JPH09295920A - Hair cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a hair cosmetic, comprising specific polymer particles excellent in film-forming propertied and suitable for reducing the oiliness of hair. SOLUTION: This hair cosmetic comprises polymer particles containing a polyorganosiloxane and a polymer of a radically polymerizable monomer (specific polymer particles) in the same particles. The specific polymer particles are obtained by polymerizing the radically polymerizable monomer in the presence of the polyorganosiloxane. The oil absorption volume of the specific polymer particles is preferably >=1mL/g, preferably >=2mL/g and the specific polymer particles are blended in an amount of preferably 0.05-5wt.% therein.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention contains specific polymer particles excellent in film-forming property and protein adsorption property, and also has excellent sebum absorption ability and usability, and is suitable for reducing oily feeling of hair, In addition, the present invention relates to a hair cosmetic that maintains flexibility.

[0002]

2. Description of the Related Art The cortex, when secreted appropriately, gives the skin and hair gloss and smoothness, but excessive secretion causes glare and stickiness. May cause makeup breakdown. In addition, excessive sebum on the hair does not cause the volume of the hair to appear, which makes it difficult to maintain the style. This excess secreted sebum can be easily removed by washing, but within a few hours on the skin and within a few days on the hair, the amount of sebum on the skin / hair surface will recover to a certain amount. Therefore, it must be washed frequently. Therefore, there are few safety problems in the method of physiologically suppressing sebum secretion by using a medicinal agent or physically absorbing excessively secreted sebum into powder, but sebum absorption capacity and usability There was a problem in effectiveness. For example, Japanese Patent Application Laid-Open No. 61-65807 discloses a method of controlling sebum by using an inorganic powder such as clay mineral and oxide. However, in general, a porous or layered inorganic substance has a drawback that its oil absorption ability is significantly reduced in the presence of sweat or dirt. Also,
In JP-A-59-144710, an attempt has been made to improve sebum absorption capacity by using silanized silica gel, which makes the surface of the inorganic powder hydrophobic so that the particle space of the agglomerates of the primary particles. It absorbs sebum in the gap, and high absorption capacity cannot be expected. U.S. Pat. No. 4,489,058 discloses a method of suppressing the occurrence of acne by using a copolymer of stearyl methacrylate and styrene, which has high compatibility with sebum, and absorbing sebum by swelling. There is. This method is excellent in that it absorbs sebum even in the presence of sweat or dirt, but the amount of absorption is not yet sufficient, and furthermore, due to simple swelling, there is a drawback that the feeling after sebum absorption is not good. there were. Further, since the particles having an average particle diameter of about 150 μm are used, there is a drawback that they are not easily attached to the hair especially when used for hair.

[0003]

SUMMARY OF THE INVENTION In order to solve the above problems, the present invention is a hair cosmetic composition which has excellent sebum absorption capacity and usability, is suitable for reducing the oiliness of hair, and has a long-lasting softness. The purpose is to develop.

[0004]

[Means for Solving the Problems]

The present invention is characterized by containing polymer particles containing a polyorganosiloxane and a polymer of a radical-polymerizable monomer in the same particle (hereinafter referred to as "specific polymer particles"). It is to provide cosmetics. Hereinafter, the present invention will be described in detail. In the present invention, the specific polymer particles are: a method of polymerizing a radically polymerizable monomer in the presence of a polyorganosiloxane polymer, and a condensation of the organosiloxane in the presence of an aqueous dispersion of a polymer of the radically polymerizable monomer. It can be produced by a method of proceeding the reaction.

The organosiloxane used in the present invention is represented by the general formula (1) R _n Si (OR ¹ ) 4- _n (wherein R is a monovalent organic group, R ¹ is a carbon number of 1 to 5). Alkyl group of 1 to 1 carbon atoms
4 is an acyl group, n is an integer of 0 to 2), a linear or branched alkoxysilane represented by the formula (2) R
² _m SiO _{(4-m) / 2} (wherein R ² is an organic group having 1 to 8 carbon atoms and m represents an integer of 0 to 3) and has a cyclic structure. It is an organosiloxane. R
Examples of the monovalent organic group of ¹ and R ² include an alkyl group such as a methyl group, an ethyl group, an n-propyl group and an i-propyl group, as well as a γ-chloropropyl group, a γ-chloropropyl group, a vinyl group, and 3 , 3,3-trifluoropropyl group,
γ-glycidoxypropyl group, γ-methacryloxypropyl group, γ-mercaptopropyl group, phenyl group,
Examples include 3,4-epoxycyclohexylethyl group and γ-aminopropyl group. Further, in the formula, R1 is an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms, for example, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, a sec-butyl group, t-butyl group,
An acetyl group etc. are mentioned.

