JP2011195553A - Hair cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hair cosmetic feeling well in use, excellent in the trim feeling of finished hair with excellent effect of sustaining the trim feeling even under high humidities, and having hair rinsability (hair washability) in washing the hair and hair-repairing effect as well.SOLUTION: The hair cosmetic is provided, being obtained by compounding together (A) a fluorine-containing copolymer obtained by copolymerization of monomers essentially including (a1) fluorine-containing monomers each represented by a specific formula and (a2) monomers essentially including alkoxy-containing monomers each represented by another specific formula; (B) amino-bearing silicone and/or derivative thereof; and (C) a hair-repairing component.

Description

  The present invention relates to a hair cosmetic containing a fluorine-containing copolymer having a specific structure, a silicone having an amino group and / or a derivative thereof, and a hair repair component. Hair cosmetics that are superior in the sense of cohesion of hair with a feeling of feeling, and that the sense of cohesion lasts even under high humidity, and is also excellent in the ability to wash off (washing) hair and repairing damaged hair It is about.

Conventionally, various components have been blended in hair cosmetics according to the desired use feeling, purpose, and effect. (For example, see Non-Patent Document 1)
When seeking a feeling of use and treatment such as smoothness and suppleness in hair cosmetics, for example, various oils, silicone oils, cationic surfactants, etc. are used. Sterols and amino acids are used for repairing and improving hair damage. (For example, see Patent Documents 1 to 5)
Among silicone oils, amino group-containing silicones are sometimes used in order to provide more flexibility. (For example, see Patent Documents 6 and 7)
"New Cosmetics" 1st edition, 3 prints, Publisher: Nanzan-do, 430-439 pages JP 2001-139437 A JP 2009-67733 A JP 2000-273026 A JP 2004-35457 A JP 2005-298447 A JP 05-70327 A Japanese Patent Laid-Open No. 08-188519

  In addition, hair cosmetics may be required to have a moderate hair feeling with a natural finish rather than a strong hair-styling ability like hard wax. However, in a humid state such as a drizzle day or a rainy season, it is difficult to maintain a sense of unity of hair because of the characteristics of the hair, which causes swell and spread. In particular, hair that has been treated with perm or hair color is easy to absorb moisture in the air because the cuticle on the hair surface peels off, or even the inside of the hair is damaged and hollowed out. It was easy to get out, the swell and spread tend to be severe, it was difficult to get a sense of unity, and it was difficult to maintain a hairstyle with a sense of unity. On the other hand, the hair repair component is difficult to keep inside the hair due to friction, shampooing, and the like, and may not always work effectively for hair repair.

As a method for giving a feeling of unity to the hair and maintaining it, there are a method using a film-forming polymer, an oil agent such as solid oil, silicone oil and the like.
The method using a film-forming polymer can form a very thin film on the hair surface, so that it can have a certain degree of moisture resistance and prevent the hair from spreading, but it is unique to the film-forming polymer. Since a hard film is formed, the hair is stiff, and there are cases where it is unsuitable for giving a supple and moderate feeling of unity.
In order to bring out a sense of unity and sustainability using solid oil, it is necessary to add more than a certain amount. If a large amount is added, stickiness may occur and a good feeling of use may not be obtained. .
In addition, when silicone oil such as dimethylpolysiloxane or methylphenylpolysiloxane is used, the surface of the hair is cleanly coated at the beginning of use, resulting in a smooth and smooth feel. In some cases, the silicone film may not be completely removed and may remain on the hair surface. Repeating this process forms a silicone film on the silicone film that cannot be removed, and the hair surface gradually becomes harder and less smooth. There was a case where I felt a feeling.
Therefore, there is a demand for the development of a hair cosmetic that is non-sticky, supple, excellent in the finish, and that maintains the sense of unity even under high humidity, and is effective in suppressing the spread and swell of the hair. In addition, there has been a demand for the development of a hair cosmetic that is excellent in washing off properties (hair washability) of components that cause wrinkles and the like and in the repairing effect of damaged hair.

  In view of this situation, the present inventors have conducted intensive studies, and as a result, blended with a specific fluorine-containing copolymer, a silicone having an amino group and / or a derivative thereof, and a hair repair component, provide a good feeling of use. It is found that it has excellent hair feeling, can suppress hair spread and swell even under high humidity, and has an excellent effect of sustaining a coherent hairstyle. The present invention has been completed by finding that the components can be easily washed off (hair washability) and the effect of repairing damaged hair, and that the above problems can be solved.

That is, the present invention includes the following components (A) to (C);
(A) A monomer that essentially contains a fluorine-containing monomer (a1) represented by the following general formula (1) and an alkoxy group-containing monomer (a2) represented by the following general formula (2) Fluorine-containing copolymer obtained by copolymerizing CH ₂ ═C (—X) —CO—Y — [— (CH ₂ ) _m —Z—] _p — (CH ₂ ) _n —Rf
(1)
[Wherein, X represents a hydrogen atom, a linear or branched alkyl group having 1 to 21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a CFX ¹ X ² group (where X ¹ and X ² is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, respectively), a cyano group, a linear or branched fluoroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted benzyl group. A substituted or unsubstituted phenyl group; Y is —O— or —NH—; Z is a direct bond, —S— or —SO ₂ —; Rf has 1 to 6 carbon atoms; A fluoroalkyl group; m is 1 to 10, n is 0 to 10, and p is 0 or 1. ]
^{_{CH 2 = C (R 1)}} -COO- (R 2 O) q -R 3 ···· (2)
[In the formula, R ¹ is a hydrogen atom or a methyl group; R ² is an alkylene group having some or all carbon atoms which may be substituted with a hydroxyl group of 2 to 4 hydrogen atoms; R ³ is hydrogen An atom or an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms; q is an integer of 1 to 50; ]
(B) A hair cosmetic comprising a silicone having amino groups and / or a derivative thereof (C) and a hair repair component is provided.

  Further, the hair repair component of component (C) is an amino acid and an amino acid derivative, a peptide, a sterol, a homopolymer of 2-methacryloyloxyethyl phosphorylcholine, a copolymer of 2-methacryloyloxyethyl phosphorylcholine and a hydrophobic monomer. The present invention provides the above-described hair cosmetic, which is selected from one kind or two or more kinds.

The hair cosmetic composition of the present invention has no stickiness, is supple, and has an excellent feeling of hair unity. In addition, it is excellent in moisture resistance, can suppress the spread and swell of hair even under high humidity and high humidity, and is excellent in the effect of maintaining a coherent hairstyle.
Furthermore, while having excellent moisture resistance, it accumulates ingredients that may cause stiffness during continuous use, such as silicone and film-forming polymers, when washing a large amount of water on the hair. It has excellent hair washability that can be washed off without losing hair, and it also has the effect of repairing damaged hair because it can confine the hair repair component inside the coating film formed on the hair surface for a certain period of time and act effectively. Also excellent.

  The fluorine-containing copolymer of the component (A) used in the hair cosmetic composition of the present invention is represented by the fluorine-containing monomer (a1) represented by the following general formula (1) and the following general formula (2). And an alkoxy group-containing monomer (a2).

The fluorine-containing monomer (a1) is represented by the following general formula (1).

_{CH 2 = C (-X) -CO} -Y - [- (CH 2) m -Z-] p - (CH 2) n -Rf
(1)
[Wherein, X represents a hydrogen atom, a linear or branched alkyl group having 1 to 21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a CFX ¹ X ² group (where X ¹ and X ² is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, respectively), a cyano group, a linear or branched fluoroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted benzyl group. A substituted or unsubstituted phenyl group; Y is —O— or —NH—; Z is a direct bond, —S— or —SO ₂ —; Rf has 1 to 6 carbon atoms; A fluoroalkyl group; m is 1 to 10, n is 0 to 10, and p is 0 or 1. ]

The alkoxy group-containing monomer (a2) is represented by the following general formula (2).
_{^{CH 2 = C (R 1)}} -COO- (R 2 O) q -R 3 ···· (2)
[In the formula, R ¹ is a hydrogen atom or a methyl group; R ² is an alkylene group having some or all carbon atoms which may be substituted with a hydroxyl group of 2 to 4 hydrogen atoms; R ³ is hydrogen An atom or an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms; q is an integer of 1 to 50; ]

In the general formula (1), p is preferably 0. A preferred example of X is a hydrogen atom.

