JP3143720B2 - Hair cosmetic composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cationic resin capable of exhibiting excellent hair-styling effects on hair and imparting excellent wet and dry sliding properties, combability and conditioning effects. And a hair cosmetic composition containing the same.

[0002]

2. Description of the Related Art Hair cosmetic resins having a hair styling effect include unsaturated monomers having a carboxyl group such as acrylic acid, crotonic acid and maleic acid, alkyl acrylate, alkyl methacrylate, alkyl vinyl ether and the like. Anionic polymers (e.g., see JP-B-50-6538 and JP-B-51-27740) represented by neutralized copolymers of the above with a hydrophobic unsaturated monomer, vinylpyrrolidone and vinyl acetate Nonionic polymer represented by a copolymer with, and a copolymer of a carboxybetaine-containing unsaturated monomer and a hydrophobic unsaturated monomer such as an alkyl acrylate, an alkyl methacrylate, and the like. Zwitterionic polymers (for example, JP-A-51-9732, JP-A-56-9280)
No. 9) is known and widely used.

[0003] However, these known resins have slipperiness,
Due to insufficient combability and conditioning effects, oil-based components such as silicone compounds, ester compounds and hydrocarbon compounds are emulsified, solubilized or dissolved and used together to supplement their performance (Japanese Unexamined Patent Publication No.
3-135319 and JP-A-63-275515).

On the other hand, cationic polymers include copolymers of a cationic group-containing unsaturated monomer and vinylpyrrolidone (see JP-A-46-750) and dimethyldiallylammonium chloride-based polymers (see JP-A-63-163). -12261
3) was known, but
Since the hair styling effect is inferior, it is only used in hair cosmetics for the purpose of simply providing a conditioning effect (see JP-A-56-92182 and JP-A-57-197206), and hair expected to have a hair styling effect Not used in cosmetics.

[0005]

DISCLOSURE OF THE INVENTION The present invention relates to a cationic resin-containing hair which can exhibit an excellent hair-styling effect, and can impart excellent sliding properties, wetness and combing properties when wet and dry. It is intended to provide a cosmetic composition.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted various studies to solve the above-mentioned problems, and as a result, by using a specific cationic resin, the object has been achieved. is there.

That is, the hair cosmetic composition of the present invention comprises:
A polymerizable unsaturated monomer 50 represented by the following general formula (I)
To 90% by weight, 10 to 50% by weight of a polymerizable unsaturated monomer represented by the following general formula (II), and another polymerizable monomer copolymerizable with each of the above polymerizable unsaturated monomers. A copolymer obtained by copolymerizing 0 to 25% by weight of a polymer is represented by a general formula XB
[Wherein, X is a bromine atom, chlorine atom, iodine atom or alkyl sulfate residue (the alkyl group has 1 to 4 carbon atoms), B is an alkyl group having 1 to 12 carbon atoms, benzyl A group or an alkyl ester residue of a fatty acid having 1 to 3 carbon atoms (the alkyl group has 1 to 4 carbon atoms). And a cationic resin modified with a cationizing agent represented by formula (1).

[0008]

Embedded image (Wherein, R ¹ is a hydrogen atom or a methyl group, R ² is an alkylene group having 1 to 4 carbon atoms, R ³ and R ⁴ are each an alkyl group having 1 to 4 carbon atoms, and A is oxygen Atom or NH group.)

[0009]

Embedded image (In the formula, R ⁵ is a hydrogen atom or a methyl group, and R ⁶ is an alkyl group having 12 to 24 carbon atoms.)

The raw material copolymer for obtaining the cationic resin used in the present invention is 50 to 90% by weight, preferably 55 to 90% by weight, of the polymerizable unsaturated monomer represented by the above general formula (I).
85% by weight, 10 to 50% by weight, preferably 15 to 45% by weight, of the polymerizable unsaturated monomer represented by the general formula (II), and copolymerizable with each of the above polymerizable unsaturated monomers. It is obtained by copolymerizing 0 to 25% by weight of another polymerizable unsaturated monomer.

Among the polymerizable unsaturated monomers represented by the above general formula (I), particularly preferred are those wherein R ¹ is a methyl group, R ² is an alkylene group having 2 to 3 carbon atoms, R ³ and R ^Four
Is a methyl or ethyl group and A is an oxygen atom.