Specific examples of these alkoxysilanes include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, and n.
-Propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, i-butyltrimethoxysilane, Vinyltrimethoxysilane, vinyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycid Xypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, phenyltrimethoxy Silane, phenyltriethoxysilane, γ-aminopropyltrimethoxysilane,
Examples thereof include 3,4-epoxycyclohexylethyltrimethoxysilane, 3,4-epoxycyclohexylethyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, and diethyldimethoxysilane. In the above method, the organosiloxane is preferably a cyclic organosiloxane such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane and trimethyltriphenylcyclotrisiloxane.

The organosiloxane may be a polyorganosiloxane which has been condensed in advance and has a polystyrene-equivalent weight average molecular weight of about 500 to 10,000. When the organosiloxane is a polyorganosiloxane, its molecular chain end is
For example, it may be blocked with a hydroxyl group, an alkoxy group, a trimethylsilyl group, a dimethylvinylsilyl group, a methylphenylvinylsilyl group, a methyldiphenylsilyl group, or the like. In the above method, it is preferable to use a graft crossing agent together with the above-mentioned organosiloxane. The graft crossing agent is a compound having both an unsaturated group and an alkoxysilyl group. Here, examples of the unsaturated group include a vinyl group, an allyl group, an acryloyl group, and a methacryloyl group, but it is preferable that the unsaturated group has a group represented by the following general formula (3).

[0009]

Embedded image

(In the formula, R3 represents a hydrogen atom or a carbon number of 1 to
6 represents an alkyl group of 6) Specific examples of the compound having a group represented by the general formula (3) include p-vinylphenylmethyldimethoxysilane,
1- (m-vinylphenyl) methyldimethylisopropoxysilane, 2- (p-vinylphenyl) ethylenemethyldimethoxysilane, 3- (p-vinylphenoxy) propylmethyldiethoxysilane, 3- (p-vinylbenzoyloxy) ) Propylmethyldimethoxysilane, 1-
(O-Vinylphenyl) -1,1,2-trimethyl-
2,2-dimethoxydisilane, 1- (p-vinylphenyl) -1,1-diphenyl-3-ethyl-3,3-diethoxysiloxane, m-vinylphenyl- [3- (triethoxysilyl) propyl] diphenyl Silane, [3-
In addition to (p-isopropenylbenzoylamino) propyl] phenyldipropoxysilane and the like, a mixture thereof can be mentioned. Among these, p-vinylphenylmethyldimethoxysilane and 2- (p-vinylphenyl)
Ethylmethyldimethoxysilane and 3- (p-vinylbenzoyloxy) propylmethyldimethoxysilane, especially p-vinylphenylmethyldimethoxysilane are preferred.

The proportion of the graft crossing agent used is 0.2 to the total amount of all the organosiloxane and the graft crossing agent.
10% by weight, preferably 0.5-5% by weight, 0.2
If it is less than wt%, a high graft ratio cannot be obtained in the polymerization of the polyorganosiloxane and the radical-polymerizable monomer,
As a result, the film forming property may decrease. On the other hand, when the proportion of the graft crossing agent exceeds 10% by weight, the grafting rate increases, but the polymerization of the grafted radical-polymerizable monomer decreases with the increase of the graft crossing agent, and the vinyl polymer has a low molecular weight. As a result, the oily feel may decrease.

