JPH0482819A - Hair cosmetic - Google Patents

Abstract

PURPOSE:To obtain a hair cosmetic having excellent touch of hair after setting and excellent effects on prevention of hair damage caused by brushing besides setting retention by blending a specific film-forming copolymer with a cationic surfactant and an oil agent. CONSTITUTION:(A) 0.01-20wt.% copolymer prepared by copolymerizing 30-80 compound shown by formula I (R<1> is H or methyl; R<2> and R<3> are H, 4-12C alkyl, etc.) with 5-45wt.% compound shown by formula II (R<4> is 1-4C alkyl), 2-30wt.% compound shown by formula III (R<5> is 2-3C alkylene; R<6> and R<7> are methyl or ethyl; a is 0 or 1) and 0-30wt.% compound shown by formula TV (R<8> and R<9> are 2-6C alkylene; R<10> is H or methyl; a ms 0 or 1), (B) 0.1-30wt.% cationic surfactant and (C) 0.1-30wt.% oil agent are dissolved in a solvent such as water or lower alcohol and optionally mixed with a propellant and packed into a pressure container to prepare the objective substance.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to hair cosmetics, and more specifically, the present invention relates to hair cosmetics that have excellent set retention properties and provide smoothness, flexibility, and other good textures to the hair after setting. The present invention relates to a hair cosmetic that can be applied to the hair and also prevent hair damage caused by brushing or the like.

[Conventional technology]

Conventionally, various hair cosmetics such as setting lotions, hair sprays, hair mist, and hair foams have been used to make hairstyles easier to create and to make hair styles last longer. It has been produced by dissolving a fixing polymer compound (hereinafter simply referred to as a "polymer compound") in an appropriate solvent such as water, a lower alcohol, or a mixed solvent of water and lower alcohol. A hair lotion is a product in which the obtained solution is used as it is, and a hair mist is a product in which the solution is made into a mist using a pump or the like, and an appropriate liquefied gas is injected into the solution. Hairspray is a product that is mixed as an agent and used as an aerosol, and hair foam is a product that is sprayed as a foam.

In addition, in recent years, with the diversification and individualization of hairstyles, there has been a demand for hard type hair cosmetics that contain large amounts of polymeric compounds and can more firmly set hair.

[Problem to be solved by the invention]

However, the polymer compounds conventionally used are film-forming resins, and although they have a certain degree of set retention power, under high humidity conditions, conventional polymers become sticky due to moisture absorption, and even become fluid. Hair set could not be maintained sufficiently.

On the other hand, hair cosmetics must be easily removed by shampooing. That is, water solubility is required on the one hand, and low hygroscopicity is required on the other hand. It is difficult to simultaneously satisfy these contradictory requirements, and in the past, water solubility has often been abandoned and other solvents or solvent mixtures have been used.

In the case of aerosol type hair cosmetics, fluorocarbon gas has traditionally been used as a propellant, but in recent years it has been replaced by hydrocarbons (LPG) such as propane, butane, isobutane, and mixtures thereof due to environmental concerns. But L
PG tends to have a lower solubility in film-forming resin than chlorofluorocarbon gas, and the propellant of current aerosols is simply LPG.
If it is replaced with , the film-forming resin in the aerosol product will precipitate and become unusable. Therefore, in order to dissolve the film-forming resin with LPG, the solvent in the spray (ethanol,
(isopropyl alcohol, etc.) must be increased, and as a result, the sprayed mist becomes large and heavy, making it difficult to style hair beautifully.

In addition, conventional setting agents using polymeric compounds have caused the hair to feel stiff and rough after drying, resulting in poor texture. In addition, there were other problems such as peeling of the resin coating on the hair surface due to brushing or the like, ie, so-called flaking, which deteriorated the luster of the hair.

Therefore, it has been desired to develop a hair cosmetic that has excellent set retention even when using a propellant such as LPG, has a good feel on the hair after setting, and does not damage the hair. .

[Means to solve the problem]

Under these circumstances, the present inventors have conducted extensive research and have found that by blending a cationic surfactant and an oil agent with a specific film-forming copolymer, in addition to providing good setting power, the hair feel and damage after setting can be reduced. The present invention was completed based on the discovery that a hair cosmetic with excellent preventive effects can be obtained.