Specific examples of the polymerizable unsaturated monomer (I) include, for example, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate. ) Acrylamide, diethylaminopropyl (meth) acrylamide and the like. In addition, "(meth) acrylate" described in this specification
Is a general term for acrylate and methacrylate,
“(Meth) acrylamide” is a general term for acrylamide and methacrylamide (others conform thereto).

As described above, the amount of the polymerizable unsaturated monomer (I) used is 50 to 90% by weight, preferably 55 to 85% by weight, based on the total amount of the monomers to be copolymerized. . If the amount is too small, the cationic resin finally obtained becomes sparingly soluble in water, and the removability at the time of hair washing becomes poor, and the cationic resin slips on the hair due to a decrease in cationic performance. Properties, combability, and the effect of imparting a conditioning effect are reduced. Conversely, if the amount used is too large, the resulting cationic resin will have a sticky feeling, or will cause problems such as a reduction in the hair styling effect.

Among the polymerizable unsaturated monomers represented by the general formula (II), particularly preferred are those wherein R ⁵ is a methyl group and R ⁶ is an alkyl group having 13 to 20 carbon atoms. It is.

Specific examples of the polymerizable unsaturated monomer (II) include lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, and behenyl (meth) acrylate.

As described above, the amount of the polymerizable unsaturated monomer (II) used is 10 to 50% by weight, preferably 15 to 45% by weight, based on the total amount of the monomers to be copolymerized. . If the amount is too small, the cationic resin finally obtained will be sticky or poor in flexibility. On the other hand, if the amount is too large, the resulting cationic resin becomes sparingly soluble in water, and the washing and removing properties during hair washing deteriorate, and the hair conditioning effect deteriorates.

The polymerizable unsaturated monomers for copolymerization include:
In addition to the polymerizable unsaturated monomers (I) and (II), other polymerizable unsaturated monomers, which are not essential components, can be used. By appropriately selecting the other polymerizable unsaturated monomer to be used, the feel and the like can be adjusted by imparting appropriate flexibility and hardness to the finally obtained cationic resin.

Specific examples of other polymerizable unsaturated monomers that can be used include, for example, methyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth).
(Meth) acryl alkyl esters such as acrylates; acrylonitrile, hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, ethylene glycol (meth) acrylate, polyethylene glycol ( Meth) acrylate, propylene glycol (meth) acrylate,
1,3-butylene glycol di (meth) acrylate,
(Meth) acrylic derivatives such as diacetone acrylamide; aromatic unsaturated monomers such as styrene, chlorostyrene and vinyltoluene; and vinyl unsaturated monomers such as N-vinylpyrrolidone and vinyl acetate. .

These other monomers are, as described above,
It is not an essential component and its amount is from 0 to 25% by weight based on the total amount of monomers to be copolymerized. If the amount of the other monomer used is too large, the amount of the polymerizable unsaturated monomer (I) or (II) used will be reduced, causing a problem.

The polymerizable unsaturated monomers (I) and (I)
The copolymerization of I), and other polymerizable unsaturated monomers used as necessary, may be performed by various radical polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. Can be. A preferred polymerization method is a solution polymerization method, in which the above polymerizable unsaturated monomer is dissolved in an appropriate solvent, a polymerization initiator is added, and the mixture is heated and stirred under a nitrogen stream to carry out polymerization.

In this case, the solvent used is water; alcohols such as methanol, ethanol, isopropanol, ethylene glycol and butyl cellosolve; ketones such as acetone and methyl ethyl ketone; hydrocarbons such as hexane and toluene; ethyl acetate and butyl acetate. Acetates such as are preferred. These solvents can be used as a mixture of two or more kinds as appropriate.

Examples of the polymerization initiator include peroxides such as benzoyl peroxide and lauroyl peroxide, and azo compounds such as azobisisobutyronitrile.

In the polymerization, the monomer and the polymerization initiator are:
It is common that all the types and amounts are present in the polymerization system from the beginning of the polymerization, but a split addition method can be used for those types and / or amounts. The amount of the solvent used is preferably such that the polymer concentration of the resulting copolymer solution becomes 10 to 65% by weight.

