JPH1087442A - Hair cosmetic composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hair cosmetic composition having excellent hair styling properties, giving a good feeling of finishing with good flexibility and good texture. (A) Weight average molecular weight of 10,000 to 5
(B) at least one kind of a cationic polymer, wherein the weight ratio of (a) / (b) is 1/10 to 10/1; A hair cosmetic composition comprising a total of 0.1 to 10% by weight of a) and (b).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a hair cosmetic composition comprising a combination of an amine oxide group-containing copolymer and a cationic polymer. The composition of the present invention has excellent hair styling properties, gives good flexibility and a good feeling of texture, and is useful for applications such as hair spray, hair mousse, hair set lotion, and hair gel.

[0002]

2. Description of the Related Art As a method for holding hair in a desired shape, a solution in which a film-forming polymer compound is dissolved in water, lower alcohol or a mixed solvent thereof is applied to hair.
It is common practice to dry hair to make hair. For the purpose of holding such hair in a desired shape, and for the purpose of improving the feel when applying cosmetics to hair, cationic polymer compounds have been widely used in the past. There are problems that the hair styling effect of maintaining the shape is not sufficient, and the formed film is flexible, so that the elasticity of the hair, which maintains the shape particularly under high humidity, is low. Furthermore, when a hair cosmetic containing a cationic polymer compound is used repeatedly for a long period of time, the cationic polymer compound accumulates in the hair and build-up such as impairing combability and impairing the appearance of the hair. There was a problem that was said to be unsatisfactory.

[0003] In order to improve such problems, especially hair styling effect and elasticity, Japanese Patent Application Laid-Open No. 55-59107 discloses a hair cosmetic comprising a combination of a cationic polymer compound and an anionic polymer. A cosmetic composition has been proposed, and JP-A-58-124712 proposes a hair cosmetic composition comprising a combination of a cationic polymer compound and a zwitterionic polymer.

[0004]

However, the above composition has not yet provided a hairdressing composition which has satisfactory hair styling effects and elasticity. An object of the present invention is to provide a hairdressing cosmetic composition which solves the above-mentioned problems of the cationic polymer compound, has excellent hairdressing properties, has good elasticity, and gives a finished feeling with a good texture. Is to do.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, by combining a cationic polymer compound and an amine oxide group-containing polymer compound, excellent hair styling has been achieved. It has been found that a cosmetic composition for hair styling, which has good properties, gives a good feeling of finish with good flexibility and good texture, and also has a good feel when applying the cosmetic to the hair, completes the present invention. I came to.

That is, the present invention provides (a) a weight average molecular weight of 1
It is composed of at least one kind of a polymer having an amine oxide group of 000 to 500,000 and (b) at least one kind of a cationic polymer, and a weight ratio of (a) / (b) is 1/1.
0 to 10/1, and the total amount of (a) and (b) is 0.1
A hair cosmetic composition characterized by being contained in an amount of from 10 to 10% by weight. Hereinafter, the present invention will be described in detail.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The amine oxide group-containing polymer (a) used in the present invention has the structure of (A) a polymer composed of an amine oxide group-containing unsaturated monomer, or (A) A) a copolymer having an amine oxide group-containing unsaturated monomer and (B) a hydrophobic unsaturated monomer, and preferably comprises (A) an amine oxide group-containing monomer 15 to It has a structure of a copolymer comprising 90% by weight and (B) 85 to 10% by weight of a hydrophobic monomer unit.

Here, the component (a) having the structure of the polymer comprising the component (A) means that the component (a) is produced by any one of the following methods. It includes the structural unit of (A). Examples of the method for producing the amine oxide group-containing polymer include the following methods (1) to (4). Among them, the method is preferable. A method of polymerizing an amine oxide group-containing monomer (A) obtained by oxidizing a nitrogen-containing monomer. A method of polymerizing a nitrogen-containing monomer and then oxidizing the nitrogen-containing group. A method comprising polymerizing a monomer having a reactive group and reacting a substance having both an active group and an amine oxide group capable of reacting with the functional group. A method comprising polymerizing a monomer having a reactive group, reacting a substance having both an active group capable of reacting with the functional group and a nitrogen-containing group, and then oxidizing the nitrogen-containing group.

