JPH03220213A - Production of non-film-forming resin emulsion containing ultraviolet absorber comonomer and cosmetic containing same resin - Google Patents

Abstract

PURPOSE:To obtain a non-film-forming resin emulsion which can protect the skin by screening ultraviolet rays, does not irritate the skin and excels in adhesion thereto by emulsion-polymerizing a radical-polymerizable monomer with a polymerizable unsaturated reactive ultraviolet absorber. CONSTITUTION:The title emulsion is produced by emulsion-copolymerizing a radical-polymerizable monomer with at least one polymerizable unsaturated reactive ultraviolet absorber selected from compounds of formulas I-III, compounds of formulas V-VIII and a compound of formula IV. In the formulas, Q1 is vinyl, a group of formula IX or 1-20C alkyl; R1 is H, methoxy or vinyl; R2 is amino or a group of formula X, XI or XII; R3 is H or vinyl; R4 is a group of formula XIII or vinyl; R5 and R6 are each H, methyl, isopropyl, t-butyl or methoxy; R7 is a group of formula IX or vinyl; R8 and R9 are each H, methyl or vinyl; R10 is a group of formula XIII or vinyl; R11 is H, methyl, isopropyl, t-butyl or methoxy; R12 and R13 are each H, vinyl or the like; and R14 and R15 are each H, vinyl, 1-20C alkyl or the like.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is a novel and useful method for producing a UV absorber copolymerized non-film-forming resin emulsion, and an ultraviolet absorber having small pores (microbords) inside. The present invention relates to a method for producing a non-film-forming resin emulsion copolymerized with an ultraviolet absorber, a method for purifying the resin emulsion, a method for pulverizing the resin emulsion, and a cosmetic containing the ultraviolet absorber copolymer resin. A method for producing a non-film-forming resin emulsion copolymerized with an ultraviolet absorber useful for protecting the skin by absorbing and blocking ultraviolet rays that have harmful effects, and such a non-film-forming resin emulsion copolymerized with such an ultraviolet absorber. Contains membrane resin, does not irritate the skin, is therefore safe, and has excellent adhesion, extensibility, and covering power to the skin.
Furthermore, the present invention relates to a cosmetic that can appropriately correct the hue of the skin and has an excellent natural finish.

[Conventional technology]

In sunlight, 200 to 400 nm is the ultraviolet region, and depending on the wavelength, there are deep ultraviolet rays of 200 to 28 Or+m, middle outer rays of 280 to 320 nm, and 320 to 320 nm.
It is divided into three parts: near ultraviolet light of 400 nm,
There is an ozone layer that extends 20 to 25 km above the atmosphere, and because this layer absorbs ultraviolet rays well, what the earth is actually exposed to is the middle ultraviolet rays and the near ultraviolet rays. Among them, the light of the middle lobe outer line part of 280 to 320 nm (hereinafter referred to as U)
V-B) causes erythema (sunburn) on the skin, and even worse, causes blisters similar to those caused by burns, resulting in post-inflammatory darkening. On the other hand, light in the near ultraviolet region of 320 to 400 nm (hereinafter referred to as UV-A) has a very weak erythema-inducing power compared to UV-B, and does not substantially cause erythema and darkens the skin (sunken). bring about. Furthermore, exposure to ultraviolet rays can cause melasma (melasma) on the skin.
This increases the possibility of causing age spots, freckles, and wrinkles, as well as skin aging, degeneration of skin elastic fibers, and induction of photosensitivity.

To prevent these disorders, cosmetics containing various UV absorbers and inorganic pigments have been developed and marketed, but the UV absorbers and inorganic pigments used in these products include p-amino Those with maximum absorption in the UV-B region such as Henshade G conductors, salicylate derivatives, benzotriazole derivatives, hensifhenone derivatives and cinnamate derivatives, and IJ V such as dihenzoylmethane derivatives, henztriazur derivatives and hensifhenone derivatives. -A Ultraviolet absorbers having maximum absorption in the IJ region include inorganic pigments such as titanium oxide, zinc oxide, and iron oxide. The former UV absorber is
If the amount added to the cosmetic base is increased, it may cause problems with solubility and feeling of use, and when applied to the skin, it may cause temporary irritation to the skin due to its irritation or absorbing light energy. There are safety issues, such as: Therefore, the use of ultraviolet absorbers on the skin is quite limited. On the other hand, the latter inorganic pigments are less susceptible to deterioration due to ultraviolet rays and are not absorbed through the skin, so there is no problem with irritation to the skin. External absorption is weak, and its hiding power is too strong, so when applied to the skin, it causes whitening or coloring, and its usage is limited.