That is, the present invention comprises the following components (A), ([]) and (C
) (A) Copolymer of the following components (a), (a), (C) and (d) (a) (meth)acrylamide monomer represented by formula (I) (hereinafter referred to as monomer (I)) 3
0 to 80% by weight, representing an alkyl group having a prime number of 1 to 4) (C) A (meth)acrylic acid ester monomer and/or a (meth)acrylamide monomer having a tertiary amino group represented by formula (III) ( Hereinafter, monomer (referred to as III>) 2 to 30% by weight, (wherein, R1 is a hydrogen atom or a methyl group, R2 and R
3 is the same or different hydrogen atom or carbon number 4-1
2 or R2 and R3 together form a ring with the adjacent nitrogen atom) Q)) A (meth)acrylic acid ester monomer represented by formula (IT) (hereinafter referred to as monomer (II) ))
5 to 45% by weight, (III) (wherein R' has the same meaning as above, and R5 has 2 carbon atoms
~3 alkylene groups, R6 and R7 are the same or different and represent a methyl group or an ethyl group, and a represents 0 or 1) (d) (meth)acrylic acid ester monomer represented by formula (rV) (hereinafter , thousand Tsuma (IV))
0 to 30% by weight (in the formula, R1 has the same meaning as above, R4 is carbon (in the formula, R1 has the same meaning as above, R8 and R9 are different alkylene groups having 2 to 4 carbon atoms) (B) Cationic surfactant (B) Hair containing oil It provides cosmetics.

In the hair cosmetic of the present invention, the copolymer of component (8) is:
It is a film-forming resin and is obtained by copolymerizing components (a) to (d). Examples of the monomer (I) used in the production of the copolymer (8) include (meth)acrylamide, N-n-butyl (meth)acrylamide, N
-t-butyl (meth)acrylamide, N-octyl (
Examples thereof include meth)acrylamide, N-lauryl(meth)acrylamide, and (meth)acryloylmorpholine, among which N-butyl(meth)acrylamide, N-octyl(meth)acrylamide, N-lauryl(meth)acrylamide, and the like are particularly preferred. These monomers are used alone or in combination of two or more in an amount of 30 to 80% by weight, preferably 40 to 70% by weight of the entire monomer.

Examples of the compound (II) include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and the like. These monomers are used alone or in combination of two or more in an amount of 5 to 45% by weight, preferably 10 to 40% by weight of the total monomer.

For example, (meth)acrylic all-N, N-dimethylaminoethyl, (meth)
Acrylic acid-N,N-diethylaminoethyl, (meth)
Acrylic acid-N,N-dimethylaminopropyl, N,N
-dimethylaminopropyl (meth)acrylamide and the like. These may be used alone or in combination of 2 or more in an amount of 2 to 30% by weight, preferably 10% by weight of the entire monomer.
~20% by weight is used.

Examples of the monomer (IV) include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and methoxypolyethylene glycol mono(meth)acrylate.
Examples include meth)acrylate, methoxypolypropylene glycol (meth)acrylate, and the like. These may be used singly or in combination of two or more in an amount of 0 to 30% by weight, preferably 5 to 15% by weight, based on the total weight of the total weight.

The copolymerization reaction of these monomers (I) to (IV) can be carried out by known polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization in the presence of a radical polymerization initiator. Although it can be produced by polymerization, solution polymerization is particularly advantageous. The solvent used in the solution polymerization method is preferably a water-miscible organic solvent (which may be a mixture with water). This organic solvent can be used alone or in combination of two or more components. Examples of water-miscible organic solvents include:
Aliphatic alcohol having 1 to 3 carbon atoms, such as methanol,
Ethanol, propatool; ketones, e.g. acetone,
Methyl ethyl ketone; ethers such as tetrahydrofuran, glyme, diglyme, dioxane, etc. are mentioned, and methanol, ethanol, acetone or a mixture thereof with water is particularly preferred.