The component (a) having the structure of a copolymer consisting of (A) and (B) (hereinafter sometimes referred to as an amine oxide group-containing copolymer)
The component (a) is produced by any one of the following methods, so that the copolymer contains the structural units (A) and (B). Examples of the method for producing the amine oxide group-containing copolymer include the following methods. Among them, the method is preferable.

A method of copolymerizing an amine oxide group-containing monomer (A) obtained by oxidizing a nitrogen-containing monomer with a hydrophobic monomer (B). A method comprising copolymerizing a nitrogen-containing monomer and a hydrophobic monomer (B) and then oxidizing the nitrogen-containing group. Monomers having reactive functional groups and hydrophobic monomers (B)
And then reacting a substance having both an active group capable of reacting with the functional group and an amine oxide group. Monomers having reactive functional groups and hydrophobic monomers (B)
, A substance having both an active group capable of reacting with the functional group and a nitrogen-containing group is reacted, and then the nitrogen-containing group is oxidized.

Amine oxide group-containing monomer (A):
Examples of the amine oxide group-containing monomer of the component (A) include monomers represented by general formulas (I) to (IV).

[0012]

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(Wherein R ¹ represents a hydrogen atom or a methyl group;
R ² and R ³ may be the same or different and have 1 to 2 carbon atoms.
4, an alkyl group, an aryl group or an arylalkyl group, R ⁴ and R ⁵ represent an alkyl group having 1 to 24 carbon atoms, an aryl group or an arylalkyl group, X represents a divalent linking group,
m is an integer of 0 to 1, n is an integer of 0 to 4, p is 0 to 3
Where Y is an integer

[0014]

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The other R ^{6 to} R ¹³ are a hydrogen atom or a C 1 to C 1
24 represents an alkyl group, an aryl group or an arylalkyl group, and a and b each represent an integer of 1 to 10 which may be the same or different)

The monomer represented by the general formula (I) includes N,
N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate (hereinafter abbreviated as N, N-dimethylaminoethyl (meth) acrylate), N, N-diethylaminoethyl (meth) acrylate, N, N- Dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl ( (Meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide, N, N-dimethylaminopropionate vinyl, p-dimethylaminomethylstyrene,
amine oxides such as p-dimethylaminoethylstyrene, p-diethylaminomethylstyrene and p-diethylaminoethylstyrene, or acid anhydrides containing unsaturated groups such as maleic anhydride, itaconic anhydride and crotonic anhydride; Reaction products with N, N-dimethyl-1,3-propanamine, N, N-dimethyl-p-phenylenediamine and the like having a reactive group with an anhydride group and a tertiary amino group at the same time, epoxy such as glycidyl methacrylate Compounds such as N, N-dimethyl-1,3-propanamine and N, N-dimethyl-p-phenylenediamine having a group-containing monomer and a reactive group for these epoxy groups and a tertiary amino group simultaneously And amine oxides such as a reaction product with the above. Also, a product of an epoxy group-containing monomer such as glycidyl methacrylate and an amine oxide-containing material containing a group reactive with an epoxy group such as hydroxyethyl-N, N-dimethylamine oxide, 2-isocyanatoethyl ( Examples of the product include an isocyanate group-containing monomer such as meth) acrylate and an amine oxide-containing product containing a group reactive with an isocyanate group such as hydroxyethyl-N, N-dimethylamine oxide.

The monomers represented by the general formula (II) include 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 2-methyl-5-vinylpyridine, and 3-methyl-5.
-Vinylpyridine, 4-methyl-5-vinylpyridine,
6-methyl-5-vinylpyridine, 2-methyl-4-vinylpyridine, 3-methyl-4-vinylpyridine, 2-
Alkyl, aryl, alkylaryl such as lauryl-5-vinylpyridine, 2-lauryl-4-vinylpyridine, 2- (t-butyl) -5-vinylpyridine, 2- (t-butyl) -4-vinylpyridine and the like Examples thereof include amine oxides such as adducts of groups.

The monomers represented by the general formula (III) include 1-vinylimidazole, 2-methyl-1-vinylimidazole, 4-methyl-1-vinylimidazole, 5-methyl-1-vinylimidazole, Examples thereof include amine oxides such as lauryl-1-vinylimidazole and 4- (t-butyl) -1-vinylimidazole. The monomer represented by the general formula (IV) includes 4-vinylmorpholine, 2
-Methyl-4-vinylmorpholine, 4-arylmorpholine, 1-vinylpiperidine, 4-methyl-4-vinylpiperidine, 2-lauryl-1-vinylpiperazine,
And amine oxides such as -methylpiperazinoethyl methacrylate. Among these, the monomer represented by the general formula (I) is the most preferable, and in particular, (meth)
Most preferred is an acryloyloxyalkylene compound in which R ² and R ^{3 in} the general formula (I) are an alkyl group having 1 to 4 carbon atoms.

