JP2000351804A - Silicone-resin-containing emulsion composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an emulsion composition which has excellent film-forming properties and can give a cured film excellent in water resistance, water repellency, etc., by emulsion-polymerizing a specified amount of a radically polymerizable compound in the presence of a silicone resin having a specified structure and a specified average molecular weight. SOLUTION: This composition is obtained by emulsion-polymerizing 10-1,000 pts.wt. radically polymerizable compound (B) in the presence of 100 pts.wt. silicone resin (A) represented by the formula and having a number-average molecular weight of 400-30,000, 0.5-15 wt.%, based on the total of components A and B, surfactant, and 0.1-10 wt.%, based on component B, polymerization initiator. Component A is obtained by hydrolyzing e.g. a hydrolyzable silane represented by the formula: R13SiX, R12SiX2, R1SiX3 or SiX4 in the presence of an acid and water. Component B is exemplified by an alkyl acrylate with a 1-18C alkyl or a glycidyl-containing vinyl monomer. In the formulae, R1 is hydrogen or a 1-10C monovalent hydrocarbon group; X is a halogen, an alkoxyl or the like; a and d>0 each; b and c>=0 each; a+b+c+d=1; and 0<=(b+c)<=0.3.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silicone resin-containing emulsion composition which gives a cured film having excellent film-forming properties and excellent properties such as water resistance, water repellency and chemical resistance.
Particularly, the present invention relates to a silicone resin-containing emulsion composition suitable as a base for cosmetics such as an external preparation for the skin, nail polish, and hair cosmetics.

[0002]

2. Description of the Related Art Conventionally, an emulsion obtained by emulsion polymerization of a radical polymerizable vinyl monomer represented by an acrylic resin system has been used for coating because of its excellent cured film forming property and chemical resistance. In addition to being widely used as a basic material of an agent, the demand as a raw material for cosmetics has been increasing in recent years.

[0003] However, this type of coating agent has a drawback that it essentially lacks water resistance and weather resistance.

On the other hand, silicone resins (resins) obtained by hydrolyzing and condensing silane compounds have high hardness,
Because of its ability to form a cured film having excellent weather resistance, water resistance, heat resistance, and water repellency, it has attracted attention as a coating agent, and in recent years, its demand as a raw material for cosmetics has been increasing. On the other hand, there are drawbacks in that the film is inferior in formability, alkali resistance, and film flexibility.

Therefore, in order to improve these disadvantages,
A method of emulsifying an alkoxysilane compound or a partial hydrolysis / condensate thereof using various surfactants to form an aqueous emulsion (JP-A-58-213046, JP-A-58-213046).
JP-A-197369, JP-A-3-115485 and JP-A-3-200793) have been proposed, and a system in which an emulsion obtained by emulsion-polymerizing a polymerizable vinyl monomer with these emulsions is also known (Japanese Patent Laid-Open No. 6-1994). -344665).

Further, a method of forcibly mechanically pulverizing and dispersing a solvent-free solid silicone resin together with a chain-like silicone compound into an aqueous emulsion (JP-A-7-24)
No. 7434), a method in which a radically polymerizable vinyl monomer is emulsion-polymerized in the presence of a water-soluble polymer obtained by hydrolyzing an alkoxysilane in water without using a surfactant (JP-A-8-60098). ), By hydrolyzing and condensing an alkoxysilane mixture containing a vinyl polymerizable alkoxysilane to form an aqueous emulsion containing a solid silicone resin, further adding a radical polymerizable vinyl monomer, and emulsion-polymerizing to obtain a graft copolymer. A method for obtaining a coalesced fine particle (solid) emulsion (JP-A-5-209149 and JP-A-7-196750), an alkoxysilane is added to an emulsion obtained by emulsion polymerization of a radical polymerizable vinyl monomer, and the emulsion is hydrolyzed and condensed. Method of introducing a silicone resin into the inside (Japanese Patent Laid-Open No. 3-4) 628 JP, same 8-3409
And a method of emulsion-polymerizing an alkoxysilane having a vinyl polymerizable functional group with a radical polymerizable vinyl monomer to form an emulsion (Japanese Patent Application Laid-Open Nos. 61-9463 and 8-27347). Attempts have been made.

