JPH04359912A - New copolymer and cosmetic containing same - Google Patents

Abstract

PURPOSE:To obtain a silicone/(meth)acrylic acid copolymer excellent in film- forming properties and lubricity, etc., by polymerizing (meth)acrylic acid with a specified silicone macromer in the presence of a radical polymerization initiator. CONSTITUTION:(Meth)acrylic acid or its salt of formula I (wherein R<1> is H or methyl) and a silicone macromer of formula II (wherein X is a radical- polymerizable group; R<2>, R<3>, R<4>, R<5> and R<6> are each methyl, alkoxy, (un) substituted phenol or phenoxyl; m is 1-10; and n is 5-150) are polymerized in the presence of a radical polymerization initiator (e.g. 2,2'-azobis-isobutyronitrile) to produce a silicone/(meth)acrylic acid copolymer. This copolymer has a property of forming a thin silicone film on the surface of a coating film, can give a good touch when applied, and is lowly sticky when applied as a hair care preparation.

Description

Detailed Description of the Invention [0001] [Industrial Application Field] The present invention provides a novel silicone/(meth)acrylic acid copolymer having excellent film-forming properties, lubricity, thickening properties, etc., and a silicone/(meth)acrylic acid copolymer containing the same. Regarding cosmetics. BACKGROUND OF THE INVENTION The demands placed on cosmetics have become higher, and various film-forming agents have come to be used in order to generally impart good properties to cosmetic films. Especially hairspray
In hair cosmetics such as setting lotions, hair styling ability,
A film-forming resin is blended for the purpose of imparting set holding power and the like. Conventionally, polyvinylpyrrolidone, polyvinylpyrrolidone/vinyl acetate copolymer, vinyl acetate/crotonic acid copolymer, etc. have been used as the film-forming resin. Further, JP-A-2-25411 describes a cosmetic composition using a copolymer mainly composed of a silicone compound and an acrylate as a film-forming agent, and discloses that it forms a moisture-resistant film. Further, various skin and hair cosmetics contain thickeners depending on the dosage form, and various water-soluble polymer substances are used as the thickeners. [0003] Problems to be Solved by the Invention [0003] However, although film-forming resins conventionally blended into hair cosmetics have a certain degree of set-holding power when used normally, they do not hold well under high humidity conditions. Due to moisture absorption, it became more sticky and more fluid, and could not maintain the hair set sufficiently. Although the copolymer disclosed in JP-A-2-25411 has improved setting properties at high humidity, it requires a hydrocarbon such as isoparaffin, volatile silicone, etc. as a solvent, and has poor water solubility. Hair cosmetics must be easily removed by shampooing, requiring water solubility on the one hand and low hygroscopicity on the other hand. It is difficult to simultaneously satisfy these contradictory requirements, and in the past, water solubility has often been abandoned and other solvents or solvent mixtures have been used, as described above. [0004] Furthermore, setting agents such as hair sprays contain large amounts of oils and active agents in order to prevent the hair from becoming stiff or coarse after drying. The combination of these oils and active agents reduces the affinity of the film-forming resin for hair.
This has caused problems such as a decrease in the ability of the hair to hold the hair set, and also a sticky feeling caused by hand-applying the oil or activator after application to the hair. Furthermore, there are also problems such as peeling of the resin coating on the hair surface due to brushing or the like, ie, so-called flaking, which deteriorates the luster of the hair. Incidentally, this flaking was often caused by the water-soluble polymeric substance blended as a thickener. [0005] Therefore, not only film forming properties but also lubricity,
A new polymer with thickening properties, and blending it,
There has been a desire for a cosmetic that has a good feel when applied, and has excellent hair styling and set holding power, especially when applied to hair, even under high humidity. [Means for Solving the Problems] Under these circumstances, the present inventors conducted intensive research and found that silicone/(meth)acrylic acid or its salt and a silicone macromer are obtained by polymerizing silicone macromer. Acrylic acid copolymers have excellent properties such as film-forming ability, lubricity, and thickening properties, and cosmetics containing them have a very good feel when applied and do not become sticky even under high humidity. The present invention was completed based on the discovery that the hair has a low amount of moisture, suppresses hygroscopicity, and has excellent hair styling and set holding power. That is, the present invention provides (a) and (b) (
a) (meth)acrylic acid or its salt (b) represented by the formula (1) [In the formula, R1 represents a hydrogen atom or a methyl group]
Formula (2) [0011] [In the formula, X represents a radically polymerizable group, and R
2, R3, R4, R5 and R6 may be the same or different and represent a methyl group, an alkoxyl group, an optionally substituted phenyl group, or an optionally substituted phenoxyl group, and m is 1 to 10. silicone/(meth)acrylic acid copolymer obtained by polymerizing a silicone macromer represented by the following integer, n is an integer from 5 to 150] in the presence of a radical polymerization initiator, and the copolymer. The purpose is to provide cosmetics that (a) used in the production of the copolymer of the present invention
The salts of the (meth)acrylic acid component include inorganic salts represented by alkali metal salts such as sodium salts and potassium salts;
Examples include organic salts represented by quaternary ammonium salts. These (a) components can be used alone or in combination of two or more, and can be used in an amount of 10 to 95% by weight (