Nitrogen-containing monomer: Examples of the nitrogen-containing monomer before being oxidized include monomers of the following formulas (VI) to (IX).

[0020]

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(Wherein R ^{1 to} R ¹⁰ , a, b, m, n,
The definitions of p, X, and Y are the same as those in the formulas (I) to (IV).) The amine oxide group-containing monomer is used in an amount of 30% by weight or less of a hydrophilic monomer other than the component (A). It may be replaced by the body (C).

Hydrophilic monomer (C): As such a hydrophilic monomer, there is a nonionic, anionic, cationic or amphoteric monomer having an anion and a cationic amphoteric in the same molecule. . Among such monomers, specific examples of nonionic monomers include (meth) acrylonitrile, N-cyclohexylmaleimide, N-phenylmaleimide, N-vinylpyrrolidone, N- (meth) acryloylmorpholine, and hydroxyethyl. (Meth) acrylic acid such as (meth) acrylate, polyethylene glycol (meth) acrylate, methoxypoly (ethylene glycol / propylene glycol) mono (meth) acrylate, polyethylene glycol di (meth) acrylate, and N-polyalkyleneoxy (meth) acrylamide Alternatively, a monomer derived from (meth) acrylamide and an alkylene oxide having 2 to 4 carbon atoms and a hydrophilic monomer such as acrylamide are exemplified.

Specific examples of the anionic monomer include:
(Meth) acrylic acid, maleic acid, maleic anhydride, itaconic acid, fumaric acid, unsaturated carboxylic acid monomers such as crotonic acid, unsaturated polybasic anhydrides (for example, succinic anhydride,
Half ester of phthalic anhydride and a hydroxyl group-containing (meth) acrylate such as hydroxyethyl (meth) acrylate, a monomer having a sulfonic acid group such as styrenesulfonic acid and sulfoethyl (meth) acrylate, and acid phosphooxyethyl A monomer having a phosphate group such as (meth) acrylate is exemplified.

These anionic unsaturated monomers can be used as they are, after being partially or completely neutralized with a basic compound, or after being subjected to copolymerization as they are, Partial or complete neutralization with a basic compound is also possible. As the basic compound used for neutralization, for example,
Hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide; inorganic basic compounds such as aqueous ammonia; ethanolamine, diethanolamine, triethanolamine, triisopropanolamine, 2-amino-2-methyl-1-propanol; 2-amino-2-methyl-
Alkanolamines such as 1,3-propanediol and aminomercaptopropanediol; basic amino acid compounds such as lysine, arginine and histidine can be used.

Specific examples of the cationic monomer include:
N, N-dimethylaminoethyl (meth) acrylate,
N, N-diethylaminoethyl (meth) acrylate,
N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N- Tertiary amino such as dimethylaminopropyl (meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide, p-dimethylaminomethylstyrene, p-dimethylaminoethylstyrene, p-diethylaminomethylstyrene, p-diethylaminoethylstyrene A group-containing monomer, a cationizing agent,
For example, alkyl halides such as methyl chloride, methyl bromide and methyl iodide, dialkyl sulfates such as dimethyl sulfate, N- (3-chloro-2-hydroxypropyl)-
Epichlorohydrin adducts of tertiary amine mineral salts such as N, N, N-trimethylammonium chloride; inorganic salts such as hydrochloric acid, hydrobromic acid, sulfuric acid, and phosphoric acid; and carboxylic acids such as formic acid, acetic acid, and propionic acid. And a cationic monomer cationized by the above.

Specific examples of the amphoteric unsaturated monomer include a tertiary amino group-containing monomer which is a precursor of the above-mentioned cationic monomer, and potassium monochloroacetate, sodium monochloroacetate and monobromopropion. Monohalo fatty acid salts such as potassium phosphate, propiolactone, butyrolactone,
It can be used as a zwitterionic monomer by amphoteric using a modifying agent such as propane sultone.