However, in any of the methods, since the active alkoxy group is easily hydrolyzed with the lapse of time, alcohol as an organic solvent is produced as a by-product in the system, resulting in poor stability of the resulting emulsion or uniform curing. The properties of the coating were not satisfactory, such as difficulty in obtaining a coating.

As described above, in each of the conventionally known methods, the emulsion has good stability, excellent low-temperature curability, good properties such as water resistance, water repellency and chemical resistance, and a uniform cured film. No emulsion has been obtained yet.

The present invention has been made in view of the above circumstances, and provides a silicone resin-containing emulsion composition which provides a cured film having excellent film forming properties and excellent properties such as water resistance, water repellency, and chemical resistance. The purpose is to:

[0010]

Means for Solving the Problems and Embodiments of the Invention The present inventors have conducted intensive studies in order to achieve the above object, and as a result, the average molecular weight represented by the following average composition formula (1) was 40.
An emulsion obtained by emulsion polymerization of 10 to 1000 parts by weight of a radical polymerizable compound in the presence of 100 parts by weight of a silicone resin of 0 to 30,000 is obtained by mixing the silicone resin and the radical polymerizable compound in the same particles of the emulsion. And a very stable interpenetrating network (Interpee) in which these two resins are intertwined with each other.
netrating Polymer Network
k; forming an IPN) structure, thereby complementing the deficiencies of the silicone resin and the vinyl polymer resin, and further increasing the advantageous points, providing excellent film-forming properties, water resistance, water repellency, Good properties such as chemical resistance and chemical resistance, a uniform cured film can be obtained, the stability of the emulsion is maintained in a good state, and a silicone resin-containing emulsion having unprecedented advantages can be obtained. ,
The silicone resin-containing emulsion is suitable for use in fields where acrylic resins and silicone resins have been conventionally applied, especially for external applications for skin, nail polish, and cosmetic bases such as hair cosmetics. This has led to the achievement of the present invention.

Accordingly, the present invention provides the following average composition formula (1)
Radical polymerizable compound 1 in the presence of 100 parts by weight of a silicone resin having an average molecular weight of 400 to 30,000
Provided is a silicone resin-containing emulsion composition obtained by emulsion polymerization of 0 to 1000 parts by weight. ^{_{(R 1 3 SiO 1/2) a}} (R 1 2 SiO 2/2) b (R 1 SiO 3/2) c (SiO 2) d (1) ( In the formula, R ¹ 1 Number hydrogen or C And a, b, c, and d are a> 0, d> 0, b ≧
0, c ≧ 0, a + b + c + d = 1, 0 ≦ (b + c) ≦
This is a number that satisfies 0.3. )

Hereinafter, the present invention will be described in more detail. The silicone resin-containing emulsion composition of the present invention is obtained by emulsion-polymerizing a radical polymerizable compound in the presence of the silicone resin represented by the above average composition formula (1). It is obtained.

[0013] The above silicone resin, R ¹ ₃ SiO _1/2 units (M units) and SiO ₂ units (Q units) as essential components, required by R ¹ ₂ SiO _3/2 units (T units), R ¹ Si
It has O _3/2 units (D units) and is selected so as to satisfy the following average composition formula (1). _{^{(R 1 3 SiO 1/2) a}} (R 1 2 SiO 2/2) b (R 1 SiO 3/2) c (SiO 2) d (1)

Here, R ¹ is a hydrogen atom or a group having 1 to 1 carbon atoms.
0 represents a monovalent hydrocarbon group, specifically, a saturated aliphatic hydrocarbon group such as a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group; and a saturated cyclic hydrocarbon group such as a cyclopentyl group and a cyclohexyl group. Group, vinyl group, allyl group, 5-hexenyl group, unsaturated aliphatic hydrocarbon group such as 9-decenyl group, aromatic hydrocarbon group such as phenyl group and tolyl group, and further bonded to the carbon atom of these groups. Substituted monovalent hydrocarbon groups such as halogenated hydrocarbon groups such as 3,3,3-trifluoropropyl group, heptadecafluoropropyl group, and chlorophenyl group in which part or all of the hydrogen atoms have been substituted with halogen atoms. No. Among them, carbon number 1
Preferred are a saturated hydrocarbon group such as a methyl group, an ethyl group, and a propyl group, a phenyl group, and a fluoropropyl group.