(hereinafter simply expressed as "%"), particularly preferably from 40 to 80%. [0013] The silicone malokumer as the component (b) is represented by the above formula (2), in which the radically polymerizable group represented by X includes a vinyl group, (meth)acryloyl group, vinylbenzyl group, styryl group, (meth)acrylamide group, vinyl ether group, vinyl ester group, etc. Specific examples of these silicone macromers include:
Polydimethylsiloxypropyl (meth)acrylic acid ester, polydimethylsiloxypropyl vinyl benzyl ether, polymethylphenylsiloxypentene, polydimethylsiloxypropyl (meth)acrylamide, polydimethylsiloxypropyl vinyl benzylate, polymethylphenylsiloxyethoxyethylene, etc. Among these, polydimethylsiloxypropyl (meth)acrylic acid ester, polydimethylsiloxypropyl (meth)acrylamide, etc. are particularly preferred. These (b)
The components can be used alone or in combination of two or more, and it is preferably used in an amount of 5 to 90%, particularly 20 to 60%, of the total monomers. The silicone/(meth)acrylic acid copolymer of the present invention is produced by combining the above components (a) and (b), and performing bulk polymerization, solution polymerization, or suspension polymerization in the presence of a radical polymerization initiator. It is produced by polymerization using a known polymerization method such as a polymerization method or an emulsion polymerization method. At this time, monomers other than the above two types of monomers may be copolymerized within a range that does not impair the effects of the present invention. Among these, it is particularly advantageous to produce by solution polymerization. The solvent used in the solution polymerization method is preferably a polar organic solvent, and a water-miscible organic solvent can also be used in combination with water. Examples of such organic solvents include aliphatic alcohols having 1 to 3 carbon atoms such as methanol, ethanol, and propanol; ketones such as acetone and methyl ethyl ketone;
Among these, methanol, ethanol, acetone, or a mixture of these and water is particularly preferred. These organic solvents can be used alone or in combination of two or more. Examples of radical polymerization initiators include 2,
2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), dimethyl-2, 2'-azobisisobutyrate,
2,2'-azobis(2-methylbutyronitrile), 1
, 1'-azobis(1-cyclohexanecarbonitrile) and the like are preferred. Moreover, organic peroxides such as t-butyl peroctoate, dicumyl peroxide, di-t-butyl peroxide, and dibenzoyl peroxide can also be used. These polymerization initiators are preferably used in an amount of 0.001 to 2.0 mol%, particularly 0.01 to 1.0 mol%, based on the monomer mixture. [0016] Polymerization is usually carried out at 30 to 100°C, preferably 50 to 80°C, for 1 to 10 hours, and is appropriately selected depending on the type of radical polymerization initiator and monomer solvent used. Further, the polymerization is preferably carried out under an inert gas atmosphere such as nitrogen. After the polymerization, the copolymer can be isolated from the reaction solution by known methods such as reprecipitation and solvent distillation. Further, the obtained copolymer can be purified by repeating reprecipitation or by removing unreacted monomers and the like by membrane separation, chromatography, extraction, etc. The silicone/(meth)acrylic acid copolymer of the present invention thus obtained not only has an excellent film-forming ability but also has a very small surface frictional force.
It can be blended into various cosmetics to impart excellent feel, hair styling ability, set retention ability, lubricity, etc. Furthermore, since it has excellent thickening properties, it can be incorporated as a thickening agent into various cream-like, gel-like, and other cosmetics. Furthermore, since it has excellent water solubility, it can be easily used in aqueous bases and can be easily removed with shampoos, skin cleansers, etc. The cosmetic of the present invention can be produced by blending the silicone/(meth)acrylic acid copolymer according to a conventional method, such as hair spray, setting foam, setting lotion, gel, shampoo, and conditioner. , nail polish, mascara, etc., in the form of aqueous solutions, hydroalcoholic solutions, emulsions, creams, gels, etc. Among these, in hair cosmetics using a propellant, the silicone/(meth)acrylic acid copolymer of the present invention is contained in the stock solution in an amount of 0.01 to 15%, preferably 0.
．． 1 to 6%; 50 to 99.8% of lower alcohols such as ethanol, polyols, and solvents such as water; 0.1 to 99.8% of solvents such as hydrocarbons, ester oils, silicones and their derivatives, and natural oils and fats. It is preferable to mix 20%. In addition, if necessary, 0.5 to 3.0% of higher alcohols, tactile enhancers such as octyldodecyl myristate, glycerin, polyethylene glycol, polyoxyethylene hexadecyl ether, and cationic agents such as polyoxyethylene stearyl ether may be added. A film forming aid such as a polymer can also be used in an amount of 0.1 to 3.0%. Furthermore, known hair styling polymers other than the copolymer of the present invention can also be blended. In addition, as a propellant, LPG, chlorofluorocarbon gas, liquefied gas such as dimethyl ether, and CO2
, N2, and other compressed gases may be used alone or in combination of two or more. [0021] Furthermore, in gel-like hair cosmetics such as hair setting gels, silicone/(meth)acrylic acid copolymer is contained in an amount of 0.5 to 10.0%, preferably 1.0 to 10.0%.
3.0%, other hair styling polymers from 0 to 10.0%, and water-soluble polymers such as polyacrylic acid and hydroxyethyl cellulose as thickeners from 0.5 to 2.0%. It is preferable to use a solvent prepared by adding purified water and, if desired, a lower alcohol. In addition, the feel can be further improved by using it in combination with conventionally widely used water-soluble polymers. In addition, hair cosmetics such as shampoos and conditioners contain the silicone/(meth)acrylic acid copolymer of the present invention in an amount of 0.1 to 5.0%, particularly 0.5 to 2.0%.
