JPH08113517A - Hair-setting agent composition - Google Patents

Abstract

PURPOSE: To obtain a hair-setting agent composition which contains a specific amphoteric polymer and a specific cationic resin, and has a combination of excellent hair set retention with good touch. CONSTITUTION: This hair-setting agent composition comprises (A) 0.05-10.0wt.% of one or more kinds of amphoteric polymers comprising betaine dialkylaminoalkyl acrylate copolymers of the formula I (R<1> , R<5> are each H, methyl; R<2> , R<3> are each an alkyl; R<4> is an alkylene; R<6> is an alkyl or an alkenyl; A is NH; (n), (m) are each a positive integer where n/m=2/8 to 8/2), having 50,000-500,000 molecular weight, and (B) 0.05-10.0wt.% of a cationizing agent- modified cationic resin which is prepared by modifying a copolymer obtained from 50-90wt.% of a compound of formula II (R<7> is H, methyl; R<8> is an alkylene; R<9> , R<10> are each an alkyl; X is O, NH), 10-50wt.% of a compound of formula III (R<11> is H, methyl; R<12> is an alkyl) and 0-25wt.% of a compound copolymerizable with them stated above with a cationizing agent of the formula: YE (Y is Br, I or the like; E is an alkyl).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hair setting composition, and more particularly to a hair setting composition such as a hair setting agent, a styling agent and a hair styling agent which have both excellent set holding power and good feel. Regarding things.

[0002]

2. Description of the Related Art Hair setting agents which have hitherto been widely used are ones in which a film-forming polymer compound is dissolved in water, a lower alcohol or a mixed solvent thereof. The polymer compound blended therein has an action of fixing the hairs to each other and holding the set, but the conventionally used ones have stickiness in the process of applying to hair and drying and finishing. ,
It wasn't smooth. In order to eliminate such drawbacks, attempts have been made to improve the feel of use by adding oils and fats for cosmetics, surfactants and the like to polymer compounds. However, a hair setting agent having both a satisfactory set holding power and a feeling of use has not yet been obtained.

In recent years, a hair treatment agent containing an amphoteric polymer compound and a cationic polymer (Japanese Patent Publication No. 2-4444).
No. 6, Japanese Patent Publication No. 3-14805) and a hair treatment agent containing an amphoteric polymer compound and an anionic polymer (Japanese Patent Publication No. 3-21524) have been developed. However, these treatment agents are not satisfactory in terms of non-greasiness and smoothness after application and drying, and also because the finished hair has a stiff feel. Therefore, the adhesion between hairs is sufficient, the formed film is elastic and does not stiffen, it has excellent style retention, and it is not sticky, smooth and dull in the process of drying after application. It has been desired to develop a hair setting composition that is easy to do.

[0004]

Therefore, as a result of earnest studies, the present inventor has found that by combining a specific amphoteric polymer and a specific cationic resin, excellent set holding power and good feel can be obtained. The present invention has been completed by finding that a hair setting composition having both of the following can be obtained.

That is, according to the present invention, the following component (A) is added in an amount of 0.05 to 10.0% by weight and the component (B) is added in an amount of 0.05 to 10.0% by weight.
It is a hair setting composition characterized by being mixed with 10.0% by weight.

(A) One or more amphoteric polymers having a molecular weight of 50,000 to 500,000, which are composed of a betaine dialkylaminoalkyl acrylate copolymer represented by the following general formula (I).

[0007]

[Chemical 4]

Wherein R ¹ and R ⁵ are hydrogen atoms or methyl groups, R ² and R ³ are alkyl groups each having 1 to 4 carbon atoms, and R ⁴ is 1 to 4 carbon atoms. Alkylene group, R ⁶ is an alkyl group or alkenyl group having 1 to 24 carbon atoms, A is an oxygen atom or NH
Each of the groups, n and m is a positive integer, and is a number such that the ratio of n: m is in the range of n: m = 2: 8 to 8: 2. )

(B) 50 to 90% by weight of the polymerizable unsaturated monomer represented by the following general formula (II), the following general formula (II
10 to 50% by weight of the polymerizable unsaturated monomer represented by I),
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 the general formula YE [wherein Y is It 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 E is 1 carbon atom.
~ 12 alkyl groups, benzyl groups or 1 to 3 carbon atoms
Is a fatty acid alkyl ester residue (the carbon number of the alkyl group is 1 to 4). ] The cationic resin modified with the cationizing agent shown by these.