Furthermore, there is a known method of performing emulsion polymerization by dissolving or dispersing an ultraviolet absorber in a resin monomer, but the resulting particles have a wide particle size distribution, with some fine particles of 0.1 micron or less, but others of 5 to 50 microns. There are also many coarse particles, and as a result, as cosmetic particles, their adhesion to the skin is low and their range of use is also poor. In addition, some of them have the drawback that the encapsulated ultraviolet absorber leaks out onto the polymer surface, and some of them lack safety and stability. You can't expect adequate concealment power either.

For this reason, the present inventors have previously proposed a method of encapsulating an ultraviolet absorber in a core-shaped non-film-forming resin emulsion having small pores inside, and We proposed a powdering method. (Unexamined Japanese Patent Publication No. 6
2-93220) However, in this case, although there is a significant improvement effect on stability and safety, the ultraviolet absorber sealed inside may leak out of the particle over time.
It was found that the stability over time was inferior, albeit slightly.

[Problems to be Solved by the Invention] The present invention can protect the skin by absorbing and blocking ultraviolet rays that have a harmful effect on the skin, when used in a sunscreen cosmetic, for example. It is safe without irritating the skin, has good adhesion to the skin, moderately corrects skin color, is transparent without being white or colored, and has good shelf life over time. The inventors of the present invention have carried out extensive research based on their strong belief that it is possible to provide excellent cosmetics.

Therefore, the problems to be solved by the present invention are as follows: The object of the present invention is to provide a cosmetic composition containing a synthetic resin, and also to provide a method for purifying and a method for powderizing the resin emulsion, respectively.

[Means to solve the problem]

The present inventors have conducted extensive research into a method for producing a non-film-forming resin emulsion that has the above-mentioned physical properties and is highly practical, resulting in the present invention.

That is, the main point of the present invention is that the radically polymerizable monomer has general formulas (I) to [I[
[) or [v] to [■] or a UV absorber copolymerizable non-film-forming resin emulsion, which is obtained by adding and emulsifying at least one of various reactive UV absorbers represented by the structural formula. In the manufacturing method of the resin emulsion, in the method for purifying the resin emulsion, in the powdering method of the resin emulsion, and in the cosmetic containing the ultraviolet absorber copolymerizable non-film-forming resin. .

Here, the reactive ultraviolet absorbent used in the present invention described above is an ultraviolet absorbent having a polymerizable unsaturated bond, especially a vinyl group, and these have radical polymerizability, and during emulsion polymerization, radical It reacts with polymerizable monomers and is incorporated into non-film-forming vinyl resins, and such reactive ultraviolet absorbers include those having polymerizable unsaturated bonds, especially vinyl groups. Although any of them can be used, the following general formula (1) ~ (I [] or [V) ~ [ ■)
Or it is represented by structural formula [IV].

(V) 7 or [■] Specific examples of the reactive ultraviolet absorbers include vinyl p-methoxycinnamate, vinyl p-N,N dimethylaminobenzoate, vinyl salicylate, vinyl cinnamate, p-vinyl vinyl cinnamate, ON, vinyl N-dimethylaminobenzoate, o-N vinyl vinyl aminobenzoate,
Vinyl urocanate, l-vinyl-5-vinyl urocanate, vinyl 1-vinyl-4-urocanate, vinyl 0-aminobenzoate, vinyl p-aminobenzoate, pN, N
-Bis(2-hydroxypropyl)-vinyl aminobenzoate, p-N,N-bis(3-hydroxypropyl)-
Vinyl aminobenzoate, 1-(2-oxycarbonyl)
-phenyl-3-(4'-methoxy)phenyl-1,3
-propanedione, 2-(N.