The amine oxide group-containing polymer compound (a) used in the present invention is preferably (A) 15 to 90% by weight of an amine oxide group-containing unsaturated monomer, and (B) a hydrophobic unsaturated monomer. It has a structure of a copolymer having a weight average molecular weight of 10,000 to 500,000 consisting of 85 to 10% by weight of a copolymer. When the amount of the component (A) is less than 15% by weight, the obtained copolymer has problems such as reduced water solubility and difficulty in washing and removing the hair during washing. If it exceeds 90% by weight, a sticky feeling is exhibited, which is not preferable.

Hydrophobic monomer (B): Examples of the hydrophobic monomer (B) include alkyl (meth) acrylates of alcohols having 1 to 24 carbon atoms, styrene, p-methylstyrene, and p-chloro. Examples thereof include hydrophobic vinyl monomers such as styrene, vinyl methyl ether, vinyl cyclohexyl ether, vinyl acetate, diethyl maleate, and dibutyl maleate, glycidyl (meth) acrylate, and fluoroalkyl esters of (meth) acrylic acid. Further, a macromonomer such as a silicone macromer having a radical polymerizable unsaturated group is exemplified.

Examples of the (meth) acrylic acid esters of alcohols having 1 to 24 carbon atoms include (meth)
Methyl acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, secondary butyl (meth) acrylate,
Tert-butyl (meth) acrylate, pentyl (meth) acrylate, secondary pentyl (meth) acrylate, 1-ethylpropyl (meth) acrylate, 2-methylbutyl (meth) acrylate, isopentyl (meth) acrylate, Tert-pentyl (meth) acrylate, 3-methylbutyl (meth) acrylate, neopentyl (meth) acrylate, hexyl (meth) acrylate,
2-methylpentyl (meth) acrylate, 4-methylpentyl (meth) acrylate, 2-ethylbutyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate, 2-heptyl (meth) acrylate, 3-heptyl (meth) acrylate, octyl (meth) acrylate,
2-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, 3,3,5-trimethylhexyl (meth) acrylate, (meth) acryl Decyl acid, undecyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, (meth)
Stearyl acrylate, eicosyl (meth) acrylate, docosyl (meth) acrylate, tetracosyl (meth) acrylate, methylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, norbornyl (meth) acrylate, (meth) Examples include benzyl acrylate and phenethyl (meth) acrylate. Among these, (meth) acrylic acid esters of alcohols having 1 to 24 carbon atoms represented by the formula (V) are preferable.

[0030]

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(Wherein R ¹ represents a hydrogen atom or a methyl group;
R ¹⁴ represents an alkyl group having 1 to 24 carbon atoms)

The component (B) is preferably used in a range of 10 to 85% by weight. If it exceeds 85% by weight, the film of the copolymer deteriorates in smoothness and transparency, and becomes hardly soluble in water, so that it is difficult to remove it by washing during hair washing, and when it is less than 10% by weight, it gives a sticky feeling. It is not preferable.

Polymerization method: The amine oxide group-containing resin is
In the presence of the above monomer component usually a radical polymerization initiator,
It is obtained by polymerizing by a known method such as solution polymerization, bulk polymerization, suspension polymerization and the like. In particular, it can be suitably obtained by solution polymerization. As the polymerization solvent, acetone,
Methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, propanol, isopropanol,
Organic solvents such as butanol, isobutanol, secondary butanol, ethyl acetate, propyl acetate, and butyl acetate are used alone or in combination of two or more. The amount of the solvent used is such that the polymer concentration of the resulting copolymer solution is 10 to 65.
%.

As the radical polymerization initiator, 2,2'-
Azobisisobutyronitrile (AIBN), 2,2'-
Azobis (2,4-dimethylvaleronitrile), 2,
2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl-2,2'-azobisisobutyrate, 2,2'-azobis (2-methylbutyronitrile), 1,1 ' Azo compounds such as -azobis (1-cyclohexanecarbonitrile), benzoyl peroxide,
Dicumyl peroxide, di-t-butyl peroxide,
A peroxide such as lauroyl peroxide is used.
These polymerization initiators are generally used in an amount of 0.01 to 5% by weight based on the components (A) to (C).

The polymerization is usually carried out in an atmosphere of an inert gas such as nitrogen or argon at 30 to 120 ° C., preferably 40 to 100 ° C.
For 1 to 20 hours. Usually, all kinds and amounts of monomers are present from the beginning of polymerization,
Divided addition can also be performed with respect to the type and / or amount of the monomer.