The molecular weight of the obtained copolymer is preferably in the range of 5,000 to 500,000 in terms of weight average molecular weight.
The molecular weight is controlled by controlling the polymerization conditions such as the polymerization temperature, the type and amount of the polymerization initiator, the amount of the chain transfer solvent such as ethanol and isopropanol, and the amount of the chain transfer agent such as butyl mercaptan and lauryl mercaptan. Selection and adjustment can be performed.

When the copolymer obtained by the above copolymerization is subjected to a modification reaction with a cationizing agent represented by the above general formula, a cationic resin used in the present invention is obtained.

Specific examples of the cationizing agent include alkyl halides such as methyl chloride, butyl chloride and ethyl iodide; benzyl halides such as benzyl chloride and benzyl bromide; and dimethyl sulfate and diethyl sulfate. Sulfuric esters: monohalogenated fatty acid esters such as ethyl monochloroacetate, propyl monobromide propionate and butyl monochloroacetate.

The modification of the copolymer with a cationizing agent, that is, the cationization reaction, is carried out by adding a cationizing agent to a copolymer solution and stirring the mixture at 40 to 100 ° C. under an inert atmosphere, for example, under a nitrogen stream. It is carried out by heating at a temperature for 4 to 30 hours.

As described above, the modification with a cationizing agent is generally carried out after copolymerization, and is preferably carried out. However, as an alternative, at the monomer stage, that is, in the above-mentioned general formula (I), Before the polymerization, the polymerizable monomer to be expressed is cationized by reacting it with a cationizing agent in advance, and then copolymerized using the cationized polymerizable monomer to form a cationic resin. Can also. And the present invention
This alternative embodiment is also included.

The hair cosmetic composition of the present invention is characterized by containing the cationic resin obtained as described above. The content of the cationic resin in the composition is as follows. Is usually 0.1% by weight or more, preferably 0.2 to 10% by weight. In this case, as the cationic resin, the produced cationic resin solution may be used as it is, or the solid cation after once removing the solvent by evaporating the solvent from the produced cationic resin solution in a solution state. A cationic resin may be used, or the solid cationic resin may be used by re-dissolving it in another solvent.

The hair cosmetic composition of the present invention can be made into compositions for various uses. For example, various use modes such as a general hairdressing agent, a shampoo, a rinsing agent, a treatment agent, a setting agent, a permanent wave solution, and a mascara can be used. Also, the dosage form of the hair cosmetic composition is liquid, creamy,
Various dosage forms such as an aqueous emulsion form and a gel form can be made.

In the case of a general hairdressing composition, the cationic resin of the present invention may be used as a sole polymer component, or may be a conventionally known natural polymer for hairdressing composition, or a natural modified product. You may use together with a polymer and a synthetic polymer. Furthermore, plastics such as silicone polymers, chemically modified silicone polymers, surfactants, thickeners, hadrotropes, emulsifiers, conditioning agents, oils and fats, humectants, higher fatty acid esters, glycerin, polyethylene glycol, etc. Various additives such as an agent, a colorant, a bactericide, and a fragrance can also be used in combination.

In the case of a shampoo, a rinsing agent, a treatment agent, a setting agent, a permanent waving agent, a mascara, etc., the cationic resin of the present invention is added to the conventionally known agents in an amount of 0.1%. By adding 1% by weight or more, preferably 0.2 to 10% by weight, the composition for hair cosmetics of the present invention can be used as a shampoo, rinsing agent, mascara, or the like.

Particularly preferred embodiments of the hair cosmetic composition of the present invention are a setting agent and mascara. The set agent includes hair styling materials such as aerosol hair spray, pump hair spray, foam aerosol, hair mist, set lotion, hair styling gel, hair liquid, hair cream, and hair oil. Can be prepared in place of, or in combination with, conventionally known anionic, nonionic and amphoteric setting polymers.

[0034]

The present invention will be described below with reference to a production example of a cationic resin and examples. “Parts” and “%” described in these examples mean parts by weight and% by weight, respectively.