[0010]

Embedded image

(Wherein R ⁷ is a hydrogen atom or a methyl group, R ⁸ is an alkylene group having 1 to 4 carbon atoms, R ⁹ and R ¹⁰ are each an alkyl group having 1 to 4 carbon atoms,
X is an oxygen atom or an NH group. )

[0012]

[Chemical 6]

(In the formula, R ¹¹ is a hydrogen atom or a methyl group, and R ¹² is an alkyl group having 12 to 24 carbon atoms.)

As the amphoteric polymer of the component (A) used in the present invention, as described above, one type or two or more types of the polymers represented by the general formula (I) can be used in combination. of ^{particular, R 1, R 2, R} 3 and R ⁵ is a methyl group, an amphoteric polymer R ⁴ is a methylene group, a is an oxygen atom are preferred, and those wherein R ⁶ is a stearyl group. among these, R ⁶ When used in combination with one having 1 to 4 carbon atoms, particularly excellent setting force and smoothness can be obtained. The molecular weight is 50,000 to 500,000. n and m are positive integers, respectively, and the ratio of n: m is
The range is n: m = 2: 8 to 8: 2. When the ratio of m to n exceeds n: m = 2: 8, there is a problem in solubility in alcohol and water, and the washability of hair deteriorates. Furthermore, there is a problem in terms of affinity with hair, and flaking becomes easy. On the other hand, the ratio of m to n is n: m
When it is smaller than 8: 2, the film forming power is poor and there is a problem in the setting power. Furthermore, the hygroscopicity is increased and stickiness occurs. The amphoteric polymer is 0.05 in the total composition.
-10.0 wt%, preferably 0.2-5.0 wt%. If it is less than 0.05% by weight, the effect as a setting agent cannot be obtained, and if it exceeds 10.0% by weight, it is used in a large amount on the hair, and there is a problem in washing hair, which is not preferable. Examples of the amphoteric polymer of the present invention include Yucaformer AM75-SM and Yukaformer AM75-R-2.
05S (all are trade names manufactured by Mitsubishi Petrochemical Co., Ltd.) and the like.

Next, the cationic resin as the component (B) will be described. The copolymer of the raw material for obtaining the cationic resin is 50 to 90% by weight, preferably 55 to 85% by weight, of the above-mentioned general formula (II). III) polymerizable unsaturated monomers 10 to 10
One obtained by copolymerizing 50% by weight, preferably 15 to 45% by weight, and 0 to 25% by weight of another polymerizable unsaturated monomer copolymerizable with each of the above polymerizable unsaturated monomers. Is.

Among the polymerizable unsaturated monomers represented by the general formula (II), particularly preferable ones are those in which R ⁷ is a methyl group, R ⁸ is an alkylene group having 2 to 3 carbon atoms, R ⁹ and R ^Ten
Is a methyl group or an ethyl group, and X is an oxygen atom. Specific examples of the polymerizable unsaturated monomer (II) include dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, Examples thereof include diethylaminopropyl (meth) acrylamide. In addition, "(meth) acrylate" described in the present specification
Is a general term for acrylate and methacrylate,
"(Meth) acrylamide" is a general term for acrylamide and methacrylamide (and other similar terms).

As described above, the amount of the polymerizable unsaturated monomer (II) 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 used is too small, the finally obtained cationic resin will be poorly soluble in water, resulting in poor wash-removability when washing the hair, and due to deterioration of the cationic performance, it will slip on the hair. Properties, combability and conditioning effect are reduced. On the other hand, if the amount used is too large, the resulting cationic resin will have problems such as sticky feeling and a decrease in hair styling effect.

Among the polymerizable unsaturated monomers represented by the general formula (III), particularly preferable ones are those in which R ¹¹ is a methyl group and R ¹² is an alkyl group having 13 to 20 carbon atoms. Is. Specific examples of the polymerizable unsaturated monomer (III) include lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate and behenyl (meth) acrylate.

As described above, the amount of the polymerizable unsaturated monomer (III) 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 used is too small, the finally obtained cationic resin will have a sticky feel or poor flexibility. On the other hand, if the amount used is too large, the resulting cationic resin becomes poorly soluble in water, the removability during washing is deteriorated, and the hair conditioning effect is deteriorated.

The polymerizable unsaturated monomer for copolymerization includes
In addition to the polymerizable unsaturated monomers (II) and (III) described above, other polymerizable unsaturated monomers can be used although they are not essential components. By appropriately selecting the other polymerizable unsaturated monomer to be used, it is possible to impart appropriate flexibility and hardness to the finally obtained cationic resin to control the feel and the like.