A, b, c, and d are a> 0, d>
0, b ≧ 0, c ≧ 0, a + b + c + d = 1, 0 ≦ (b +
c) A number that satisfies ≦ 0.3. Silicone resin component of formula _{^{(1), R 1 3 SiO}} 1/2 units and (M basis) S
The iO ₂ unit (Q unit) is essential, and the ratio of M unit to Q unit (M / Q ratio) is 0.4: 1 to 4: 1, preferably 0.6: 1 to 3: 1. Preferably 0.6: 1 to 1
2: 1. If the M / Q ratio is too small, the molecular weight of the resin increases and the gel component increases, so that the solubility in a solvent may be deteriorated. On the other hand, if the M / Q ratio is too large, the molecular weight of the resin decreases. In some cases, an excellent cured film cannot be obtained.

The above silicone resin has an average molecular weight of 40.
0 to 30,000, preferably 400 to 20,000,
More preferably, it is 400 to 10,000. When the average molecular weight is less than 400, an excellent cured film cannot be obtained. On the other hand, when the average molecular weight is too large, the gel component in the silicone resin increases and the viscosity increases, making emulsification difficult.

[0017] The silicone resin of the present invention, R ¹ ₃ SiX,
_{^{R 1 2 SiX 3, R 1}} SiX 3, SiX 4 ( wherein, R ¹ represents the same monovalent hydrocarbon groups as above, X is chlorine, a halogen group such as bromine, methoxy, alkoxy groups ethoxy, A hydrolyzable group such as an acyloxy group) or a partially hydrolyzed product thereof is hydrolyzed in the presence of an acid and water.

Methods for obtaining the silicone resin usable in the present invention by hydrolyzing the hydrolyzable silane compound include aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane and octane, and methyl ethyl ketone. , A ketone compound such as methyl isobutyl ketone, an ester compound such as ethyl acetate and isobutyl acetate, an organic solvent selected from alcohols such as methanol, ethanol, isopropanol, butanol, isobutanol and t-butanol, or octamethylcyclotetra Hydrolysis or condensation in a cyclic siloxane such as siloxane may be mentioned.

In the case of the above-mentioned hydrolysis or condensation method, it is recommended to remove the organic solvent from the silicone resin which is not dissolved in water by itself under normal pressure or reduced pressure. In this case, simply remove the organic solvent, even as a viscous liquid,
It may be a solid, or if it is produced in an organic solvent, add a high boiling radical polymerizable vinyl monomer or a cyclic siloxane such as octamethylcyclotetrasiloxane to be used in the next step, and add a low boiling point The organic solvent may be distilled off and taken out as a solution containing no organic solvent.

In carrying out the hydrolysis, an acid is added. As the acid, a conventionally known acid can be used. Particularly, an acidic hydrogen halide, a carboxylic acid, a sulfonic acid, an acidic or weak acid is used. Acidic inorganic salts and solid acids such as ion exchange resins are preferred. Specifically, organic carboxylic acids represented by hydrogen fluoride, hydrochloric acid, nitric acid, sulfuric acid, fuming sulfuric acid, sulfurous acid, phosphoric acid, acetic acid, maleic acid, citric acid, etc., p-toluenesulfonic acid, methylsulfonic acid, trifluoromethane And cation exchange resins having sulfonic acid groups or carboxylic acid groups on the surface.

In this case, the amount of the acid used is in the range of 0.001 to 10 mol% based on 1 mol of the hydrolyzable group on the silicon atom.