The polyorganosiloxane is obtained by stirring and mixing the above-mentioned organosiloxane and, if necessary, a graft crossing agent (hereinafter referred to as "siloxane component") with a homomixer in the presence of an emulsifier such as alkylbenzene sulfonic acid. Then, it can be produced by condensation. This emulsifier acts as an emulsifier for the organosiloxane and also serves as a condensation initiator. The amount of the emulsifier used is usually 0.1 to 5% by weight, preferably 0.3 to
It is about 3% by weight. The amount of water used at this time is usually 100 to 5 with respect to 100 parts by weight of the siloxane component.
00 parts by weight, preferably 200 to 400 parts by weight.
The condensation temperature is usually 5 to 100C. In addition,
A cross-linking agent may be added as a third component in the production of polyorganosiloxane. As this crosslinking agent,
Examples thereof include trifunctional crosslinking agents such as methyltrimethoxysilane, phenytrimethoxysilane, and ethyltriethoxysilane, and tetrafunctional crosslinking agents such as tetraethoxysilane. The amount of the crosslinking agent added is usually 10% by weight or less, preferably 5% by weight or less, based on the total amount of the organosiloxane and the graft crossing agent. The polystyrene-converted weight average molecular weight of the polyorganosiloxane thus obtained is usually 3
20,000 to 1,000,000, preferably 50,000
It is about 00 to 300,000.

Next, by polymerizing the radical-polymerizable monomer in the presence of the thus obtained polyorganosiloxane, specific polymer particles can be obtained. Examples of the radical-polymerizable monomer used in the present invention include methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, butyl acrylate and acryl methacrylate; methyl acrylate, ethyl acrylate, butyl acrylate, hydroxyethyl methacrylate and dimethyl. Acrylic esters such as aminoethylmethacrylate;
Hydroxyl group-containing monomers such as 2-hydroxyethyl methacrylate, ethylene oxide and propylene oxide; epoxy group-containing monomers such as glycidyl methacrylate; amide group-containing monomers such as acrylamide and methacrylamide; acrylic acid, methacrylic acid, itaconic acid, fumaric acid and the like Carboxy group-containing monomers; sulfonic acid group-containing monomers such as isoprene sulfonate sodium; and vinylpyrrolidone. These may be used alone or as a mixture. Moreover, you may copolymerize other vinyl monomers as needed.

Of the above radical-polymerizable monomers, those containing an amino group such as dimethylaminoethyl methacrylate are preferred because they improve the adsorptivity with proteins. Further, among the radically polymerizable monomers, by using a hydrophilic monomer such as a hydroxyl group-containing monomer, an epoxy group-containing monomer, a carboxy group-containing monomer, or a sulfonic acid group-containing monomer, the specific polymer particles are rendered hydrophilic. be able to. The proportion of the polyorganosiloxane and the radical-polymerizable monomer used is 5 to 80% by weight of the siloxane component (solid content), preferably 10 to 60%.
% By weight, 95-20% by weight of radical-polymerizable monomer, preferably 90-40% by weight (however, siloxane component +
Radical polymerizable monomer = 100% by weight), and if the siloxane component is less than 5% by weight, sufficient strength cannot be obtained,
On the other hand, if it exceeds 80% by weight, the ratio of the polymer of the radical-polymerizable monomer to be complexed decreases, and as a result, the film-forming property may deteriorate.

In the method (1), when the radical-polymerizable monomer is polymerized, a method of emulsion-polymerizing the radical-polymerizable monomer in a state where the polyorganosiloxane is dispersed in an aqueous medium (emulsion polymerization method) and a polyaorganosiloxane are used. There are two methods of solution polymerization of a radically polymerizable monomer in a state of being dissolved in an organic solvent (solution polymerization method). In the emulsion polymerization method, first, an organosiloxane and, if necessary, a Gragg's crossing agent are condensed in the presence of an emulsifier to obtain an aqueous dispersion having an average particle size of 0.005 to 90 μm, preferably 0.01 to 50 μm. After that, the radical polymerizable monomer is added to carry out emulsion polymerization. Examples of the emulsifier that can be used here include anionic emulsifiers such as sodium dodecylbenzene sulfonate, sodium lauryl sulfate, sodium diphenyl ether disulfonate, and sodium succinate dialkali ester sulfonate, or polyoxyethylene alkyl ester, polyoxyethylene alkyl allyl. One or more nonionic emulsifiers such as ether can be used. The amount of the emulsifier used is usually about 0.5 to 5% by weight with respect to the radical-polymerizable monomer.