In the general formula (1), Rf generally represents a perfluoroalkyl group and / or a partially fluorinated fluoroalkyl group, and is preferably a perfluoroalkyl group. The alkyl group of Rf has 1 to 6 carbon atoms, preferably 4, 5 or 6, and particularly preferably 6. Examples of Rf _{are, -CF 3, -CF 2 CF 3} , -CF 2 CF 2 CF 3, CF (CF 3) 2, -CF 2 CF 2 CF 2 CF 3, -CF 2 CF (CF 3) 2, _{-C (CF 3) 3, -} (CF 2) 4 CF 3, - (CF 2) 2 CF (CF 3) 2, -CF 2 C (CF 3) 3, -CF (CF 3) CF 2 CF 2 _{CF 3, - (CF 2)} 5 CF 3 , and the like.

The fluorine-containing monomer (a1) may be used alone or in combination of two or more.

As a fluorine-containing monomer (a1), the following are mentioned, for example.
_{CH 2 = C (-X) -COO-} (CH 2) m -S- (CH 2) n -Rf
_{CH 2 = C (-X) -COO-} (CH 2) m -SO 2 - (CH 2) n -Rf
_{CH 2 = C (-X) -COO-} (CH 2) n -Rf
_{CH 2 = C (-X) -CO} -NH- (CH 2) n -Rf
[Wherein, X represents a hydrogen atom, a linear or branched alkyl group having 1 to 21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a CFX ¹ X ² group (where X ¹ and X ² is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, respectively), a cyano group, a linear or branched fluoroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted benzyl group. A substituted or unsubstituted phenyl group; Y is —O— or —NH—; Z is a direct bond, —S— or —SO ₂ —; Rf has 1 to 6 carbon atoms; A fluoroalkyl group; m is 1 to 10, n is 0 to 10, and p is 0 or 1. ]

Specific examples of the general formula (1) include, but are not limited to, the following.
_{CH 2 = C (-H) -COO-} (CH 2) 2 -S-Rf
_{CH 2 = C (-H) -COO-} (CH 2) 2 -S- (CH 2) 2 -Rf
_{CH 2 = C (-H) -COO-} (CH 2) 3 -SO 2 -Rf
_{CH 2 = C (-H) -COO-} (CH 2) 2 -SO 2 - (CH 2) 2 -Rf
_{CH 2 = C (-H) -COO-} (CH 2) 2 -Rf
_{CH 2 = C (-H) -CO} -NH- (CH 2) 2 -Rf
_{CH 2 = C (-H) -COO} -CH 2 CH 2 N (C 2 H 5) SO 2 -Rf
_{CH 2 = C (-H) -COO} -CH 2 CH 2 N (CH 3) SO 2 -Rf
_{CH 2 = C (-H) -COO} -CH 2 CH (OCOCH 3) SO 2 -Rf
_{CH 2 = C (-CH 3)} -COO- (CH 2) 2 -S-Rf
_{CH 2 = C (-CH 3)} -COO- (CH 2) 2 -S- (CH 2) 2 -Rf
_{CH 2 = C (-CH 3)} -COO- (CH 2) 3 -SO 2 -Rf
_{CH 2 = C (-CH 3)} -COO- (CH 2) 2 -SO 2 - (CH 2) 2 -Rf
_{CH 2 = C (-CH 3)} -COO- (CH 2) 2 -Rf
_{CH 2 = C (-CH 3)} -CO-NH- (CH 2) 2 -Rf
_{CH 2 = C (-CH 3)} -CO-OCH 2 CH 2 N (C 2 H 5) SO 2 -Rf
_{CH 2 = C (-CH 3)} -CO-OCH 2 CH 2 N (CH 3) SO 2 -Rf
_{CH 2 = C (-CH 3)} -CO-OCH 2 CH (OCOCH 3) CH 2 -Rf

_{CH 2 = C (-F) -COO-} (CH 2) 2 -S-Rf
_{CH 2 = C (-F) -COO-} (CH 2) 2 -S- (CH 2) 2 -Rf
_{CH 2 = C (-F) -COO-} (CH 2) 2 -SO 2 -Rf
_{CH 2 = C (-F) -COO-} (CH 2) 2 -SO 2 - (CH 2) 2 -Rf
_{CH 2 = C (-F) -COO-} (CH 2) 2 -Rf
_{CH 2 = C (-F) -CO} -NH- (CH 2) 2 -Rf
_{CH 2 = C (-Cl) -COO-} (CH 2) 2 -S-Rf
_{CH 2 = C (-Cl) -COO-} (CH 2) 2 -S- (CH 2) 2 -Rf
_{CH 2 = C (-Cl) -COO-} (CH 2) 2 -SO 2 -Rf
_{CH 2 = C (-Cl) -COO-} (CH 2) 2 -SO 2 - (CH 2) 2 -Rf
_{CH 2 = C (-Cl) -COO-} (CH 2) 2 -Rf
_{CH 2 = C (-Cl) -CO} -NH- (CH 2) 2 -Rf

_{CH 2 = C (-CF 3)} -COO- (CH 2) 2 -S-Rf
_{CH 2 = C (-CF 3)} -COO- (CH 2) 2 -S- (CH 2) 2 -Rf
_{CH 2 = C (-CF 3)} -COO- (CH 2) 2 -SO 2 -Rf
_{CH 2 = C (-CF 3)} -COO- (CH 2) 2 -SO 2 - (CH 2) 2 -Rf
_{CH 2 = C (-CF 3)} -COO- (CH 2) 2 -Rf
_{CH 2 = C (-CF 3)} -CO-NH- (CH 2) 2 -Rf
_{CH 2 = C (-CF 2 H} ) -COO- (CH 2) 2 -S-Rf
_{CH 2 = C (-CF 2 H} ) -COO- (CH 2) 2 -S- (CH 2) 2 -Rf
_{CH 2 = C (-CF 2 H} ) -COO- (CH 2) 2 -SO 2 -Rf
_{CH 2 = C (-CF 2 H} ) -COO- (CH 2) 2 -SO 2 - (CH 2) 2 -Rf
_{CH 2 = C (-CF 2 H} ) -COO- (CH 2) 2 -Rf
_{CH 2 = C (-CF 2 H} ) -CO-NH- (CH 2) 2 -Rf
_{CH 2 = C (-CN) -COO-} (CH 2) 2 -S-Rf
_{CH 2 = C (-CN) -COO-} (CH 2) 2 -S- (CH 2) 2 -Rf
_{CH 2 = C (-CN) -COO-} (CH 2) 2 -SO 2 -Rf
_{CH 2 = C (-CN) -COO-} (CH 2) 2 -SO 2 - (CH 2) 2 -Rf
_{CH 2 = C (-CN) -COO-} (CH 2) 2 -Rf
_{CH 2 = C (-CN) -CO} -NH- (CH 2) 2 -Rf

_{CH 2 = C (-CF 2 CF} 3) -COO- (CH 2) 2 -S-Rf
_{CH 2 = C (-CF 2 CF} 3) -COO- (CH 2) 2 -S- (CH 2) 2 -Rf
_{CH 2 = C (-CF 2 CF} 3) -COO- (CH 2) 2 -SO 2 -Rf
_{CH 2 = C (-CF 2 CF} 3) -COO- (CH 2) 2 -SO 2 - (CH 2) 2 -Rf
_{CH 2 = C (-CF 2 CF} 3) -COO- (CH 2) 2 -Rf
_{CH 2 = C (-CF 2 CF} 3) -CO-NH- (CH 2) 2 -Rf
_{CH 2 = C (-F) -COO-} (CH 2) 3 -S-Rf
_{CH 2 = C (-F) -COO-} (CH 2) 3 -S- (CH 2) 2 -Rf
_{CH 2 = C (-F) -COO-} (CH 2) 3 -SO 2 -Rf
_{CH 2 = C (-F) -COO-} (CH 2) 3 -SO 2 - (CH 2) 2 -Rf
_{CH 2 = C (-F) -COO-} (CH 2) 3 -Rf
_{CH 2 = C (-F) -CO} -NH- (CH 2) 3 -Rf

