JPH0436218A - Hair cosmetic - Google Patents

Abstract

PURPOSE:To provide the title cosmetic favorable in settability, combability and rinsability, giving a gloss, formulated with a specific silicone-based copolymer such as a copolymer obtained by radical copolymerization between N- vinylpyrrolidone and an acrylic modified silicone. CONSTITUTION:The objective cosmetic formulate with a silicone-based copolymer obtained by further modifying, with a lower alkyl halide or dilower alkyl sulfate, (A) a copolymer produced by radical copolymerization between (1) N-vinylpyrrolidone and (2) an acrylic modified silicone of (B) a copolymer produced by radical copolymerization between (3) N-vinylpyrrolidone, (4) 2- dimethylaminoethyl acrylate and/or 2-dimethylaminoethyl methacrylate and (5) an acrylic modified silicone. The present cosmetic is excellent in hair settability, rinsability, improving combing, no stickiness and giving the hair gloss.

Description

Detailed Description of the Invention "Field of Industrial Application" The present invention relates to hair cosmetics characterized by blending a specific silicone-based copolymer, and more specifically, to hair cosmetics that have good setting power and combability. The object of the present invention is to provide a hair cosmetic that has cleansing properties and also imparts shine to hair.

[Prior Art] Hair cosmetics intended for hair styling, such as hair sprays, hair mousses, hair liquids, hair greases, hair blowers, hair creams, and hair gels, are often blended with resins for hair setting agents. Resins for hair setting agents can be broadly classified into nonionic, anionic, cationic, and amphoteric resins. Polyvinylpyrrolidone, polyvinyl methyl ether, and the like are used as nonionic resins. The anionic resin is used by neutralizing an acrylic copolymer containing acrylic acid or methacrylic acid, a half ester of maleic acid, or the like with a base. As the cationic resin, an acrylic copolymer having a quaternary ammonium salt structure in the molecule, polydimethylmethylenepiperidinium chloride, cationized cellulose, etc. are used. As the amphoteric resin, an acrylic copolymer having a betaine structure in the molecule is used. These resins are generally used dissolved or homogeneously dispersed in water, a water-ethanol mixture, or ethanol, and serve to fix and set the hair.

On the other hand, silicone oil is added to hair cosmetics for the purpose of improving the slipperiness of the hair and improving its shearability.

Dimethylpolysiloxane, methylphenylpolysiloxane, etc. are used as the silicone oil, and these hydrophobic silicones are added after being emulsified with a suitable surfactant, or dissolved in a small amount in ethanol or the like.

Among polyether-modified silicones having polyoxyethylene groups or polyoxypropylene groups, water-soluble ones are used after being dissolved in water or ethanol.

[Problem to be solved by the invention] When a hair setting agent resin and silicone oil are blended in order to obtain a hair cosmetic with excellent setting power, slipperiness, and combability, the product becomes unstable due to emulsification and dissolution. A good product is made, but when it is applied to the hair, after the volatile component evaporates, the non-volatile component remains on the hair, but the hair setting agent resin and silicone oil are not compatible with each other. It gave a sticky feel with an oily feel, and there was no improvement in uniform combability.Furthermore, the combability did not last long, and the combability tended to worsen over time.

Therefore, it has been desired to develop a resin for hair setting that is non-sticky, has good setting power, smoothness, and good combability.

JP-A-52-57337 describes a conditioning lotion containing a vinylpyrrolidone-silicon copolymer, but the silicone used here is tris(trimethylsiloxy)vinylsilane and trisvinylsilane. However, these copolymers of silicone, vinyl, and lolidone have a low proportion of silicone groups in the copolymer, making it difficult to obtain a product with sufficient combability. Furthermore, these silicones have low radical polymerizability and are therefore not easy to polymerize.

Furthermore, according to JP-A No. 2-25411, a dimethylpolysiloxane compound having a radically polymerizable group at one end of its molecular chain and a radically polymerizable monomer mainly composed of acrylate and/or methacrylate are obtained by radical copolymerization. Cosmetics containing acrylic-silicone graft copolymers are mentioned, and hair cosmetics such as hair conditioners are also included, or the copolymers used here are oil-soluble polymers. , isoparaffin, ethyl acetate, butyl acetate, acetone, toluene, etc., and does not dissolve or uniformly disperse in water or ethanol. Generally, it is desired that hair cosmetics have a setting power when used or that they can be washed off when hair is washed, but the ones that contain oil-soluble polymers that are used here have poor cleansing properties when washing hair. Furthermore, since this polymer does not dissolve or uniformly disperse in water or ethanol, it is difficult to incorporate it into hair sprays, hair mousses, hair liquids, hair greases, hair blowers, hair creams, and hair gels.

