JPWO2010041530A1 - Hair cosmetics - Google Patents

Abstract

（式中、Ｒ¹は水素原子又はメチル基、Ｒ²は水素原子又は−ＣＨ₂ＯＨ基、Ａは酸素原子又は−ＮＨ−、Ｒ³は水素原子又はメチル基を示し、Ｍは水素原子、アルカリ金属原子、アンモニウム又はアミンを示す。）(A) 0.1-2% by mass of acrylic acid polymer, (B) 0.1-3% by mass of nonionic surfactant of HLB 14-18, (C) 0.5-5% by mass of cationic surfactant And (D) 0.5 to 10% by mass of a linear saturated aliphatic alcohol, and the mass ratio represented by (A) / (B) is 0.05 to 18.00. Fee.
(A) Acrylic acid polymer containing 70 to 95 mol% of monomer units represented by general formula (1) and 5 to 30 mol% of monomer units represented by general formula (2)

(Wherein R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom or a —CH ₂ OH group, A represents an oxygen atom or —NH—, R ³ represents a hydrogen atom or a methyl group, M represents a hydrogen atom, (Indicates an alkali metal atom, ammonium or amine.)

Description

  The present invention relates to a hair cosmetic composition that imparts smoothness of hair and smoothness of hair.

  A conditioning polymer is mentioned as one of the hair cosmetics (patent document 1: Unexamined-Japanese-Patent No. 2007-137830) developed corresponding to damaged hair. This polymer exhibits not only a hair repair effect but also an effect of imparting gloss and smoothness to the hair. However, this anionic polymer and a cationic component, which is an indispensable system for current conditioners, form a complex, and due to the decrease in viscosity, the elongation at the time of coating is poor and the storage stability is poor. is there. For this reason, there has been a demand for a technique for solving the above problems while maintaining the hair repairing action (the roughness of the hair and the smoothness of the hair).

JP 2007-137830 A JP 2007-161986

  The present invention has been made in view of the above circumstances, and while maintaining the hair repairing action (hairiness and smoothness of hair), even when an acrylic polymer and a cationic component are used in combination, An object of the present invention is to provide a hair cosmetic that has good elongation and good storage stability.

  As a result of intensive studies to achieve the above object, the present inventor, in hair cosmetics containing a specific (A) acrylic acid polymer and (C) a cationic surfactant, (A) and (B) components In addition, (B) HLB14-18 nonionic surfactant and (D) linear saturated aliphatic alcohol are blended in specific amounts, respectively, and (A) component represented by (A) / (B) and (B) By making the mass ratio with the component 0.05-18.00, the acrylic polymer and the cationic component are used in combination while maintaining the hair repairing action (the lack of hairiness and smoothness of the hair). However, the present inventors have found that hair cosmetics with good agent elongation and good storage stability can be provided, and have made the present invention.

（式中、Ｒ¹は水素原子又はメチル基を示し、Ｒ²は水素原子又は−ＣＨ₂ＯＨ基を示し、Ａは酸素原子又は−ＮＨ−を示す。）

（式中、Ｒ³は水素原子又はメチル基を示し、Ｍは水素原子、アルカリ金属原子、アンモニウム又はアミンを示す。）
[２]．（Ｂ）成分が、モノ脂肪酸ポリエチレングリコール（エチレンオキシド平均付加モル数：１２〜１５０）又はポリオキシエチレン硬化ヒマシ油（エチレンオキシド平均付加モル数：６０〜１００）である[１]記載の毛髪化粧料。Accordingly, the present invention provides the following hair cosmetics.
[1]. The following (A) 0.1-2 mass% of acrylic acid polymer, (B) 0.1-3 mass% of nonionic surfactant of HLB 14-18, (C) 0.5-5 mass of cationic surfactant %, And (D) 0.5 to 10% by mass of a linear saturated aliphatic alcohol, and the mass ratio of the component (A) and the component (B) represented by (A) / (B) is 0.05. Hair cosmetic characterized by ˜18.00.
(A) 70-95 mol% of monomer units represented by the following general formula (1) and 5-30 mol% of monomer units represented by the following general formula (2) are included as structural units. Acrylic acid polymer

(In the formula, 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]. The hair cosmetic composition according to [1], wherein the component (B) is mono fatty acid polyethylene glycol (average number of added moles of ethylene oxide: 12 to 150) or polyoxyethylene hydrogenated castor oil (average number of added moles of ethylene oxide: 60 to 100).