_{CH 2 = C (-Cl) -COO-} (CH 2) 3 -S-Rf
_{CH 2 = C (-Cl) -COO-} (CH 2) 3 -S- (CH 2) 2 -Rf
_{CH 2 = C (-Cl) -COO-} (CH 2) 3 -SO 2 -Rf
_{CH 2 = C (-Cl) -COO-} (CH 2) 3 -SO 2 - (CH 2) 2 -Rf
_{CH 2 = C (-CF 3)} -COO- (CH 2) 3 -S-Rf
_{CH 2 = C (-CF 3)} -COO- (CH 2) 3 -S- (CH 2) 2 -Rf
_{CH 2 = C (-CF 3)} -COO- (CH 2) 3 -SO 2 -Rf
_{CH 2 = C (-CF 3)} -COO- (CH 2) 3 -SO 2 - (CH 2) 2 -Rf
_{CH 2 = C (-CF 2 H} ) -COO- (CH 2) 3 -S-Rf
_{CH 2 = C (-CF 2 H} ) -COO- (CH 2) 3 -S- (CH 2) 2 -Rf
_{CH 2 = C (-CF 2 H} ) -COO- (CH 2) 3 -SO 2 -Rf
_{CH 2 = C (-CF 2 H} ) -COO- (CH 2) 3 -SO 2 - (CH 2) 2 -Rf

_{CH 2 = C (-CN) -COO-} (CH 2) 3 -S-Rf
_{CH 2 = C (-CN) -COO-} (CH 2) 3 -S- (CH 2) 2 -Rf
_{CH 2 = C (-CN) -COO-} (CH 2) 3 -SO 2 -Rf
_{CH 2 = C (-CN) -COO-} (CH 2) 3 -SO 2 - (CH 2) 2 -Rf
_{CH 2 = C (-CF 2 CF} 3) -COO- (CH 2) 3 -S-Rf
_{CH 2 = C (-CF 2 CF} 3) -COO- (CH 2) 3 -S- (CH 2) 2 -Rf
_{CH 2 = C (-CF 2 CF} 3) -COO- (CH 2) 3 -SO 2 -Rf
_{CH 2 = C (-CF 2 CF} 3) -COO- (CH 2) 2 -SO 2 - (CH 2) 2 -Rf
[In the above formula, Rf is a 1-6 fluoroalkyl group. ]

Of these, in particular CH ₂ ═C (—H) —COO— (CH ₂ ) ₂ —Rf
_{CH 2 = C (-CH 3)} -COO- (CH 2) 2 -Rf
Is preferred.

The alkoxy group-containing monomer (a2) is a non-fluorine monomer and is a compound (alkylene glycol (meth) acrylate) represented by the following general formula (2).
_{^{CH 2 = C (R 1)}} -COO- (R 2 O) q -R 3 ···· (2)
[In the formula, R ¹ is a hydrogen atom or a methyl group; R ² is an alkylene group having some or all carbon atoms which may be substituted with a hydroxyl group of 2 to 4 hydrogen atoms; R ³ is hydrogen An atom or an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms; q is an integer of 1 to 50; ]

In the general formula (2), R ³ is preferably a hydrogen atom.
Further, q is preferably 1 to 30, more preferably 2 to 10, and particularly preferably 2 to 5.

Furthermore, in the general formula (2), R ² is preferably ethylene or propylene, and particularly preferably ethylene. R ² in the general formula (2) may be one kind or a combination of two or more kinds of alkylene. In that case, at least one of R ² is preferably ethylene. Examples of the R ² combination include an ethylene group / propylene group combination and an ethylene group / butylene group combination.

The alkoxy group-containing monomer (a2) may be a mixture of two or more.

Specific examples of the alkoxy group-containing monomer (a2) include, for example, the following, but are not limited thereto.
^{_{CH 2 = C (R 1)}} COO- (CH 2 CH 2 O) q -R 3
(Hereinafter, “CH ₂ CH ₂ O” may be described as “C ₂ H ₄ O”.)
^{_{CH 2 = C (R 1)}} COO- (CH 2 CH (CH 3) O) q -R 3
^{_{CH 2 = C (R 1)}} COO- (CH 2 CH 2 O) q '- (CH 2 CH (CH 3) O) q "-R 3
[Where q ′ + q ″ = q]

More specific examples include the following.
_{CH 2 = C (H) COO} -CH 2 CH 2 O-H
_{CH 2 = C (H) COO-} (CH 2 CH 2 O) 4 -H
_{CH 2 = C (H) COO-} (CH 2 CH 2 O) 5 -H
_{CH 2 = C (H) COO-} (CH 2 CH 2 O) 9 -H
_{CH 2 = C (H) COO-} (CH 2 CH 2 O) 30 -H
_{CH 2 = C (CH 3)} COO- (CH 2 CH 2 O) 9 -H
_{CH 2 = C (CH 3)} COO- (CH 2 CH 2 O) 23 -H
_{CH 2 = C (CH 3)} COO- (CH 2 CH 2 O) 50 -H
_{CH 2 = C (CH 3)} COO- (CH 2 CH (CH 3) O) 9 -H
_{CH 2 = C (CH 3)} COO- (CH 2 CH 2 CH 2 O) 9 -H
_{CH 2 = C (H) COO-} (CH 2 CH (CH 3) O) 9 -H
_{CH 2 = C (CH 3)} COO- (CH 2 CH (CH 3) O) 9 -H
_{CH 2 = C (CH 3)} COO- (C 2 H 4 O) 5 - (CH 2 CH (CH 3) O) 2 -H
_{CH 2 = C (CH 3)} COO- (C 2 H 4 O) 8 - (CH 2 CH (CH 3) O) 6 -H
_{CH 2 = C (H) COO-} (C 2 H 4 O) 5 - (CH 2 CH (CH 3) O) 3 -CH 3

Of these, CH ₂ ═C (H) COO—CH ₂ CH ₂ O—H
_{CH 2 = C (H) COO-} (CH 2 CH 2 O) 4 -H
_{CH 2 = C (H) COO-} (CH 2 CH 2 O) 5 -H
_{CH 2 = C (CH 3)} COO-CH 2 CH 2 O-H
_{CH 2 = C (CH 3)} COO- (CH 2 CH 2 O) 4 -H
_{CH 2 = C (CH 3)} COO- (CH 2 CH 2 O) 5 -H
Is preferred.

If the fluorine-containing copolymer (A) of the present invention is within a range not impairing the effects of the present invention, the fluorine-containing monomer (a1) represented by the above general formula (1) and the above general formula (2) The copolymer obtained by copolymerizing the alkoxy group-containing monomer (a2) represented by (2) and another copolymerizable monomer (a3) may be used.

  The other copolymerizable monomer (a3) is not particularly limited. For example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, vinyl sulfonic acid, allyl sulfonic acid, acrylic acid Polymerizable acids such as amidomethylpropanesulfonic acid and acid phosphoaxalkyl alkyl acrylate, polymerizable esters such as alkyl acrylate and alkyl methacrylate, polymerizable vinyl derivatives such as N-vinylformamide and N-vinylpyrrolidone, silicone macromers, Examples thereof include polymerizable macromonomers such as polyacryl macromonomer, polyester macromonomer, polyamide macromonomer, and polyoxyalkylene macromonomer, polymerizable sugar, and styrene.

Further, the other copolymerizable monomer (a3) may further contain a crosslinkable monomer.
The crosslinkable monomer can be a compound that has at least two reactive groups and / or carbon-carbon double bonds and does not contain fluorine. The crosslinkable monomer can be a compound having at least two carbon-carbon double bonds, or a compound having at least one carbon-carbon double bond and at least one reactive group. Examples of reactive groups are hydroxyl groups, epoxy groups, chloromethyl groups, blocked isocyanates, carboxyl groups and the like. In the present invention, a monomer having an amino group is not used.
When the crosslinkable monomer is contained, the water solubility is improved, and the ease of washing off at the time of washing the hair is preferable.

The crosslinkable monomer is preferably a non-fluorine crosslinkable monomer, and more preferably di (meth) acrylate.

The crosslinkable monomer has the general formula:

^{_{CH 2 = C (R 4)}} -COO- (R 5 O) s -CO-C (R 4) = CH 2 ···· (3)

Wherein each R ⁴ is a hydrogen atom or a methyl group; R ⁵ is an alkylene group having 2 to 10 carbon atoms in which part or all of the hydrogen atoms may be substituted with a hydroxyl group; Is an integer from 1 to 50. ]
The compound represented by the formula (alkylene glycol di (meth) acrylate) is particularly preferred.
The number of carbon atoms of ^{R 5} may, 2-10, for example 2-6, preferably in particular 2 to 4, ^{R 5} is preferably an ethylene group.