[Means for Solving the Problems] In view of the above-mentioned circumstances, the present inventors conducted extensive research and found that by blending a specific silicone copolymer,
The present invention was completed based on the discovery that it is possible to obtain a hair cosmetic that has good setting power, combability, and cleansing properties, and also imparts gloss to hair.

That is, the present invention provides a silicone copolymer obtained by copolymerizing N-vinylpyrrolidone and an acrylic-modified silicone, or a silicone copolymer obtained by copolymerizing N-vinylpyrrolidone and 2-dimethylaminoethyl acrylate and/or 2-dimethylaminoethyl methacrylate. A hair cosmetic comprising a silicone-based copolymer obtained by radical copolymerizing a copolymer with an acrylic-modified silicone and further modified with a lower alkyl halide or a di-lower alkyl sulfate. be.

The configuration of the present invention will be described below.

In the present invention, the hair setting agent resin used is a silicone copolymer of N-vinylpyrrolidone and acrylic-modified silicone, or N-vinylpyrrolidone,
- A silicone type obtained by further modifying a copolymer obtained by radical copolymerization of dimethylaminoethyl acrylate and/or 2-dimethylaminoethyl methacrylate and an acrylic-modified silicone with a lower alkyl halide or a di-lower alkyl sulfate. It is a copolymer, and as the acrylic modified silicone, those represented by the following general formula are used.

Here, R1 is a hydrogen atom or a methyl group. R2 represents a divalent hydrocarbon group having 1 to 10 carbon atoms and having a linear or branched carbon chain that is optionally interrupted by one or two ether bonds; -CH2-
1-(CH2)2-1-(C)+2)3-1-CH2C
H(CH3)CH2-1-(CH2)20 (CH2)
3-1-(CH2)20(CH2)20(CH2)3
- and so on. R3 represents a hydroxyl group or a methyl group. n is a positive number of 1 or more, preferably 5
-150 is used.

These acrylic-modified silicones can be synthesized by condensation reaction of a silicone represented by the following general formula (A) and an acrylic compound represented by the general formula (B) according to a conventional method, or are limited to this. isn't it.

(R3 is a hydroxyl group or a methyl group, n is a positive number of 1 or more) R1CR3 CH2=CCOR2Si (X is a halogen atom, a lower alkoxy group such as a methoxy group, or an ethoxy group.) N-vinylpyrrolidone and a silicone-based copolymer of acrylic-modified silicone, and N-vinylpyrrolidone,
2-dimethylaminoethyl acrylate and/or 2-
The polymerization ratio of the acrylic modified silicone in the copolymer of dimethylaminoethyl methacrylate and the acrylic modified silicone is selected such that the ratio of the acrylic modified silicone # in the copolymer is 0.1 to 20% by weight. If it is less than 0.1% by weight, the combability will be insufficient, and if it is more than 20% by weight, the solubility in water or ethanol will be poor. Moreover, it is preferably 1 to 10% by weight.

In the present invention, the silicone copolymer that can be blended is one that dissolves or is uniformly dispersed in water, a water-ethanol mixture, or ethanol at room temperature.

The silicone copolymer used in the present invention may be copolymerized with other radically polymerizable monomers within a range that does not impede the solubility in water or ethanol. For example, (meth)acrylic acid, methyl (meth)acrylate,
Alkyl (meth)acrylates such as ethyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, hydroxyalkyl such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, etc. (meth)acrylate, perfluoroalkyl (meth)acrylate,
Styrene, vinyl acetate, maleic anhydride, maleic ester, ethylene, propylene, etc.