Next, the radical polymerizable compound of the present invention comprises:
There is no particular limitation as long as it is capable of radical polymerization. In particular, the following radically polymerizable vinyl monomers can be suitably used.

Specifically, (a) the number of carbon atoms of an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, octyl, 2-ethylhexyl, lauryl, stearyl or cyclohexyl ester of acrylic acid or methacrylic acid; (B) a vinyl monomer containing a carboxyl group such as acrylic acid, methacrylic acid, and maleic anhydride or an anhydride thereof, (c) 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl Hydroxyl group-containing vinyl monomers such as (meth) acrylate, (d) (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide,
Amide group-containing vinyl monomers such as N-butoxymethyl (meth) acrylamide and diacetone (meth) acrylamide; (e) amino group-containing vinyl monomers such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate; ) Vinyl monomers containing an alkoxy group such as methoxyethyl (meth) acrylate and butoxyethyl (meth) acrylate; (g) vinyl monomers containing a glycidyl group such as glycidyl (meth) acrylate and glycidyl allyl ether; (h) vinyl acetate and propionic acid Vinyl ester monomers such as vinyl; (i) aromatic vinyl monomers such as styrene, vinyl toluene and α-methylstyrene; (j) vinyl cyanide monomers such as (meth) acrylonitrile; (k) vinyl chloride and vinyl bromide Vinyl halide monomer,
(L) Two radical polymerizable unsaturated groups in one molecule such as divinylbenzene, allyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and trimethylolpropane tri (meth) acrylate. A vinyl monomer containing the above, (m) a (poly) oxyethylene chain-containing vinyl monomer such as a (poly) oxyethylene mono (meth) acrylate having 1 to 100 ethylene oxide groups,
(N) a dimethylpolysiloxane containing a (meth) acryloxypropyl group at one end; a dimethylpolysiloxane containing a styryl group or an α-methylstyryl group at one end; and a radically polymerizable functional group at one end. A diorganopolysiloxane having 1 to 200 siloxane units (radical polymerizable silicone macromer), (o) vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, 5-hexenyltrimethoxy Silane, 3- (meth) acryloxypropyltrimethoxysilane, 3-
(Meth) acryloxypropyltriethoxysilane, 3
-(Meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, 4-vinylphenyltrimethoxysilane, 3
Specific examples include silane compounds containing a radical polymerizable functional group such as-(4-vinylphenyl) propyltrimethoxysilane and 4-vinylphenylmethyltrimethoxysilane, and these (a) to (o) )
Can be used alone or in combination of two or more.

Among these, the content of the alkyl (meth) acrylate having an alkyl group having 1 to 18 carbon atoms in the radical polymerizable vinyl monomer is 1 to 100.
Molar%, preferably in the range of 30 to 99 mole% is suitable. If the content of the alkyl (meth) acrylate is less than 1 mol%, characteristics such as chemical resistance of the cured film may not be obtained.

In order to impart properties such as solvent resistance or chemical resistance to the cured film, it is preferable to copolymerize a radically polymerizable vinyl monomer having a crosslinkable functional group, and particularly to conduct a condensation reaction. A silane compound containing the radical polymerizable functional group of the above (o) capable of forming a siloxane bond, and the above-mentioned (g) having an epoxy functional group capable of crosslinking by a ring-opening reaction of a carboxylic acid / epoxy group.
Glycidyl group-containing vinyl monomers such as glycidyl (meth) acrylate and glycidyl allyl ether are preferably used.

When it is desired to impart lubricity to the surface of the cured film, it is preferable to copolymerize a diorganopolysiloxane containing a radically polymerizable functional group at one end of the above (n).

The radical polymerizable compound (radical polymerizable vinyl monomer) is used in an amount of 10 to 1000 parts by weight, preferably 30 to 500 parts by weight, per 100 parts by weight of the silicone resin.
It is used in an amount of 50 parts by weight, more preferably 50 to 150 parts by weight. If the amount of the radical polymerizable vinyl monomer is too small, the film forming property and the chemical resistance become insufficient,
If it is too large, the weather resistance and the water resistance are insufficient.

