JPH08253539A - Copolymer for hairdressing cosmetic - Google Patents

Abstract

PURPOSE: To obtain a copolymer which is easily sol. in water, excellent in hairdressing effect when used for a hairdressing cosmetic, not sticky, soft and smooth to the touch, and esp. suitable for a mousse. CONSTITUTION: A silicone-graft copolymer for hairdressing is provided which comprises 15-75wt.% structural units derived from a cationic-group-contg. free- radical polymerizable monomer, 2-20wt.% structural units derived from a polysiloxane-block-contg. free-radical-polymerizable monomer, 3-80wt.% structural units derived from a (meth)acrylic ester of a 1-6C alcohol, and 2-80wt.% structural units derived from a (meth)acrylic ester of a 7-24C alcohol.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silicone graft copolymer for hair styling. The silicone graft copolymer for hairdressing of the present invention has good water solubility, has excellent setting power for hair when used in cosmetics for hairdressing, and has a non-greasy, soft and slippery refreshing texture, and is particularly mousse. Suitable for

[0002]

2. Description of the Related Art Hair sprays, mousses, set lotions, gels and the like have hitherto been used as hair styling cosmetics for maintaining the style of hair. Conventionally, hydrophilic polymers such as polyvinylpyrrolidone resin and ionic acrylic resin have been used as hair styling polymers in these hair styling cosmetics, but although these polymers have good hair styling properties, hair after setting There were drawbacks such as giving a stiff feel. In recent years, there has been proposed a silicon graft resin having a good setting force and a good feeling of combing, in which the above-mentioned drawbacks have been improved (Japanese Patent Laid-Open No. Hei 3 (1999) -311).
-128909 and 3-128311).

On the other hand, from the viewpoint of environmental protection, there is a demand for water-based cosmetics that do not use volatile organic solvents. In the above publication, however, it is volatile to dissolve a polymer having a good setting power and a good feel. An organic solvent is used, and a hair styling polymer that dissolves in water without using a volatile organic solvent together and has a good setting force and a good feel is not disclosed.

[0004]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, is substantially free of a volatile organic solvent, is soluble in water, and has a good hair setting power, and Another object of the present invention is to provide a water-soluble hair styling polymer that has good slipperiness and a good feel without stickiness.

[0005]

Means for Solving the Problems The present inventors have found that a silicone graft polymer having the following specific monomers in a specific ratio solves the above-mentioned problems, and is a cosmetic for hairdressing, particularly for mousses. The present invention has been found out that is suitable for. That is, the present invention provides the following (A), (B),
It is intended to provide a silicone graft copolymer for hair styling, which comprises the structural units (C) and (D) in the following proportions.

(A): Cationic group-containing radically polymerizable monomer unit 15 to 75% by weight (B): Polysiloxane group-containing radically polymerizable monomer unit 2 to 20% by weight (C): 1 carbon atom To 6 alcohol (meth) acrylic acid ester units 3 to 80% by weight (D): C7 to C7 alcoholic (meth) acrylic acid ester units 2 to 80% by weight.

<Cationic Monomer> The radical-polymerizable monomer forming the structural unit (A) is a radical-polymerizable monomer containing a cationic group, for example, the following formula (II)
And a monomer represented by the formula (III) and the like are used.

[0008]

Embedded image

(However, R⁸Is H or CH₃To R⁹Over
And R^TenCan be the same or different C ₁~ C_{twenty four}The archi
R, aryl, arylalkyl group, R¹¹Is H, C₁
~ C_{twenty four}Alkyl, aryl, arylalkyl groups,
Or -CH₂CH (OH) CH ₂-N⁺R¹²R¹³R
¹⁴To R¹²~ R¹⁴Can be the same or different C₁~ C_{twenty four}
Is an alkyl, aryl, or arylalkyl group of
Elementary, bromine, chlorine ions, or carbon number C₁~ C_{twenty four}Things
Alkyl sulfate ion, n is 0 or 1, and p is 1 to 1
An integer of 0 and q are 1 or 2, respectively. )

[0010]

[Chemical 4]