The polymerization method of the silicone copolymer used in the present invention is as follows:
An ordinary radical polymerization method is used, and any of solution polymerization method, emulsion polymerization method, suspension polymerization method, and bulk polymerization method may be used, but among these, solution polymerization method is the most preferable because the polymerization can be easily controlled. As the polymerization initiator, azobisisobutyronitrile, benzoyl peroxide, etc. are used, and as the solvent, THF, ethanol, isopropanol, n-hexane, benzene, toluene, xylene,
Examples include methyl ethyl ketone and ethyl acetate.

In the case of a copolymer of N-vinylpyrrolidone and acrylic-modified silicone, if it is polymerized using ethanol or isopropanol as a solvent, it is possible to incorporate it into hair cosmetics as it is in the solvent, but it is possible to incorporate it into hair cosmetics as it is in the solvent, but it can be used in other solvents. After the polymerization reaction, the solvent is removed and the resin is taken out as a solid, and then dissolved or dispersed in water, water-ethanol, or ethanol, and incorporated into hair cosmetics. In the case of a copolymer of N-vinylpyrrolidone and 2-dimethylaminoethyl acrylate and/or 2-dimethylaminoethyl methacrylate and acrylic-modified silicone, if it is polymerized using ethanol as a solvent, it can be polymerized as it is, or it can be polymerized using another solvent. When this happens, remove the solvent and take out the resin as a solid, then dissolve it again in water, water-ethanol or ethanol, add lower alkyl halide or di-lower alkyl sulfate and heat to react to form the dimethylamino group. Modified into quaternary ammonium group. Examples of lower alkyl halides used here include methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide, ethyl iodide, propyl chloride, propyl bromide, propyl iodide, etc. For alkyl, dimethyl sulfate,
Examples include diethyl sulfate and dipropyl sulfate.

The amount of the silicone copolymer blended in the hair cosmetic of the present invention is preferably 0.1 to 30% by weight, more preferably 0.5 to 10% by weight. If it is less than 0.1% by weight, the setting force and sliding properties will be insufficient, and 30
If it exceeds % by weight, the viscosity of the product will become too high and it will be difficult to apply it to the hair.

In addition to the above-mentioned essential components, the hair cosmetic composition of the present invention contains a cosmetic t1 base, which is usually blended in hair cosmetic compositions, within a quantitative and qualitative range that does not impair the effects of the present invention, depending on the purpose. be done. Examples of these include hydrocarbon oils, oils and fats, waxes, higher fatty acids, higher alcohols, ester oils, oily components such as silicone oil, moisturizing agents such as polyhydric alcohols and hyaluronic acid, cationic activators, and highly cationic Molecules, nonionic activators, ultraviolet absorbers, preservatives, antioxidants, fragrances, etc. may be added.

The hair cosmetics of the present invention are not limited to products for the purpose of hair styling such as hair spray, hair mousse, hair liquid, hair grease, hair blow, hair cream, hair gel, etc., and are not limited to products for hair styling, such as one or two agents for permanent waving. It can be applied to all products that are applied to hair, such as hair dyes, hair coloring agents, one agent or two agents.

[Example] Next, the present invention will be explained in more detail by referring to Examples and Comparative Examples. The present invention is not limited thereby. The blending amount is in weight%. Prior to the Examples, a production example of the silicone copolymer of the present invention will be shown.

Production Example I 48 g of N-vinylpyrrolidone 2 g of acrylic modified silicone represented by the following structural formula, 0 azoisobutyronitrile
．． After dissolving 5 g in THFloog and reacting at a temperature of 70 to 80° C. for 5 hours, the solvent was removed to obtain a resinous silicone copolymer.

Production Example 2 45 g of N-vinylpyrrolidone, 5 g of acrylic modified silicone represented by the following structural formula, and 0.5 g of benzoyl peroxide are dissolved in 100 g of ethanol to give a solution of 70 to 80 g.
After 5 hours at a temperature of .degree. C., the solvent was removed to obtain a resinous silicone copolymer.

Production Example 3 38.4 g of N-vinylpyrrolidone, 9.6 g of 2-dimethylaminoethyl methacrylate, 2 g of acrylic modified silicone represented by the following structural formula, and 1.0 g of azobisisobutyronitrile were dissolved in 100 g of benzene, 70
After reacting at a temperature of ~80°C for 5 hours, the solvent was removed to obtain a resinous solid. Further, after dispersing this solid in water, 2.82 g of diethyl sulfate was added and reacted at 80°C for 5 hours. The desired silicone copolymer was obtained.