As the radical initiator which can be used in the emulsion polymerization method, an oxidizing agent composed of an organic hydroperoxide such as cumene hydroperoxide, diisopropylbenzene hydroperoxide and paramenthane hydroperoxide is used. ,
Redox initiators in combination with reducing agents such as sugar-containing iron pyrophosphate formulations, sulfoxylate formulations, and mixed sugar-containing iron pyrophosphate formulations / sulfoxylate formulations.
Persulfates such as potassium persulfate and ammonium persulfate;
Azo compounds such as azobisisobutyronitrile, dimethyl-2,2'-azobisisobutyrate, and 2-carbamoylazaisobutyronitrile; organic peroxides such as benzoyl peroxide and lauroyl peroxide Among them, the above Redox type initiator or persulfate is preferable. The amount of these radical polymerization initiators used is usually about 0.05 to 5 parts by weight, preferably about 0.1 to 3 parts by weight, based on 100 parts by weight of the acrylic monomer (IV) used. The radical polymerization at this time is preferably carried out by emulsion polymerization or solution polymerization.

Further, a chain transfer agent may be used in the emulsion polymerization method. Specifically, halogen compounds such as t-dodecyl mercaptan, octyl mercaptan, n-tetradecyl mercaptan and n-hexyl mercaptan are radically polymerized. In general, 0.
Used in an amount of 02 to 1% by weight. At the time of emulsion polymerization, in addition to a radical polymerization initiator, an emulsifier, a chain transfer agent, etc., various electrolytes, a pH adjusting agent, etc. are used in combination, if necessary, with respect to 100 parts by weight of the radical-polymerizable monomer, usually water is added. 100 to 500 parts by weight, and the radical polymerization initiator,
Emulsion polymerization is carried out using an emulsifier, a chain transfer agent and the like in an amount within the above range, at a polymerization temperature of 5 to 100 ° C, preferably 50 to 90 ° C and a polymerization time of 0.1 to 10 hours.

On the other hand, in the case of solution polymerization, a polyorganosiloxane and a radically polymerizable monomer are dissolved in an organic solvent, and a radical initiator similar to that used in the emulsion polymerization method, a chain transfer agent, and various additives as required are added to these. In addition, radical polymerization is performed. Examples of the organic solvent used in this solution polymerization include toluene, n-hexane, cyclohexane, chloroform and tetrahydrofuran. In solution polymerization, a radical polymerization initiator (I) and, if necessary, a chain transfer agent, etc. are used together to produce a radically polymerizable monomer (I
V) 80 to 5 parts by weight of an organic solvent is usually added to 100 parts by weight.
00 parts by weight, the radical polymerization initiator, the chain transfer agent, etc. are used in an amount within the above range, and the polymerization temperature is 5 to 150 ° C.
Solution polymerization is preferably carried out under conditions of 50 to 130 ° C. and polymerization time of 1 to 10 hours. In the case of this solution polymerization, impurities may be able to be significantly reduced as compared with the case of emulsion polymerization. In the solution polymerization, after the completion of the polymerization reaction, the specific polymer particles can be produced by re-emulsifying the polymer by a known method.

For the emulsion or suspension in the state where the emulsion polymerization or solution polymerization reaction is completed,
If necessary, steam stripping method, vacuum distillation method,
It is preferable to remove the organic solvent by centrifugation, filtration or the like. As means for separating polymer particles in the emulsion or suspension from water, means for evaporating water all at once using a spray dryer or the like, and centrifugation or emulsion processing for suspending the polymer particles to separate the polymer particles , Means for drying the obtained solid matter, means for drying the solid matter after concentrating the emulsion or suspension using a water separation membrane, and the like. If necessary, the polymer particles can be washed with water or the like to remove the emulsifier. The average particle size of the specific polymer particles obtained by the method of 0.01 to 100 μm
m, preferably in the range of 0.05 to 50 μm. The coefficient of variation (CV value) of the average particle diameter of the ultraviolet absorbing particles is 1 to 30%, preferably 1 to 20%. The graft ratio of the specific polymer particles obtained by the method is usually 20% by weight or more, preferably 80% by weight.
As described above, more preferably about 100% by weight or more.