The silicone resin-containing emulsion composition of the present invention is obtained by emulsion polymerization of a radical polymerizable compound (radical polymerizable vinyl monomer) in the presence of the above silicone resin. Agent is used.

As the surfactant, various known nonionic, cationic and anionic surfactants and a reactive emulsifier having a radically polymerizable functional group can be used.

Specifically, nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene carboxylic acid ester, sorbitan fatty acid ester and polyoxyethylene sorbitan fatty acid ester, alkyl trimethyl ammonium chloride , A cationic surfactant such as alkylbenzylammonium chloride, an anionic surfactant such as an alkyl or alkyl allyl sulfate, an alkyl or alkyl allyl sulfonate, or a dialkyl sulfosuccinate; an amphoteric such as an amino acid type or a betaine type; Ionic surfactants, radical polymerizable compounds containing hydrophilic groups such as sulfonates, polyoxyethylene chains and quaternary ammonium salts in the molecule described in JP-A-8-27347 A (meth) acrylate, styrene, and various reactive surfactants containing derivatives such as maleic acid ester compound can be mentioned, these can be used in alone or in combination of two or more.

The amount of the surfactant used is 0.5 to 0.5 with respect to the total amount of the silicone resin and the radical polymerizable compound.
It is 15% by weight, preferably 1 to 10% by weight.

In the emulsion polymerization, a radical polymerization initiator is used. Examples of the radical polymerization initiator include persulfates such as potassium persulfate and ammonium persulfate, hydrogen peroxide, and t-butylhydrogen. Water-soluble types such as peroxide, t-butylperoxymaleic acid, succinic peroxide, 2,2′-azobis- [2-N-benzylamidino] propane hydrochloride, benzoyl peroxide, cumene hydroperoxide, dibutyl peroxide Oil-soluble types such as oxide, diisopropyl peroxy dicarbonate, cumyl peroxy neodecanoate, cumyl peroxy octoate, azoisobutyronitrile, sodium acid sulfite, Rongalit,
A redox system using a reducing agent such as ascorbic acid in combination can be used.

The amount of the polymerization initiator to be used is 0.1 to 10% by weight, preferably 0.5 to 5% by weight, based on the radical polymerizable compound (radical polymerizable vinyl monomer).

Next, a preferred method for producing the silicone resin-containing emulsion of the present invention will be specifically described. First, in a first step, the organic solvent is distilled off from the silicone resin solution, and in a second step, the silicone resin from which the organic solvent has been removed is added and dissolved in a radically polymerizable compound to obtain a silicone resin-containing vinyl monomer. Solution and the third
In the step (2), the solution prepared in the second step is emulsion-polymerized using a surfactant to obtain an emulsion.

The above-mentioned emulsion polymerization methods include conventionally known methods such as a batch preparation method of emulsifying all at once and polymerization, and a monomer addition method of polymerizing while continuously adding a solution containing a radical polymerizable vinyl monomer or an emulsion thereof. Are applicable. In addition, after previously polymerizing a part of the emulsion, a seed polymerization method in which polymerization is performed while adding the remaining emulsion, and further,
A core / shell polymerization method in which the monomer composition of the core and the shell is changed can also be applied.

For example, for the emulsification of a radical polymerizable vinyl monomer-containing solution, it is preferable to add the radical polymerizable vinyl monomer-containing solution to an aqueous surfactant solution and carry out emulsion polymerization using a homomixer or a high-pressure homogenizer. This emulsion polymerization is carried out at 10 to 90C, preferably 30 to 8C.
It is completed at a temperature of 0 ° C., usually in 3 to 8 hours.

In the thus obtained emulsion containing silicone resin, the silicone resin and the vinyl polymer resin obtained from the above-mentioned radically polymerizable vinyl monomer are present in the same emulsion particles, and both resins have an interpenetrating network structure. Are formed, and the obtained emulsion is stable.