Oxidation: An oxidizing agent is added to a resin solution obtained by polymerizing the monomer components, and the resulting solution is added at 20 to 100 ° C.
By carrying out the oxidization in the range of 0.1 to 100 hours, preferably 1 to 50 hours, an amine oxide group-containing resin can be obtained.

As an oxidizing agent for oxidizing the obtained precursor polymer, an oxidizing agent such as peroxide or ozone is used. The peroxide includes hydrogen peroxide, ammonium persulfate, sodium persulfate, peracetic acid, metachloroperbenzoic acid, benzoyl peroxide, t-butyl hydroperoxide, and the like, but hydrogen peroxide is generally used. . The amount of the oxidizing agent used is 0.2 to 3 based on the oxidizable functional group contained in the precursor polymer.
It is more preferably used in a molar equivalent ratio of 0.5 times to 2 times. The remaining peroxide can be used without any treatment, but can also be treated and used by a known method. Specifically, treatment by addition of a reducing agent or addition of a metal catalyst, ion exchange treatment, activated carbon treatment and the like can be mentioned.

The obtained resin solution can be used as it is, but if necessary, an amine oxide group-containing resin can be isolated and used by a known method such as reprecipitation or solvent evaporation. The isolated amine oxide group-containing resin can be further purified, if necessary, by reprecipitation, solvent washing, membrane separation, adsorption treatment and the like. The resin thus obtained usually has a weight average molecular weight of 10,000 to 500,0.
00 resin. If the weight average molecular weight is less than 10,000, the hair styling power decreases, and if it exceeds 500,000, the compatibility with water and the like deteriorates, and the solution viscosity further increases, causing problems in workability and applicability. .

Specific examples of the cationic polymer of the component (b) used in the present invention include synthetic cationic polymers such as Guffcut 755N, 755, 734 (all manufactured by ISP) and Rubycut. N-vinylpyrrolidone / quaternized dimethylaminoethyl methacrylate copolymer such as PQ11 (manufactured by BASF); Copolymer 845;
N-vinylpyrrolidone / dimethylaminoethyl methacrylate copolymers such as 937 and 958 (all manufactured by ISP); N-vinylpyrrolidone / dimethylaminoethyl methacrylate copolymers such as GAPIX VC-713 (manufactured by ISP)
-Vinylpyrrolidone / N-vinylcaprolactam / dimethylaminoethyl methacrylate copolymer; N-vinylpyrrolidone / methacrylamidopropyl trimethylammonium chloride copolymer such as Guffcut HS-100 (manufactured by ISP); Rubicut FC370, FC550;
N-vinylpyrrolidone / quaternized methylvinylimidazolium copolymer such as FC905 and HM-552 (all manufactured by BASF); dimethyldiallylammonium chloride polymer such as Mercoat 100 and 550 (all manufactured by Calgon); Dimethyldiallylammonium chloride / acrylamide copolymer; JP-A-4-21623;
And quaternized dialkylaminoalkylene methacrylate / (meth) acrylic acid alkyl ester copolymers described in JP-A-5-310538.

The natural product-modified cationic polymers include:
Hydroxyethyl cellulose / dimethyldiallylammonium chloride copolymers such as Cellcut, H-100, L200 (all manufactured by National Starch); Cellcut SC-240, SC-240C, SC-230M
(Above, manufactured by National Starch Co., Ltd.), Ucare Polymer JR-125, JR-400, JR-30M (above,
Amagor), Leogard G (Lion),
Reaction products of hydroxyethylcellulose with epoxidized trimethylammonium compounds such as Katinal HC and LC (manufactured by Toho Chemical Co., Ltd.); and quaternized chitosans such as Kitamar KC (Amacor).

In the hair cosmetic composition of the present invention, the weight ratio of the amine oxide group-containing copolymer of the component (a) to the cationic polymer of the component (b) ((a) / (b)) Is 1
/ 10 to 10/1, preferably 1/5 to 10/1
It is. When the ratio of (a) / (b) is less than 1/10,
The hair styling effect is insufficient and the desired shape cannot be maintained, and under high humidity, the elasticity of the hair is insufficient and the hair becomes sticky. Furthermore, when used repeatedly for a long period of time, problems such as a build-up problem may occur. When this ratio exceeds 10/1, there is a problem that when applying the cosmetic composition to the hair, slipperiness is insufficient, combing is difficult, and smoothness after drying is also insufficient. The total amount of component (a) and component (b) is from 0.1 to 10% by weight, preferably from 0.5 to 8% by weight, based on the total amount of the hair cosmetic. Enough, 10
Exceeding the weight percentage causes a problem that the feeling of stiffness increases and the feel deteriorates.