Specific examples of the other polymerizable unsaturated monomer that can be used include, for example, methyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth).
(Meth) acrylic alkyl ester such as acrylate; 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; 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 used is 0 to 25% by weight based on the total amount of monomers to be copolymerized. If the amount of the other monomer used becomes too large, the amount of the polymerizable unsaturated monomer (II) or (III) used will decrease, which will cause trouble.

The polymerizable unsaturated monomers (II) and (II
I), and the copolymerization of other polymerizable unsaturated monomer used as necessary, include bulk polymerization, solution polymerization, suspension polymerization,
It can be carried out by various radical polymerization methods such as an emulsion polymerization method. A preferred polymerization method is a solution polymerization method, in which the above-mentioned 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.

The solvent used in that case 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 preferably used. 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, it is general that all kinds and all amounts of the monomer and the polymerization initiator are present in the polymerization system from the beginning of the polymerization.
Alternatively, a divided addition method may be used for the amount.
The amount of solvent used is such that the polymer concentration in the resulting copolymer solution is 1
The amount is preferably 0 to 65% by weight.

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

The copolymer obtained by the above copolymerization is subjected to a modification reaction with the cationizing agent represented by the above general formula YE to obtain the cationic resin used in the present invention. 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; sulfuric acid esters such as dimethyl sulfate and diethyl sulfate. And monohalogenated fatty acid esters such as ethyl monochloroacetate, propyl monopropionate propionate and butyl monochloroacetate. Modification of the copolymer with a cationizing agent, that is, cationization reaction,
A cationizing agent is added to the copolymer solution, and the mixture is stirred under an inert atmosphere, for example, in a nitrogen stream while stirring at 40 to 100%.
It is carried out by heating at a temperature of ℃ for 4 to 30 hours.

The modification with a cationizing agent is generally carried out after the copolymerization as described above, and is preferable, but as an alternative, at the monomer stage, that is, with the above-mentioned general formula (II), Prior to the polymerization, the polymerizable monomer represented is reacted with a cationizing agent to be cationized, and then copolymerized with the cationized polymerizable monomer to form a cationic resin. You can also The present invention also includes this alternative embodiment. As for the obtained cationic resin, the solution of the manufactured cationic resin may be used as it is, or the solid cation after the solvent is once removed by evaporation from the manufactured solution of the cationic resin solution. Resin may be used, or the solid cationic resin may be redissolved in another solvent before use.

The cationic resin is 0.05% in the total composition.
˜10.0% by weight, preferably 1.0 to 8.0% by weight. If it is less than 0.05% by weight, sufficient setting force for hair cannot be obtained, and if it exceeds 10.0% by weight, stiffening or flaking appears on the hair after styling, which is not preferable in any case. Because. Examples of the cationic resin of the present invention include those disclosed in JP-A-5-310538.

In addition to the above-mentioned essential constituents, the hair setting composition of the present invention has a quantitative and qualitative range that does not impair the effects of the present invention depending on the purpose, and further liquid paraffin, squalane, and lanolin derivatives. , Higher alcohols, various ester oils, avocado oils, palm oils, beef tallow, jojoba oils, silicone oils, polyalkylene glycol polyethers and their carboxylic acid oligoester compounds, oils such as terpene hydrocarbon oils, ethylene glycol, propylene glycol, 1,3-butylene glycol, glycerin,
Soluble polyhydric alcohols such as sorbitol and polyethylene glycol, moisturizers such as hyaluronic acid, chondroitin sulfate and pyrrolidone carboxylate, ultraviolet absorbers, ultraviolet scattering agents, resins such as acrylic resins, silicone resins and polyvinylpyrrolidone, soybeans Proteins such as proteins, gelatin, collagen, silk fibroin, elastin, or protein degradation products, preservatives such as ethylparaben and butylparaben, activators such as various amino acids, biotin, pantothenic acid derivatives, γ-oryzanol, dextran sulfate sodium,
Blood circulation promoters such as vitamin E derivatives and nicotinic acid derivatives,
An antiseborrheic agent such as sulfur and thiantol, a diluent such as ethanol, isopropanol and tetrachlorodifluoroethane, a thickener such as carboxyvinyl polymer, a drug, a fragrance, a coloring agent and the like may be appropriately blended as necessary.