In the method (1), the radical-polymerizable monomer is emulsion-polymerized to add the organosiloxane to the seed particle emulsion, and preferably the organosiloxane is condensed in a state where the seed particle absorbs the organosiloxane and the specific weight is reduced. Produce coalesced particles. As the radically polymerizable monomer, the same monomer as in the above method can be mentioned. Further, in the emulsion polymerization, an emulsifier, a radical polymerization initiator, etc. are used, and those similar to these methods can be mentioned. . In this method, the organosiloxane is 0.1 to 500 parts by weight, preferably 0.5 to 25 parts by weight, based on 100 parts by weight (solid content) of the seed particles.
Use 0 parts by weight.

In the method (1), the organosiloxane can be absorbed by the seed particles by adding the organosiloxane all at once, continuously or in a divided manner in the presence of the seed particles and stirring well. The organosiloxane absorbed by the seed particles is 5% by weight or more, preferably 10% by weight or more, based on the total amount of the organosiloxane used.
More preferably, it is 30% by weight or more. Further, in order to prevent the reaction from proceeding in a state where the absorption of the organosiloxane is not sufficient, the pH in the reaction system is 4 to 10, preferably p.
The organosiloxane is added and absorbed under the conditions of H5-9, more preferably pH 6-8, and temperature of 90 ° C or lower, preferably 70 ° C or lower, more preferably 50 ° C or lower, and particularly preferably 30 ° C or lower. Is desirable.
The condensation reaction of the organosiloxane absorbed by the seed particles can be controlled by changing the carbon number of the substituent of the organosiloxane, the reaction temperature and the hydrogen ion concentration, and the concentration of the polysiloxane can be adjusted. The condensation reaction of the organosiloxane is performed at a temperature of 30 ° C.
Or more, preferably 50 ° C or more, more preferably 70 ° C
This can be done. The average particle size of the specific polymer particles thus obtained is preferably 0.02 to 0.5.
μm, and more preferably about 0.03 to 0.3 μm. The average particle size can be adjusted by appropriately selecting the particle size of the seed particles, the absorption amount of the organosiloxane, and the like.

For the oil absorption of the specific polymer particles used in the present invention, squalene is used, and JIS K5101 (1978) is used.
Year)) and the pigment oil absorption measurement method. The oil absorption measurement method is as follows: 1 g of the powder is placed on a glass plate and kneaded with a spatula while dropping squalene little by little.
The required squalene amount (ml) per g is taken as the oil absorption amount.
In the JIS method, boiled linseed oil is used as the oil, but in this method, squalene is used because of its similarity to sebum. The oil absorption of the polymer particles according to the present invention is 1 ml / g or more, preferably 2 ml / g or more.

In the present invention, the specific polymer particles are water,
A suspension is prepared by dispersing it in a lower alcohol or a mixture thereof to obtain a hair cosmetic. The most preferred base of the hair cosmetic composition of the present invention is a water / ethanol mixed system, and the weight ratio is 99/1 to 20/80, and more preferably 95/5.
Used as ~ 40/60. The preferred blending amount of the specific polymer particles in the hair cosmetic composition is 0.05 to 5% by weight, more preferably 0.1 to 2% by weight. In the hair cosmetic composition of the present invention, various water-soluble polymers can be used for dispersion stabilization or hair styling. As the water-soluble polymer, polyvinyl alcohol, polyvinylpyrrolidone,
Nonionic water-soluble polymers such as hydroxyethyl cellulose, carboxymethyl cellulose, crosslinked polyacrylic acid (carboxyvinyl polymer), anionic water-soluble polymers such as xanthan gum and guar gum can be used. The blending amount of these water-soluble polymers is preferably 0.01 to 5% by weight, more preferably 0.05 to 5% by weight of the hair cosmetic composition.
1% by weight. The hair cosmetic preparation of the present invention contains, in addition to the above-mentioned components, other components that are commonly added, for example,
Polyhydric alcohols such as glycerin, dipropylene glycol and 1,3-butylene glycol, nonionic activators, cationic activators, anion activators, dyes, preservatives,
Fragrances, antioxidants, chelating agents, bactericides, vitamins, hormones and other agents, hair restorers, antidandruff agents and the like can be added within a qualitative and quantitative range that does not impair the effects of the present invention.

[0026]

EXAMPLES Examples of the present invention will now be described in detail, but the present invention is not limited to these examples. The average particle size of the polymer particles in the following examples is measured by observing with a transmission electron microscope, and the CV value of the polymer particles shows a value calculated from the formula represented by the following mathematical formula 1.