Radical polymerization initiators that can be used in this method include azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4dimethylvaleronitrile), 2,2'-azobis( 4-methoxy-2,4-
Preferred examples include dimethylvaleronitrile), dimethyl-2,2'-azobisisobutyrate, 2,2'-azobis(2-methylbutyronitrile), and 1,1'-azobis(1-cyclohexanecarbonitrile). be. Organic peroxides such as t-butylberoctoate, dicumyl peroxide, di-t-butyl peroxide, dibenzoyl peroxide can also be used, but monomer (III)
Because there is a possibility of a redox reaction occurring with the tertiary amino group of
It is difficult to control the reaction, so it is not very desirable from an industrial perspective. The amount of polymerization initiator used is preferably between 0.001 and 2.0 mol%, and 0.001 to 2.0 mol% based on the monomer mixture. Old~1
．． θ mol % is more preferred.

Polymerization may be carried out by charging the monomer mixture and the polymerization initiator in their entirety and then heating, or may be carried out by appropriately dropping or dividing each monomer and/or polymerization initiator.

The polymerization temperature is appropriately selected depending on the radical polymerization initiator used, the seed stone of the solvent, etc., but is usually 30 to 1.
00°C, preferably 50-90°C. Further, the copolymerization can be carried out under an atmosphere of an inert gas such as nitrogen, as is commonly carried out.

After the polymerization step, the copolymer can be isolated from the polymerization reaction solution by a known method such as reprecipitation or solvent distillation.

Further, unreacted monomers can be removed from the copolymer obtained by repeating reprecipitation or by known methods such as membrane separation, chromatography, and extraction. The molecular weight of the copolymer thus obtained (gel filtration chromatography (
The weight average molecular weight (based on polystyrene equivalent) can be controlled within the range of 1.000 to 1.000.000 by selecting polymerization conditions, but for the purpose of the present invention, the weight average molecular weight is 10.
, 000 to 500.000, particularly preferably a weight average molecular weight of 20.000 to 200.000.

Further, the copolymer (A) can be used as it is or after neutralizing its tertiary amino groups using an inorganic or organic acid. Examples of inorganic acids used for neutralization include hydrochloric acid, sulfuric acid, and phosphoric acid; examples of organic acids include acetic acid, glycolic acid, lactic acid, dimethylolpropionic acid, tartaric acid, citric acid, maleic acid, and malic acid. etc.

Examples of the cationic surfactant as component (B) in the present invention include quaternary ammonium salts represented by the following general formula (V) or (VI).

Margin below Examples include ammonium salts.

[Wherein, R11, R12, It13 and R14,
At least one alkoxy group having a total of 8 to 28 carbon atoms,
Indicates an alkyl group or alkenyl group that may be substituted with an alkenyloxy group, an alkanoylamino group, or an alkenoylamino group, and the remainder is a benzyl group, and the number of carbon atoms is 1.
~5 alkyl group or hydroxyalkyl group.

RI5 represents an alkylene group having 2 to 3 carbon atoms, X- represents a halogen ion or an organic anion, and n is 1 to 20
] Among such cationic surfactants, quaternary ammonium salts of general formula (V) are preferred. Furthermore, preferred examples of general formula (V) include, for example, branched quaternary a represented by the following general formulas (■) to (IX) [wherein Ro is (i) Ct
A branched alkyl group represented by (3ffcL廿CHCl1 (where R22 represents a methyl group or an ethyl group, and p represents an integer such that the total number of carbon atoms in the alkyl group is 8 to 16) and (b) CH3-( CH2→T (here q is 7~
A mixture of straight alkyl groups represented by the integer of 15) whose branching ratio (a)/(a)+(b) is from 10 to 10.
0%, R17 and R18 are benzyl groups,
represents an alkyl group or hydroxyalkyl group having 1 to 3 carbon atoms, R19 and R20 represent an alkyl group having 1 to 3 carbon atoms, and ! 121 is the group CH3electron C
H2 piece CH lid C11, tr or an alkyl group having 1 to 3 carbon atoms, S is an integer of 2 to 14, t is an integer of 3 to 11, and the sum of S and t is 9 to 21; X- represents a halogen ion or an organic anion.] The branched quaternary ammonium salt represented by the general formula (■) is usually synthesized using an oxo alcohol having 8 to 16 carbon atoms as a raw material. Examples include dialkyldimethylammonium salts, dialkylmethylhydroxyethylammonium salts, and dialkylmethylbenzylammonium salts having an alkyl group derived from oxo alcohol.

