0, the volume feeling and gloss may be deteriorated.

(C) Cationic surfactants Cationic surfactants include aliphatic amines and their quaternary ammonium salts, fatty acid amide amine salts, alkyltrialkylene glycol ammonium salts, acylguanidine derivatives, mono-N-long chain acyl basics. Amino acid-based cationic surfactants such as amino acid lower alkyl ester salts, alkylbenzalkonium salts, alkylpyridinium salts, imidazolinium salts and the like can be mentioned, and these can be used singly or in appropriate combination of two or more. . Among them, quaternary ammonium salts of aliphatic amines are preferable, and quaternary ammonium salts having 18 to 22 carbon atoms are more preferable. Specific examples include behenyltrimethylammonium chloride and stearyltrimethylammonium chloride.

The blending amount of the component (C) is preferably 0.1 to 5.0% by mass in the hair cosmetic, and more preferably 0.2 to 2.0% by mass in terms of improving the smoothness of the hair. If the blending amount is less than 0.1% by mass, the conditioning effect may be insufficient, and if it exceeds 5.0% by mass, the stability of the preparation may be adversely affected.

The hair cosmetic composition of the present invention can be blended with various additive components commonly used in general hair cosmetic compositions as long as the effects of the present invention are not impaired. These can be used individually by 1 type or in combination of 2 or more types. Examples of the additive component include silicones such as dimethylpolysiloxane and amino-modified silicone, anionic surfactants such as alkyl sulfate ester salts and sodium polyoxyethylene alkyl ether sulfate, coconut oil fatty acid amidopropyl betaine, lauryldimethylaminoacetic acid Amphoteric surfactants such as betaine, hydrogenated soybean phospholipid, alkyldiaminoethylglycine hydrochloride, sodium laurylaminopropionate, sucrose fatty acid ester, sorbitan fatty acid ester, sorbitol fatty acid ester, glycerin fatty acid ester, polyglycerin fatty acid ester, polyoxy Nonionic surfactants such as ethylene hydrogenated castor oil, polyoxyethylene alkyl ether, olive squalane, rice germ oil, rice bran oil, camellia oil, marmond oil, water Fats and waxes such as jojoba oil, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, pantothenic acid, gallic acid-3,5-diglucoside, gallic acid-3,4-diglucoside, methyl gallate-3 , 5-diglucoside, edetic acid, hyaluronic acid, amino acids, pyrrolidone carboxylic acid and other organic acids and salts thereof, ethylene glycol, propylene glycol, butylene glycol, glycerin and copolymers thereof, sorbitol, glucose, sucrose, pullulan, etc. Polyhydric alcohol, hydrocarbons, ester oils, higher alcohols such as stearyl alcohol, herbal medicines, various protein hydrolysates, vitamins, bactericides, ultraviolet absorbers, antioxidants, colorants, pH buffering agents, fragrances, A solvent (water, ethanol, etc.), fine particle powder, etc. are mentioned. These additive components can be used singly or in appropriate combination of two or more, and can be blended at an appropriate stage when preparing a hair cosmetic.

The pH of the hair cosmetic composition of the present invention is preferably 3-6. This pH is close to the pH of the hair and is difficult to damage the hair. Examples of the pH adjuster include inorganic acid salts such as sodium pyrophosphate, and organic acids such as glycolic acid and citric acid. In the present invention, pH is measured with a HM-30G pH meter manufactured by Toa DKK Corporation at a measurement temperature of 25 ° C.

The viscosity (25 ° C.) of the hair cosmetic composition of the present invention is preferably 1,000 to 20,000 mPa · s, more preferably 3,000 to 10,000 mPa · s. By setting it as this range, it is difficult to use and easy to extend. In the present invention, the viscosity is measured (25 ° C.) using a BM type viscometer manufactured by TOKIMEC. 4 rotors, 30 rpm, 20 seconds later.

The hair cosmetic composition of the present invention can be widely used in many dosage forms such as liquid, cream, foam, spray, gel, etc., and is a conditioner, treatment, hair color, non-washing type treatment, hair serum. Suitable for hair packs and the like. The hair cosmetic composition of the present invention can be prepared based on a conventional method of dosage form, and can be appropriately filled in a container.

Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In the following examples, unless otherwise specified, “%” in the composition indicates mass%, the ratio indicates the mass ratio, and the amount of each component in the table is an amount converted into a pure component.

[Preparation Example 1]
A-1
A reactor equipped with a reflux condenser, a dropping funnel, a thermometer, a nitrogen gas inlet tube and a stirrer was charged with 100 parts by mass of ethanol, and 88.6 parts by mass of 2-hydroxyethylacrylamide and 11.4 parts by mass of acrylic acid were added to the dropping funnel. A monomer mixed solution consisting of 80 parts by mass of ethanol and 80 parts by mass of ethanol was charged, the reactor was purged with nitrogen, and then heated to 80 ° C. Into the reactor, 1 part by weight of dimethyl 2,2′-azobis (2-methylpropionate) (V-601; manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the monomer mixture was added over 2 hours. It was dripped. After the completion of the dropwise addition, the mixture was reacted for 6 hours, cooled, and neutralized with sodium hydroxide to obtain polymer A-1.

[Preparation Example 2]
A-2
A reactor equipped with a reflux condenser, a dropping funnel, a thermometer, a nitrogen gas inlet tube and a stirrer was charged with 100 parts by mass of ethanol, 82.5 parts by mass of 2,3-dihydroxypropylacrylamide, and acrylic acid 17. A monomer mixture consisting of 5 parts by mass and 80 parts by mass of ethanol was charged, and the reactor was purged with nitrogen, and then heated to 80 ° C. Into the reactor, 1 part by weight of dimethyl 2,2′-azobis (2-methylpropionate) (V-601; manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the monomer mixture was added over 2 hours. It was dripped. After reacting for 6 hours after completion of the dropwise addition, the mixture was cooled, and sodium hydroxide corresponding to half of the molar ratio of acrylic acid was added to neutralize to obtain polymer A-2.

[Preparation Example 3]
A-3
A reactor equipped with a reflux condenser, a dropping funnel, a thermometer, a nitrogen gas inlet tube and a stirrer was charged with 100 parts by mass of ethanol, and 97.5 parts by mass of 2,3-dihydroxypropyl acrylamide, acrylic acid 2. A monomer mixture consisting of 5 parts by mass and 80 parts by mass of ethanol was charged, and the reactor was purged with nitrogen, and then heated to 80 ° C. Into the reactor, 1 part by weight of dimethyl 2,2′-azobis (2-methylpropionate) (V-601; manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the monomer mixture was added over 2 hours. It was dripped. After reacting for 6 hours after completion of the dropwise addition, the mixture was cooled, and sodium hydroxide corresponding to half the molar ratio of acrylic acid was added to neutralize to obtain polymer A-3.

[Preparation Example 4]
A-4
Polymer A-4 was obtained in the same manner as in Preparation Example 1 except that the blending amount was adjusted so as to be the structural unit shown in Table 1 below.

[Preparation Example 5]
A-5
Polymer A-5 was obtained in the same manner as in Preparation Example 1 except that the blending amount was adjusted so as to be the structural unit shown in Table 1 below.

[Preparation Example 6]
A'-6
Polymer A′-6 was obtained in the same manner as in Preparation Example 1 except that the blending amount was adjusted so as to be the structural unit shown in Table 1 below.

Table 1 shows the functional groups of the general formula (1) or (2) of the polymers A-1 to A′-6, the ratio (molar ratio) of the monomer units of the general formula (1) or (2), and the weight average molecular weight. Show. The weight average molecular weight is as follows: apparatus: manufactured by Tosoh Corporation, SC8010, SD8022, RI8020, CO8011, PS8010, column: Wako Pure Chemical Industries, Ltd., Wakopak (Wakobeads G-50), developing solvent: water / methanol / acetic acid / acetic acid. Sodium = 6/4 / 0.3 / 0.41) was used to obtain polyethylene glycol as a standard substance.

What was used by (B) component is shown below.

[Examples 1 to 21, Comparative Examples 1 to 5]
Non-washing type hair conditioners having the compositions shown in Tables 3 to 6 were prepared by the following method. The following evaluation was performed about the obtained hair conditioner. The results are also shown in the table.