% is preferable. Furthermore, in mascara, nail polish, etc., it is preferable to blend the silicone/(meth)acrylic acid copolymer of the present invention in an amount of 0.001 to 10.0%. [0024] The cosmetics of the present invention may contain commonly used medicinal agents such as preservatives, ultraviolet absorbers, sequestering agents, anti-dandruff agents, pigments, fragrances, etc., depending on the purpose. You can also do that. Effects of the Invention The silicone/(meth)acrylic acid copolymer of the present invention has excellent film-forming ability and contains silicone macromer, so it is possible to form a thin silicone film on the surface of the film. Form. As a result, it is possible to obtain lubricity that could not be obtained with conventional film-forming resins, and the coating feels very good when applied. For this reason, it is possible to reduce the amount of oils, etc. that are conventionally blended into cosmetics to suppress stiffness, etc., and when used in hair cosmetics, the film-forming resin's hair affinity and set retention It is also possible to reduce stickiness after application without reducing the viscosity. Furthermore, since it exhibits a thickening effect, it can be added to cosmetics as a thickener to make the cosmetics difficult to run or crumble when molded. Furthermore, cosmetics containing the copolymer of the present invention have excellent feel and film retention not only under normal humidity but also under high humidity, and can be easily washed off. [Examples] Next, the present invention will be further explained with reference to Examples, but the present invention is not limited to these Examples. Example 1 After introducing nitrogen gas into a four-necked flask equipped with a reflux condenser, dropping funnel, thermometer, nitrogen gas inlet tube, and stirring device, the flask was heated to raise its temperature and replaced with nitrogen for 1 hour. . On the other hand, the dropping funnel (referred to as dropping funnel A) has 2,2'-
Add 1 part by weight of azobisisobutyronitrile (AIBN) and 10 parts by weight of ethyl acetate to the other dropping funnel (
Polydimethylsiloxypropyl methacrylate ester (n=140 in formula (2)) was added to the dropping funnel (referred to as dropping funnel B).
50 parts by weight, 50 parts by weight of methacrylic acid and 1 part by weight of ethyl acetate
00 parts by weight were added. While keeping the flask at 60° C., the contents of dropping funnel A and dropping funnel B were added dropwise over 4 hours to polymerize. After polymerization, 2
It was purified by washing twice and vacuum-dried at 80° C. and 20 mmHg for 12 hours. The resulting polymer is a white solid, N
The composition ratio of the polymer according to MR is dimethylsiloxane:
The ratio of methacrylic acid was 46:54, and the weight average molecular weight in terms of polystyrene by GPC was about 113,000. Example 2 After introducing nitrogen gas into a four-necked flask equipped with a reflux condenser, dropping funnel, thermometer, nitrogen gas inlet tube, and stirring device, the flask was heated to raise its temperature and replaced with nitrogen for 1 hour. . On the other hand, put AIBN5 into the dropping funnel (referred to as dropping funnel A).
parts by weight and 10 parts by weight of ethyl acetate, and into the other dropping funnel (referred to as dropping funnel B) polydimethylsiloxypropyl methacrylate (in formula (2), n=
140), 70 parts by weight of methacrylic acid, and 100 parts by weight of ethyl acetate. While keeping the flask at 60° C., the contents of dropping funnel A and dropping funnel B were added dropwise over 4 hours to polymerize. After polymerization, it was purified by washing twice with ethyl acetate, and then heated at 80°C and 20mmHg for 1 time.
It was vacuum dried for 2 hours. The obtained polymer was a white solid, and the composition ratio of the polymer according to NMR was dimethylsiloxane:methacrylic acid = 29:71, and the composition ratio of the polymer was determined by GPC.
The weight average molecular weight in terms of polystyrene is approximately 54,000
Met. Test Example 1 Silicone/(meth)acrylic acid copolymer of the present invention and commercially available film-forming resin for hair styling agent (polyvinylpyrrolidone)
A tactile evaluation was conducted for slippage and resistance to collapse of the set under high humidity. The results are shown in Table 1. (Sample) Copolymer A of the present invention: methacrylic acid/polysiloxylpropyl methacrylate (in formula (2), n=
140 ) = 46/54 (%) Copolymer B of the present invention: methacrylic acid/polysiloxylpropyl methacrylate (in formula (2), n = 140
) = 24/76 (%) 0030 (Test method) (1) Set retention Wet a hair bundle with a length of 18 cm and a weight of 1.5 g with water, towel dry it, and then dry it with 2% polymer (in 50% KOH). 2 g of ethanol solution was applied, wound around a rod with a diameter of 2 cm, and air-dried. After drying, the rod was removed from the curled hair. Place this in a constant humidity box (20℃, 98%RH)
The curls were hung for 30 minutes, the curls were observed for elongation, and the set holding power was judged based on the following criteria. The results are shown in Table 1. (2) Smoothness A hair bundle with a length of 18 cm and a weight of 10 g was wetted with water, towel-dried, and then 0.2 g of a 2% polymer (neutralized with 50% KOH) ethanol solution was applied and air-dried. This was evaluated by 10 expert panelists according to the following criteria. ◎: Very good ○: Good △: Average ×: Bad 0031 [Table 1] Example 3 Mist: The following components were mixed to produce a mist. (component)
(%
) Copolymer A of the present invention (same as Test Example 1)
3.0 amphoteric polymer (Yukaformer M75*)
1.0 Nonionic activator (glycer isostearate) 0.5 Ethanol