  According to the present invention, even when an acrylic acid polymer and a cationic component are used in combination while maintaining the hair repairing action (the smoothness of the hair and the smoothness of the hair), the agent has good elongation and the storage stability. Can provide a good hair cosmetic.

Hereinafter, the present invention will be described in detail.
The hair cosmetic composition of the present invention comprises (A) 0.1-2% by mass of an acrylic acid polymer, (B) 0.1-3% by mass of a nonionic surfactant of HLB 14-18, and (C) a cationic surfactant. (A) component and (B) component represented by (A) / (B) including 0.5 to 5% by mass of the agent and (D) 0.5 to 10% by mass of the linear saturated aliphatic alcohol Is a hair cosmetic having a mass ratio of 0.05 to 18.00.

(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.

（式中、Ｒ¹は水素原子又はメチル基を示し、Ｒ²は水素原子又は−ＣＨ₂ＯＨ基を示し、Ａは酸素原子又は−ＮＨ−を示す。）

（式中、Ｒ³は水素原子又はメチル基を示し、Ｍは水素原子、アルカリ金属原子、アンモニウム又はアミンを示す。）

(In the formula, 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.)

  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, and the monomer unit represented by the following general formula (2) is preferable. As the monomer unit, R ³ is preferably a hydrogen atom, and M is preferably a hydrogen atom and / 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 (in 100 mol% of all monomer units), preferably 75 to 90 mol%, The ratio 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 smoothness of the hair decreases, such as poor fingering. When the proportion is less than 70 mol%, the fingering becomes poor. Etc., the smoothness of the hair is lowered and the storage stability is also deteriorated.

  As long as the effects of the present invention are not impaired, the acrylic acid-based polymer can contain monomer units other than the monomer unit represented by the general formula (1) or (2). 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. As for the ratio of monomer units other than the monomer unit represented by General formula (1) or (2), 0-25 mol% in an acrylic acid polymer is preferable. 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 comprising 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 , 3-propylene glycol, etc. and (meth) acrylic acid monoesters, esters in which the monoester's hydroxyl group is etherified 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, and examples of the cationic monomer include quaternary ammonia. Um 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 such as methyl group and methylene group, or ¹³ C-NMR thereof.

  The weight average molecular weight of the acrylic acid polymer is preferably 3,000 to 100,000. If it is less than 3,000, there is a fear that the hair is not smooth, the smoothness of the hair and the conditioning effect are weak, and if it exceeds 100,000, the ease of elongation of the agent may deteriorate. It is more preferably 10,000 to 30,000, more preferably 10,000 to 20,000, and more preferably 12,000 to 17 in order to increase the roughness of the hair, the ease of elongation of the agent and the smoothness of the hair. Is more preferred.

  The weight average molecular weight can be measured by gel permeation chromatography. Specifically, 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 / sodium acetate = 6/4 / 0.3 / 0.41 (volume ratio)), 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 polymer can be obtained in accordance with the method described in JP-A-2007-161986. 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 carried out in a hydrophilic solvent such as ethanol, and a known polymerization initiator such as dimethyl 2,2'-azobis (2-methylpropionate) can be used as the polymerization initiator. 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 the hydrophilic solvent 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) ), Benzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, lauroyl peroxide, etc., persulfate, or redox thereof. Scan system and the like, can be used without particular limitation. The polymerization initiator is preferably used in the range of 0.01 to 5% by mass with respect to all monomers.

  The polymerization reaction can be performed, for example, under 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.

  Content of the (A) component in hair cosmetics is 0.1-2 mass%, and 0.2-1.5 mass% is preferable. If the amount is less than 0.1% by mass, the effects of the lack of hairiness, the smoothness of the hair, and the ease of elongation of the agent are difficult to obtain, and if it exceeds 2% by mass, the smoothness of the hair is deteriorated.

