JPH1192530A - Film-forming resin and hair cosmetic containing it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To reduce the stickiness and improve both the touch and the capability of being shampooed by polymerizing seven specified monomers in the presence of a siloxane compound containing azo groups. SOLUTION: A film-forming resin having a molecular weight of 1,000 to 1,000,000 is obtained by polymerizing 30-80 mol.% (meth)acrylamide monomer of formula I, 2-50 mol.% (meth)acrylamide monomer of formula II, 0-50 mol.% (meth)acrylic ester or (meth)acrylamide monomer of formula III, 0-50 mol.% nitrogenous (meth)acrylic ester or (meth)acrylamide monomer of formula IV, 0-50 mol.% nitrogenous (meth)acrylic ester or (meth)acrylamide monomer of formula V, 0-40 mol.% (meth)acrylic ester monomer of formula VI, and 0-20 mol.% crosslinking vinyl monomer in the presence of 0.001-10 mol.% polymerization initiator comprising a polysiloxane compound containing azo groups. In the formulas, R<1> to R<14> are each H, alkyl or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a film-forming resin and a hair cosmetic containing the same.

[0002]

2. Description of the Related Art Conventionally, a film-forming resin has been added to hair cosmetics such as set foams and set lotions for the purpose of hair styling and set holding power. Examples of such a film-forming resin include polyvinylpyrrolidone, polyvinylpyrrolidone / vinyl acetate copolymer, vinyl acetate /
Crotonic acid copolymers and the like are used.

[0003] The film-forming resin contained in hair cosmetics is
It is required that the set hairstyle can be held for a long time and that it must be easily removed with shampoo or water when washing the hair. However, conventional polymers having good water solubility have the drawback that stickiness is conspicuous because they are very easy to absorb moisture under high humidity, and demands that they are not sticky under high humidity and have excellent hair washability. Was not satisfied at the same time. For this reason, conventional film-forming resins have been given a method of reducing stickiness by giving up shampoo washing properties, or incorporating an oil agent such as silicone oil in order to make stickiness under high humidity less noticeable. . In addition, when these film-forming resins absorb moisture, the film on the hair is softened, so that the set hairstyle cannot be sufficiently retained under high humidity, and furthermore, when used in a hair setting foam as a hairdressing resin, There is a problem that the set foam for hair picked up forms a complex with a salt contained in sweat or the like of a finger and causes a salting out, so that it has no sufficient effect.

The inventors of the present invention have conducted research to solve the above problems, and have found a film-forming resin having excellent hair-setting holding power even under high humidity conditions, and have previously filed a patent application (Japanese Patent Application Laid-Open No. 2-180911). However, this film-forming resin also has the disadvantage that it becomes sticky due to moisture absorption under high humidity, and it has been necessary to improve the feel by blending a special oil agent. Furthermore, this film-forming resin is very excellent in water solubility, but has the drawback that it is difficult to dissolve in a shampoo solution because the constituent cationic unit forms a complex with an anionic surfactant. Was.

[0005]

Accordingly, the present invention provides a non-greasy, high-touch feel, and can maintain a set hairstyle for a long period of time even under high humidity, and has excellent hair washing and cleaning properties. A film-forming resin that can be easily removed with shampoo or water, and does not cause salting out, has a beautiful finish, and does not peel off its surface film due to brushing, etc., even when used in hair setting foam as a hair-styling resin The purpose is to provide.

[0006]

Under such circumstances, the present inventors have conducted further studies.
Japanese Patent Application Laid-Open No. HEI 9-101605 discloses a method in which a low-molecular-weight (meth) acrylamide-based monomer is used in place of the (meth) acrylate-based monomer which is a component of the copolymer of No. 911, and an azo group-containing polysiloxane compound is used as a polymerization initiator. No. 2-180911 maintains the basic performance of the film-forming resin, has salting-out resistance, contains polysiloxane in the molecule, has a good feel, and has problems of stickiness and shampoo detergency under high humidity. The inventors have found that the present invention can be solved, and have completed the present invention.

That is, the present invention uses an azo group-containing polysiloxane compound as a polymerization initiator and uses a monomer as a monomer.