In the present invention, the branching rate of R16 in formula (■) is usually 10
~100% is used, and 10~50% is particularly preferred. In addition, the total number of carbon atoms in R16 is 8 to 16
Those having a certain distribution are preferred, and those having the distribution shown below are particularly preferred.

C8-C++: 5% or less C, 2: 10-35% C+3: 15-40% C, +20-45% C, 5: 5-30% C+e: 5% or less A specific example is dialkyldimethylammonium chloride having an alkyl group having 8 to 16 carbon atoms and a branching rate of 10 to 50%.

In addition, the branched quaternary ammonium salt represented by the - format (■) is usually a gelpe alcohol (R") having 8 to 28 carbon atoms.
-CH, CH2CHCN, 011) as a raw material. Preferred examples of this branched quaternary ammonium salt include an alkyltrimethylammonium salt having an alkyl group derived from Guerbet alcohol, an alkyldimethylbenzylammonium salt, a dialkyldimethylammonium salt, a dialkylmethylhydroxyethylammonium salt, and a dialkylmethylbenzylammonium salt. etc. Furthermore, particularly preferred specific examples of these include 2-decyltetradecyltrimethylammonium chloride, 2-dodecylhexadecyltrimethylammonium chloride, di-2hexyldecyldimethylammonium chloride, di-2-octyldodecyldimethylammonium chloride, and the like. be able to.

Examples of the methyl branched quaternary ammonium salt represented by the general formula (IX) include those in which the sum of S and t is 15.

In addition, general formulas (V), (VI), (■), (■) and (
Specific examples of X-, which is the counter ion of the quaternary ammonium salt represented by IX), include halogen ions such as chlorine, iodine, and bromine; methosulfate, ethosulfate,
Examples include organic anions such as methophosphate and ethophosphate.

As the oil agent of component (C), all the oils normally included in hair cosmetics can be used, such as hydrocarbons such as squalane and liquid paraffin; castor oil, cacao oil, mink oil, and avocado oil. , glycerides such as olive oil; waxes such as beeswax, spermaceti, lanolin, and carnauba wax; cetyl alcohol, oleyl alcohol, hexadecyl alcohol, lauryl alcohol,
Stearyl alcohol, isostearyl alcohol, 2
-Alcohols such as octyldodecanol, propylene glycol, polypropylene glycol, glycerin; isopropyl myristate, hexyl laurate, epityl lactate, propylene glycol monostearate, oleyl oleate, hexadecyl 2-ethylhexanoate, octyl myristate Esters such as dodecyl; Higher alcohol oxide propylene oxide ethylene oxide adducts such as polyoxyethylene ethyl ether, polyoxypropylene cetyl ether, polyoxyethylene polyoxypropylene stearyl ether; dimethylpolysiloxane, methylphenylpolysiloxane, polyether-modified silicone Examples include silicone derivatives such as oil, epoxy-modified silicone oil, amino-modified silicone oil, and alkyl-modified silicone oil. Among these oils, hydrocarbons, esters, and higher alcohol propylene oxide adducts are preferred.

The hair cosmetics of the present invention include, for example, hair sprays, setting foams, setting lotions, gels, etc., and are intended to remain on the hair such as aqueous solutions, hydroalcoholic solutions, emulsions, creams, and gels. It can be used in various dosage forms.

In the hair cosmetic of the present invention, component (A) is preferably blended in an amount of 0.01 to 20% by weight (hereinafter simply expressed as %), particularly preferably 1 to 7%; component (B) is preferably blended in an amount of 0.01 to 20% by weight; The content of component (C) is preferably 0.1 to 30%, particularly preferably 0.1 to 10%. (If the content of A>llii is less than 0.01%, the set retention force is insufficient,
When it exceeds 20%, the stiffness increases and the feel decreases. Furthermore, if the content of component (B) is less than 0.1%, the feel such as slipperiness will not be sufficient, and if it exceeds 30%, an oily or sticky feeling may occur.

If the content of (C)III is less than 0.1%, the anti-flaking effect will not be sufficient.

The hair cosmetic of the present invention comprises the above (A), (B) and (C).
The ingredients are dissolved in a solvent such as water, a lower alcohol, or a mixed solvent of water and lower alcohol in the proportions listed above according to a conventional method, and if necessary, mixed with a propellant and filled into a pressure container. Manufactured by

The solvent is preferably selected according to the form of the hair cosmetic of the present invention, and in the case of a setting lotion, it is preferable to use water or a mixed solvent of monohydric alcohol having 2 to 3 carbon atoms and water. When preparing a pump spray type hair mist, it is preferable to use a mixed solvent of monohydric alcohol having 2 to 3 carbon atoms and water as the solvent; Preference is given to using monohydric alcohols, especially ethanol.