By controlling the molecular weight and molar ratio of each monomer constituting the fluorine-containing copolymer (A) of the present invention, solubility and viscosity can be adjusted. The weight average molecular weight of the fluorine-containing copolymer (A) of the present invention can be about 1000 to 1000000, preferably about 5000 to 500000.
If it is less than 1000, the film-forming ability is weak and the characteristics as a polymer may not be fully exhibited. If it is more than 1000000, the polymer may be viscous and the polymer may have poor solubility or dispersibility.
The weight average molecular weight is a value obtained by gel permeation chromatography in terms of polystyrene.

In the fluorine-containing copolymer (A) of the present invention, the amount of the alkoxy group-containing monomer (a2) with respect to 100 parts by mass of the fluorine-containing monomer (a1) is 10 to 400 parts by mass, preferably 25 to 150 parts by mass. More preferably, it is 43-100 mass parts.
If the amount of (a2) is small, hydrophilicity may not be obtained, and if it is large, oil repellency may be reduced.
Moreover, when using another copolymerizable monomer (a3), the ratio is less than 30 mass% with respect to a copolymer.
In particular, when a crosslinkable monomer is contained, the amount of the crosslinkable monomer is 30 parts by mass or less, for example, 0.1 to 20 parts by mass, particularly 100 parts by mass of the fluorine-containing monomer (a1). 0.5-10 mass parts is preferable. If it is larger than 30 parts by mass, a hard film may be formed and the feeling in use may be deteriorated.
In addition, the polymerization method of the fluorine-containing copolymer (A) used in the present invention is not particularly limited, and various methods such as bulk polymerization, solution polymerization, emulsion polymerization, and radiation polymerization can be selected. For example, solution polymerization using an organic solvent or emulsion polymerization using water or an organic solvent and water in combination is generally selected. More generally, it is diluted with water after polymerization, or is added to an emulsifier in water by adding an emulsifier to prepare a treatment solution, which is then blended into cosmetics, external medicines and the like.
Specifically, for example, it can be produced by a method disclosed as a production example of a copolymer in JP 2000-290640 A or WO 2009/142047 pamphlet, but is not limited thereto.

The fluorine-containing copolymer of the component (A) in the hair cosmetic composition of the present invention can be used singly or in combination of two or more, and the blending amount is not particularly limited, but is 0.01 to 20% by mass. (Hereinafter, simply referred to as “%”) is preferable, and 0.1 to 10% is more preferable. When component (A) is blended in this range, it is excellent in solubility and dispersibility in water and ethanol at the time of formulation, and handling is good, and when applied to hair, the hair feels cohesive even under high humidity. It is excellent in sustainability, excellent in hair washing properties, and can effectively promote hair repair.
More specifically, since the copolymer contains an alkoxy group at the time of preparation and at the time of washing the hair, it is excellent in solubility and dispersibility in water and ethanol, and the handling on the preparation is good. It works to quickly and cleanly wash away silicone oil and film-forming polymers that can lead to hardening, stiffening, reduction of smoothness, and squeaky feeling.
On the other hand, when it is applied to the hair as a cosmetic, since a coating film having airtightness and moisture resistance resulting from the fluorine content of the copolymer is formed on the hair surface, high humidity during drizzle or rainy season, etc. Even underneath, moisture from the outside of the hair can be prevented from being taken in, and the hairstyle with a sense of unity can be maintained without spreading or swelling of the hair. Since components such as hair repair components can be retained, these active components work effectively.

The silicone having an amino group of the component (B) used in the hair cosmetic composition of the present invention is an organopolysiloxane having an amino group or an ammonium group in the molecule, and the silicone derivative having an amino group refers to the amino group. The derivative which has the silicone which has in a structure.
The silicone having an amino group of component (B) or a derivative thereof is not particularly limited as long as it is usually used in cosmetics. Specifically, amino group-containing organopolysiloxane, polyoxyethylene, Block polymer or graft polymer, block polymer of amino group-containing organopolysiloxane and polyvinylpyrrolidone, or graft polymer, condensate of amino group-containing organopolysiloxane with amino acid and / or polyamino acid, and the like.
As a commercially available product, SM8904 Cosmetic Emulsion (containing 40% amodimethicone: manufactured by Toray Dow Corning), SILSTLE 401 (containing 21.5% (bisbutoxyoxydimethicone / PEG-60) copolymer: manufactured by Toray Dow Corning), SILSTLE 104 ((Bisisobutyl PEG-14 / Amodimethicone) copolymer: manufactured by Toray Dow Corning), SILSTLE 201 ((Bisisobutyl PEG-14 / Amodimethicone) copolymer: manufactured by Toray Dow Corning) may be used. Is possible.

  The component (B) in the present invention can be used singly or in combination of two or more, and the blending amount thereof is not particularly limited, but is preferably 0.01 to 20%, and a particularly excellent usability is obtained. Is more preferably 0.1 to 10%. When the component (B) is blended in this range, a product having a supple finish and a feeling of unity hair can be obtained. Moreover, the function of a component (A) is helped, moisture resistance can be improved more, and the component (C) which is a hair repair component mentioned later can be made to act effectively.

The hair repair component of the component (C) used in the hair cosmetic composition of the present invention acts on the damaged portion of the hair surface and inside, and returns the hair to a state of elasticity and stiffness before damage ( It has an effect of approaching.
Examples of the hair repair component of component (C) include amino acids and amino acid derivatives, peptides, sterols, homopolymers of 2-methacryloyloxyethyl phosphorylcholine, and copolymers of 2-methacryloyloxyethyl phosphorylcholine and hydrophobic monomers. And the like are preferable.
Specifically, examples of amino acids include glycine, alanine, valine, isoleucine, serine, threonine, aspartic acid, glutamic acid, acetylglutamic acid, asparagine, glutamine, lysine, hydroxylysine, arginine, cystine, cysteine, acetylcysteine, methionine. , Phenylalanine, tyrosine, proline, hydroxyproline, ornithine, citrulline, theanine, trimethylglycine and the like. As amino acid derivatives, N-lauroyl-L-glutamate di (phytosteryl 2-octyldodecyl), N-lauroyl-L-glutamate di (cholesteryl behenyl octyldodecyl), N-lauroyl-L-glutamate di (cholesteryl Octyldodecyl), N-lauroyl-L-glutamate di (phytosteryl, behenyl, 2-octyldodecyl), N-lauroylsarcosine isopropyl, N-lauroyl-L-glutamate dioctyldodecyl, and the like. Commercially available products include L-Du PS-203, L-Du CL-301, L-Du CL-202, L-Du PS-304, L-Du PS-306, L-Du SL-205, L-Du APS-307 (all manufactured by Ajinomoto Co., Inc.), Amitel LGOD ( Nippon Emulsion Co., Ltd.) can be used.
Peptides may be derived from animals, fish, shellfish, plants and silk. Specifically, collagen and derivatives thereof or hydrolysates thereof, elastin and derivatives thereof or hydrolysates thereof, keratin and derivatives thereof Alternatively, a degradation product thereof, wheat protein and a derivative thereof or a hydrolyzate thereof, soybean protein and a derivative thereof or a hydrolyzate thereof, and the like can be given.
Examples of sterols include cholesterol and phytosterol. More specifically, a homopolymer of 2-methacryloyloxyethyl phosphorylcholine or a copolymer of 2-methacryloyloxyethyl phosphorylcholine and a hydrophobic monomer may be specifically exemplified as MPIP homopolymers such as LIPIDURE-HM, LIPIDURE. -HM-500, LIPIDURE-HM-600 (all manufactured by NOF Corporation), as a copolymer of MPC and butyl methacrylate, LIPIDURE-PMB, LIPIDURE A, LIPIDURE C, LIPIDURE-NA, LIPIDURE-NR, LIPIDURE Commercially available products such as -S (both manufactured by NOF Corporation) can be used.
These component (C) hair repair components may be appropriately selected from one or two or more in combination.