(A) The following equation (1)

[0009]

Embedded image

(Wherein R ¹ represents a hydrogen atom or a methyl group;
R ² and R ³ are the same or different and each represent a hydrogen atom or
Wherein R ² and R ³ are not both hydrogen atoms.
30-80 mol%,

(B) The following equation (2)

[0012]

Embedded image

(Wherein, R ¹ has the above-mentioned meaning, and R ⁴ and R ⁵ are the same or different and each represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms).
2 to 50 mol%,

(C) The following equation (3)

[0015]

Embedded image

(Wherein R¹Has the meaning described above, and R⁶Is
An alkylene group having 2 or 3 carbon atoms is represented by R ⁷And R⁸Are the same
Or, differently, a methyl group or an ethyl group. R⁹Are the same
Or a different alkyl group having 1 to 22 carbon atoms or phenyl
A group represented by R^TenRepresents a methyl group or an ethyl group, and a represents 0 or 1.
An integer, b is an integer of 2 or 3, c is 2 to 10,000
Indicates an integer. X^-Represents the counter ion of the quaternary ammonium salt
Show. ) Represented by the (meth) acrylate monomer or
Is a (meth) acrylamide monomer
 0 to 50 mol%,

(D) The following equation (4)

[0018]

Embedded image

(Wherein, R ¹ , R ⁶ , R ⁷ , R ⁸ and a have the above-mentioned meanings, R ¹¹ represents a methyl group or an ethyl group, Y ⁻ represents Cl ⁻ , CH ₃ OSO ₃ ⁻ Or C ₂ H ₅ OSO ₃
^- N atom-containing represented by the illustrated) (meth) acrylic acid ester monomer or a (meth) acrylamide monomer
0 to 50 mol%,

(E) The following equation (5)

[0021]

Embedded image

(Wherein R ¹ , R ⁷ , R ⁸ and a have the above-mentioned meanings) N-containing (meth) acrylate-based monomer or (meth) acrylamide-based monomer
0 to 50 mol%,

(F) The following equation (6)

[0024]

Embedded image

(Wherein, R ¹ has the same meaning as above, R ¹² and R ¹³ are the same or different and each represents an alkylene group having 2 to 4 carbon atoms, R ¹⁴ represents a hydrogen atom, and an alkyl group having 1 to 10 carbon atoms. A) or a phenyl group, d and e each represent a number of 0 to 50, but d and e are not simultaneously 0.
0 to 40 mol%, (g) crosslinkable vinyl monomer
0 to 20 mol%, and a film-forming resin obtained by polymerization using an azo group-containing polysiloxane compound as an initiator.

Further, the present invention provides a hair cosmetic containing the above film-forming resin.

[0027]

BEST MODE FOR CARRYING OUT THE INVENTION In the above formula (1), examples of the alkyl group having 4 to 12 carbon atoms represented by R ² and R ³ include a linear or branched alkyl group. Alkyl groups are preferred. Further, one or both of R ² and R ³ are an alkyl group having 4 to 12 carbon atoms, and it is more preferable that one is an alkyl group having 4 to 12 carbon atoms and the other is a hydrogen atom. Examples of the (meth) acrylamide-based monomer (1) represented by the formula (1) include, for example, Nn-
Butyl (meth) acrylamide, N-tert-butyl (meth) acrylamide, N-octyl (meth) acrylamide, N-lauryl (meth) acrylamide, N-
1-methylundecyl (meth) acrylamide, N-2
-Ethylhexyl (meth) acrylamide, N-ter
t-octyl (meth) acrylamide and the like, among which N-tert-butyl (meth) acrylamide, N
-Tert-octyl (meth) acrylamide, N-2
N-branched alkyl (meth) acrylamide of -ethylhexyl (meth) acrylamide and the like are particularly preferred. These are used alone or in combination of two or more, and are used in an amount of 30 to 80 mol%, preferably 40 to 70 mol% of the whole monomer.

In the above formula (2), examples of the alkyl group having 1 to 3 carbon atoms represented by R ⁴ and R ⁵ include a linear or branched alkyl group, and a methyl group or an ethyl group is particularly preferable. . Examples of the (meth) acrylamide-based monomer (2) represented by the formula (2) include (meth) acrylamide, N-methyl (meth) acrylamide, N-
Ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, etc., among which N-methyl (meth) acrylamide, N-ethyl (Meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide and the like are particularly preferred. These may be used alone or in combination of two or more to form 2 to 50 mol
l%, preferably 10 to 35 mol%.