The hair cosmetic composition of the present invention contains, in addition to the essential components (a) and (b), components used in ordinary cosmetics, such as castor oil, cocoa oil, mink oil, and avocado. Glycerides such as oil, jojoba oil, macadamian nut oil and olive oil; waxes such as beeswax and lanolin;
Hydrocarbons such as liquid paraffin, solid paraffin, isoparaffin and squalane; linear and branched higher alcohols such as cetyl alcohol, oleyl alcohol, stearyl alcohol, isostearyl alcohol, lauryl alcohol and 2-octyldodecanol; ethylene glycol; Polyhydric alcohols such as polyethylene glycol, propylene glycol, polypropylene glycol, glycerin and sorbitol; polyoxyethylene lauryl ether, polyoxypropylene cetyl ether,
Ethylene oxide and / or propylene oxide adducts of higher alcohols such as polyoxyethylene polyoxypropylene stearyl ether; esters such as isopropyl myristate, octyl dodecyl myristate, hexyl laurate, and cetyl lactate; diethanolamide oleate and laurin Amides such as acid diethanolamide; dimethylpolysiloxane, methylphenylpolysiloxane,
Silicone derivatives such as polyether-modified silicone and amino-modified silicone; Cationic surfactants such as stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryltrimethylammonium chloride; polyoxyethylene lauryl ether sulfate, polyoxyethylene lauryl sulfosuccinate Anionic surfactants; amphoteric surfactants such as laurylhydroxysulfobetaine and lauryldimethylcarboxybetaine; protein derivatives such as collagen hydrolysates, keratin hydrolysates, and polyamino acids; amino acid derivatives; plant extracts, crude drugs, and vitamins , An ultraviolet absorber such as oxybenzene, a chelating agent such as EDTA-Na, a preservative such as paraben, an antioxidant, a dye, a pigment, a fragrance, etc. of the present invention. It may be appropriately blended within a range that does not impair the result.

The use and form of the hair cosmetic composition of the present invention are not particularly limited. For example, an aerosol hair spray, a pump hair spray, a foam hair spray, a hair mist,
It can be used as set lotion, hair gel, hair cream and hair oil.

In the hair cosmetic composition of the present invention, each component including the components (a) and (b) is dissolved or dispersed in water and / or a solvent of alcohol such as ethanol and isopropanol according to a conventional method. Can be manufactured. In addition, chlorofluoroalkanes such as trichloromonofluoromethane and dichlorodifluoromethane; liquefied petroleum gas composed of alkanes; dimethyl ether; compressed gas such as carbon dioxide gas and nitrogen gas; or a mixed gas thereof is used as a propellant. However, it can be made into an aerosol formulation according to a conventional method.

[0045]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Production Examples and Examples. However, the present invention is not limited to these Production Examples and Examples unless it exceeds the gist of the invention. is not. Parts and percentages in the production examples and examples are expressed on a weight basis unless otherwise specified.

Production Example 1 In a reactor equipped with a reflux condenser, a dropping funnel, a thermometer, a nitrogen gas inlet tube and a stirrer, 50 parts of N, N-dimethylaminoethyl methacrylate, 30 parts of methyl methacrylate,
After 20 parts of isobutyl methacrylate and 150 parts of absolute ethanol were added, 0.6 part of 2,2'-azobisisobutyronitrile was added, and the mixture was reacted at 80 ° C. for 8 hours under a nitrogen atmosphere, and then cooled to 60 ° C.

Next, a 31% aqueous solution of N, N-dimethylaminoethyl methacrylate and an equimolar amount of hydrogen peroxide was added dropwise to the polymerization solution in a dropping funnel over 1 hour, and stirring was further continued for 20 hours to obtain a dimethylamino group. Is oxidized, and anhydrous ethanol is added to reduce the polymer concentration to 3.
It was adjusted to 0%. Completion of the oxidation reaction was confirmed by measuring the amine value of the reaction solution. The obtained polymer is referred to as “P
-1 ". The weight average molecular weight of the obtained polymer was 110,000. In addition, N-O absorption was recognized from the infrared absorption spectrum, and formation of an amine oxide group was confirmed.