  Although the compounding quantity of the component (C) in this invention is not specifically limited, 0.001 to 10% is preferable and 0.01 to 5% is more preferable in order to acquire the especially outstanding repair effect. When component (C) is blended in this range, the effect of repairing the hair is excellent, and beautiful hair without rustling can be obtained. In particular, in the present invention, when used in combination with the above components (A) and (B), the coating film having a sealing property formed on the hair surface is constant not only on the hair surface but also inside. Since it acts to keep time, the repair from the inside of the hair is effectively carried out, and as a result, it is possible to make the hair smooth, elastic, firm, and firm and beautiful.

  For the hair cosmetic of the present invention, components other than the above components (A) to (C), usually used in cosmetics, hydrocarbon oils, ester oils, higher alcohols, waxes, silicones other than component (B) Oils, anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, UV absorbers, water-soluble polymers, thickeners, polyhydric alcohols, sugars, lower alcohols and other aqueous components Antibacterial agents, antiseptics, pH adjusters, refreshing agents, vitamins, cosmetic ingredients, fragrances, powders, and the like can be appropriately blended within a range that does not impair the effects of the present invention.

  Examples of the oil agent include lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, behenyl alcohol, hexadecyl alcohol, oleyl alcohol, isostearyl alcohol, hexyl decanol, octyldodecanol, cetostearyl alcohol, 2-decyltetradecinol. , Cholesterol, phytosterol, sitosterol, lanosterol, higher alcohols such as monostearyl glycerol ether (batyl alcohol), ozokerite, squalane, squalene, paraffin, paraffin wax, liquid paraffin, pristane, polyisobutylene, microcrystalline wax, petrolatum, etc. Hydrocarbons, diisobutyl adipate, 2-hexyldecyl adipate , Di-2-heptylundecyl adipate, monoisostearic acid-alkyl glycol, isocetyl isostearate, trimethylolpropane triisostearate, ethylene glycol di-2-ethylhexanoate, cetyl 2-ethylhexanoate, tri-2- Trimethylolpropane ethylhexanoate, pentaerythritol tetra-2-ethylhexanoate, cetyl octoate, octyldodecyl gum ester, oleyl oleate, octyldodecyl oleate, decyl oleate, neopentyl glycol dicaprate, triethyl citrate, succinate 2-ethylhexyl acid, amyl acetate, ethyl acetate, butyl acetate, isocetyl stearate, butyl stearate, diisopropyl sebacate, di-2-ethylhexyl sebacate, Cetyl acid, myristyl lactate, isopropyl palmitate, 2-ethylhexyl palmitate, 2-hexyldecyl palmitate, 2-heptyl undecyl palmitate, cholesteryl 12-hydroxystearylate, isopropyl myristate, octyldodecyl myristate, myristic acid 2 -Ester oils such as hexyldecyl, myristyl myristate, hexyldecyl dimethyloctanoate, ethyl laurate, hexyl laurate, diisostearyl malate, waxes such as beeswax, carnauba wax, candelilla wax, whale wax, beef tallow, Beef leg fat, beef bone fat, hardened beef fat, hardened oil, turtle oil, pork fat, horse fat, mink oil, liver oil, egg yolk oil and other animal oils, lanolin, liquid lanolin, reduced lanolin, lanolin alcohol, hard lanolin, lanolin acetate , Lanolin derivatives such as lanolin fatty acid isopropyl, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, undecylenic acid, oleic acid, linoleic acid, arachidonic acid, docosahexaenoic acid (DHA), isostearic acid, 12-hydroxystearic acid, etc. Fatty acids, low polymerization dimethylpolysiloxane, high polymerization dimethylpolysiloxane, methylphenylpolysiloxane, decamethylcyclopentasiloxane, octamethylcyclotetrasiloxane, polyether-modified polysiloxane, polyoxyalkylene alkylmethylpolysiloxane Methyl polysiloxane copolymer, alkoxy-modified polysiloxane, alkyl-modified polysiloxane, cross-linked organopolysiloxane, fluorine-modified polysiloxane, glycerin-modified polysiloxane Hexane, higher alkoxy-modified silicones, higher fatty acid-modified silicones, silicone resins, silicone rubber, silicone or the like other than the component (B) of the silicone resin and the like.

Surfactants include cationic surfactants such as alkylamine salts, amine salts such as polyamines and aminoalcohol fatty acid derivatives, alkyl quaternary ammonium salts, aromatic quaternary ammonium salts, pyridium salts, imidazolium salts and the like; Examples of the ionic surfactant include sorbitan fatty acid ester, glycerin fatty acid ester, polyglycerin fatty acid ester, propylene glycol fatty acid ester, polyethylene glycol fatty acid ester, sucrose fatty acid ester, polyoxyethylene alkyl ether, polyoxypropylene alkyl ether, polyoxy Ethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polio Siethylene glycerin fatty acid ester, polyoxyethylene propylene glycol fatty acid ester, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene phytostanol ether, polyoxyethylene phytosterol ether, polyoxyethylene cholestanol ether, polyoxyethylene Cholesteryl ether, polyoxyalkylene-modified organopolysiloxane, polyoxyalkylene / alkyl co-modified organopolysiloxane, lauric acid diethanolamide, coconut oil fatty acid diethanolamide, coconut oil fatty acid monoethanolamide, polyoxyethylene coconut oil fatty acid monoethanolamide, Lauric acid monoisopropanolamide, palm oil fatty acid monoisopropanolamide, polyoxy Roren'yashi oil fatty monoisostearate Pas alkanolamides, alkanolamides, sugar ethers, and sugar amides.

  Examples of water-soluble polymers include chondroitin sulfate, hyaluronic acid, mucin, dermatan sulfate, mucopolysaccharides selected from heparin and keratan sulfate and salts thereof, gum arabic, tragacanth, galactan, carob gum, guar gum, caraya gum, carrageenan, pectin, agar Plant polymers such as quince seed, algae colloid, Trant gum, locust bean gum, galactomannan, microbial polymers such as xanthan gum, dextran, succinoglucan, pullulan, starch, carboxymethyl starch, methylhydroxypropyl starch, etc. Starch polymers, methylcellulose, ethylcellulose, methylhydroxypropylcellulose, carboxymethylcellulose, hydroxymethylcellulose, hydroxypropylcellulose Nitrocellulose, sodium cellulose sulfate, sodium carboxymethyl cellulose, crystalline cellulose, cellulose polymer of cellulose powder, alginic acid polymers such as sodium alginate, propylene glycol alginate, polyvinyl methyl ether, carboxyvinyl polymer, alkyl-modified carboxyvinyl Inorganic water such as vinyl polymers such as polymers, polyoxyethylene polymers, polyoxyethylene polyoxypropylene copolymer polymers, sodium polyacrylate, polyethyl acrylate, polyethyleneimine, bentonite, laponite, hectorite Functional polymers. Examples of the anionic polymer widely used as a setting agent include acrylic acid / ethyl acrylate / N-tert-butylacrylamide copolymer, acrylic resin alkanolamine, vinyl methyl ether / ethyl maleate copolymer, vinyl Examples thereof include a methyl ether / butyl maleate copolymer and a vinyl acetate / crotonic acid copolymer. As amphoteric polymers, N-methacryloylethyl N, N-dimethylammonium / α-N-methylcarboxybetaine / alkyl methacrylate copolymer, hydroxypropyl acrylate / butylaminoethyl methacrylate / octylamide acrylate copolymer Examples thereof include acrylic acid / dimethyldiallylammonium chloride / acrylamide copolymer, dimethyldiallylammonium chloride / acrylic acid copolymer, and the like. As cationic polymers, vinylpyrrolidone / N, N-dimethylaminoethyl methacrylate copolymer diethyl sulfate, diallyldimethylammonium chloride / hydroxyethylcellulose, glycidyltrimethylammonium chloride / hydroxyethylcellulose, dimethyldiallylammonium chloride polymer, dimethyl chloride Examples thereof include diallylammonium / acrylamide copolymer. Examples of the nonionic polymer include polyvinyl pyrrolidone, vinyl pyrrolidone / vinyl acetate copolymer, polyvinyl alcohol, polyurethane and the like.

  Examples of aqueous components include glycerin, diglycerin, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, polyethylene glycol and other lower alcohols, ethyl alcohol, isopropanol and other lower components. There is alcohol.