In this case, in order to improve the stability of the emulsion, the inside of the system is preferably adjusted to pH 3 to 9, particularly pH 4 to 8. pH range is less than pH 3 or p
If it exceeds H9, the surfactant used for emulsion polymerization may become unstable, or silanol groups may be easily condensed.

The acid / basic compound combination serving as a buffer for adjusting the pH includes, for example, acetic acid and sodium acetate, disodium hydrogen phosphate and citric acid.

Further, the silicone resin-containing emulsion composition of the present invention is added to the emulsion composition of the present invention within the range that does not affect the properties of the composition of the present invention for the purpose of imparting excellent cured film performance.
Preservatives, fungicides, antioxidants, ultraviolet absorbers (benzophenone, triazole, phenyl salicylate,
Various substances such as diphenyl acrylate, acetophenone and the like can be added in a usual amount.

The silicone resin-containing emulsion composition of the present invention provides a uniform cured film having excellent film forming properties and excellent properties such as water resistance, water repellency, and chemical resistance.
It can be widely used as a basic material such as a coating agent where acrylic resin and silicone resin have been applied in the past, and is most suitable for cosmetic applications such as skin external preparations, nail polish, hair cosmetics, etc. It is.

In this case, the external preparation for the skin includes not only cosmetics but also all products used externally on the skin, which has a problem in feel when using external medicines. For example, lotions, emulsions, creams, packs, massages, lip balms, hand creams, skin cares such as detergents, foundations, makeup bases, blushes, eye shadows, mascaras, eyeliners, eyebrows, overcoats, lipsticks And other make-up cosmetics.

Various types of nail polish can be selected, such as a general nail enamel containing toluene, a nail enamel free of toluene, a nail enamel of an aqueous system, an enamel top coat, an enamel base coat, and a remover.

The hair cosmetics include all products externally applied to hair, such as shampoos, rinses, rinse-in shampoos, treatments, conditioners, hair creams, hair oils, brushing agents, setting agents, and hair restoration agents. The dosage form is solid, creamy, milky, liquid,
Various forms such as a multilayer form, a mousse form, and a spray form can be selected.

[0045]

According to the silicone resin-containing emulsion composition of the present invention, it is possible to obtain a uniform cured film having excellent film forming properties, good properties such as water resistance, water repellency and chemical resistance. .

[0046]

EXAMPLES The present invention will be described below in detail with reference to examples and comparative examples, but the present invention is not limited to the following examples. “Parts” and “%” indicate “parts by weight” and “% by weight” unless otherwise specified.

Example 1 (CH ₃ ) ₃ SiO _1/2 unit: S
Average composition formula (CH ₃ ) consisting of iO ₂ units = 0.85: 1
_1.38 20 parts of a silicone resin having an average molecular weight of 5,000 represented by SiO _1.31 and CH ₂ ＣC (CH ₃ ) COOC ₃ H ₆ SiO [(CH ₃ ) ₂ S
iO] ₄₀ Si (CH ₃ ) ₃ , one-terminal acrylic-modified silicone 10 parts, methyl methacrylate 7 parts, butyl methacrylate 1.5
, A uniform solution of 1.5 parts of 2-ethylhexyl methacrylate was prepared, and 6 parts of methacryloyloxypolyoxyalkylene sulfate sodium salt was added thereto, and 30 parts of water was added while stirring at a low speed with a homomixer. After phase inversion, the phase inversion material was kneaded at high speed rotation. afterwards,
After adding 18.66 parts of water and diluting, secondary emulsification was performed with a high-pressure homogenizer.

Next, a stirrer, a thermometer, a reflux condenser, a Y-shaped tube, a dropping funnel filled with the above emulsion and two dropping funnels containing an aqueous solution obtained by dissolving 0.05 part of ascorbic acid in 5 parts of water are provided. The emulsion and the aqueous solution of ascorbic acid were added dropwise to each of the four-necked flasks in an amount of 1/10 and stirred. Further, 0.29 parts of a hydrogen peroxide solution was added, and 50
Stirred at C for 1 hour. Thereafter, the emulsion and ascorbic acid were simultaneously added dropwise at 70 ° C., and the mixture was stirred for 5 hours after completion of the addition. Next, the temperature was returned to normal temperature, 0.9 parts of a 5% aqueous sodium hydrogen carbonate solution was added to adjust the pH to 5, 0.5 parts of sodium benzoate was added, and the mixture was sufficiently stirred and filtered to prepare a silicone-containing emulsion.