In the case of hair spray, the stock solution prepared in the above ratio is used, and the ratio of the stock solution to the propellant is preferably 5/95 to 70/30 weight ratio, particularly 20/80 to 50150 weight ratio, and in the case of hair foam, , Non-concentration of stock solution and propellant from 3/97
A 30/70 weight ratio is preferred, especially a 5/95 to 15/85 weight ratio.

As a propellant, for example, chlorofluorocarbon gases such as trichloromonofluoromethane and dichlorodifluoromethane can be used, but liquefied petroleum gas (LPG), dimethyl ether (
DMB), carbon dioxide gas, nitrogen gas, or a mixture thereof is preferred. Especially LPG SDMB 'i or LPG/
DMB mixed gas is preferred. These propellants have an internal pressure of 2.0 to 4.5 kg/ant in the aerosol can after filling.
Prepare and fill so that it becomes G.

In addition, in gel form such as hair setting gel,
0.5 to 10.0% of film forming resin, preferably 1.0%
~3.0%, 0.5~2.0% thickener consisting of a water-soluble polymer such as polyacrylic acid, hydroxyethyl cellulose, etc.
%, and preferably a solvent consisting of water and, if desired, a lower alcohol.

In addition to the above-mentioned ingredients, the hair cosmetic of the present invention may contain high-containing ingredients such as polyvinylpyrrolidone, vinyl acetate, acidic polyvinyl acetate, acidic acrylic, and amphoteric acrylic, within limits that do not impede the effects of the present invention. Molecular compounds can be added. Furthermore, in order to increase the commercial value, fragrances or pigments are added as necessary. Furthermore, preservatives or antioxidants may be added to prevent oral deterioration of the hair cosmetic.

〔Example〕

Hereinafter, the structure and effects of the present invention will be specifically clarified with reference to Examples.

Synthesis Examples 1 to 6 100 parts of ethanol was placed in a four-hole flask equipped with a reflux condenser, dropping funnel, thermometer, nitrogen gas introduction tube, and stirring device, and heated to 60°C. Thereafter, an initiator solution consisting of 100 parts of the monomer mixture and 200 parts of ethanol (with water added if necessary) and an initiator solution prepared by dissolving the initiator in 33 parts of ethanol were heated for 1.5 hours in a nitrogen atmosphere. Dropped simultaneously at the bottom and continued for 60 hours for another 8 hours.
The reaction was carried out while maintaining the temperature. After polymerization, reprecipitation purification with water,
Vacuum drying was performed at 80° C. and 23 mm) Ig for 12 hours. The obtained polymer was a pale yellow solid. The average molecular weight of the synthesized polymer was 104,300 (GPC in tetrahydrofuran solution: polystyrene equivalent). Furthermore, the polymers of Synthesis Examples 2 to 6 had an average molecular weight of 60.000.
~160.000. Table 1 shows the monomer composition ratio of each polymer.

=24 Space below Example 1 1.5 parts by weight of the copolymer obtained in Synthesis Example 1 was dissolved in 57.5 parts by weight of absolute ethanol, and 0.15 parts by weight of lactic acid,
Dialkyldimethylammonium chloride *3) 0.3
Parts by weight, polyoxyethylene (30) polyoxypropylene (4) stearyl ether 0.4 parts by weight, and fragrance 0
．． 15 parts by weight were added. The obtained solution was placed in an aerosol container, and 40 parts by weight of liquefied petroleum gas (LPG) was pressurized into the container to prepare an aerosol composition. The setting holding power of the obtained composition, the moist feeling of the hair after setting, the presence or absence of stickiness, and the slipperiness were evaluated by the following test methods. The results are shown in Table 2.

(Note) *3: A branched quaternary ammonium salt derived from a commercially available oxo-method synthesized alcohol having 12 to 15 carbon atoms (equal mixture of Dopanol 23 and 45, manufactured by Mitsubishi Yuka Co., Ltd.), with a branching rate of 20% by weight. %.