  Antibacterial agents include benzoic acid, sodium benzoate, salicylic acid, coalic acid, sorbic acid, potassium sorbate, parachlorometacresol, hexachlorophene, benzalkonium chloride, chlorhexidine chloride, trichlorocarbanilide, photosensitizer, bis (2 -Pyridylthio-1-oxide) zinc, isopropylmethylphenol and the like, and examples of the preservative include paraoxybenzoic acid ester, phenoxyethanol and the like.

  Examples of pH adjusters include lactic acid, citric acid, glycolic acid, succinic acid, tartaric acid, malic acid, potassium carbonate, sodium bicarbonate, ammonium bicarbonate, sodium hydroxide, potassium hydroxide, triethanolamine, monoethanolamine, Examples of the refreshing agent include L-menthol and camphor.

  Vitamins such as vitamin A and derivatives thereof, vitamin B and derivatives thereof, vitamin C and derivatives thereof, vitamin E and derivatives thereof, linolenic acid and derivatives thereof, and vitamins such as phytonadione, menaquinone, menadione, menadiol Ks; vitamin Ps such as eriocitrin and hesperidin; and biotin, carcinine, ferulic acid and the like.

  If the powder is used in ordinary cosmetics, its shape (spherical, needle-like, plate-like, etc.), particle size (smoke-like, fine particles, pigment grade, etc.), particle structure (porous) , Non-porous, etc.) can be used.

  The method for producing the hair cosmetic of the present invention is not particularly limited and can be carried out as a solid, cream, emulsion, cloudy lotion, etc., and hair wax, hair cream, hair milk, hair treatment, split hair coating agent Alternatively, it can be used as a hair foam using a propellant such as liquefied petroleum gas (LPG) for various out bath hair cosmetics.

  Hereinafter, the present invention will be described in more detail with reference to examples. Note that these do not limit the present invention.

[Reference Production Examples 1 to 7]: Reference Production Examples of Fluorine-Containing Copolymer Reference production examples of the fluorine-containing copolymer used in the present invention are shown below.

[Reference Production Example 1]
In a 100 ml four-necked flask equipped with a reflux condenser, a nitrogen inlet tube, a thermometer, and a stirrer, a fluorine-containing monomer —CH ₂ ═C (H) COO—CH ₂ CH ₂ C ₆ F ₁₃ (hereinafter referred to as “C6FA ( a1) ”) and 18.6 g of polyethylene glycol acrylate CH ₂ ═C (H) COO— (CH ₂ CH ₂ O) _n —H (BLEMMER AE90, manufactured by NOF CORPORATION, the average value of n is 2 0.0, hereinafter referred to as “AE90 (a2)”) and 11.4 g of methyl ethyl ketone (hereinafter referred to as “MEK”) 45 g were charged, and nitrogen bubbling was performed for 30 minutes. After raising the internal temperature to 50 to 65 ° C. under a nitrogen stream, 0.4 g of perbutyl PV (hereinafter referred to as “PV”) was added and reacted at 60 to 65 ° C. for 6 hours. After the MEK was distilled off at about 70 ° C. under reduced pressure to obtain a pale yellow polymer residue, 122.4 g of purified water was added, and the internal temperature was kept at about 80 ° C. for 1 hour or longer. Thereafter, the mixture was cooled to prepare an aqueous dispersion having a solid concentration of about 20%.
The weight average molecular weight (Mw) of the obtained copolymer was 18200 by GPC measurement in terms of polystyrene.

[Reference Production Example 2]
AE90 in Reference Production Example 1 is polyethylene glycol methacrylate acrylate CH ₂ ═C (CH ₃ ) COO— (CH ₂ CH ₂ O) _n —H (BLEMMER PE350 manufactured by NOF CORPORATION, average value of n is 8.0, (Hereinafter referred to as “PE350 (a2)”), the same polymerization reaction as in Reference Production Example 1 was performed to prepare an aqueous dispersion having a solid content concentration of about 20%.
The weight average molecular weight (Mw) of the obtained copolymer was 16400 by GPC measurement in terms of polystyrene.

[Reference Production Example 3]
In a 100 ml four-necked flask equipped with a reflux condenser, a nitrogen inlet tube, a thermometer and a stirrer, 18.6 g of C6FA (a1), 5.7 g of AE90 (a2), polyethylene glycol acrylate CH ₂ = 5.7 g of C (H) COO— (CH ₂ CH ₂ O) _n —H (BLEMMER AE200, manufactured by NOF Corporation, n is 4.5, hereinafter referred to as “AE200 (a2)”) and MEK Then, the same polymerization reaction as in Reference Production Example 1 was carried out to prepare an aqueous dispersion having a solid concentration of about 20%.
The weight average molecular weight (Mw) of the obtained copolymer was 15500 by GPC measurement in terms of polystyrene.

[Reference Production Example 4]
In a 100 ml four-necked flask equipped with a reflux condenser, a nitrogen inlet tube, a thermometer and a stirrer, 18.6 g of C6FA (a1), 10.5 g of PE350 (a2), polyethylene glycol diacrylate CH ₂ = C (H) COO— (CH ₂ CH ₂ O) _n —CO—CH═CH ₂ (BLEMMER ADE300 manufactured by NOF Corporation has an average value of 7.0, hereinafter referred to as “ADE300 (a3)”) 0.9 g and 45.0 g of isopropanol (hereinafter referred to as “IPA”) were charged, and the same polymerization reaction as in Reference Production Example 1 was carried out to prepare an aqueous dispersion having a solid content concentration of about 20%.
The weight average molecular weight (Mw) of the obtained copolymer was 16400 by GPC measurement in terms of polystyrene.

[Reference Production Example 5]
In a 100 ml four-necked flask equipped with a reflux condenser, a nitrogen inlet tube, a thermometer and a stirrer, 18.6 g of C6FA (a1), hydroxyethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd., hereinafter referred to as “HEA (a3 ) "), 2.5 g of AE200 (a2), 0.9 g of ADE300 (a3), and 45 g of IPA, and bubbled with nitrogen for 30 minutes. After raising the internal temperature to 50-65 ° C. under a nitrogen stream, 0.4 g of PV was added and reacted at 60-65 ° C. for 6 hours. From the obtained solution, IPA was removed at 70 ° C. under reduced pressure to obtain a pale yellow copolymer.
The weight average molecular weight (Mw) of the obtained copolymer was 16280 by GPC measurement in terms of polystyrene.
This copolymer was washed with purified water, and then IPA was added to prepare a solution having a solid content concentration of 30%.

[Reference Production Example 6]
In a 100 ml four-necked flask equipped with a reflux condenser, a nitrogen inlet tube, a thermometer, and a stirrer, 18.6 g of C6FA (a1), 2.5 g of HEA (a3), 8.0 g of AE90 (a2), 0.9 g of ADE300 (a3) and 45 g of IPA were charged, and the same polymerization reaction as in Reference Production Example 5 was performed to obtain a pale yellow copolymer.
The weight average molecular weight (Mw) of the obtained copolymer was 17900 by GPC measurement in terms of polystyrene.
This copolymer was washed with purified water in the same manner as in Reference Production Example 5, and then IPA was added to prepare a solution having a solid content concentration of 30%.

[Reference Production Example 7]
In a 100 ml four-necked flask equipped with a reflux condenser, a nitrogen inlet tube, a thermometer and a stirrer, 18.6 g of C6FA (a1), 3.5 g of HEA, 7.2 g of AE200 (a2), ADE300 (a3 ) And 45 g of IPA were charged, and the same polymerization reaction as in Reference Production Example 5 was performed to obtain a pale yellow copolymer.
The weight average molecular weight (Mw) of the obtained copolymer was 17200 by GPC measurement in terms of polystyrene.
This copolymer was washed with purified water in the same manner as in Reference Production Example 5, and then IPA was added to prepare an IPA solution having a solid content concentration of 40%.

Example 1 (Invention products 1 to 7 and Comparative products 1 to 7): Hair milk Hair milks shown in Tables 1 and 2 below were prepared by the following production method, (i) suppleness, (b) sense of unity, (c) For each item of unity feeling, (d) hair wash, (e) moisture resistance, and (d) hair repair effect (elasticity), the evaluation method and criteria shown below are evaluated and determined, and the results are also shown The results are shown in Tables 1 and 2.
In the formulations of the following examples, all of the reference production examples and commercially available raw materials for the fluorine-containing copolymer of the component (A) of the present invention are described in pure amounts.