[0027]

[Equation 1]

The graft ratio and graft efficiency were determined by the following methods. A constant weight (x) of the graft polymerization product was put into acetone, and shaken for 2 hours with a shaker to dissolve the free copolymer, and then using a centrifuge at a rotation speed of 23,000 rpm for 30 minutes. Centrifuge to obtain the unwanted content. Next, it was dried at 120 ° C. for 1 hour using a vacuum dryer to obtain the insoluble content weight (y).
Graft efficiency was calculated.

[0029]

Production Example 1 1.5 parts of p-vinylphenylmethyldimethoxysilane and 98.5 parts of octamethylcyclotetrasiloxane were mixed, and this was added to 300 parts of distilled water in which 2.0 parts of dodecylbenzenesulfonic acid was dissolved. The mixture was put in and stirred for 3 minutes with a homomixer to emulsify and disperse. The mixture was transferred to a separable flask equipped with a condenser, a nitrogen inlet and a stirrer, heated with stirring at 90 ° C. for 6 hours and cooled at 5 ° C. for 24 hours to complete the condensation. The condensation rate of octamethylcyclotetrasiloxane in the obtained modified polyorganosiloxane (III) was 9
It was 2.8%. The modified polyorganosiloxane latex was neutralized to pH 7 with an aqueous sodium carbonate solution.
35 parts of this modified polyorganosiloxane latex in terms of solid content, 0.5 part of sodium dodecylbenzenesulfone and 140 parts of distilled water were mixed and placed in a separable flask equipped with a dropping bottle, a condenser, a nitrogen inlet and a stirrer. Transfer, and the total amount of butyl acrylate is 3
15.81 parts of butyl acrylate corresponding to 4%, 6.29 parts of dimethylaminoethyl methacrylate corresponding to 34% of the total amount of dimethylaminoethyl methacrylate, 0.2 parts of sodium pyrophosphate, 0.25 parts of glucose, sulfuric acid first 0.004 parts iron and 0,0 cumene hydroperoxide.
074 parts was added, and the temperature was raised to 70 ° C. while flowing nitrogen. After polymerization for 1 hour, the remaining butyl acrylate 30.6
9 parts, remaining 1 dimethylaminoethyl methacrylate 1
2.21 parts, sodium dodecylbenzene sulfonate 1.
A mixture of 084 parts, distilled water 42 parts, cumene hydroperoxide 0.12 parts and t-dodecyl mercaptan 0.06 parts was added over 3 hours using a dropping bottle. After completion of the dropping, the specific polymer particles were obtained by carrying out a polymerization reaction for 3 hours. The specific polymer particles thus obtained had an average particle diameter of 3.5 μm, a CV value of 19%, a graft ratio of 101%, a graft efficiency of 54%, and a squalene oil absorption of 2.0 ± 0.1 ml / It was g.

Production Example 2 The amount of the modified polyorganosiloxane latex used in Example 1 was 60 parts, the amount of butyl acrylate was 16/8 parts, and the amount of dimethylaminoethyl methacrylate was 10.5 / 5.5 parts. Specific polymer particles were obtained in the same manner as in Example 1 except that the above was changed to. The specific polymer particles thus obtained have an average particle diameter of 3 μm and a CV value of 18
%, The graft ratio was 117%, the graft efficiency was 63%, and the squalene oil absorption was 2.2 ± 0.1 ml / g.

Production Example 3 Specific polymer particles were obtained in the same manner as in Example 1 except that potassium persulfate was used as the initiator for the graft polymerization reaction of the modified polyorganosiloxane. The average particle size of the specific polymer particles thus obtained is 2.5 μm.
m, CV value 19%, graft rate 96%, graft efficiency 51%, squalene oil absorption 2.5 ± 0.1 ml / g
Met.

Comparative Production Example 1 The oil absorptions of talc, kaolin, and Hensei polyorganosiloxane particles before graft polymerization in Example 1 were 0.5 ± 0.1, 0.5 ± 0.1, 0.1, respectively. It was 6 ± 0.1.