The hair setting composition of the present invention can be used in various forms. For example, general hair styling agents, shampoo agents, rinse agents, treatment agents, setting agents, permanent wave liquids, and mascara can be used in various modes of use. Further, the hair setting agent composition may have various dosage forms such as a liquid form, a cream form, an aqueous emulsion form and a gel form.

In the case of general hair styling products, the amphoteric polymer of the present invention and the cationic resin may be used as the only polymer component, or natural polymers for hair styling products, which have hitherto been known, You may use together with a natural type modified polymer and a synthetic type polymer. In addition, surfactants, thickeners,
Various additives such as a hadrotrope, an emulsifying agent, a conditioning agent, oils and fats, a humectant, a higher fatty acid ester, a plasticizer such as glycerin and polyethylene glycol, a coloring agent, a bactericidal agent, and a perfume can be used in combination.

Further, in the case of shampoo agents, rinse agents, treatment agents, setting agents, permanent wave agents, mascaras, etc., those known agents are added to the amphoteric polymer of the present invention and the cationic resin. 0.1% by weight or more, preferably 0.2 to 10% by weight, respectively, to obtain shampoo agents, rinse agents, mascaras and the like as the hair setting composition of the present invention.

Particularly preferred use modes of the hair setting composition of the present invention are aerosol type hair spray, pump type hair spray, foam aerosol, hair mist,
Includes hair styling products such as set lotions, hair styling gels, hair liquids, hair creams, hair oils, which are solubilizing systems, emulsifying systems, powder dispersion systems, oil-water two-layer systems, oil-water-powder systems. Any of a three-layer system or the like may be used.

[0035]

The present invention will be described in more detail with reference to the following examples. The present invention is not limited by these. All compounding amounts are weight%. Prior to the examples, an example of producing the cationic resin used in this example is shown.

Cationic Resin Production Example 1 55 parts of dimethylaminoethyl methacrylate, 15 parts of lauryl acrylate and cetyl were placed in a five-necked flask equipped with a reflux condenser, a dropping funnel, a thermometer, a glass tube for nitrogen substitution, and a stirrer. 20 parts of methacrylate, 10 parts of behenyl methacrylate, and 100 parts of absolute ethanol
Azobisisobutyronitrile (hereinafter referred to as "AI
BN "is abbreviated. ) 0.3 part was added and the flow rate was 80
The mixture was heated under reflux at 0 ° C., and after 2 hours, 0.6 part 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) and 10 parts of absolute ethanol were added.
0 part was added, and the denaturation reaction was further performed at 50 ° C. for 10 hours under a nitrogen stream. Then, the ethanol content was adjusted to obtain a cationic resin solution having a polymer content of 30%.
The weight average molecular weight of the resin before modification was 120,000.

Cationic Resin Production Example 2 A flask similar to that used in Production Example 1 was charged with 85 parts of dimethylaminoethyl methacrylate and 15 parts of stearyl methacrylate.
Parts, and 54 parts of absolute ethanol were added, 0.1 parts of AIBN was added, the mixture was heated under reflux at 80 ° C. under a nitrogen stream, 0.6 parts of AIBN was added after 2 hours, and polymerization was carried out at the same temperature for 6 hours. I let it. Then, 72.8 parts of ethyl monochloroacetate (1.1 times the molar amount relative to dimethylaminoethyl methacrylate) and 100 parts of absolute ethanol were added, and the denaturation reaction was carried out by heating under reflux at 80 ° C. for 12 hours under a nitrogen stream. Let Then, the ethanol content 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.

Cationic Resin Production Example 3 In the same flask as in Production Example 1, 80 parts of dimethylaminoethyl methacrylate and 12 parts of tridecyl methacrylate were added.
Parts, stearyl acrylate 8 parts, and absolute ethanol 400 parts were added, AIBN 2.0 parts was added, and the mixture was heated under reflux at 80 ° C. under a nitrogen stream, and after 2 hours, 0.6 parts of AIBN was added and the same temperature was maintained for 6 hours. Polymerized. Then
32.9 parts of butyl chloride (0.7 mole times the amount of dimethylaminoethyl methacrylate) was added, and the mixture was heated under reflux at 80 ° C. under a nitrogen stream to carry out a modification reaction for 30 hours.
Then, adjust the ethanol content to obtain a polymer content of 30
After the content was set to%, the column was passed through a column filled with activated carbon in advance for deodorization treatment. Furthermore, the treatment liquid is put in a flask,
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 the cationic resin before modification was 6,000.