Preparation Example 1 of a Cationic Resin A five-necked flask equipped with a reflux condenser, a dropping funnel, a thermometer, a glass tube for purging nitrogen, and a stirrer was charged with 55 parts of dimethylaminoethyl methacrylate, 15 parts of lauryl acrylate, and cetyl. 20 parts of methacrylate, 10 parts of behenyl methacrylate, and 100 parts of absolute ethanol were added, and azobisisobutyronitrile (hereinafter, “AIB”) was added.
N) was heated under reflux at 80 ° C. under a nitrogen stream. After 2 hours, 0.6 parts of AIBN was added, and polymerization was carried out at the same temperature for 6 hours.

Next, 53.9 parts of diethyl sulfate (equimolar amount to dimethylaminoethyl methacrylate) was added thereto.
And 100 parts of anhydrous ethanol were added, and a denaturation reaction was further performed at 50 ° C. for 10 hours under a nitrogen stream.

Next, the content of ethanol was adjusted to obtain a cationic resin solution having a polymer content of 30%. The weight average molecular weight of this resin before modification was 120,000.

Preparation Example 2 of a Cationic Resin In the same flask as in Preparation Example 1, 85 parts of dimethylaminoethyl methacrylate and 15 parts of stearyl methacrylate were added.
Parts, and 54 parts of absolute ethanol.
1 part, and heated under reflux at 80 ° C. under a nitrogen stream.
After an hour, 0.6 parts of AIBN was added, and polymerization was carried out at the same temperature for 6 hours.

Next, ethyl monochloroacetate 7
2.8 parts (1.1 times the molar amount of dimethylaminoethyl methacrylate) and 100 parts of anhydrous ethanol were added, and the mixture was further subjected to a denaturation reaction by heating at 80 ° C. under reflux in a nitrogen stream.

Next, the content of ethanol was adjusted to obtain a cationic resin solution having a polymer content of 25%. The weight average molecular weight of this resin before modification was 200,000.

Preparation Example 3 of Cationic Resin A flask similar to that of Preparation Example 1 was charged with 80 parts of dimethylaminoethyl methacrylate and 12 parts of tridecyl methacrylate.
Parts, 8 parts of stearyl acrylate and 400 parts of absolute ethanol, 2.0 parts of AIBN was added, and the mixture was refluxed and heated at 80 ° C. in a nitrogen stream.
6 parts were added and polymerization was carried out at the same temperature for 6 hours.

Then, 32.9 parts of butyl chloride (0.7 mole times the amount of dimethylaminoethyl methacrylate)
Was added thereto, and the mixture was heated under reflux at 80 ° C. under a nitrogen stream to carry out a denaturation reaction for 30 hours.

Next, the content of ethanol was adjusted to 30% of the polymer content, and the mixture was deodorized by passing through a column previously filled with activated carbon. Further, the treated liquid was put into a flask, and water was added while distilling off ethanol to obtain a cationic resin aqueous solution having a polymer content of 35%. The weight average molecular weight of this cationic resin before modification is 6,000.
It was 0.

Preparation Example 4 of Cationic Resin In the same flask as in Preparation Example 1, 70 parts of diethylaminoethyl methacrylate, 5 parts of cetyl acrylate, 10 parts of stearyl methacrylate and 10 parts of N-vinylpyrrolidone
Parts, 5 parts of butyl methacrylate, and 100 parts of acetone
Part, add 0.3 parts of AIBN, and add 60 parts
After 2 hours, 0.1 part of AIBN was added, and a polymerization reaction was carried out at the same temperature for 15 hours under a nitrogen stream.

Next, 68.6 parts of diethyl sulfate (equimolar amount to diethylaminoethyl methacrylate) and 100 parts of absolute ethanol were added, and the mixture was refluxed and heated at 50 ° C. for 10 hours under a nitrogen stream to carry out a denaturation reaction. I let you.

From the obtained viscous liquid, ethanol was removed at 70 ° C. under reduced pressure to obtain a solid. After pulverizing this solid, it is thoroughly washed with diethyl ether, and again under reduced pressure for 7 hours.
Drying well at 0 ° C. gave a solid cationic resin. The weight average molecular weight of this resin before modification was 400,000.