Appropriate amount of fragrance

trace meter

100.0 *:
Manufactured by Diachemco Co., Ltd. Example 4 Blowing agent: A blowing agent was prepared by mixing the following components. (component)
(%
) Copolymer B of the present invention (same as Test Example 1)
0.5 fragrance

trace amount of ethanol

10.0 Purified water

Appropriate amount total

100.
Example 5 Shampoo: A hair shampoo was prepared by mixing the following ingredients. (component)
(%
) Lauryl polyoxyethylene sulfate triethanolamine salt (40% aqueous solution)
32.0 lauroyl diethanolamide
3.0 polyethylene glycol
1.0 Copolymer B of the present invention (same as Test Example 1)
1.0 purified water

Appropriate amount of fragrance

Trace amount meter

Example 6 Foam agent: A foam agent was prepared by mixing the following components. (component)

(%) Copolymer B of the present invention (same as Test Example 1)
3.5 Nonionic surfactant (Softanol 90, manufactured by Nippon Shokubai) 1
．． 0 fragrance

trace amount of ethanol

2.0 Purified water

Appropriate amount of liquefied petroleum gas

7.0 total

100.0 0
Test Example 2 Example 6 and commercially available hair foam A (polyvinylpyrrolidone (PVP)/vinyl acetate (VA) as film-forming resin)
c) = 6/4) was evaluated by touch. The results are shown in Table 2. (Test method) After wetting the hair of two sets of experimental human head models (wigs) with water, Example 6 and commercially available hair foam A
2 g of each was applied, wound around a rod with a diameter of 2 cm, and air-dried. After drying, the rod was removed from the hair, and ten expert panelists evaluated the sliding and setting power. Thereafter, the set was left in a constant humidity box (20° C., 98% RH) for 30 minutes, and the set was observed for deterioration. This wig was washed with shampoo and the ease with which it was washed off was evaluated. ◎: Very good ○: Good △: Average ×: Bad 0037] [Table 2]

Claims (2)

[Claims] Claim 1: (a) and (b) (a) Formula (1) (meth)acrylic acid or its salt (b ) Formula (2) [Formula, X represents a radically polymerizable group, R2, R3, R
4, R5 and R6 may be the same or different and represent a methyl group, an alkoxyl group, an optionally substituted phenyl group, or an optionally substituted phenoxyl group, and m is 1
10, n is an integer of 5 to 150] in the presence of a radical polymerization initiator. [Claim 2] The silicone/(meth) according to Claim 1.
A cosmetic containing an acrylic acid copolymer.