(However, R^FifteenIs H or CH₃, R¹⁶, R
¹⁷And R¹⁸Can be the same or different C₁~ C_{twenty four}Al
Kill, aryl, arylalkyl group, R¹⁹Is H,
Is C ₁~ C_{twenty four}Of alkyl, aryl, arylalkyl
Group, or -CH₂CH (OH) CH₂-N⁺R²⁰R^{twenty one}
R^{twenty two} Indicates R²⁰~ R^{twenty two}Can be the same or different C
₁~ C_{twenty four}Of alkyl, aryl, arylalkyl groups of
X is iodine, bromine, chlorine ion, or carbon number C₁
~ C_{twenty four}Is a monoalkyl sulfate ion, and r is 0 to 4
Is an integer, s is an integer of 1 to 10, and t is 1 or
Indicates 2. )

Specific examples of the monomer represented by the above formula (II) include N- (meth) acryloyloxyethyl-N,
N, N-trimethylammonium chloride, N- (meth) acryloyloxyethyl-N-ethyl-N, N-
Dimethylammonium = monoethylsulfate, N- (meth) acryloyloxyethyl-N, N, N-triethylammonium chloride, N- (meth) acryloyloxyethyl-N, N, N-triethylammonium = monoethylsulfate, N- [3- (N '-(meth) acryloyloxyethyl-N', N'-dimethylammonium) -2-hydroxypropyl] -N, N, N-trimethylammonium chloride, N- [3- (N '-( (Meth) acryloyloxyethyl-N ', N'-diethylammonium) -2-hydroxypropyl] -N, N,
Cationic group-containing (meth) acrylic acid esters such as N-triethylammonium chloride, N- (meth) acryloylaminopropyl-N, N-dimethyl-N-laurylammonium chloride, N- (meth) acryloylaminopropyl- N-ethyl-N, N-dimethylammonium = monoethylsulfate, N- (meth) acryloylaminopropyl-N, N-diethyl-N-methylammonium chloride, N- (meth) acryloylaminopropyl-N-methyl-N , N-diethyl ammonium =
Monomethyl sulfate, N- [3- (N '-(meth) acryloylaminopropyl-N', N'-dimethylammonium) -2-hydroxypropyl] -N, N, N-trimethylammonium chloride, N- [3 -(N '-(meth) acryloylaminopropyl-N', N'-diethylammonium) -2-hydroxypropyl] -N,
(Meth) such as N, N-trimethylammonium chloride
Examples include acrylamides.

Specific examples of the monomer represented by the formula (III) include Np-styrylmethyl-N, N, N-trimethylammonium chloride, Np-styrylethyl-N,
N-dimethyl-N-ethylammonium = monoethylsulfate and the like can be mentioned. Among these, the monomer represented by the formula (II) is more preferable from the viewpoint of copolymerizability with a monomer component forming another structural unit.

The monomer forming the structural unit (A) is such that the content of the structural unit (A) in the resulting silicon graft copolymer is 15 to 75% by weight, preferably 25 to 65% by weight.
Use within the range. When the content of the component (A) monomer is less than 15% by weight, the water solubility of the obtained copolymer is lowered, and when it exceeds 75% by weight, the setting force and the slipperiness when used for hair styling are lowered. .

As the monomer forming the structural unit (A), in place of the above-mentioned cationic group-containing radically polymerizable monomer,
The precursor in the precursor polymer obtained after copolymerizing a non-cationized cationizable radically polymerizable monomer as a precursor thereof with a monomer component forming another structural unit The copolymer of the present invention can be more preferably obtained by cationizing the monomer unit.
Examples of the precursor monomer used at this time include monomers represented by the following formulas (IV) and (V).

[0016]

Embedded image

(Wherein R ^{8 to} R ¹⁰ , n and p have the same meanings as defined in formula (I), and R ^{15 to} R ¹⁸ , r and s have the same meanings as in formula (II)) Formula ( Specific examples of the monomer represented by IV) include N, N-
Dimethylaminoethyl (meth) acrylate, N, N-
Diethylaminoethyl (meth) acrylate, N, N-
Dimethylaminopropyl (meth) acrylate, N, N
-Tert-amino group-containing (meth) acrylic acid esters such as diethylaminopropyl (meth) acrylate, N,
N-dimethylaminoethyl (meth) acrylamide,
Examples include tertiary amino group-containing (meth) acrylamides such as N, N-diethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide, and the like. It

Specific examples of the monomer represented by the formula (V) include p-dimethylaminomethylstyrene, p-dimethylaminoethylstyrene, p-diethylaminomethylstyrene and p-diethylaminoethylstyrene. Furthermore, after copolymerizing a radically polymerizable monomer containing a halogenated alkyl group such as (meth) acrylic acid 2-chloroethyl ester, the obtained precursor polymer is reacted with a tertiary amine such as triethylamine. The copolymer of the present invention can also be obtained by cationization.