Example 2 (CH ₃ ) ₃ SiO _1/2 unit: S
Average composition formula (CH ₃ ) consisting of iO ₂ units = 0.85: 1
_1.38 33.4 parts of a 50% decamethylcyclopentasiloxane solution of a silicone resin having an average molecular weight of 5,000 represented by SiO _1.31 and CH ₂ ＣC (CH ₃ ) COOC ₃ H ₆ SiO [(CH ₃ ) ₂ S
iO] ₃ Si (CH ₃ ) ₃ 8.3 parts of one-terminal acrylic-modified silicone, 5.8 parts of methyl methacrylate, 1.25 parts of butyl methacrylate, 1.2 parts of 2-ethylhexyl methacrylate
5 parts, 13.3 parts of 15% sodium lauryl sulfate (SLS) aqueous solution, 31.5 parts of dilution water, 0.0 ascorbic acid
4 parts dissolved in 5 parts water, aqueous solution of hydrogen peroxide 0.24
In the same manner as in Example 1, a silicone-containing emulsion was prepared using 1.0 part of a 5% aqueous sodium hydrogen carbonate solution and 0.5 part of sodium benzoate.

Example 3 (CH ₃ ) ₃ SiO _1/2 unit: S
Average composition formula (CH ₃ ) consisting of iO ₂ units = 0.85: 1
_1.38 16 parts of a silicone resin having an average molecular weight of 5,000 represented by SiO _1.31 and CH ₂ ＣC (CH ₃ ) COOC ₃ H ₆ SiO [(CH ₃ ) ₂ S
iO] ₄₀ Si (CH ₃ ) ₃ , one end acrylic modified silicone 16 parts, methyl methacrylate 5.6 parts, butyl methacrylate
4 parts, sodium methacryloyloxypolyoxyalkylene sulfate 6 parts, 48.66 parts of diluting water, an aqueous solution obtained by dissolving 0.05 part of ascorbic acid in 5 parts of water, 0.29 part of aqueous hydrogen peroxide, 5% carbonic acid Aqueous sodium hydrogen solution 1.
Using 0 part and 0.5 part of sodium benzoate, a silicone-containing emulsion was prepared in the same manner as in Example 1.

Example 4 (CH ₃ ) ₃ SiO _1/2 unit: S
Average composition formula (CH ₃ ) consisting of iO ₂ units = 1.15: 1
25 parts of a 50% decamethylcyclopentasiloxane solution of a silicone resin having an average molecular weight of 2,500 represented by _1.6 SiO _1.2 and CH ₂ ＣC (CH ₃ ) COOC ₃ H ₆ SiO [(CH ₃ ) ₂ S
iO] ₃ Si (CH ₃ ) ₃ , 12.5 parts of an acrylic modified silicone at one end,
6.3 parts of methyl methacrylate, 3.1 parts of butyl methacrylate, 3.1 parts of 2-ethylhexyl methacrylate
Parts, 15% sodium lauryl sulfate (SLS) aqueous solution 1
3.3 parts, dilution water 31.42 parts, ascorbic acid 0.0
4 parts dissolved in 5 parts water, aqueous solution of hydrogen peroxide 0.24
In the same manner as in Example 1, a silicone-containing emulsion was prepared using 1.0 part of a 5% aqueous sodium hydrogen carbonate solution and 0.5 part of sodium benzoate.

Comparative Example 1 (CH ₃ ) ₃ SiO _1/2 unit: S
Average composition formula (CH ₃ ) consisting of iO ₂ units = 1.6: 1
_A silicone-containing emulsion was prepared in the same manner as in Example 1, except that 20 parts of a silicone resin having an average molecular weight of 350 represented by _1.85 SiO _1.08 was used.