Example 1 Using the polymer particles of Reference Examples 1 to 3, paste-like hair cosmetics having the following composition were prepared. Each hair cosmetic was applied to the cheeks of the test subjects, and after 1 hour, it was peeled off, and the absorbed sebum was quantified by the gravimetric method. The results are shown in Table 1. Specific polymer particles obtained in Production Examples 1 to 15% by weight Carboxymethyl cellulose 0.5% by weight Ethyl alcohol 30% by weight Perfume 0.1% by weight Purified water is 100% by weight.

Comparative Example 1 Kaolin, talc, and modified polyorganosiloxane particles before graft polymerization in Production Example 1 were used to prepare a paste-like hair cosmetic composition in the same formulation as in Example 1. Each hair cosmetic was applied to the cheeks of the test subjects, and after 1 hour, it was peeled off, and the absorbed sebum was quantified by the gravimetric method. The results are shown in Table 1.

Example 2 Using the specific polymer particles obtained in Production Examples 1 to 3, a hair cosmetic composition having the following composition was prepared. Specific polymer particles obtained in Production Examples 1 to 0.3% by weight Carboxyvinyl polymer 0.04% by weight (Carbopol 941, Goodrich Co.) t-menthol 0.05% by weight Perfume 0.2% by weight Ethyl Alcohol 48% by weight Purified water to 100% by weight. This hair cosmetic composition was applied to one side of the subject's head, and the hair composition similar to the above composition was applied to the other side except that the specific polymer particles of the present invention were not blended. 1 day, 2 days, 3
The difference in oily feeling on the left and right after day was sensory-evaluated by a monitor. Table 2 shows the results. In this table, ◯ means good oily feeling, and x means poor feeling.

[0037]

Example 3 A hair conditioner having the following composition was prepared using the specific polymer particles obtained in Production Examples 1 to 3. Polymer particles of Preparation Examples 1 to 3% by weight Stearyl trimethyl ammonium chloride 1.5% by weight Ethanol 2.3% by weight Propylene glycol 5% by weight Methyl parapen 0.2% by weight Hydroxyethyl cellulose 0.8% by weight Blue No. 1 proper amount Fragrance Appropriate amount of 100% by weight with purified water This hair cosmetic was applied to one side of the subject's head, and the other side was applied with a comparative product of the present invention not blended with polymer particles, and after rinsing The oily feel of was evaluated according to Example 2. The results are shown in Table 3.

[0039]

Production Example 4 1.5 parts of p-vinylphenylmethyldimethoxysilane and 98.5 parts of octamethylcyclotetrasiloxane were mixed, and this was added to 300 parts of distilled water in which 2.0 parts of dodecylbenzenesulfonic acid was dissolved. The mixture was put in and stirred for 3 minutes with a homomixer to emulsify and disperse. The mixture was transferred to a separable flask equipped with a condenser, a nitrogen inlet and a stirrer, heated with stirring at 90 ° C. for 6 hours and cooled at 5 ° C. for 24 hours to complete the condensation. The condensation rate of octamethylcyclotetrasiloxane in the obtained modified polyorganosiloxane was 92.8%. The modified polyorganosiloxane latex was neutralized to pH 7 with an aqueous sodium carbonate solution. 35 parts of this modified polyorganosiloxane latex in terms of solid content, 0.5 part of sodium dodecylbenzenesulfone and 140 parts of distilled water were mixed and placed in a separable flask equipped with a dropping bottle, a condenser, a nitrogen inlet and a stirrer. Then, 15.81 parts of 2-hydroxyethyl methacrylate corresponding to 34% of the total amount of 2-hydroxyethyl methacrylate, and 34% of the total amount of methyl methacrylate.
6.29 parts of methyl ethyl methacrylate corresponding to
Sodium pyrophosphate (0.2 parts), glucose (0.25 parts), ferrous sulfate (0.004 parts) and cumene hydroperoxide (0.074 parts) were added, and the temperature was raised to 70 ° C while flowing nitrogen. After polymerization for 1 hour, the remaining 2-hydroxyethyl methacrylate 30.69 parts, the remaining methyl methacrylate 12.21 parts, sodium dodecylbenzenesulfonate 1.084 parts, distilled water 42 parts, cumene hydroperoxide 0.12 parts and t-dodecyl mercaptan 0.0
6 parts of the mixture was added using a dropping bottle over 3 hours. After the dropping was completed, a polymerization reaction was performed for 3 hours to obtain a graft copolymer. The water-soluble polymer thus obtained had a viscosity of 50 cps at a solid content concentration of 10% at 25 ° C., a graft ratio of 101%, a graft efficiency of 54%, and a squalene oil absorption of 2.0 ± 0.1 ml / g
Met.