(B) Nonionic surfactant of HLB14-18 The nonionic surfactant of this invention uses HLB14-18, Preferably the thing of 15-18 is used. With a nonionic surfactant having an HLB of less than 14, the smoothness of the hair is deteriorated and the effect of improving the storage stability cannot be exhibited. The HLB value is a value indicating the balance between the strength of the hydrophilic group and the hydrophobic group constituting the surfactant, and is calculated according to the following Kawakami's equation. In the present invention, HLB is a value obtained by rounding off the first decimal point.
HLB value = 7 + 11.7 log (M _W / M _O )
M _W : Molecular weight of hydrophilic part of surfactant M _O : Molecular weight of surfactant lipophilic part The above HLB means a weighted average value when two or more kinds of nonionic surfactants are used in combination. If the weighted average value is in the range of 14-18, the HLB of each nonionic surfactant may not be 14-18, but it is preferable to include a nonionic surfactant of HLB14-18 in one type. Note that the weighted average HLB value is a value obtained by multiplying the HLB value of the nonionic surfactant by the used weight of the nonionic surfactant for all the nonionic surfactants. It means a value obtained by dividing the sum by the total used mass of all nonionic surfactants.

  Nonionic surfactants of HLB14-18 include polyoxyethylene glycerin fatty acid ester, polyglycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbit sorbitan fatty acid ester, polyoxyethylene castor oil, polyoxyethylene hardened Castor oil (average number of moles of added ethylene oxide: 60 to 100), ethylene glycol fatty acid ester, polyethylene glycol fatty acid ester such as mono-fatty acid polyethylene glycol (average number of added moles of ethylene oxide: 12 to 150), alkyl glyceryl ether, polyoxyethylene alkyl ether And polyoxyethylene alkyl ether fatty acid esters. These can be used individually by 1 type or in combination of 2 or more types.

  Specifically, as HLB14, polyethylene glycol monolaurate (12EO), polyethylene glycol monostearate (20EO), tetraoleic acid POE (60) sorbit, POE (60) hydrogenated castor oil, decaglyceryl monomyristate, POE (25) Stearyl ether and the like. As HLB15, polyethylene glycol stearate (30EO), POE (80) hydrogenated castor oil, POE (100) hydrogenated castor oil, monoisostearic acid POE (20) sorbitan, monooleic acid POE (20) sorbitan, POE (25) Examples include isocetyl ether, POE (20) lauryl ether, POE (30) stearyl ether, and polyoxyethylene glyceryl isostearate (30EO). Examples of HLB 16 include polyethylene glycol monostearate (40 EO), POE (15) oleyl ether, POE (40) stearyl ether, polyoxyethylene glyceryl isostearate (50 EO), and the like. Examples of HLB18 include polyethylene glycol monostearate (150EO). Among them, a nonionic surfactant of HLB15 or higher is preferable, and polyethylene glycol monostearate (150EO) of HLB18 is more preferable in terms of exhibiting effects on smoothness of hair and storage stability. Note that EO is an abbreviation for ethylene oxide, and POE is an abbreviation for polyoxyethylene.

  Content of (B) component in hair cosmetics is 0.1-3 mass%, and 0.3-1 mass% is preferable. If it is less than 0.1% by mass, the storage stability will be poor, and if it exceeds 3% by mass, the hair will not be crisp and the hair will not be smooth, making it difficult to dissolve in other ingredients and making it difficult to blend. .

  Moreover, mass ratio of (A) component represented by (A) / (B) and (B) component is 0.05-18.00, and 0.60-5.00 are preferable. When the mass ratio is less than 0.05, the smoothness of the hair is deteriorated, and when it exceeds 18.00, the storage stability, the ease of extending the agent, and the smoothness of the hair are adversely affected. The above ratio is rounded off to the third decimal place.

(C) Cationic surfactants Cationic surfactants include aliphatic amine salts such as behenamidopropyldimethylamine and quaternary ammonium salts thereof, fatty acid amidoamine salts such as dimethylaminopropylamide stearate, and alkyltrialkylenes. Amino acid cationic surfactants such as glycol ammonium salts, acylguanidine derivatives, mono-N-long chain acyl basic amino acid lower alkyl ester salts, alkylbenzalkonium salts, alkylpyridinium salts, imidazolinium salts, etc. 1 type can be used individually or in combination of 2 or more types as appropriate. 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 (Arcard T-800; Lion Corporation).