[Preparation method]
(A) Acrylic acid-based polymer and (B) nonionic polymer were previously made into small aqueous solutions, and all other components were mixed and dissolved at room temperature. The small article and amino-modified silicone emulsion were added to this and stirred until uniform.

[Evaluation (Volume, gloss, smoothness of hair on top of head)]
Thirty 40 to 60 year old women who are worried that there is no elasticity or hair in their hair and that there is no volume at the top of their heads use a conditioner composition that does not wash away for 7 days. Normal product), “volume of hair on top of head” and “gloss” were evaluated. Regarding the compositions of Examples 16 to 21 containing the component (C) cationic surfactant, in addition to “volume of hair at the top of the head” and “luster”, “smoothness of hair” was also evaluated. It was. Results are shown based on the following evaluation criteria, depending on the number of respondents who answered good.
<Evaluation criteria>
◎: More than 25 out of 30 respondents: ○: 15-24 out of 30 respondents: △; 5-14 out of 30 respondents: Excellent; Less than 5

[Examples 22 to 43, Comparative Examples 6 to 10]
Wash-out type hair conditioners having the compositions shown in Tables 7 to 10 were prepared by the following method. The following evaluation was performed about the obtained hair conditioner. The results are also shown in the table.

[Preparation method]
In a hot water bath at 80 ° C, (A) acrylic acid polymer, polyoxyethylene (40) hydrogenated castor oil, (C) cationic surfactant, stearyl alcohol are mixed and dissolved, and sorbite and purified water are added for phase inversion. Emulsified. It cooled to 50 degreeC, stirring, (B) After adding a nonionic polymer and an amino modified silicone emulsion, it cooled to room temperature, stirring further.

[Evaluation (Volume, gloss, smoothness of hair on top of head)]
30 women aged 40 to 60 years who are worried that there is no elasticity or hair in their hair, and that there is no volume at the top of their heads, used a conditioner composition that washes away for 7 days (shampoo made by Lion Co., Ltd.) "Plant story herb blend refreshing smooth type" was used, and "volume of hair on top of head" and "luster" were evaluated. Regarding the compositions containing the component (C) cationic surfactant in Examples 38 to 43, in addition to “volume of hair on the top of the head” and “luster”, “smoothness of hair” was also evaluated. It was. Results are shown based on the following evaluation criteria, depending on the number of respondents who answered good.
<Evaluation criteria>
◎: More than 25 out of 30 respondents: ○: 15-24 out of 30 respondents: △; 5-14 out of 30 respondents: Excellent; Less than 5

Evaluation results “Volume of hair on top of head”: ◎
“Glossy”: ◎
"Smoothness of hair": ◎

Evaluation results “Volume of hair on top of head”: ◎
“Glossy”: ○
"Smoothness of hair": ◎

Evaluation result “Volume of hair on top of head” ○
“Glossy” ◎
“Smoothness of hair” ◎

The raw materials used in preparing the examples and comparative examples are shown below.

The fragrance compositions A, B, and C used in the above examples conform to the fragrance compositions A to C described in JP-A-2003-95895.

Claims

A hair cosmetic comprising the following (A) acrylic acid polymer and (B) nonionic polymer, wherein the mass ratio represented by (A) / (B) is 0.1 to 10.0 .
(A) As a constituent unit, 70 to 95 mol% of a monomer unit represented by the following general formula (1) and 5 to 30 mol% of a monomer unit represented by the following general formula (2) are included. Acrylic acid polymer

(Wherein R 1 represents a hydrogen atom or a methyl group, R 2 represents a hydrogen atom or a —CH 2 OH group, and A represents an oxygen atom or —NH—).

(In the formula, R 3 represents a hydrogen atom or a methyl group, and M represents a hydrogen atom, an alkali metal atom, ammonium or an amine.)
The hair cosmetic according to claim 1, wherein the component (B) is a vinylpyrrolidone polymer or a cellulose polymer.
The hair cosmetic according to claim 1 or 2, further comprising (C) a cationic surfactant.