Production Example 5 The amount of the modified polyorganosiloxane latex used in Example 4 was 60 parts, the amount of 2-hydroxyethyl methacrylate was 16/8 parts, and the amount of methyl methacrylate was 10.5 / 5.5. A polymer latex was obtained in the same manner as in Example 1 except that the parts were changed. The water-soluble polymer thus obtained had a solid content concentration of 10% at 25 ° C.
Viscosity of 20 cps, grafting rate of 117%, grafting efficiency of 63%, squalene oil absorption of 2.2 ± 0.1 ml
/ G.

Production Example 6 A graft copolymer was obtained in the same manner as in Example 1 except that the initiator for the graft polymerization reaction of the modified polyorganosiloxane in Example 4 was changed to potassium persulfate. The water-soluble polymer thus obtained had a viscosity of 40 cps at a solid content of 10% at 25 ° C. and a graft ratio of 96.
%, Graft efficiency 51%, squalene oil absorption 2.5
It was ± 0.1 ml / g.

Production Example 7 A graft copolymer was obtained in the same manner as in Example 4 except that ethylene glycol was used instead of 2-hydroxyethyl methacrylate. The viscosity of the water-soluble polymer thus obtained at 25 ° C. at a solid content concentration of 10% was 20 cps, the graft ratio was 96%, the graft efficiency was 51%, and the squalene oil absorption was 2.5 ± 0.1 ml / It was g.

Comparative Production Example 2 The oil absorption of Henssei polyorganosiloxane particles before graft polymerization in Example 1 was 0.5 ± 0.
The values were 1, 0.5 ± 0.1 and 0.6 ± 0.1.

Example 4 Production examples 4 to 7 as specific polymer particles in Example 1
A paste-like hair cosmetic composition was prepared in the same manner as in Example 1 except that the specific polymer particles obtained in 1. were used. Each hair material was applied to the cheeks of the test subjects, and after 1 hour, it was peeled off, and the absorbed sebum material was quantified by the gravimetric method. The results are shown in Table 4.

Comparative Example 2 Kaolin, talc, and modified polyorganosiloxane particles before graft polymerization in Production Example 4 were used to prepare a paste-like hair cosmetic amount in the same formulation as in Example 4. Each hair material was applied to the cheeks of the test subjects, and after 1 hour, it was peeled off, and the absorbed sebum material was quantified by the gravimetric method. The results are shown in Table 4.

Example 5 In Example 2, as specific polymer particles, Production Examples 4 to 7 were performed.
A paste-like hair cosmetic composition was prepared in the same manner as in Example 2 except that the specific polymer particles obtained in step 1 were used. Each hair material was applied to the cheeks of the test subjects, and after 1 hour, it was peeled off, and the absorbed sebum material was quantified by the gravimetric method. Table 5 shows the results.
This hair cosmetic composition was applied to one side of the subject's head, and the hair cosmetic composition of the present invention containing no polymer particles was applied to the other side.
The difference in oily feeling on the left and right after 1 day, 2 days, and 3 days was sensory-evaluated by a monitor. Table 5 shows the results.

Example 6 In Example 3, as the specific polymer particles, Production Examples 4 to 7 were performed.
A hair conditioner similar to that in Example 2 was prepared, except that the specific polymer particles obtained in (1) were used. Each hair material was applied to the cheek of the test subject, peeled off after 1 hour, and the sebum absorbed was applied to one side of the head of the test subject, and the other side was compared with the specific polymer particles of the present invention not blended. After applying the product and rinsing, the oily feeling with time was evaluated according to Example 5. Table 6 shows the results.

[0049]

EFFECTS OF THE INVENTION The hair cosmetic composition of the present invention has excellent sebum absorption ability and usability, and is suitable for reducing the oily feeling of hair.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Nobuo Bessho 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd.

Claims (1)

[Claims] 1. A hair cosmetic composition comprising polymer particles comprising a polyorganosiloxane and a polymer of a radical-polymerizable monomer in the same particle.