  Content of (C) component in hair cosmetics is 0.5-5 mass%, and 1-3 mass% is preferable. When the content is less than 0.5% by mass, the agent is easily stretched and the smoothness of the hair is deteriorated. When the content is more than 5% by mass, the hair becomes brittle and the storage stability is adversely affected.

(D) Linear saturated aliphatic alcohol As the linear saturated aliphatic alcohol, those having an alkyl group of 12 to 24 carbon atoms can be used, and those having 16 to 22 carbon atoms are preferred. Specific examples include cetyl alcohol, stearyl alcohol, cetostearyl alcohol, and behenyl alcohol. Among them, cetyl alcohol and stearyl alcohol are preferable.

  Content of (D) component in hair cosmetics is 0.5-10 mass%, and 2-6 mass% is preferable. When the content is less than 0.5% by mass, the agent is easily stretched and the smoothness of the hair is deteriorated. When the content exceeds 10% by mass, the smoothness of the hair and the storage stability are adversely affected.

  In addition to the above-described components, the hair cosmetic of the present invention can be blended as desired with various additive components that are widely used in hair cosmetics as long as the effects of the present invention are not impaired. Examples of these additional components include silicone compounds such as dimethylpolysiloxane and amino-modified silicone, anionic surfactants such as alkyl sulfate ester salts, sodium polyoxyethylene alkyl ether sulfate, coconut oil fatty acid amidopropyl betaine, and lauryl dimethyl. Betaine amphoteric surfactants such as betaine aminoacetate, hydrogenated soybean phospholipids, amphoteric surfactants such as alkyldiaminoethylglycine hydrochloride, sodium laurylaminopropionate, rice germ oil, rice bran oil, camellia oil, marmond oil, water Fats and waxes such as added 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-digluco , Edetic acid, hyaluronic acid, amino acids, lactic acid, malic acid, pyrrolidone carboxylic acid, glycolic acid and other organic acids and their salts, ethylene glycol, propylene glycol, glycerin, polyethylene glycol, dipropylene glycol and other polyhydric alcohols, erythritol , Sugar alcohols such as sorbitol, hydrocarbons such as liquid paraffin and squalane, ester oil, anionic polymers excluding component (A), cationic polymers such as cationized cellulose and cationized guar gum, polyvinylpyrrolidone, PVP / VA (vinyl) Nonionic polymers such as pyrrolidone / vinyl acetate copolymer, amphoteric polymers, cellulose compounds such as hydroxyethyl cellulose, herbal medicines, plant extracts, various protein hydrolysates, vitamins, fungicides, UV absorbers, Antioxidant, coloring agents, pH buffering agents, perfumes, solvents (such as ethanol), fine particles, and the like. 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 composition.

  The hair cosmetic composition of the present invention can be prepared based on a conventional method by mixing the above-mentioned essential and optional components and water residue as necessary. Examples of the hair cosmetic of the present invention include shampoo, rinse, conditioner, treatment, styling agent and the like. There are types of rinses, conditioners, and treatments that wash away after application, and types that do not wash away. Among these, a rinse, a conditioner, and a treatment are preferable, and a rinse type is particularly preferable.

  EXAMPLES 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 reactor equipped with a reflux condenser, a dropping funnel, a thermometer, a nitrogen gas inlet tube and a stirring device 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 mass 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 the completion of the dropping, the mixture was cooled and neutralized with sodium hydroxide to obtain an acrylic acid polymer (A-1). 2-hydroxyethylacrylamide / sodium acrylate = 83 mol% / 17 mol%

[Preparation Example 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, and 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 mass 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 neutralized with sodium hydroxide corresponding to half of the molar ratio of acrylic acid to obtain an acrylic acid polymer (A-2). 2,3-dihydroxypropylacrylamide / acrylic acid (sodium) = 70 mol% / 30 mol%

[Preparation Example 3]
A reactor equipped with a reflux condenser, a dropping funnel, a thermometer, a nitrogen gas inlet tube and a stirring device was charged with 100 parts by mass of ethanol, and 97.5 parts by mass of 2,3-dihydroxypropylacrylamide was added to the dropping funnel. 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 mass 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 neutralized with sodium hydroxide corresponding to half of the molar ratio of acrylic acid to obtain an acrylic acid polymer (A-3). 2,3-dihydroxypropylacrylamide / acrylic acid (sodium) = 95 mol% / 5 mol%

[Preparation Example 4]
An acrylic acid 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]
An acrylic acid 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.