The (meth) acrylate monomer or (meth) acrylamide monomer represented by the formula (3)

[0030]

Embedded image

(Wherein R ¹ , R ⁷ , R ⁸ and a have the same meanings as above), and a tertiary amino group of a (meth) acrylate monomer or a (meth) acrylamide monomer represented by the following formula: The following equation (7)

[0032]

Embedded image

(In the formula, b represents a number of 2 or 3, and R ⁹ has the above-mentioned meaning.)

The terminally reactive poly (N) obtained by ring-opening polymerization of the cyclic imino ether represented by the formula (R ¹⁰ ) ₂ SO ₄ ... (8) (R ¹⁰ has the above-mentioned meaning)
-Acylalkyleneimine).
However, the reaction between the tertiary amino group of the (meth) acrylamide monomer represented by the formula (5) and the terminal-reactive poly (N-acylalkylenimine) is represented by the formulas (1), (2),
Copolymerizing the monomers represented by (4), (5) and (6); or (1), (2), (4), (5),
It may be carried out after copolymerizing the monomer represented by (6) and the crosslinkable monomer to obtain a polymer containing a tertiary amino group.

R ⁹ is the same or different and represents an alkyl group having 1 to 22 carbon atoms or a phenyl group, more preferably a linear or branched alkyl group having 1 to 12 carbon atoms, and methyl,
Ethyl, n-propyl and isopropyl groups are particularly preferred. c indicates a number of 2 to 10,000, but 50 to 200
Is preferred.

Examples of the cyclic imino ether represented by the formula (7) include 2-substituted-2-oxazoline and 2-substituted-2-oxazine. In addition, poly (N-
Acylalkylenimine) has a molecular weight of 200 to 100,
A range of 000 is preferred.

The monomers represented by the formula (3) may be used alone or in combination of two or more to form 0 to 50 mol of the total monomers.
l%, preferably 0.01 to 10 mol%, more preferably 0.1 to 10 mol%.

The (meth) acrylate-based or (meth) acrylamide-based monomer represented by the formula (4)
It is obtained by reacting the monomer represented by the formula (5) with methyl chloride, ethyl chloride, dimethyl sulfate or diethyl sulfate.

Examples of the (meth) acrylate or (meth) acrylamide-based monomer represented by the formula (4) include quaternary alkyl chloride salts and sulfate quaternary salts of N, N-dimethylaminoethyl (meth) acrylate. , N, N-dimethylaminopropyl (meth) acrylamide alkyl quaternary salts and alkyl sulfate quaternary salts. These may be used alone or in combination of two or more kinds, in an amount of 0 to 50 mol%, preferably 0 to 1
0 mol% is used.

The (meth) acrylate or (meth) acrylamide monomer represented by the formula (5) is, for example, N, N-dimethylaminoethyl (meth).
Acrylate, N, N-diethylaminoethyl (meth)
Acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide and the like can be mentioned. These may be used alone or in combination of two or more to form 0 to 0 of the entire monomer.
It is used in an amount of 50 mol%, preferably 0.01 to 10 mol%, and more preferably 0.1 to 1 mol%.

The monomer represented by the formula (6) is a (meth) acrylate having a polyoxyalkylene chain. In the formula, R ¹² is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a phenyl group, preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and most preferably a methyl group. Examples of the (meth) acrylate-based monomer (6) include, for example, hydroxyethyl (meth)
Acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxypolyethylene glycol mono (meth) acrylate, methoxypolypropylene glycol mono (meth) acrylate, ethoxy polyethylene glycol mono (meth) acrylate Acrylate, butoxy polyethylene glycol mono (meth) acrylate, phenoxy polyethylene glycol mono (meth) acrylate and the like can be mentioned. The polyoxyalkylene chain is a homopolymer or copolymer of C _2-4 alkylene oxide, and in the case of a copolymer, it may be a block copolymer such as ethylene oxide or propylene oxide or a random copolymer. The degree of polymerization of the alkylene oxide can be analyzed by gas chromatography, and preferably has an average value of 1 to 50. These may be used alone or in combination of two or more, and 0 to 40 mol%, preferably 0 to 20 mol% of the whole monomer,
More preferably, 0 to 5 mol% is used.