(Production method)
A: Components 1 to 9 are heated to 80 ° C. and mixed.
B: Components 10 to 13 are heated to 80 ° C. and mixed.
C: A is added to B and emulsified.
D: C is cooled.
E: Components 14 to 21 were sequentially added to D, and mixed uniformly to obtain hair milk.

[Evaluation methods for evaluation items (a) to (c) and (d)]
In the morning of rainy day (under high humidity), which has been raining all day and night since the previous day, 10 cosmetic panel evaluation specialists used the hair milk of the present invention and the comparative product on dry hair, and (i) suppleness. , (B) Each sense of unity, (c) Sustainability of unity, and (d) Hair washability, each one was subjected to sensory evaluation in five stages according to the following evaluation criteria (I). The average score was determined according to the following criteria (II).
(I) The suppleness and (b) the sense of unity were evaluated for the feel and appearance of the finished product when the hair milk of the present invention and the comparative product were applied to dry hair. After 3 hours from the application, the feeling of unity of hair was evaluated by touch and appearance.
Regarding the hair washability of (d), the ease of dropping the hair milk of the present invention product and the comparative product when washing with the shampoo A of the following Reference Preparation Example on the night of application, and the absence of washing are (i) to ( Evaluation and determination were performed in the same manner as in (c).

Evaluation criteria (I)
[Evaluation Result]: [Score]
Very good: 5 points Good: 4 points Normal: 3 points Somewhat bad: 2 points Bad: 1 point Judgment criteria (II)
[Average score]: [Judgment]
4.5 or more: ◎
3.5 or more and less than 4.5: ○
1.5 or more and less than 3.5: △
Less than 1.5: ×

[(E) Moisture resistance evaluation method]
After hair bleaching and damaging Asian hair bundles (length 10 cm, 1 g), wash with shampoo A of the following reference preparation example, and rinse by applying rinse B of the following reference preparation example, After towel drying, 0.3 g of hair milk of Tables 1 and 2 was applied thereto, and further dried with a drier to prepare a hair bundle for evaluation. This hair bundle was allowed to stand for 90 minutes in a constant temperature and humidity chamber having a temperature of 40 ° C. and a humidity of 90%.
Immediately after the production of the evaluation hair bundle, the width of the most widened portion on the tip side (the unbound side) of the hair bundle after standing for 90 minutes in the constant temperature and humidity chamber was measured, and 90 minutes after the production. The change rate of the width | variety of the back hair | bristle bundle was determined and evaluated using the following criterion (III) as (e) moisture resistance.

Criteria (III)
[Evaluation]: [Judgment]
Change rate of hair bundle width + less than 5%: ◎
Change rate of hair bundle width + 5% or more and less than 10%: ○
Change rate of hair bundle width + 10% or more and less than 20%: △
Change rate of hair bundle width + 20% or more: ×

[(F) Evaluation method of hair repair effect (elasticity)]
Similar to the evaluation of the moisture resistance of (e) above, the hair bundle (length: 10 cm, 1 g) that had been subjected to hair bleaching treatment and damaged was washed with shampoo A of the following reference preparation example, and rinse B was applied. After rinsing, towel drying was performed, and after applying 0.2 g of hair milk of Tables 1 and 2 to the hair, drying with a dryer was repeated once a day for 5 days.
A hair bundle for evaluation was prepared by taking 10 pieces each having a length of 5 cm from the center of the hair bundle.
Further, the stress load value when the hair bundle is bent is measured with a hair elasticity measuring machine (see Japanese Patent Laid-Open No. 2000-32186), and the load value when compared with the stress load value of the hair bundle to which hair milk is not applied. Based on the rate of change, the hair repair effect (elasticity) was determined using the following criteria (IV).

Judgment criteria (IV)
[Evaluation]: [Judgment]
Change rate of load value + 20% or more: ◎
Change rate of load value + 10% or more and less than 20%: ○
Change rate of load value + 5% or more and less than 10%: △
Load value change rate + Less than 5%: ×

Reference preparation example: Shampoo A
Shampoo A was prepared by the following formulation and manufacturing method.
(Ingredient) (%)
1. Sodium tetradecenesulfonate 10
2. Palm oil fatty acid methyl taurine sodium 6
3. Palm oil fatty acid amidopropyl betaine 4
4). Coconut oil fatty acid acyl glutamic acid triethanolamine 3
5. Palm oil fatty acid diethanolamide 6
6.1,3-Butylene glycol 2
7). Cationized guar gum 1
8). Edetate disodium 0.2
9. Preservative 0.1
10. Fragrance 0.1
11. Purified water remaining amount (production method)
Ingredients 1 to 11 are uniformly heated and mixed at 70 ° C. and then cooled.

Reference Preparation Example: Rinse B
A rinse was prepared by the following formulation and manufacturing method.
(Ingredient) (%)
1. Cetostearyl alcohol 5
2. Isopropyl myristate 2
3. Stearyltrimethylammonium chloride 2
4). Propylene glycol 5
5. Hydroxyethyl cellulose 0.5
6). Preservative 0.1
7). Fragrance 0.1
8). Purified water remaining amount (production method)
Ingredients 1 and 2 are uniformly heated and mixed at 70 ° C., added to ingredients 3 to 6 and 8 dissolved by heating, and emulsified. After cooling, component 7 is added.

As is clear from the results of Tables 1 and 2, the hair milks of the present invention products 1 to 7 have the characteristics of each component sufficiently by using the components (A) to (C) in combination as compared with the comparative products 1 to 7. Since it was exhibited in two minutes, all had a smooth and supple finish, and were excellent in unity feeling, persistence of unity feeling, hair washability, moisture resistance, and hair repair effect (elasticity).
On the other hand, comparative product 1, which does not contain component (A) and instead contains a general-purpose film-forming polymer as a hair setting agent, has a sense of unity and has a sense of unity, but a certain degree of unity can be obtained. (Hair bundle) A hard film was formed on the surface, and it was stiff, inferior in flexibility, and did not feel so much that the damage was repaired in spite of the evaluation of elasticity. Further, the hair washability was very poor, and the hair milk coating film remained unwashed.
Further, in Comparative Product 2 in which the film-forming polymer was reduced from Comparative Product 1, the coating was still hard, not supple, inferior in hair washability, and the persistence of the unity decreased.
Furthermore, instead of not blending the component (A), the comparative product 3 in which the blending amounts of the components (B) and (C) are increased is supple and harmonious, but the component (A) is not blended. Therefore, due to the characteristics of this, the unity feeling lacks durability and moisture resistance, the hair bundle spreads under high humidity, and on the other hand, the feeling of not being washed off remains and the hair washability is inferior. It was.
Comparative product 4, which does not contain component (B), but instead contains high viscosity dimethicone, has moisture resistance and a feeling of unity, but is originally inferior in unity when finished. The hair milk had a feeling that the hair milk was not completely washed out, and the hair restoration effect was not felt for the evaluation of the elasticity of (f).
Furthermore, the comparative product 5 in which the blending amount of the components (A) and (C) is increased instead of blending the component (B) is good in moisture resistance and hair washability, but lacks flexibility and inferior in unity. Met.
Moreover, the comparative product 6 which mix | blended the cationized guar gum instead of the hair repair component of a component (C) becomes the feel of the surface of a hair bundle hard, is inferior in the softness and the hair repair effect, and mixes a component (C). In Comparative product 7 in which the blending amounts of components (A) and (B) were increased, the hair did not feel firm, stiff or shiny, and the repair effect of damaged hair was low.

Example 2: Cloudy hair lotion (ingredient) (%)
1. Dicocoylethylhydroxyethylmonium
Methosulfate 1
2. Amodimethicone (Note 2) 5
3. Behenyltrimethylammonium chloride 0.1
4.1,3-Butylene glycol 5
5. Creatine 0.5
6). L-proline 0.5
7). Creatinine 0.5
8). Acetylglutamic acid 0.2
9. L-serine 0.2
10. L-Arginine 0.1
11. Theanine 0.1
12 Glycine 0.1
13. Acetylcysteine 0.1
14 Trimethylglycine 1.0
15. Glycerin 5
16. Dipropylene glycol 5
17. Fluorine-containing copolymer of Reference Production Example 2 1
18. Fluorine-containing copolymer of Reference Production Example 5 4
19. Ethanol 15
20. Fragrance 0.5
21. Purified water remaining amount (Note 2) SM8904 Cosmetic Emulsion (Toray Dow Corning)

(Production method)
A: Components 1 to 21 were mixed and dissolved uniformly to obtain a cloudy hair lotion.