Cationic Resin Production Example 4 In a flask similar to that of Production Example 1, 70 parts of diethylaminoethyl methacrylate, 5 parts of cetyl acrylate, 10 parts of stearyl methacrylate and 10 parts of N-vinylpyrrolidone were used.
Parts, 5 parts butyl methacrylate, and 10 parts acetone
Add 0 parts, add 0.3 parts AIBN, and under nitrogen stream 60
The mixture was heated to reflux at 0 ° C., and 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.
Then, 68.6 parts of diethyl sulfate (equimolar amount to diethylaminoethyl methacrylate) and 100 parts of absolute ethanol were added, and the mixture was further added at 50 ° C. under a nitrogen stream at 1 ° C.
The denaturing reaction was performed by heating under reflux for 0 hours. The obtained viscous liquid was depressurized at 70 ° C. to remove ethanol as a solvent to obtain a solid. After crushing this solid, it was washed well with diethyl ether and dried again at 70 ° C. under reduced pressure to obtain a solid cationic resin. The weight average molecular weight of the resin before modification was 400,000.

Example 1 Hairblow (1) Decamethylcyclopentasiloxane 15.0 wt% (2) Dimethylpolysiloxane (n = 3000) 3.0 (3) 1,3-Butylene glycol 2.0 (4) Poly Oxyethylene hydrogenated castor oil (60EO) 2.0 (5) Amphoteric polymer 1.0 (R ¹ , R ² , R ³ , R ⁵ are methyl groups, R ⁴ is methylene group, R ⁶ is butyl group, A is A Oxygen atom, n: m = 7: 3) (6) Cationic resin solution obtained in Production Example 1 5.0 (resin amount) (7) Ethanol 15.0 (8) Ion-exchanged water balance (9) Perfume Proper amount manufacturing method (1), (2) is dissolved, added to the mixture of (3), (4) and emulsified,
Mix with (5), (6), (7), (8), (9).

Example 2 Hair Mousse (1) Octamethylcyclotetrasiloxane 10.0 wt% (2) Dimethylpolysiloxane (n = 10000) 2.0 (3) Glycerin 1.0 (4) Polyoxyethylene hydrogenated castor oil (120EO) 2.0 (5) Amphoteric polymer 3.0 (R ¹ , R ² , R ³ , R ⁵ are methyl groups, R ⁴ is methylene group, R ⁶ is stearyl group, A is oxygen atom, n: m = 4: 6) (6) Cationic resin solution obtained in Production Example 2 8.0 (resin amount) (7) Ethanol 10.0 (8) Ion-exchanged water balance (9) n-Butane 7.0 (10) Perfume An appropriate amount of (2) is dissolved in the manufacturing method (1), and the mixture is added to the mixture of (3) and (4) and emulsified, (5), (6), (7), (8), ( Put the solution mixed with 10) in the aerosol container, attach the valve, and then fill (9).

Example 3 Hair Cream (1) Decamethylcyclohexasiloxane 25.0% by Weight (2) Dimethylpolysiloxane (n = 10000) 6.0 (3) Glycerin 3.0 (4) Polyoxyethylene Cured Castor Oil (120EO) 3.0 (5) Amphoteric polymer 1.0 (R ¹ , R ² , R ³ , R ⁵ are methyl groups, R ⁴ is methylene group, R ⁶ is ethyl group, A is oxygen atom, n : m = 7: 3) (6) Cationic resin aqueous solution obtained in Production Example 3 3.0 (resin amount) (7) Ethanol 10.0 (8) Ion-exchanged water balance (9) Polyvinyl alcohol 1.0 (10) Perfume An appropriate amount of (2) is dissolved in the manufacturing method (1), and the mixture is added to the mixture of (3) and (4) and emulsified, (5), (6), (7), (8), ( Mix with 9) and (10).

Example 4 Hair Oil (1) Decamethylcyclopentasiloxane 57.0 wt% (2) Dimethylpolysiloxane (5 cps) 20.0 (3) Dimethylpolysiloxane (n = 7000) 10.0 (4) Amphoteric Polymer 3.0 (R ¹ , R ² , R ³ , R ⁵ are methyl groups, R ⁴ is methylene group, R ⁶ is stearyl group, A is oxygen atom, n: m = 5: 5) (5) Production Solid cationic resin obtained in Example 4 5.0 (6) Ethanol 10.0 (7) Perfume Proper amount The production methods (1) to (7) are dissolved under stirring at 70 to 80 ° C. Viscosity 5
A viscous and transparent liquid hair oil of 00 cps was obtained.