Production Example 2 70 parts of N, N-dimethylaminoethyl methacrylate and 10 parts of methyl methacrylate were placed in the same reactor as in Production Example 1.
, 20 parts of stearyl methacrylate and 100 parts of anhydrous ethanol, 0.2 part of 2,2'-azobisisobutyronitrile was charged, reacted at 80 ° C under a nitrogen atmosphere for 8 hours, and then cooled to 60 ° C. . Next, a 31% aqueous solution of hydrogen peroxide, 1.2 times the molar amount of N, N-dimethylaminoethyl methacrylate, was added dropwise over 1 hour, and stirring was continued for another 15 hours to oxidize the dimethylamino group. To increase the polymer concentration to 35%
Was adjusted. Completion of the oxidation reaction was confirmed by measuring the amine value of the reaction solution.

Further, 100 parts of the obtained solution was passed through a column filled with 50 parts of a regenerated anion exchange resin (Diaion PA416), and the remaining hydrogen peroxide was treated. Was adjusted to 30%. The obtained polymer is designated as "P-2". still,
The weight average molecular weight of the obtained polymer was 200,000. In addition, N-O absorption was recognized from the infrared absorption spectrum, and formation of an amine oxide group was confirmed.

Production Example 3 A reactor equipped with a reflux condenser, a dropping funnel, a thermometer, a nitrogen gas inlet tube and a stirrer was charged with 60 parts of N, N-dimethylaminoethyl methacrylate and 10 parts of methyl methacrylate.
Parts, 15 parts of butyl methacrylate, 15 parts of stearyl methacrylate, and 100 parts of absolute ethanol,
0.2 parts of 2,2'-azobisisobutyronitrile was charged, reacted at 80 ° C for 8 hours in a nitrogen atmosphere, and then cooled to 45 ° C. Next, diethylsulfate in an equimolar amount to N, N-dimethylaminoethyl methacrylate was added dropwise, and the mixture was stirred at 60 ° C. for 3 hours to cationize the dimethylamino group. %. The weight average molecular weight of the obtained polymer was 180,000. The obtained cationic polymer is designated as "P-3".

Examples 1-6, Comparative Examples 1-4 Hair cosmetics (pump type hair spray) having the composition shown in Table 1
Are prepared by a conventional method, and when they are used for hair, hair styling power (set holding power), elasticity of the hair under high humidity, and feelings such as stickiness, slipperiness during application, and combability ,
The smoothness of the dried hair was tested and evaluated by the following method.
As is clear from Table 1, the hair cosmetics of Examples 1 to 6 have excellent hair styling properties, can maintain the shape of curled hair even at high temperature and high humidity, and have a sticky feeling even under high humidity. It had good elasticity without rubbing, had good touch feeling and combability even at the time of application, and the hair after drying had a smooth feel. On the other hand, the hair cosmetics of Comparative Examples 1 to 4 have problems such as insufficient hair styling, sticky feeling under high humidity, insufficient elasticity, and the like. It was not satisfactory.

<Test evaluation method> (1) Hair styling power (set holding power) A fixed amount of each of the test cosmetics was applied to 23 cm, 2 g of hair without habit, and immediately wound around a curler having a diameter of 1.2 cm. dry. Next, remove the hair from the curler
Hang the hair in a thermo-hygrostat at 30 ° C./95% RH, measure the elongation of the hair after 3 hours, and substitute it into the curl retention formula to determine the curl holding power (%). ○ −− Curl holding power: 71% or more Δ−− Curl holding power: 40 to 70% × −− Curl holding power: less than 40%

(2) Elasticity of Hair Curled hair obtained by operating in the same manner as the above-mentioned hair styling power (set holding power) is allowed to stand under a condition of constant temperature and humidity of 25 ° C./80% RH, and the curl is applied with a finger. The elasticity of the hair when crushing is evaluated. ○ −− Good elasticity △ −− Elasticity × −− Low elasticity

(3) Feeling of Stickiness of Hair Curled hair obtained in the same manner as in the above hair styling power (set holding power) was allowed to stand under conditions of constant temperature and humidity of 25 ° C./80% RH. Evaluate the stickiness when touching. ○ −− No sticky feeling △ −− Some sticky feeling × −− Great sticky feeling