Test method: (1) Set retention Wet a hair bundle with a length of 18 cm and a weight of 1.5 g with water, wrap it around a rod and let it dry naturally, then remove the rod from the curled hair bundle and check the curls. Each composition was sprayed onto the hair from four directions and allowed to air dry. After that, the dry curled hair was placed in a constant temperature box (20°C).
, 98% R-H) for 30 minutes, the curl growth was observed, and the set holding power was determined. Judgment is made by measuring the length of curled hair, setting the length of the hair when spraying, setting the holding power at 100%, and the original length of the hair without curls (
18 cm) with a set holding force of 0%.

Set holding power 081% or more 061-80% △ 21-60% × 0-20% (2) Moist feeling, stickiness, and slipperiness Apply each composition to hair bundles curled using the same method as in (1) above. After spraying and air drying, a sensory evaluation was conducted by a panel of 10 female experts in comparison with hair tresses to which the composition was not applied (control).

Evaluation ◎: Very good compared to the control ○: Slightly better than the control △: Equal to the control ×: Poor compared to the control (3) Hair damage prevention effect Hair bundles consisting of 1000 hairs were made and each composition was sprayed. The number of split ends and broken hair was counted after brushing was performed 5000 times, and the results were ranked according to the following evaluation.

Evaluation: 0720 or less ○: 21 to 50 pieces △: 51 to 100 pieces It was evaluated in the same manner.

Composition (wt%) High molecular compound (Table 3) 1.5 Squalane Fragrance Absolute ethanol 0.5 0.3 Balance below margin Example 3 A hair mist having the following composition was prepared.

composition Polymer compound of Synthesis Example 3 Isopropyl myristate fragrance water ethanol (weight%) 5.0 Propellant (DMB) Example 5 A hair blower with the following composition was prepared.

composition Polymer compound of Synthesis Example 5 10.0 100, 0 (weight%) 1.0 Example 4 A hair foam having the following composition was prepared.

composition Polymer compound of Synthesis Example 4 ether fragrance ethanol water 100.0 (weight%) 1.0 0.2 5.0 balance fragrance ethanol water Example 6 Heasiel having the following composition was prepared.

Composition Polymer compound of Synthesis Example 6 Um chloride 10.0 Balance 100, 0 (wt%) 3.0 Chemical [ampanyilQ) Glycerin 1. .

Triethanolamine 0.7 scent
Fee 0
．． 3 ethanol 12. .

water balance 100
, 0 The compositions of Examples 3 to 6 had excellent set holding power, and the hair after setting was moist, smooth, and non-sticky, and there was no damage to the hair.

〔Effect of the invention〕

The hair cosmetic of the present invention has excellent set holding power, gives a good feel to the hair after setting, and has an excellent hair damage prevention effect, and can be used as a hair spray, setting lotion, or hair mist. The effect is particularly noticeable in cases where

that's all hand Continued Supplementary Positive calligraphy (spontaneous)

Claims (1)

[Claims] 1. Copolymer (a) of the following components (A), (B) and (C) (A) the following components (a), (b), (c) and (d) 30 to 80% by weight of (meth)acrylamide monomer represented by formula (I), 5% by weight (I) (wherein, R^1 is a hydrogen atom or a methyl group, and R^2 and R^3 are the same or (b) Represented by formula (II) (Meth)acrylic acid ester monomer 5 to 45% by weight, ▲Mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, R^1 has the same meaning as above, and R^4 has the number of carbon atoms of 1 ~4 alkyl group) (c) having a tertiary amino group represented by formula (III) (
2 to 30% by weight of meth)acrylic acid ester monomer and/or (meth)acrylamide monomer, ▲Mathematical formulas, chemical formulas, tables, etc.▼(III) (In the formula, R^1 has the same meaning as above. (d) Formula (IV) 0 to 30% by weight of (meth)acrylic acid ester monomer represented by ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (IV) (In the formula, R^1 has the same meaning as above, R^6 and R
^9 represents a different alkylene group having 2 to 4 carbon atoms, R^1
^0 represents a hydrogen atom or a methyl group, b and c each represent a number from 0 to 50, but b and c cannot be 0 at the same time) (B) Hair makeup containing a cationic surfactant (C) Oil agent fee.