Production Example 4 39.2 g of N-vinylpyrrolidone, 9.8 g of 2-dimethylaminoethyl methacrylate, acrylic modified silicone Ig represented by the following structural formula, 1.0 g of azobisisobutyronitrile: dissolved in 100 g of feT HF, After reacting at a temperature of ~80°C for 5 hours, the solvent was removed to obtain a resinous solid. Further, after dispersing this solid in water, 2.88 g of diethyl sulfate was added and reacted at 80°C for 5 hours. The desired silicone copolymer was obtained.

Example 1 Hairspray ■ Polyethylene glycol monooleate ■ Silicone copolymer (obtained in Production Example 1) ■ 2-Hydroxy-4-methoxybenzophenone ■ Ethanol (99%) ■ Fragrance ■ Liquefied petroleum gas (3,0Kg) /am2at20℃) ■ Dimethyl ether 0.1 0.1 Stir and dissolve the remaining appropriate amount Φ ~ 0 to obtain a stock solution. After putting this stock solution into an aerosol container, a valve was attached and the injection gas 0, ■ was filled to obtain a hair spray. .

Comparative Example 1 Δ, Earthbrae A hair spray was obtained by replacing the same amount of the silicone copolymer of Example 1 with polyvinylpyrrolidone.

Example 2 Hair mist ■ Silicone copolymer (obtained in Production Example 2) 10 ■ Ethanol (95%) 85 ■
A mist-like setting agent was obtained by filling a dispenser-type container with the dissolved product of ion-exchanged water 5.about.5.

Comparative Example 2 Hair Mist A hair mist was obtained by replacing the same amount of the silicone copolymer of Example 2 with methylphenylpolysiloxane (20C3at 25°C).

Example 3 Foam aerosol ■ Liquid paraffin 3 ■ Bupyrene glycol 5 ■ Polyoxyethylene (60 mol) Hardened castor oil ester 3 ■ Behenyltrimethylammonium chloride 0.5 0 Cetanol 0.10 Ion exchange water Remaining ■ Silicone type Polymer (as active ingredient) (obtained in Production Example 3)
5 ■Ethanol (95 surprise) 20 ■Liquefied petroleum gas 10■～
Add to the solution from (2) and emulsify. Next, the dissolved products of ① and ② are added to obtain a stock solution. After putting this stock solution into an aerosol container, the valve was closed and the injection gas (2) was filled to obtain a foam aerosol.

Comparative Example 3 Foam Aerosol A foam aerosol was obtained by replacing the same amount of the silicone copolymer of Example 3 with polyvinylpyrrolidone.

When Examples 1 to 3 and Comparative Examples 1 to 3 were subjected to sensory evaluation by 20 expert panels, the results shown in Table 1 were obtained.

The symbols in the table are as follows.

(1) Test on sticky palms [11 g was taken and rubbed with hands for 30 seconds, and the stickiness of the hands was sensory evaluated.

○: Not sticky △: Slightly sticky ×: Significantly sticky, sticky (II) Hair styling fixing power Apply 2g Jt of sample to a hair strand (4g), shape with a comb, and dry for 1 hour. Hair fixing power was evaluated.

O: Excellent hair fixing power ×: Inferior hair fixing power (Ill) The ease of combing was evaluated.

○: Smooth △: Slightly stuck ×: Stuck (IV) 2 g of the hair nozzle sample was applied to the left and right sides of the hair, and after adjusting the shape with a comb, a sensory evaluation was performed.

○: Shiny △: Slightly poor shine × Not dull Example 4 Hair blow ■ Dimethylpolysiloxane 20CS 3 ■ Isoparaffin 3 ■ 1,3-butylene glycol 2 ■ Polyoxyethylene (40 mole addition) hydrogenated castor oil ester
2 ■ Ion exchange water Remaining ■ Silicone copolymer (as active ingredient) (obtained in Production Example 4) 0.5 0 Ethanol 15 ■ Fragrance
Add an appropriate amount of the molten matter of ① and ② to the molten matter of ① to ② and emulsify it, then add and mix the molten substances of ① to ②.

The hair blow of Example 4 was easy to apply tension during blow-drying and was excellent in hair styling.