(G) A crosslinkable vinyl monomer is a compound having two or more carbon-carbon unsaturated double bonds in one molecule, and has a property of crosslinking with another monomer.
Representative examples of the crosslinkable vinyl monomer include, for example, ethylene glycol di (meth) acrylate, polyoxyethylene di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, polypropylene glycol di ( (Meth) acrylic monomers having two or more carbon-carbon unsaturated double bonds in one molecule such as (meth) acrylate; methylenebis (meth) acrylamide, 1,2-
(Meth) acrylamide monomers having two or more carbon-carbon unsaturated double bonds in one molecule such as bis (meth) acrylamidoethane, 1,5-bis (meth) allylamidopentane, and the like, The present invention is not limited to only such examples. In the present invention, the crosslinkable vinyl monomer may be used alone or in combination of two or more.

(G) The crosslinkable vinyl monomer is, for example,
When a high-viscosity gel such as a gel for hair is suitable, it is used in an amount of 0.1 to 20 mol%, preferably 1 to 10 mol%, based on the whole monomer. Further, for example, when a low-viscosity material such as an aerosol composition or a set foam for hair is suitable, 0 to 10
mol%, preferably 0 to 5 mol%.

The film-forming resin of the present invention uses an azo group-containing polysiloxane compound as a radical polymerization agent, and combines monomers represented by formulas (1), (2), (4), (5) and (6). Or (1), (2),
The monomers represented by (4), (5) and (6) and the crosslinkable monomer are combined and copolymerized by a known polymerization method.
Tertiary amino groups of the obtained polymer are reacted with terminal reactive poly (N
-Acylalkyleneimine).
Alternatively, (R ¹⁰ ) ₂ SO ₄ [compound (8)] is used as a polymerization initiator, and a terminal-reactive poly (N-acylalkylenimine) is added to the tertiary amino group of the (meth) acrylamide monomer represented by the formula (5). ) To give a (meth) acrylamide monomer represented by the formula (3),
Combined with the monomers represented by (2), (4), (5) and (6), or (1), (2), (4),
It can be produced by combining with the monomers represented by (5) and (6) and a crosslinkable monomer, and copolymerizing by a known polymerization method using an azo group-containing polysiloxane compound as a radical polymerization initiator.

The azo group-containing polysiloxane compound used as the polymerization initiator is not particularly limited. For example, a macroazo initiator VPS-0501 or VPS-0501 manufactured by Wako Pure Chemical Industries, Ltd.
PS-1001 and the like. The amount used is preferably 0.001 to 10 mol% based on the whole monomer,
0.01 to 5 mol% is more preferable.

Examples of the polymerization method used for producing the film-forming resin of the present invention include a bulk polymerization method, a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method. Particularly, a solution polymerization method is preferable. As a solvent used in the solution polymerization method, a water-miscible organic solvent (a mixture with water) is preferable. This organic solvent can be used alone or as a mixture of two or more components. Examples of the water-miscible organic solvent include carbon atoms of 1
Aliphatic alcohols such as methanol, ethanol, and propanol; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran, glyme, diglyme and dioxane; esters such as methyl acetate and ethyl acetate; Acetone or a mixture of these with water is preferred.

The polymerization may be carried out by heating after charging the monomer mixture and the polymerization initiator in their entirety, or may be carried out by appropriately dropping or separately charging each monomer and / or polymerization initiator.

The polymerization temperature is appropriately selected depending on the type of radical polymerization initiator, monomer and solvent used, and is usually 30 to 100 ° C., preferably 40 to 90 ° C. Further, the copolymerization can be carried out in an atmosphere of an inert gas such as nitrogen as usual.

After the polymerization step, the copolymer can be isolated from the polymerization reaction solution by a known method such as reprecipitation or solvent evaporation. Further, unreacted monomers can be removed from the obtained copolymer by repeating reprecipitation or by a known method such as membrane separation, chromatography, or extraction.

The molecular weight (based on gel filtration chromatography (in terms of polyethylene glycol)) of the copolymer thus obtained can be 1,000 to 1,000 if polymerization conditions are selected.
Can be controlled to 1,000,000, and the present invention has a molecular weight of 1
Those having a molecular weight of from 000 to 500,000 are preferred.

Examples of hair cosmetics containing the film-forming resin of the present invention include set foams for hair, hair sprays, set lotions, gels, shampoos, rinses, etc., and include aqueous solutions, aqueous alcohol solutions, emulsions, It can be used in various dosage forms such as cream and gel. These hair cosmetics include those using a propellant such as a set foam for hair and a hair spray, and a set lotion,
The hair cosmetics of the present invention are broadly classified into those which do not use a propellant, such as hair set gels, shampoos, and rinses, but those which use a propellant are preferred as the hair cosmetics of the present invention.