Comparative Example 2 CH ₂ ＣC (CH ₃ ) COOC ₃
20 parts of one-terminal acrylic-modified silicone represented by H ₆ SiO [(CH ₃ ) ₂ SiO] ₄₀ Si (CH ₃ ) ₃ , 14 parts of methyl methacrylate, 3 parts of butyl methacrylate,
An emulsion was prepared in the same manner as in Example 1 using 3 parts of 2-ethylhexyl methacrylate.

The appearance, pencil hardness, and water resistance of the cured films of the emulsions prepared in Examples 1 to 4 and Comparative Examples 1 and 2 were evaluated according to the following procedures. The results are shown in Tables 1 and 2.

A polished steel sheet having a clean pencil hardness and water-resistant surface was coated so as to have a cured film thickness of 20 μm, and cured at room temperature. For these cured coatings, a method for measuring the pencil hardness of the cured coatings according to JIS K-5400 and checking of water resistance (25 ° C., deionized water × 18 hours) were performed and evaluated according to the following criteria. <Evaluation Criteria for Pencil Hardness> Pencil hardness (B, H, 2H), which was less than twice the film breakage, was expressed. <Evaluation Criteria for Water Resistance> ：: No cracking, peeling, etc. were observed in the coating. Δ: Slight cracking, peeling, etc. were observed in the coating. X: Cracking, peeling, etc. were observed in the coating, and the adhesion of the coating was poor.

[0056]

[Table 1]

[0057]

[Table 2] * N is n in the formula of the average composition formula R _n SiO _{(4-n) / 2} . * Acrylic dimethyl silicone A at one end: CH ₂ ＣC (CH ₃ ) COOC ₃ H ₆ [(CH ₃ ) ₂ SiO]
₄₀ Si (CH ₃ ) ₃ * Acrylic dimethyl silicone at one end B: CH ₂ ＣC (CH ₃ ) COOC ₃ H ₆ [(CH ₃ ) ₂ SiO]
₃ Si (CH ₃ ) ₃ * Emulsifier A: sodium methacryloyloxypolyoxyalkylene sulfate ester * Emulsifier B: sodium lauryl sulfate (SLS)

Continued on the front page (72) Inventor Hisashi Aoki 1-10 Hitomi, Matsuida-cho, Usui-gun, Gunma Prefecture F-term in the Silicon Electronics Research Laboratory, Shin-Etsu Chemical Co., Ltd. 4J002 BC02X BC08X BC09X BD03X BD11X BF02X BG01X BG04X BG07X BG10X BG13X BH02X CF18Y CH01Y CP03W EB026 EB126 EG006 EV236 FD31Y FD316 GC00 HA07 4J011 KA01 KA02 KA08 KA10 KA12 KA15 PA99 PB40 PC06 4J027 AC02 AC03 AC06 AF05 BA04 BA05 BA06 BA07 BA08 BA09 BA13 BA03 BA18

Claims (3)

[Claims] The present invention is characterized in that 10 to 1000 parts by weight of a radical polymerizable compound is emulsion-polymerized in the presence of 100 parts by weight of a silicone resin having an average molecular weight of 400 to 30,000 represented by the following average composition formula (1). A silicone resin-containing emulsion composition. ^{_{(R 1 3 SiO 1/2) a}} (R 1 2 SiO 2/2) b (R 1 SiO 3/2) c (SiO 2) d (1) ( In the formula, R ¹ 1 Number hydrogen or C And a, b, c, and d are a> 0, d> 0, b ≧
0, c ≧ 0, a + b + c + d = 1, 0 ≦ (b + c) ≦
This is a number that satisfies 0.3. ) 2. The silicone resin-containing emulsion composition according to claim 1, wherein the radical polymerizable compound contains a radical polymerizable silicone macromer. 3. The silicone resin-containing emulsion composition according to claim 1, which is a cosmetic base.