<Cationizing Agent> Examples of the cationizing agent used for cationizing the precursor polymer include methyl chloride, ethyl chloride, butyl chloride, lauryl chloride, stearyl chloride, methyl bromide, ethyl bromide and butyl bromide. , Alkyl bromides such as lauryl bromide, stearyl bromide and methyl iodide, dialkyl sulphates such as dimethylsulfate and diethylsulfate, N- (3-chloro-2-hydroxypropyl) -N, N, N-trimethyl Ammonium chloride,
N- (3-chloro-2-hydroxypropyl) -N,
Examples include epichlorohydrin adducts of tertiary amine mineral salts such as N, N-triethylammonium chloride, inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid and phosphoric acid, and carboxylic acids such as formic acid, acetic acid and propionic acid. To be done. The amount of the cationizing agent used is 0.2 to 3 times, and preferably 0.5 to 2 times the molar equivalent of the cationizable functional group contained in the precursor polymer.

<Silicon Macromonomer> The polysiloxane group-containing radically polymerizable monomer forming the structural unit (B) is preferably a polysiloxane group (having a polymerization degree of the polysiloxane group of 7 to 500) in the molecule. And a monomer having a radical polymerizable unsaturated bond, for example, a polymerizable monomer represented by the following formula (I) is preferably used.

[0021]

[Chemical 6]

(However, D is a radical polymerizable group selected from the group consisting of vinyl, vinylalkyl, vinylaryl, vinylarylalkyl, vinyloxyalkyl, (meth) acryloyloxyalkyl and (meth) acryloylaminoalkyl groups. , R ^{1 to} R ⁷ may be the same or different, and each represents H, a C _{1 to} C ₁₀ alkyl group or an aryl group, and m represents an integer of 5 to 500.)

As the monomer represented by the formula (I), α-
(Vinylphenyl) polydimethylsiloxane, α- (vinylbenzyloxypropyl) polydimethylsiloxane, α- (vinylbenzyl) polymethylphenylsiloxane, α- (methacryloyloxypropyl) polydimethylsiloxane, α- (methacryloyloxypropyl) poly Methylphenyl siloxane, α- (methacryloylaminopropyl) polydimethylsiloxane, etc. are exemplified, and among these, m of polydimethylsiloxane group is included.
Is preferably 30 to 300.

The monomer forming the structural unit (B) is used within a range such that the content of the structural unit (B) in the copolymer is 2 to 20% by weight, preferably 4 to 15% by weight. (B)
When the amount of the component monomer used is less than 2% by weight, the slipperiness of the copolymer is lowered, while when it exceeds 20% by weight, no further improvement in the slipperiness is observed, which is economically disadvantageous. In addition, water solubility is also reduced.

<(Meth) acrylic acid short chain alcohol ester> The (meth) acrylic acid short chain alcohol ester forming the structural unit (C) is a (meth) acrylic acid ester of an alcohol having 1 to 6 carbon atoms, Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, (meth) Secondary butyl acrylate, (meth)
Tertiary butyl acrylate, Pentyl (meth) acrylate, Secondary pentyl (meth) acrylate,
1-Ethylpropyl (meth) acrylate, 2-methylbutyl (meth) acrylate, isopentyl (meth) acrylate, tertiary pentyl (meth) acrylate, 3-methylbutyl (meth) acrylate, neopentyl (meth) acrylate Hexyl (meth) acrylate, (meth)
2-Methylpentyl acrylate, (meth) acrylic acid 4
-Methylpentyl, 2-ethylbutyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate and the like are exemplified. Among these, (meth) acrylic acid ester of alcohol having 1 to 4 carbon atoms is preferable. The content of the structural unit (C) in the copolymer of these monomers is 3 to 80% by weight, preferably 10 to 6
It is used in a proportion of 0% by weight. When the amount of the component (C) monomer used is less than 3% by weight, the non-adhesiveness decreases, and when it exceeds 80% by weight, the water solubility decreases, which is not preferable.