In hair cosmetics using a propellant, 0.01 to 15% by weight of the film-forming resin of the present invention is contained in a stock solution.
Preferably, 2 to 8% by weight of a solvent selected from lower alcohols such as ethanol, polyols and water is 50 to 9%.
9.8% by weight of an oil agent selected from hydrocarbons, ester oils, silicones and derivatives thereof, and natural fats and oils.
It is preferable to contain 1 to 20% by weight. In addition, if necessary, higher alcohols, octyldodecyl myristate, glycerin, polyethylene glycol, polyoxyethylene hexadecyl ether, etc. are in the form of a transparent liquid or transparent paste at 50 ° C., and solid or white wax at 25 ° C. 0.5 to
3.0% by weight, alkyl ether oxide-added alkyl ethers such as polyoxyethylene stearyl ether,
A film forming aid such as a cationic polymer such as cationized cellulose is preferably used in an amount of 0.1 to 3.0% by weight.

As the propellant, LPG 100% by weight, dimethyl ether (DME) 100% by weight, Freon gas 1
00% by weight, LPG / CFC mixed gas, LPG / DME
A mixed gas and the like can be mentioned.
A system of 0 to 100% by weight is suitably used. The ratio of the stock solution to the propellant in the spray hair cosmetic is 5 /
95-70 / 30, especially 20 / 80-50 / 50 is preferred.

In a gel form such as a hair setting gel, the film-forming resin of the present invention is used in an amount of 0.5 to 10.0.
0.5 to 2.0% by weight of a water-soluble polymer such as polyacrylic acid or hydroxyethylcellulose, and purified water and It is preferable to use a solvent composed of a lower alcohol.

In addition, the film-forming resin of the present invention can be used for shampoos, rinses and the like.
It is preferable to use 5.0% by weight, preferably 0.5 to 2.0% by weight.

Further, in these hair cosmetic compositions, in addition to commonly used preservatives, ultraviolet absorbers, sequestering agents, antidandruff agents and other pharmaceutically active agents, pigments, fragrances and the like may be used according to the purpose. May be added.

[0057]

The film-forming resin of the present invention has very low stickiness not only under normal humidity but also under high humidity, and has a good feel and excellent hair styling power because it contains polysiloxane in the molecule. While having set holding power, it can be easily washed away by ordinary water washing or shampoo hair washing. Further, the film-forming resin of the present invention has high compatibility with LPG. In addition, it shows good compatibility not only with hydrocarbon solvents such as LPG, but also with various organic solvents such as aromatics, halogens, ketones and esters, so that it can be used in various forms. it can. For example, natural leather,
Can be used as a surface treatment agent for synthetic leather, rubber, plastic, glass, etc.
Gloss and gloss can be imparted, and a preservative effect, antistatic effect and the like can be imparted by selecting the composition. Furthermore, it shows good adhesion to nails and proteins such as skin, so it can be used for nail polish and the like.

[0058]

EXAMPLES The present invention will be described in more detail with reference to Synthesis Examples and Examples, but the present invention is not limited thereto.

Synthesis Examples 1 to 7 Ethanol was placed in a four-necked flask equipped with a reflux condenser, a dropping funnel, a thermometer, a nitrogen gas inlet tube and a stirrer.
Then, the mixture was heated to 60 ° C. Then, Table 1
A monomer solution consisting of 100 parts by weight of a monomer mixture having the composition shown in (1) and 200 parts by weight of ethanol (water is added if necessary) and an initiator solution obtained by dissolving the initiator in 33 parts by weight of ethanol were taken for 1.5 hours. Under a nitrogen atmosphere at the same time, and the mixture was further reacted at 60 ° C. for 8 hours. After the polymerization, an ethanol solution of the polymer was poured into n-hexane for reprecipitation purification, followed by vacuum drying at 60 ° C. and 20 mmHg for 12 hours.

The obtained polymers were all white solids. Its weight average molecular weight (dimethylformamide (DM
F) GPC in solution: polyethylene glycol (PE
G) (conversion) is 118,900 for the polymer of Synthesis Example 1.
And those of Synthesis Examples 2 to 12 are 70,000 to 500,0.
00 range.

[0061]

[Table 1]

Synthesis Examples 8 to 10 Diethyl sulfate and 2-ethyl-2-oxazoline at the weights shown in Table 2 were dissolved in 60 g of dehydrated ethyl acetate, and the mixture was heated under reflux in a nitrogen atmosphere for 5 hours to give a terminal-reactive poly (N- Propionylethyleneimine) was synthesized.