[Comparative Preparation Example 6]
An acrylic acid 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.

  The functional group of the general formula (1) or (2) of the acrylic acid polymer (A-1 to A-5, A′-6), the ratio of the monomer units of the general formula (1) or (2) (molar ratio) ), And weight average molecular weight are shown in Table 1. 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 (volume ratio)) was used to obtain polyethylene glycol as a standard substance.

[Examples 1 to 29, Comparative Examples 1 to 12]
[Preparation method]
In accordance with the compositions shown in Tables 2 to 9, rinse-type hair conditioners were prepared by the following method. Specifically, the oil component is dissolved and mixed, and polyols (polyhydric alcohol or sugar alcohol) are added and mixed to form a gel liquid crystal and make it uniform. (A) Acrylic acid polymer is added to the gel liquid crystal, and further mixed uniformly. Thereafter, an aqueous phase in which an organic acid and a water-soluble component were dissolved was added to carry out phase inversion emulsification. The mixture was further cooled to room temperature with stirring. The pH was adjusted to 3.7 with sodium hydroxide.
In addition, pH and a viscosity measuring method are as showing below, and the following evaluation was performed about the obtained hair conditioner.
Measurement conditions pH: pH meter; HM-30G manufactured by Toa DKK Corporation, measurement temperature: 25 ° C
Viscosity: Viscometer; BM viscometer No. manufactured by TOKIMEC 4 rotors 30rpm 20 seconds later, measured temperature; 25 ° C

[Evaluation methods]
(1) “Hardness of hair”, “Smoothness of hair”, “Ease of agent growth”
Thirty women aged 50 to 60 who have been dyed gray hair within the last two months and feel hairiness and damage used the conditioner composition of each wash type for 7 days (Shampoo is Lion Corporation " Plant Story Herb Blend Refreshing Smooth Type ”). Evaluation was made on the items of “the lack of hairiness”, “the smoothness of the hair”, and “the ease of elongation of the agent”. The results are shown based on the following criteria, according to the number of people who answered good.
<Evaluation criteria>
◎: 25 or more out of 30 respondents: ○: 15-24 out of 30 respondents △: 5-14 out of 30 respondents: X: Good Less than 5

(2) Storage stability A 50 ml PET (polyethylene terephthalate) vial was filled with a rinse-type hair conditioner, stored for 6 months in a constant temperature bath at 40 ° C., and evaluated based on the following evaluation criteria. .
<Evaluation criteria>
◎: No separation or precipitation is observed ○: Slight separation or precipitation is observed, but there is no problem in commercial value ×: The two layers are completely separated

  According to the manufacturing method mentioned above, the following hair conditioners and hair treatment preparations were prepared. All of these hair cosmetics were excellent in hairiness, smoothness of hair, ease of extension of the agent, and storage stability.

[Example 30] Hair conditioner composition%
Alkyltrimethylammonium chloride 1.5
Stearyl alcohol 3.8
Glycolic acid 0.3
Sorbitol 10.0
Propylene glycol 8.0
Acrylic acid polymer (A-1) 0.6
Polyethylene glycol monostearate (150EO) (HLB18)
0.3
Hydroxyethyl cellulose 0.3
Dimethyl silicone 1.0
Highly polymerized amino-modified silicone 2.0
Polyoxyethylene / methylpolysiloxane copolymer 0.2
Bentonite 0.2
Hydroxypropyl methylcellulose 0.3
Sodium hydroxide proper amount perfume 0.5
Purified water balance total 100.0
pH 3.5, viscosity 8.0 Pa · s (25 ° C)
(A) / (B) = 2.00
No hairiness ◎
Smooth hair ◎
Ease of agent growth ◎
Storage stability (40 ℃, 6 months) ◎