Example 5 Hairblow (1) Decamethylcyclopentasiloxane 15.0 wt% (2) Dimethylpolysiloxane (n = 3000) 3.0 (3) 1,3-Butylene glycol 2.0 (4) Poly Oxyethylene hydrogenated castor oil (60EO) 2.0 (5) Amphoteric polymer 1.0 (R ¹ , R ² , R ³ , R ⁵ are methyl groups, R ⁴ is a methylene group, A is an oxygen atom, R ⁶ A butyl group and a stearyl group are used together: n: m = 8: 2) (6) Cationic resin solution obtained in Production Example 1 1.0 (resin amount) (7) Ethanol 15.0 (8) Ion-exchanged water balance (9) Perfume proper amount Manufacturing method (1), (2) is dissolved, added to the mixture of (3), (4) and emulsified,
Mix with (5), (6), (7), (8), (9).

Comparative Example 1 Hair Mousse (1) Octamethylcyclotetrasiloxane 10.0 wt% (2) Dimethylpolysiloxane (n = 10000) 2.0 (3) Glycerin 1.0 (4) Polyoxyethylene hydrogenated castor oil (120EO) 2.0 (5) (Vinylpyrrolidone / vinyl acetate) Copolymer 2.0 (6) Ethanol 10.0 (7) Ion-exchanged water balance (8) n-Butane 7.0 (9) Fragrance Suitable amount Dissolve (2) in the manufacturing method (1), add to the mixture of (3), (4) and emulsify, and mix with (5), (6), (7), (9) to form a solution. Put it in the aerosol container, attach the valve, and then fill (8).

Comparative Example 2 Hair Mousse (1) Octamethylcyclotetrasiloxane 10.0 wt% (2) Dimethylpolysiloxane (n = 10000) 2.0 (3) Glycerin 1.0 (4) Polyoxyethylene hydrogenated castor oil (120EO) 2.0 (5) Amphoteric polymer 3.0 (R ¹ , R ² , R ³ , R ⁵ are methyl groups, R ⁴ is methylene group, R ⁶ is ethyl group, A is oxygen atom, n: m = 5: 5) (6) Ethanol 10.0 (7) Ion-exchanged water balance (8) n-butane 7.0 (9) Perfume An appropriate amount of (2) is dissolved in the production method (1), and (3), Add (5), (6), (7) and (9) to the mixture of (4) and emulsify it, and put the solution into the aerosol container, attach the valve and then fill (8). To do.

Comparative Example 3 Hair Mousse (1) Octamethylcyclotetrasiloxane 10.0 wt% (2) Dimethylpolysiloxane (n = 10000) 2.0 (3) Glycerin 1.0 (4) Polyoxyethylene hydrogenated castor oil (120EO) 2.0 (5) Amphoteric polymer 1.5 (R ¹ , R ² , R ³ , R ⁵ are methyl groups, R ⁴ is a methylene group, R ⁶ is an ethyl group, A is an oxygen atom, n: m = 4: 6) (6) Polyvinylpyrrolidone / dimethylamino ethyl methacrylate copolymer 1.5 (7) Ethanol 10.0 (8) Ion-exchanged water balance (9) n-Butane 7.0 (10) Perfume proper amount Dissolve (2) in the manufacturing method (1), add to the mixture of (3), (4) and emulsify, mix with (5), (6), (7), (8), (10). Put the resulting solution in the aerosol container, attach the valve, and then fill (9).

Comparative Example 4 Hair Mousse (1) Octamethylcyclotetrasiloxane 10.0 wt% (2) Dimethylpolysiloxane (n = 10000) 2.0 (3) Glycerin 1.0 (4) Polyoxyethylene hydrogenated castor oil (120EO) 2.0 (5) Amphoteric polymer 1.5 (R ¹ , R ² , R ³ , R ⁵ are methyl groups, R ⁴ is a methylene group, R ⁶ is an ethyl group, A is an oxygen atom, n: m = 8: 2) (6) Acrylic resin Alkanol amine liquid (50%) 3.0 (7) Ethanol 10.0 (8) Ion-exchanged water balance (9) n-Butane 7.0 (10) Perfume Proper amount Manufacturing method Dissolve (2) in (1), add to the mixture of (3), (4) and emulsify, mix with (5), (6), (7), (8), (10) Put the solution into the aerosol container, attach the valve, and then fill (9).