[0063]

[Table 2]

Synthesis Examples 11 to 20 50 parts by weight of dehydrated ethyl acetate were obtained in Synthesis Examples 1 to 7 in a four-necked flask equipped with a reflux condenser, a dropping funnel, a thermometer, a nitrogen gas inlet tube and a stirrer. Polymer 5
0 parts by weight, heated to 70 ° C., and combined with the combinations shown in Table 3, the terminal-reactive poly (N
-Propionylethyleneimine) was added to the polymer obtained in Synthesis Examples 1 to 7 in a molar number corresponding to the ratio shown in the table of molar number of tertiary amino groups, and heated and refluxed for 12 hours in a nitrogen atmosphere. The reaction mixture was concentrated under reduced pressure, and ethyl acetate was removed by drying to obtain a target polymer.

[0065]

[Table 3]

Examples 1 to 17 The following components were mixed to obtain a set foam for hair.

[0067]

[Table 4]

[0068]

[Table 5]

Example 18 The following components were mixed to obtain a set lotion for hair.

[0070]

Ingredient (% by weight) Copolymer of Synthesis Example 1 2.0 Polyether-modified silicone (KF-352A, manufactured by Shin-Etsu Chemical Co., Ltd.) 1.0 Ethanol 86.5 Purified water 10.0 Perfume 0.5 Total 100.0

Example 19 The following components were mixed to obtain a shampoo for hair.

[0072]

Table 7 Ingredients (% by weight) Lauryl polyoxyethylene sulfate triethanolamine salt (40% by weight aqueous solution) (Emal 20C, manufactured by Kao Corporation) 32.0 Lauroyl diethanolamide 4.0 Polyethylene glycol (PEG6000, Sanyo Chemical Industries, Ltd.) 1.0 Copolymer of Synthesis Example 4 1.0 Purified water 61.5 Perfume 0.5 Total 100.0

Example 20 The following components were mixed to obtain a gel for hair.

[0074]

Table 8 Ingredients (% by weight) Copolymer of Synthesis Example 5 5.0 Purified water 77.0 Carbopol 940 (manufactured by BFGoodrich) 0.5 Triethanolamine 0.5 Ethanol 16.8 Perfume 0.2 meter 100.0

Example 21 The following components were mixed to obtain an aerosol composition.

[0076]

Table 9 Components (% by weight) Copolymer of Synthesis Example 16 2.5 Dimethylpolysiloxane 0.3 Fragrance 0.15 Absolute ethanol 47.05 LPG 50 Total 100.0

Example 22 The following components were mixed to obtain a hair rinse.

[0078]

Table 10 Component (% by weight) Copolymer of Synthesis Example 18 1.0 Stearyltrimethylammonium chloride 2.0 Cetyl alcohol 2.0 Purified water 94.8 Fragrance 0.2 Total 100.0

Comparative Examples 1 to 4 Comparative Examples 1 to 4 were used in place of the copolymer of Synthesis Example 1 used in Example 1.
3 to 3, the copolymers of Synthesis Examples 1 to 3 (neutralized with 100% lactic acid) of JP-A-2-180911 (note that the monomer composition ratios of these copolymers are shown in Table 11) are commercially available in Comparative Example 4. A set foam for hair was obtained in the same manner as in Example 1 except that the copolymer methylvinyl ether / monobutyl maleate (Gantrez ES425, manufactured by ISP) was used.

[0080]

[Table 11]

Example 23 The following performance evaluations were performed on the hair setting foams of Examples 1 to 17 and Comparative Examples 1 to 4 and the film-forming resin contained therein.

(1) Set Retention Test A hair bundle having a length of 18 cm and a weight of 1.5 g was wetted with water, wound around a rod and air-dried, and then the rod was removed from the hair bundle with the curl. Examples 1 to 1
5. The same amount of each of the set foams of Comparative Examples 1 to 4 was applied and air-dried. Thereafter, the hair with the dried curls was hung in a thermo-hygrostat (20 ° C., 98% RH), and the curl spread was observed to determine the set holding power. Judgment was performed by measuring the length of the curled hair in the vertical direction in the suspended state, setting the length of the hair immediately after hanging to a set holding power of 100%, and holding the set length of the original hair without curling (18 cm). With a force of 0%, the relative value (%) of the length of the hair 30 minutes after hanging was determined, and evaluated based on the following criteria.
The results are shown in Tables 16 and 17.