A solution of Φ~0 at 70°C is added to the melts of ■~■ and emulsified, and then a melt of 01■ is added and cooled using a heat exchanger.

The hair cream of Example 5 had excellent hair styling fixing power and was easy to comb.

Example 5 Hair cream ■Liquid paraffin ■Glyceryl tri-2-ethylhexanoate ■Vaseline ■Stearyl alcohol ■Sorbitan monooleate ■Polyoxyethylene (40 mol addition) Hardened castor oil ester ■Glycerin ■Preservative ■Ion-exchanged water 0 silico Copolymer (obtained in Production Example 1) ■ Ethanol (95X) Appropriate amount remaining Example 6 Hair liquid ■ Ethanol (95X) 60 ■
Silicone copolymer (as active ingredient) (obtained in Production Example 4) 2 ■Propylene glycol 2 ■Polyoxypropylene (40 mol addition) butyl ether
10 ■ Polyoxyethylene (60 mol addition) hardened castor oil ester 1 0 Perfume Appropriate amount ■ Ion-exchanged water The remainder ■ to ■ were added and mixed in the same manner to obtain a hair liquid. The hair liquid obtained in Example 6 had excellent hair styling and fixing power and was easy to comb.

Example 7 Hair gel ■ Water 1 soluble carboxyvinyl polymer 1 ■ Sorbitol 3 ■ 1,3-butylene glycol 4 ■ Potassium hydroxide
0.20 ion exchange water
Remaining ■Polyoxyethylene (40 mol addition) Hardened castor oil ester 0.50 Silicone copolymer (as active ingredient) (obtained in Production Example 3)
5■ Methylparaben
0.10 Perfume Appropriate amount @ Ethanol (95%) 30 The dissolved material of ■ to 0 was added to the dissolved material of 0 to 0, and the mixture was stirred and mixed to obtain a hair gel. The hair gel obtained in Example 7 had excellent hair styling fixing power and was easy to comb.

Example 8 Permanent agent 1 ■ Silicone copolymer (obtained in Production Example 1) 0.5 ■ Ammonium thioglycolate (contains 50% as thioglycolic acid) 12.0 ■
Monoethanolamine 1.5 ■ Ammonium hydrogen carbonate 3.00 Propylene glycol 5.00 Methylparaben appropriate amount ■ Fragrance
Appropriate amount■Ion exchange water
The remaining perm agent 1 of Example 8 was non-sticky and gave shine to the hair.

Example 9 Permanent agent 2 ■ Silicone copolymer (obtained in Production Example 2) ■ Sodium bromate ■ Potassium monophosphate ■ Disodium hydrogen phosphate dodecahydrate ■ Sodium benzoate ■ Fragrance 8.0 0.5 0.05 0.1 Appropriate amount■Ion exchange water Remaining Example 9
The two perming agents were non-sticky and gave shine to the hair.

[Effects of the Invention] The hair cosmetic of the present invention has excellent hair styling fixing power and cleansing properties, improves combability, is non-sticky, and gives shine to hair.

Claims (5)

[Claims] (1) A hair cosmetic comprising a silicone copolymer obtained by radical copolymerization of N-vinylpyrrolidone and acrylic-modified silicone. (2) A copolymer obtained by radical copolymerization of N-vinylpyrrolidone, 2-dimethylaminoethyl acrylate and/or 2-dimethylaminoethyl methacrylate, and acrylic-modified silicone, and further halogenated lower alkyl or sulfuric acid. A hair cosmetic comprising a silicone copolymer modified with di-lower alkyl. (3) A hair cosmetic in which the structure of the acrylic-modified silicone according to claim 1 or 2 is represented by the following general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (R_1 is a hydrogen atom or methyl group, R_2 is a straight or branched carbon chain interrupted by one or two ether bonds, depending on the case) A divalent hydrocarbon group having 1 to 10 carbon atoms, R_3 is a hydroxyl group or a methyl group, and n is a positive number of 1 or more.) (4) A hair cosmetic in which the silicone copolymer according to claim 1 or 2 is dissolved or uniformly dispersed in water or ethanol at room temperature. (5) The hair cosmetic according to claim 1 or 2, wherein the proportion of acrylic modified silicone in the silicone copolymer is 0.1 to 20% by weight.