<(Meth) acrylic acid long chain alcohol ester> The (meth) acrylic acid long chain alcohol ester forming the structural unit (D) is a (meth) acrylic acid ester of an alcohol having 7 to 24 carbon atoms, Specifically, heptyl (meth) acrylate, 2-heptyl (meth) acrylate, 3-heptyl (meth) acrylate, octyl (meth) acrylate, 2-octyl (meth) acrylate, (meth) acrylic 2-ethylhexyl acid, isooctyl (meth) acrylate, nonyl (meth) acrylate, 3,3,5-trimethylhexyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, (meth) Lauryl acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, eicosyl (meth) acrylate, Docosyl (meth) acrylate, tetracosyl (meth) acrylate, methylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, norbornyl (meth) acrylate, benzyl (meth) acrylate,
Examples include phenethyl (meth) acrylate and the like. Among these, (meth) acrylic acid ester of alcohol having 8 to 18 carbon atoms is preferable.

These monomers are used in a proportion such that the content of the structural unit (D) in the copolymer is 2 to 80% by weight, preferably 5 to 40% by weight. When the amount of the component (D) monomer used is less than 2% by weight, the water-solubility of the resulting silicon graft polymer is reduced, and even when it exceeds 80% by weight, the water-solubility is reduced and the non-adhesiveness is also reduced. To do.

<Other Monomers> As a constituent component of the silicon graft copolymer of the present invention, a radically polymerizable monomer other than the monomers (A) to (D) is used within a range not impairing the effects of the present invention. It can be copolymerized. These monomers include styrene, p-methylstyrene, p-
Hydrophobic vinyl monomers such as chlorostyrene, vinyl methyl ether, vinyl cyclohexyl ether, vinyl acetate, vinyl chloride, vinylidene chloride, diethyl maleate and dibutyl maleate, and (meth) acrylonitrile,
(Meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, etc. (Meth) acrylamide and its derivatives, N-cyclohexylmaleimide, maleimides such as N-phenylmaleimide, N-vinylpyrrolidone, N-
(Meth) acryloylmorpholine, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, methoxyethoxy (meth) acrylate,
Examples of hydrophilic monomers include (meth) acrylic acid derivatives such as polyethylene glycol (meth) acrylate and methoxy polyethylene glycol (meth) acrylate. The (meth) acrylate in the above description is a generic term for both acrylate and methacrylate. Similarly, (meth) acrylic acid is a generic term for both acrylic acid and methacrylic acid, and (meth) acryloyl is a generic term for both acryloyl and methacryloyl.

<Polymerization Method> The silicone graft copolymer of the present invention is usually prepared by solution polymerization, bulk polymerization, or suspension of the above-mentioned monomers (A) to (D) in the presence of a radical polymerization initiator. It can be obtained by polymerizing by a known method such as polymerization, and particularly preferably by solution polymerization. Further, instead of the (A) component monomer, a precursor monomer is copolymerized with the (B) to (D) component monomers, and then the obtained precursor polymer is cationized to obtain more cations. The copolymer of the present invention can be preferably obtained.

As the polymerization solvent, organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, ethyl acetate, propyl acetate and butyl acetate may be used alone or in combination. The above is mixed and used. 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,
Azo compounds such as 2′-azobisisobutyrate, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (1-cyclohexanecarbonitrile), benzoyl peroxide, dicumyl peroxide ,
Peroxides such as di-t-butyl peroxide and lauroyl peroxide are used. The polymerization initiator is usually used in an amount of 0.01 to 5% by weight based on the total amount of all the monomers used.

The polymerization is usually carried out in an atmosphere of an inert gas such as nitrogen or argon at 30 ° C to 120 ° C, preferably 40 ° C to 10 ° C.
It is carried out at 0 ° C. for 1 to 20 hours. When a cationizable radically polymerizable radically polymerizable monomer that is not cationized is used as the precursor monomer instead of the component (A) monomer, copolymerization is performed under the same conditions.

<Cationization> The cationization of the precursor polymer obtained by using the precursor monomer in place of the component (A) monomer is carried out by adding a cationizing agent to the polymer solution and adding 20
It is formed by cationization in the range of 100 to 100 ° C for 1 to 10 hours.

<Isolation and Purification> In order to obtain the copolymer of the present invention from the obtained polymer solution, isolation is carried out by a known method such as reprecipitation or solvent distillation. If necessary, the isolated copolymer may be further purified by reprecipitation, solvent washing, membrane separation, column chromatograph treatment, or the like. In the cationization of the precursor polymer, the precursor polymer once isolated from the polymerization reaction solution may be dissolved or dispersed again in a solvent and then subjected to a cationizing agent reaction. The copolymer thus obtained has a molecular weight of 10,000-
500,000, preferably 50,000 to 250,000
00.