[Example 31] Hair treatment composition%
Alkyltrimethylammonium chloride 2.5
Stearyl alcohol 3.0
Behenyl alcohol 3.0
Glycolic acid 0.5
Acrylic acid polymer (A-1) 0.6
Sorbitol 30.0
Propylene glycol 5.0
Polyethylene glycol monostearate (40EO) (HLB16)
0.5
Hydroxyethyl cellulose 0.3
Dimethyl silicone 1.0
Highly polymerized amino-modified silicone 2.0
Polyoxyethylene / methylpolysiloxane copolymer 0.2
Aqueous ammonia appropriate amount perfume 0.7
Purified water balance total 100.0
pH 3.3, viscosity 15.0 Pa · s (25 ° C)
(A) / (B) = 1.20
No hairiness ◎
Smooth hair ◎
Ease of agent growth ◎
Storage stability (40 ℃, 6 months) ◎

[Example 32] Conditioner composition%
Alkyltrimethylammonium chloride 1.5
Stearyl alcohol 3.8
Glycolic acid 0.3
Sorbit 10.0
Propylene glycol 8.0
A-1 0.6
Polyethylene glycol monostearate (150EO) (HLB18)
0.2
Polyethylene glycol monostearate (10EO) (HLB11)
0.1
Hydroxyethyl cellulose 0.3
Dimethyl silicone 1.0
Highly polymerized amino-modified silicone 2.0
Polyoxyethylene / methylpolysiloxane copolymer 0.2
Bentonite 0.2
Hydroxypropyl methylcellulose 0.3
Sodium hydroxide appropriate amount Fragrance 0.5
Purified water balance total 100.0
pH 3.5, viscosity 8.0 Pa · s (25 ° C)
Weighted average HLB value of nonionic surfactant 15.7 (2nd decimal place, 2nd digit, rounded 5)
(A) / (B) = 2
No hairiness ◎
Smooth hair ◎
Ease of agent growth ◎
Storage stability (40 ℃, 6 months) ◎

[Example 33] Treatment composition%
Alkyltrimethylammonium chloride 2.5
Stearyl alcohol 3.0
Behenyl alcohol 3.0
Glycolic acid 0.5
A-1 0.6
Sorbit 30.0
Propylene glycol 5.0
Polyethylene glycol monostearate (150EO) (HLB18)
0.3
Polyoxyethylene hydrogenated castor oil (100EO) (HLB15)
0.1
Polyethylene glycol monostearate (10EO) (HLB11)
0.3
Hydroxyethyl cellulose 0.3
Dimethyl silicone 1.0
Highly polymerized amino-modified silicone 2.0
Polyoxyethylene / methylpolysiloxane copolymer 0.2
Aqueous ammonia appropriate amount perfume 0.7
Purified water balance total 100.0
pH 3.3, viscosity 15.0 Pa · s (25 ° C)
Weighted average HLB value of nonionic surfactant 14.6 (2nd decimal place, 2nd digit rounded to 5)
(A) / (B) = 1.2
No hairiness ◎
Smooth hair ◎
Ease of agent growth ◎
Storage stability (40 ℃, 6 months) ◎

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

Claims (2)

The following (A) 0.1-2 mass% of acrylic acid polymer, (B) 0.1-3 mass% of nonionic surfactant of HLB 14-18, (C) 0.5-5 mass of cationic surfactant %, And (D) 0.5 to 10% by mass of a linear saturated aliphatic alcohol, and the mass ratio of the component (A) and the component (B) represented by (A) / (B) is 0.05. Hair cosmetic characterized by ˜18.00.
(A) 70-95 mol% of monomer units represented by the following general formula (1) and 5-30 mol% of monomer units represented by the following general formula (2) are included as structural units. Acrylic acid polymer

(In the formula, 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 composition according to claim 1, wherein the component (B) is mono fatty acid polyethylene glycol (ethylene oxide average addition mole number: 12 to 150) or polyoxyethylene hydrogenated castor oil (ethylene oxide average addition mole number: 60 to 100).