Example 1 An aerosol hair spray having the following composition was prepared. Cationic resin solution obtained in Production Example 1 5.0% (resin amount) Dimethyl polysiloxane / polyoxyalkylene copolymer * 1 0.1% Perfume Appropriate amount Absolute ethanol Balance LPG (3 kg / cm ² · G) 25 0.0% Total 100% Note) * 1 ... Toray Silicon Co., Ltd. Product name SH3771

When this hair spray is applied to the hair by spraying, the applied hair has excellent set holding power and can be easily combed, and has excellent gloss, luster and smoothness to the hair. I was able to give a nice feeling.

Example 2 A pump hair spray having the following composition was prepared. The cationic resin solution obtained in Production Example 2 4.0% (resin amount) Perfume Appropriate amount Pure water 20.0% Absolute ethanol Balance Total 100%

The result of spray application of this pump type hair spray to hair was the same as in Example 1.

Example 3 A pump type hair spray having the following composition was prepared. Aqueous cationic resin solution obtained in Production Example 3 9.0% (resin amount) Perfume Appropriate amount Pure water 30.0% Absolute ethanol Balance Total 100%

The result of spray application of this hair spray to the hair was the same as in Example 1.

Example 4 A foam aerosol for hair having the following composition was prepared. Aqueous solution of cationic resin obtained in Production Example 3 6.0% (resin amount) Polyoxyethylene (10) cetyl ether 0.3% Polyoxyethylene (2) cetyl ether 0.1% Dimethylpolysiloxane / polyoxyalkylene Copolymer * 1 0.1% Perfume Appropriate amount Pure water Balance Absolute ethanol 5.0% LPG (3Kg / cm ² · G) 10.0% Total 100% Note) * 1 ... * 1 in Example 1 the same

The result of applying this foam aerosol to the hair was the same as in Example 1.

Example 5 A foam aerosol for hair having the following composition was prepared. Yuka Former AM-75 SM * 2 3.0% (resin amount) Solid cationic resin obtained in Production Example 4 0.3% (resin amount) Polyoxyethylene (10) cetyl ether 0.3% polyoxyethylene (2) Cetyl ether 0.1% Dimethyl polysiloxane / polyoxyalkylene copolymer * 1 0.1% Perfume Appropriate amount Pure water Balance Absolute ethanol 10.0% LPG (3Kg / cm ² · G) 8.0% Total 100% Note) * 1: Same as * 1 in Example 1. * 2: Mitsubishi Yuka Corporation, carboxybetaine-type amphoteric polymer

The result of applying this foam aerosol to the hair was the same as in Example 1.

[0057]

The present invention exhibits an excellent hair-styling effect and can impart excellent set holding power, gloss, gloss, combability, smooth feel, and the like to hair.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) A61K 7/06 A61K 7/11

Claims (3)

(57) [Claims] 1. A polymerizable unsaturated monomer represented by the following general formula (I): 50 to 90% by weight, and a polymerizable unsaturated monomer represented by the following general formula (II): 10 to 50% by weight. And a copolymer obtained by copolymerizing 0 to 25% by weight of another polymerizable monomer copolymerizable with each of the above-mentioned polymerizable unsaturated monomers is represented by a general formula XB [wherein X is Is a bromine atom, a chlorine atom, an iodine atom or an alkyl sulfate residue (the alkyl group has 1 to 4 carbon atoms), and B is an alkyl group having 1 to 12 carbon atoms, a benzyl group or a 1 carbon atom. Alkyl ester residues of up to 3 fatty acids (where the alkyl group has 1 to 4 carbon atoms)
Individual). A hair cosmetic composition comprising a cationic resin modified with a cationizing agent represented by the formula (1). Embedded image (Wherein, R ¹ is a hydrogen atom or a methyl group, R ² is an alkylene group having 1 to 4 carbon atoms, R ³ and R ⁴ are each an alkyl group having 1 to 4 carbon atoms, and A is oxygen Atom or NH group.) (In the formula, R ⁵ is a hydrogen atom or a methyl group, and R ⁶ is an alkyl group having 12 to 24 carbon atoms.) 2. The weight average molecular weight of the cationic resin is 5,000 in terms of the molecular weight of the copolymer before being modified with a cationizing agent.
The hair cosmetic composition according to claim 1, wherein the amount is from 0 to 500,000. 3. The hair cosmetic composition according to claim 1, wherein the cationic resin is contained in an amount of 0.1% by weight or more.