<Uses> The copolymer of the present invention is excellent in touch such as slipperiness, has good setting power and non-adhesiveness, and has excellent water solubility. Therefore, it can be used as a hair spray, mousse and set lotion. , Gel, various hair styling cosmetics such as aqueous solution, hydroalcoholic solution, as a hair styling polymer,
It is used in various forms such as suspensions and gels. In particular, it can be suitably used for a mousse as an aqueous solution containing substantially no volatile organic solvent.

<Additives> When the copolymer of the present invention is used in hair styling cosmetics, oily agents such as hydrocarbon oils, ester oils and silicone oils, and feels of higher alcohols, polyethylene glycols, glycerin, etc., may be added as necessary. Improver, LP
Propellants such as G and dimethyl ether, thickeners such as hydroxyethyl cellulose, polyvinylpyrrolidone, and other hair styling polymers such as amphoteric acrylic polymers can be used in combination.
In addition, antiseptics, antifungal agents, ultraviolet absorbers, light stabilizers, foam stabilizers, antioxidants, metal ion capture agents, colorants, pigments,
Gloss imparting agent, fragrance, foaming agent, foam stabilizer, surfactant, p
An H regulator, a plasticizer, a bleaching agent, a reducing agent and the like can be added as appropriate.

[0036]

EFFECT OF THE INVENTION By using the copolymer of the present invention in a hair styling cosmetic product, a hair styling cosmetic product having an excellent feel such as slipperiness and excellent properties such as good setting power and non-adhesiveness, for example, hair Products such as sprays, mousses, set lotions and gels are obtained. In particular, it is possible to obtain an environmentally friendly aqueous hair styling cosmetic product which is substantially free of a volatile organic solvent, especially an aqueous mousse product.

[0037]

The reason why the cosmetic for hairdressing having the above-mentioned excellent performance can be obtained by using the copolymer of the present invention is that the structural units (A) to (D) are introduced into the copolymer in a well-balanced manner. It is that you are. The reason why a water-soluble silicon graft polymer is obtained by using the component (C) monomer and the component (B) monomer together is not clear,
It is speculated that the structural unit (D) formed from the component (D) monomer acts as a compatibilizing agent for the highly hydrophobic polysiloxane side chain polymer and the water-soluble main chain polymer.

[0038]

【Example】

Example 1 120 parts by weight of acetone, N, N in a reactor equipped with a reflux condenser, a dropping funnel, a thermometer, a nitrogen gas introducing pipe and a stirring device.
21 parts by weight of N-dimethylaminoethyl methacrylate,
9 parts by weight of polystyrene-converted molecular weight α- (methacryloyloxypropyl) polydimethylsiloxane, 33 parts by weight of tertiary butyl methacrylate, 17 parts by weight of stearyl methacrylate, 0.8 parts by weight of 2,2′-azobisisobutyronitrile Part, and after purging with nitrogen, 4
The temperature was raised to 60 ° C. in 0 minutes, reacted at 60 ° C. for 10 hours, and then cooled to room temperature.

When the molecular weight of the polymer was measured at this point, the polystyrene-reduced weight average molecular weight was 102,000.
It was 0. Diethylsulfuric acid 20 in a dropping funnel in the polymerization liquid
By weight, 1 part by weight was added dropwise, the temperature was raised to 60 ° C. over 1 hour, and stirring was continued for 1 hour to cationize the dimethylamino group. The completion of the cationization reaction was confirmed by measuring the amine value of the reaction solution. The reaction solution was poured into a large amount of n-hexane for reprecipitation, and the cake collected by filtration was washed with hexane and dried to obtain a white silicon graft copolymer (I) (calculation of weight average molecular weight). Value 127,000).

3 parts by weight of this polymer was heated and stirred with 97 parts by weight of deionized water at 60 ° C. for 2 hours, cooled and allowed to stand at room temperature for 1 day, and then the appearance of the aqueous solution was observed. The aqueous solution had a slight fluorescent color and was a transparent and uniform solution. In addition, when the polymer was evaluated, it was found that there was no tackiness, and that the slidability and setting force were good.

Examples 2 to 4 and Comparative Examples 1 to 3 Silicone graft polymers (II) to (VII) were produced in the same manner as in Example 1 using the compositions shown in Table 1. Further, the results of evaluating these polymers in the same manner as the polymer of Example 1 are shown in Table 2.