[0083]

[Table 12] Evaluation criteria rank of “set holding power” State ◎: 81% or more. ：: 61 to 80%. Δ: 51 to 60%. ×: 0 to 50%.

(2) Sensory Test of Stickiness and Stickiness Each hair set foam was sprayed on an experimental human head model (wig), and the sensory evaluation of stickiness and stickiness was performed according to the following evaluation criteria. The results are shown in Tables 16 and 17.

[0085]

[Table 13] Evaluation criteria of “stiffness / stickiness” A : Very good. ：: Good. Δ: Normal. ×: Bad.

(3) Hair Gloss Test Each hair set foam was sprayed on an experimental human head model (wig), and the condition was visually evaluated according to the following evaluation criteria. The results are shown in Tables 16 and 17.

[0087]

[Table 14] Evaluation criteria of "luster of hair" A : Very good. ：: Good. Δ: Normal. ×: Bad.

(4) Water solubility test Each set foam for hair was applied on a glass plate, the formed film was immersed in water for 5 minutes, and the dissolution state was evaluated according to the following evaluation criteria. The results are shown in Tables 16 and 17.

[0089]

[Table 15] "Evaluation criteria for water solubility / detergency" A : Very good. ：: Good. Δ: Normal. ×: Bad.

(5) Detergency test In the water solubility test of (4), what was immersed in water was 3% by weight.
Apart from immersing in shampoo-containing water,
Detergency by shampoo was evaluated by the same method and evaluation criteria as in the water solubility test of (4).

[0091]

[Table 16]

[0092]

[Table 17]

As can be seen from Tables 16 and 17, the set foams for hair of Comparative Examples 1 to 4 have stickiness, and those of Comparative Examples 1 to 3 have poor shampoo detergency. On the other hand, the hair set foams of Examples 1 to 17 satisfy both of these conditions at the same time, and are excellent in set holding power.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08F 220: 28)

Claims (2)

[Claims] (A) The following formula (1):(Where R¹Represents a hydrogen atom or a methyl group;^TwoAnd R^Three
Are the same or different and each represent a hydrogen atom or an alkyl having 4 to 12 carbon atoms.
Represents a kill group, but R^TwoAnd R^ThreeAre both hydrogen atoms
(Meth) acrylamide monomer represented by
 (B) the following formula (2):(Where R¹Has the meaning described above, and R^FourAnd R^FiveAre the same
Or differently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
(Meth) acrylamide-based monomer represented by
 (C) the following formula (3):(Where R¹Has the meaning described above, and R⁶Has 2 carbon atoms or
3 is an alkylene group represented by R ⁷And R⁸Are the same or different
It represents a methyl group or an ethyl group. R⁹Are the same or different
To form an alkyl group having 1 to 22 carbon atoms or a phenyl group with R
^TenIs a methyl group or an ethyl group, a is an integer of 0 or 1,
b is an integer of 2 or 3, c is an integer of 2 to 10,000
Show. X^-Represents a counter ion of a quaternary ammonium salt).
Is a (meth) acrylamide monomer
 0 to 50 mol%, (d) the following formula (4):(Where R¹, R⁶, R⁷, R⁸And a are as defined above.
Has, R¹¹Represents a methyl group or an ethyl group;^-Is Cl
^-, CH_ThreeOSO_Three ^-Or C_TwoH_FiveOSO_Three ^-N-containing (meth) acrylates represented by
Monomer or (meth) acrylamide monomer
 0 to 50 mol%, (e) the following formula (5)(Where R¹, R⁷, R⁸And a have the above-mentioned meaning
N-containing (meth) acrylates represented by
Monomer or (meth) acrylamide monomer
 0 to 50 mol%, (f) the following formula (6):(Where R¹Has the meaning described above, and R¹²And R¹³Are the same
Or differently, an alkylene group having 2 to 4 carbon atoms¹⁴Is water
An atom, an alkyl group having 1 to 10 carbon atoms or a phenyl group
Show. d and e each represent a number from 0 to 50;
And e do not become 0 at the same time.)
 0 to 40 mol%, (g) crosslinkable vinyl monomer
 Azo group-containing polysiloxy.
A polymer obtained by polymerization using a sun compound as an initiator.
Film forming resin. 2. A hair cosmetic comprising the film-forming resin according to claim 1.