When the white cloudy hair lotion of Example 2 was evaluated in the same manner as in Example 1, it was excellent in flexibility and finished feeling of unity, high in moisture resistance, and excellent in sustainability of feeling of unity. Moreover, it was excellent in that it had both wash-off properties (hair-washing properties) and hair-repairing effect (elasticity) during hair washing.

Example 3: Hair milk (component) (%)
1. Distearyldimethylammonium chloride 0.5
2. Stearyltrimethylammonium chloride 0.5
3. Cetostearyl alcohol 2
4). Behenyl alcohol 1
5. Liquid paraffin 3
6). Octyl palmitate 1
7). Cetyl palmitate 1
8). Methylphenyl polysiloxane 0.5
9. Octyldodecanol 0.5
10. N-lauroyl-L-glutamate di (phytosteryl, 2-octyldodecyl) (Note 3) 0.5
11. N-lauroyl-L-glutamate di (cholesteryl behenyl octyldodecyl) (Note 4) 0.5
12 N-lauroyl-L-dioctyldecyl glutamate (Note 5) 0.5
13. N-lauroyl-L-glutamate di (phytosteryl, behenyl, 2-octyldodecyl) (Note 6) 0.5
14 N-lauroyl sarcosine isopropyl (Note 7) 0.5
15. (Bisbutyroxyamodimethicone / PEG-60)
Copolymer (Note 1) 5
16. Ethanol 2
17. Fragrance 0.3
18. Fluorine-containing copolymer of Reference Production Example 1 2
19. Fluorine-containing copolymer of Reference Production Example 5 2
20. Fluorine-containing copolymer of Reference Production Example 6 2
21.1,2-Pentanediol 5
22. Phenoxyethanol 0.5
23. Purified water remaining amount (Note 3) El Dew PS-203 (Ajinomoto Co., Inc.)
(Note 4) El Deu CL-301 (Ajinomoto Co., Inc.)
(Note 5) Amitel LGOD (manufactured by Nippon Emulsion)
(Note 6) El Dew PS-304 (Ajinomoto Co., Inc.)
(Note 7) El Dew SL-205 (Ajinomoto Co., Inc.)

(Production method)
A: Components 1 to 14 are heated to 80 ° C. and mixed.
B: Components 21 to 23 are heated to 80 ° C. and mixed.
C: A is added to B and emulsified.
D: C is cooled.
E: Components 15 to 20 were sequentially added to D and mixed uniformly to obtain hair milk.

The hair milk of Example 3 was evaluated in the same manner as in Example 1. As a result, all the items of suppleness, cohesiveness, persistence of cohesiveness, hair washability, moisture resistance, and hair repair effect (elasticity) were excellent. .

Example 4: Hair cream (ingredient) (%)
1. N-stearoyl-L-glutamic acid 0.7
2. Dipropylene glycol 5
3. Methylparaben 0.1
4.1,3-Butylene glycol 5
5. Behenyl alcohol 0.3
6). Myristyl alcohol 0.2
7). Beeswax 1
8). Cholesterol 0.5
9. Phytosterol 0.5
10. Dimethicone (100 mPa · s) 0.5
11. (Bisisobutyl PEG-14 / Amodimethicone)
Copolymer (Note 8) 10
12 Polyoxyethylene hydrogenated castor oil (40 EO) 0.5
13. Fluorine-containing copolymer of Reference Production Example 3
14 Fluorine-containing copolymer of Reference Production Example 7
15. Hydrolyzed wheat peptide 1
16. Hydrolyzed silk 1
17. Fish-derived collagen 0.5
18. Hydrolyzed conchiolin 0.5
19. Hydrolyzed soy peptide 0.5
20. Hydrolyzed keratin 0.5
21. Fragrance 0.1
22. Monoethanolamine 0.3
23. Purified water remaining amount (Note 8) SILSTYLE 104 (Toray Dow Corning)

(Production method)
A: Components 1 to 12 are heated to 80 ° C. and mixed.
B: Components 22 to 23 are heated to 80 ° C. and mixed.
C: A is added to B and emulsified.
D: C is cooled.
E: Components 13 to 21 were sequentially added to D, and mixed uniformly to obtain a hair cream.

The hair cream of Example 4 was evaluated in the same manner as in Example 1. As a result, it was excellent in suppleness and a sense of unity in the finish, high in moisture resistance, and very excellent in unity. Moreover, it was excellent in that it had both shampooing properties and a hair repair effect (elasticity).

Example 5: Foam hair treatment Aerosol stock solution formulation (component) (%)
1. Behenyltrimethylammonium chloride 0.5
2. Amodimethicone (Note 2) 1
3. Dimethylpolysiloxane (10 mPa · s) 2
4). N-lauroyl-L-glutamate di (phytosteryl, behenyl, 2-octyldodecyl) (Note 3) 0.5
5.1,3-Butylene glycol 5
6). Fluorine-containing copolymer of Reference Production Example 4 2
7). Fluorine-containing copolymer of Reference Production Example 1
8). Polyquaternium-51 (Note 9) 0.5
9. Polymethacryloyloxyethyl phosphorylcholine (Note 10) 0.5
10. Polyquaternium-65 (Note 11) 0.5
11. Polyquaternium-64 (Note 12) 0.5
12 Polyquaternium-61 (Note 13) 0.5
13. Fragrance 0.1
14 Methylparaben 0.3
15. Purified water remaining amount (Note 9) LIPIDURE-PMB (manufactured by NOF Corporation)
(Note 10) LIPIDURE-HM-600 (manufactured by NOF Corporation)
(Note 11) LIPIDURE-A (manufactured by NOF Corporation)
(Note 12) LIPIDURE-C (manufactured by NOF Corporation)
(Note 13) LIPIDURE-S (manufactured by NOF Corporation)

(Production method)
A: Components 1 to 15 were uniformly mixed and dissolved to obtain an aerosol stock solution.
The aerosol can was filled so that the mass ratio of B: A aerosol stock solution and propellant (liquefied petroleum gas) was 97: 3 to obtain a foamy hair treatment.

When the foam-like hair treatment of Example 5 was evaluated in the same manner as in Example 1, all items of suppleness, cohesiveness, persistence of cohesiveness, hair washability, moisture resistance, and hair repair effect (elasticity) It was excellent.
more than

Claims (2)

The following components (A) to (C);
(A) A monomer that essentially contains a fluorine-containing monomer (a1) represented by the following general formula (1) and an alkoxy group-containing monomer (a2) represented by the following general formula (2) Fluorine-containing copolymer obtained by copolymerizing CH ₂ ═C (—X) —CO—Y — [— (CH ₂ ) _m —Z—] _p — (CH ₂ ) _n —Rf
(1)
[Wherein, X represents a hydrogen atom, a linear or branched alkyl group having 1 to 21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a CFX ¹ X ² group (where X ¹ and X ² is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, respectively), a cyano group, a linear or branched fluoroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted benzyl group. A substituted or unsubstituted phenyl group; Y is —O— or —NH—; Z is a direct bond, —S— or —SO ₂ —; Rf has 1 to 6 carbon atoms; A fluoroalkyl group; m is 1 to 10, n is 0 to 10, and p is 0 or 1. ]
^{_{CH 2 = C (R 1)}} -COO- (R 2 O) q -R 3 ···· (2)
[In the formula, R ¹ is a hydrogen atom or a methyl group; R ² is an alkylene group having some or all carbon atoms which may be substituted with a hydroxyl group of 2 to 4 hydrogen atoms; R ³ is hydrogen An atom or an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms; q is an integer of 1 to 50; ]
(B) A hair cosmetic comprising an amino group-containing silicone and / or a derivative thereof (C) a hair repair component. The hair repair component of component (C) is selected from amino acids and amino acid derivatives, peptides, sterols, homopolymers of 2-methacryloyloxyethyl phosphorylcholine, and copolymers of 2-methacryloyloxyethyl phosphorylcholine and hydrophobic monomers. The hair cosmetic composition according to claim 1, wherein the hair cosmetic composition is one kind or two or more kinds.