Comparative Example 5 Hair Mousse (1) Octamethylcyclotetrasiloxane 10.0 wt% (2) Dimethylpolysiloxane (n = 10000) 2.0 (3) Glycerin 1.0 (4) Polyoxyethylene hydrogenated castor oil (60EO) 1.0 (5) Cationic resin solution obtained in Production Example 2 8.0 (resin amount) (6) Ethanol 10.0 (7) Ion-exchanged water balance (8) n-Butane 7.0 (9) Fragrance A suitable amount of (2) is dissolved in the manufacturing method (1), added to the mixture of (3) and (4) and emulsified, and mixed with (5), (6), (7) and (9). Put the resulting solution in the aerosol container, attach the valve, and then fill (8).

Comparative Example 6 Hair Mousse (1) Octamethylcyclotetrasiloxane 10.0 wt% (2) Dimethylpolysiloxane (n = 10000) 2.0 (3) Glycerin 1.0 (4) Polyoxyethylene hydrogenated castor oil (120EO) 2.0 (5) Amphoteric polymer 3.0 (R ¹ , R ² , R ³ , R ⁵ are methyl groups, R ⁴ is a methylene group, A is an oxygen atom, and R ⁶ is a butyl group N: m = 7: 3) (6) Ethanol 10.0 (7) Ion-exchanged water balance (8) n-Butane 7.0 (9) Perfume Suitable amount For production method (1). Dissolve (2), add to the mixture of (3), (4) and emulsify, put the solution formed by mixing with (5), (6), (7), (9) in an aerosol container. After installing the valve, fill (8).

Comparative Example 7 Hair Mousse (1) Octamethylcyclotetrasiloxane 10.0 wt% (2) Dimethylpolysiloxane (n = 10000) 2.0 (3) Glycerin 1.0 (4) Polyoxyethylene hydrogenated castor oil (120EO) 2.0 (5) Amphoteric polymer 3.0 (R ¹ , R ² , R ³ , R ⁵ are methyl groups, R ⁴ is methylene group, R ⁶ is stearyl group, A is oxygen atom, n: m = 1: 9) (6) Cationic resin solution obtained in Production Example 2 8.0 (resin amount) (7) Ethanol 10.0 (8) Ion-exchanged water balance (9) n-Butane 7.0 (10) Perfume An appropriate amount of (2) is dissolved in the manufacturing method (1), and the mixture is added to the mixture of (3) and (4) and emulsified, (5), (6), (7), (8), ( Put the solution mixed with 10) in the aerosol container, attach the valve, and then fill (9).

Comparative Example 8 Hair Mousse (1) Octamethylcyclotetrasiloxane 10.0 wt% (2) Dimethylpolysiloxane (n = 10000) 2.0 (3) Glycerin 1.0 (4) Polyoxyethylene hydrogenated castor oil (120EO) 2.0 (5) Amphoteric polymer 3.0 (R ¹ , R ² , R ³ , R ⁵ are methyl groups, R ⁴ is methylene group, R ⁶ is stearyl group, A is oxygen atom, n: m = 9: 1) (6) Cationic resin solution obtained in Production Example 2 8.0 (resin amount) (7) Ethanol 10.0 (8) Ion-exchanged water balance (9) n-Butane 7.0 (10) Perfume An appropriate amount of (2) is dissolved in the manufacturing method (1), and the mixture is added to the mixture of (3) and (4) and emulsified, (5), (6), (7), (8), ( Put the solution mixed with 10) in the aerosol container, attach the valve, and then fill (9).

As described above, with respect to the products of the present invention obtained in Examples 1 to 5 and the conventional products obtained in Comparative Examples 1 to 8, (1) little stickiness after application and drying, (2) application After that, smoothness until dryness, (3) set holding power, and (4) less stiff feeling of the finished hair were evaluated. Table 1 shows the results. The evaluation method is as follows.

[Evaluation Method] (1) Low stickiness till drying after application A 2 g sample was applied to a hair strand (4 g), the shape was adjusted with a comb, and the stickiness till dried was evaluated organoleptically. ○: There is no stickiness at all. Δ: Somewhat sticky. X: There is considerable stickiness.

(2) Smoothness after application After drying, 2 g of a sample was applied to a hair strand (4 g), the shape was adjusted with a comb, and the smoothness until drying was evaluated organoleptically. ：: Smooth. Δ: Slightly stuck. ×: Scratch.