Example 5 Polymerization was carried out in the same manner as in Example 1 with the composition shown in Table 1. A polymerization solution diluted with methyl ethyl ketone to a solid content of 20% by weight was charged in a pressure reaction vessel equipped with a gas introduction tube, and after purging with nitrogen, methyl chloride gas was introduced for about 3 hours while maintaining the internal temperature at 50 ° C. did. Completion of the cationization reaction of the diethylamino group was confirmed from the measurement results of the amine value of the polymerization liquid and the amount of inorganic chlorine. The modification reaction liquid was treated in the same manner as in Example 1 to obtain a white silicon graft polymer (VIII). The evaluation results are shown in Table 2.

<Evaluation Method> Water solubility: 3 parts by weight of the polymer and 97 parts by weight of deionized water were added.
After heating and stirring at 0 ° C for 2 hours, and after cooling and standing at room temperature for 1 day, the appearance of the aqueous solution was observed. ○: uniform and almost transparent solution; △, uniform and slightly turbid solution. The separated or insoluble solids were evaluated as x.

Adhesiveness: Surface treatment A biaxially stretched polyethylene terephthalate film was coated with a polymer aqueous solution with a # 30 bar coater and dried with a hot air drier, and the film was adjusted to 23 ° C and a humidity of 80%. The pressure-sensitive adhesive strength was evaluated from the feeling of resistance when the finger was pressed for 1 second and then separated. ○: No resistance. X: Great resistance.

Lubricity: Surface treatment A biaxially stretched polyethylene terephthalate film is coated with an aqueous polymer solution using a # 30 bar coater, dried with a hot air dryer, adjusted to 23 ° C. and 50% humidity, and the coated surface is rubbed with a finger. The slipperiness was evaluated by this. ○ = good slip feeling, × = poor slip feeling.

Setting power: 2.0 g of a Japanese hair bundle having a length of 23 cm was immersed in an aqueous polymer solution, pulled out from the aqueous solution, lightly squeezed, wrapped around a rod having a diameter of 1 cm to dry, and then removed from the rod and curled hair Got a bunch.
This hair bundle was hung vertically in a thermo-hygrostat for 30 hours at 20 ° C. and 80% humidity for 3 hours, and the setting force was evaluated from the degree of elongation of the hair bundle after being hung vertically for 30 minutes. ◯: Almost no change; X: Clearly elongation is recognized.

[0047]

[Table 1]

[0048]

[Table 2]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yukitaka Goto 1 Toho-cho, Yokkaichi-shi, Mie Mitsubishi Chemical Corporation Yokkaichi Research Institute

Claims (3)

[Claims] 1. A hair-grafting silicone graft copolymer (A) comprising the following structural units (A), (B), (C) and (D) in the following proportions: cationic group-containing radical polymerization Polymeric monomer unit 15 to 75% by weight (B): Polysiloxane group-containing radically polymerizable monomer unit 2 to 20% by weight (C): C1-C6 alcohol (meth) acrylate unit 3 -80 wt% (D): C7-C24 alcohol (meth) acrylate unit 2-80 wt%. 2. The copolymer according to claim 1, wherein the monomer unit of the structural unit (B) is represented by the following general formula (I). Embedded image (However, D is vinyl, vinylalkyl, vinylaryl, vinylarylalkyl, vinyloxyalkyl,
It is a radically polymerizable group selected from the group consisting of (meth) acryloyloxyalkyl and (meth) acryloylaminoalkyl group, wherein R ^{1 to} R ⁷ may be the same or different and each is an H or C _{1 to} C ₁₀ alkyl group. Or an aryl group, and m represents an integer of 5 to 500. ) 3. A monomer unit of the structural unit (A) is the following general unit:
The compound according to claim 1 or 2, which is represented by the formula (II).
Polymer. [Chemical 2](However, R⁸Is H or CH₃To R⁹And R^TenAre the same
Or different good C ₁~ C_{twenty four}Of alkyl, aryl,
An arylalkyl group, R¹¹Is H, C₁~ C_{twenty four}The archi
Group, aryl, arylalkyl group, or -CH₂・
CH (OH) / CH₂-N⁺R¹²R¹³R¹⁴To R¹²~ R
¹⁴Can be the same or different C₁~ C_{twenty four}The alkyl of a
Reel, arylalkyl group, X is iodine, bromine, chlorine
Ion or carbon number C₁~ C_{twenty four}Of monoalkyl sulfate
ON, n is 0 or 1, p is an integer of 1 to 10, q
Represents 1 or 2, respectively. ).