(4) Slip feeling when wet A fixed amount of each of the test cosmetics was applied to hair having no habit of 23 cm and 2 g, and the slip feeling when touching with a finger immediately and the feeling when combing were used. Evaluate the ease of combing. ○ −− Smooth feeling and easy combing △ −− Slight feeling of insufficiency and easy combing × −− No slipping and difficult to comb

(5) Smoothness of Hair After Drying A fixed amount of each test cosmetic was applied to 23 cm, 2 g of hair without habit, and dried with a hair dryer. Next, the hair is left under the condition of constant temperature and humidity of 23 ° C./60% RH, and the smoothness when touching the hair with a finger is evaluated. ○ −− Smooth feeling △ −− Smoothness is slightly insufficient × −− Smooth feeling and feeling of catching

Examples 7 to 10 and Comparative Examples 5 to 8 Hair cosmetics (foam hairsprays) having the compositions shown in Table 2 were prepared by a conventional method, and these were evaluated in the same manner as in Example 1. As is clear from Table 2, Example 7
The hair cosmetics of No. 10 to No. 10 have excellent hair styling properties, can maintain the shape of curled hair even at high temperature and high humidity, and provide good elasticity without stickiness even under high humidity, Also, the hair had a good feel and combability, and the hair after drying had a smooth feel. On the other hand, the hair cosmetics of Comparative Examples 5 to 8 have problems such as insufficient hair styling, sticky feeling under high humidity, and insufficient elasticity. It was not satisfactory.

[0058]

[Table 1]

[0059]

[Table 2]

[0060]

The present invention provides various hair cosmetics such as hair sprays, hair mousses, hair set lotions, and hair gels which have excellent hair styling properties, give good elasticity, and give a good texture finish. I can do it.

 ──────────────────────────────────────────────────の Continued on the front page (72) Inventor Kayo Ito 1 Tohocho, Yokkaichi-shi, Mie Mitsubishi Chemical Corporation Yokkaichi Research Institute (72) Inventor Kazuhide 1 Tohocho, Yokkaichi-shi, Mie Mitsubishi Chemical The inside of Yokkaichi Research Institute

Claims (5)

[Claims] (1) a weight-average molecular weight of 10,000 to 5
(B) at least one kind of a cationic polymer, wherein the weight ratio of (a) / (b) is 1/10 to 10/1; A hair cosmetic composition comprising a total of 0.1 to 10% by weight of a) and (b). 2. A copolymer wherein the amine oxide group-containing polymer of component (a) comprises 15 to 90% by weight of an amine oxide group-containing unsaturated monomer and 85 to 10% by weight of a hydrophobic unsaturated monomer. The hair cosmetic composition according to claim 1, which has the following structure. 3. The hair cosmetic composition according to claim 1, wherein the cationic polymer as the component (b) is at least one polymer selected from the following. Cationic polymer which is a copolymer of N-vinylpyrrolidone and / or N-vinylcaprolactam Polymer of dimethyldiallylammonium or cationic polymer of a copolymer Acrylic ester-based or methacrylic ester-based quaternary Cationic polymer which is polymer or copolymer of ammonium salt Cationic polymer which is quaternary ammonium salt of cellulosic or chitosan type 4. An amine oxide group-containing unsaturated monomer,
The hair cosmetic composition according to claim 1, which is a compound represented by the following general formulas (I) to (IV). Embedded image (Wherein, R ¹ represents a hydrogen atom or a methyl group; R ² and R ³ represent an alkyl group having 1 to 24 carbon atoms, an aryl group or an arylalkyl group which may be the same or different, and R ⁴ and R ⁵
Is an alkyl group, an aryl group or an arylalkyl group having 1 to 24 carbon atoms, X is a divalent linking group, m is an integer of 0 to 1, n is an integer of 0 to 4, and p is 0 to 3 And Y is the following: The other R ^{6 to} R ¹³ represent a hydrogen atom or an alkyl group having 1 to 24 carbon atoms, an aryl group or an arylalkyl group, and a and b each represent an integer of 1 to 10 which may be the same or different) 5. The hair cosmetic composition according to claim 1, wherein the hydrophobic unsaturated monomer is a compound represented by the following general formula (V). Embedded image (Wherein, R ¹ represents a hydrogen atom or a methyl group, and R ¹⁴ represents an alkyl group having 1 to 24 carbon atoms)