(3) Set Retaining Force A hair bundle having a length of 25 cm and a weight of 2 g was wetted with water, and the sample was washed with water.
5 g was applied, wound on a rod having a diameter of 15 mm, and naturally dried. After drying, the rod was removed from the curled hair bundle, and the hair bundle was hung in a constant temperature and constant humidity box (28 ° C., 90% RH) for 1 hour to measure the curl length. The set holding force was calculated by the following formula from the curl length immediately after being removed from the rod (l ₁₎ and the length after left for 1 hour (l ₂ ).

[0057]

[Equation 1] [Set holding power] = {(25-l ₂ ) / (25
−l ₁ )} × 100 (%)

(Display of measurement results) ：: Set holding force 90 to 100% ：: Set holding force 67 to 89% Δ: Set holding force 34 to 66% ×: Set holding force 0 to 33%

(4) Less stiff feeling of finished hair (1) The dried hair strand was sensory-evaluated according to the following criteria. ○: There is no feeling of stiffness. Δ: Somewhat rough feeling. X: There is a stiff feeling.

[0060]

[Table 1] ────────────────────────────── (1) (2) (3) (4) ──── ────────────────────────── Example 1 ○ ○ ○ ○ Example 2 ○ ○ ○ ○ Example 3 ○ ○ ○ ○ Example 4 ○ ○ ○ ○ Example 5 ○ ○ ◎ ○ ────────────────────────────── Comparative Example 1 △ △ △ △ Comparative Example 2 △ × × △ Comparative Example 3 △ △ ○ △ Comparative Example 4 × × ○ △ Comparative Example 5 ○ △ ○ △ Comparative Example 6 △ × △ △ Comparative Example 7 △ ○ ○ × Comparative Example 8 × ○ × ○ ── ────────────────────────────

As is clear from the results shown in Table 1, the hair setting agent composition of the present invention was excellent in set holding power and had a good feel.

[0062]

As described above, the hair setting composition of the present invention has a good feel such as non-greasiness and easy stickiness in the process from application to dry finishing, and finished hair not being stiff. In addition, it has excellent set holding power.

Claims (4)

[Claims] 1. A hair setting composition comprising the following component (A) in an amount of 0.05 to 10.0 wt% and component (B) in an amount of 0.05 to 10.0 wt%. Stuff. (A) One or more amphoteric polymers having a molecular weight of 50,000 to 500,000, which are composed of a betaine dialkylaminoalkyl acrylate copolymer represented by the following general formula (I). Embedded image (Wherein R ¹ and R ⁵ are a hydrogen atom or a methyl group, R ²
And R ³ are each an alkyl group having 1 to 4 carbon atoms, R ⁴ is an alkylene group having 1 to 4 carbon atoms, R ⁶ is an alkyl group or an alkenyl group having 1 to 24 carbon atoms, A is an oxygen atom or an NH group, n and m are positive integers, and the ratio of n: m is n: m.
= 2: 8 to 8: 2. (B) 50 to 90% by weight of the polymerizable unsaturated monomer represented by the following general formula (II), 10 to 50% by weight of the polymerizable unsaturated monomer represented by the following general formula (III), And other polymerizable monomers copolymerizable with each of the above polymerizable unsaturated monomers
The copolymer obtained by copolymerizing 25 to 25% by weight is represented by the general formula YE [wherein Y represents a bromine atom, a chlorine atom, an iodine atom or an alkyl sulfate residue (wherein the alkyl group has 1 to
There are four. And E is an alkyl group having 1 to 12 carbon atoms, a benzyl 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). . ] The cationic resin modified with the cationizing agent shown by these. Embedded image (In the formula, R ⁷ is a hydrogen atom or a methyl group, R ⁸ is an alkylene group having 1 to 4 carbon atoms, R ⁹ and R ¹⁰ are each an alkyl group having 1 to 4 carbon atoms, and X is oxygen. Atom or NH group.) (In the formula, R ¹¹ is a hydrogen atom or a methyl group, and R ¹² is an alkyl group having 12 to 24 carbon atoms.) 2. The weight average molecular weight of the cationic resin is 5,000 as the molecular weight of the copolymer before being modified with a cationizing agent.
The hair setting composition according to claim 1, which is 0 to 500,000. 3. The hair setting agent according to claim 1, wherein R ¹ , R ² , R ³ and R ⁵ are methyl groups, R ⁴ is a methylene group and A is an oxygen atom as the component (A). Composition. 4. The hair setting composition according to claim 3, wherein R ⁶ is a stearyl group and R ⁶ is a C 1 to C 4 component as component (A).