N-dimethyl)amino-5-vinyloxycarbonyl-
1,3-indanedione, 2-(3-vinyloxycarbonyl)benzylidene-5-benzylidene-cyclopentanone, 4-(2,3-dimethoxybenzylidene)-2
, 5-dioxo-1-imidazolidine vinyl acetate, 4-
(2,3,4-trimethoxybenzylidene)-2,5-
Dioxo-1-imidapridine vinyl acetate, 4-(4-
t-butylbenzylidene) 2,5-dioxo-1-imidazolidine vinyl acetate, 4-(3,4-dimethoxybenzylidene) -2,5-dioxo-3-imidazolidine propionate vinyl, 4-(2,4- dimethoxybenzylidene) -2,5-dioxo-3-imidazolidine propionate vinyl, 4- (2,5-dimethoxybenzylidene) -2,5-dioxo-3-imidazolidine propionate vinyl, 4-(4-methoxybenzylidene) )
-2,5-dioxo-3-imidazolidine propionate vinyl, 4-(3,4-dimethoxybenzylidene)
-2,5-dioxo-3-imidazolidine vinyl acetate,
4-(2゜4-dimethoxybenzylidene) 1,5-dioxo-3 imidazolidine vinyl acetate, 4-(2,5-
dimethoxybenzylidene)-2,5-dioxo-3-imidazolidine vinyl acetate, 4-(4-methoxybenzylidene)-2,5-dioxo-3-imidazolidine vinyl acetate, 4-(3,4-dimethoxybenzylidene) 25 −
Dioxo-1-imidazolidine propionate vinyl, 4
-(2,4-dimethoxybenzylidene)2,5-dioxo-1-imidazolidine vinyl propionate, 4-(4
-methoxybenzylidene) 2.5-dioxo-1-imidazolidine propionate vinyl, 4-(2,5-dimethoxybenzylidene) 2.5-dioxo-1-imidapridine propionate vinyl, 4- (2,3, 4-trimethoxybenzylidene) = vinyl 2,5-dioxo-1-imidazolidine propionate, 4-(4-t-butylbenzylidene) 2,5-dioxo-1-imidazolidine propionate vinyl, 4-(2, 3-dimethoxybenzylidene) 2,5-dioxo-1-imidazolidine vinyl propionate, 4-(3,4-dimethoxybenzylidene)
2.5-dioxo-1-imidapridine vinyl acetate, 4
- (2,4-dimethoxybenzylidene) -2,5-
Dioxo-1-imidazolidine vinyl acetate, 4-(25
-dimethoxybenzylidene)'-2,5-dioxo 1
= imidazolidine vinyl acetate, 4-(4-methoxybenzylidene)-2,5-dioxo-1-imidazolidine vinyl acetate, 4-(3,4-dimethoxybenzylidene)-
Vinyl 2,5-dioxo-3-methyl-1-imidazolidinepropionate, 4-(4-methoxybenzylidene)
Vinyl -2,5-dioxo-3-methyl-1-imidazolidinepropionate, 4-(3,4-dimethoxybenzylidene) -2,5-dioxo-3-ethyl-1-imidazolidinepropionate, 4-( 4-methoxybenzylidene) -2゜5-dioxo-3-ethyl-1-
Vinyl imidazolidine propionate, 4-(3,4-dimethoxybenzylidene)-2,5-dioxo-3-octyl-1-imidapridine vinyl propionate, 4-
(4-methoxybenzylidene) -2,5-dioxo-
Vinyl 3-octyl-1-imidazolidine propionate, 4-(3,4-dimethoxybenzylidene) -2,5
-Dioxo-1-methyl-3-imidazolidine vinyl propionate, 4- (4-methoxybenzylidene) 25
-Dioxo-1-methyl-3-imidazolidine vinyl propionate, 4-(3,4-dimethoxybenzylidene)
-2,5-dioxo-1-ethyl-3-imidazolidinepropionate vinyl, 4-(4-methoxybenzylidene) -2,5-dioxo-1-ethyl-3-imidazolidinepropionate vinyl, 4-(3 ,4-dimethoxybenzylidene)-2,5-dioxo-1-octyl-3-imidazolidinepropionyl, 4-(4-
Vinyl methoxybenzylidene)-2,5-dioxo-1-octyl-3-imidazolidine propionate, 4-(
3,4-dimethoxybenzylidene) -2,5-dioxo-3-methyl-1 imidazolidine vinyl acetate, 4-(
4-methoxybenzylidene) -2,5-dioxo-3
-Methyl-1-imidazolidine vinyl acetate, 4- (3
,4-:,'methoxybenzylidene)-2,5-dioxo-3-ethyl-1-imidazolidine vinyl acetate, 4
- (4-methoxybenzylidene) -2,5-dioxo-3-ethyl-1-imidapridine vinyl acetate, 4-
(3゜4-dimethoxybenzylidene)-2,5-dioxo-3octyl-1-imidazolidine vinyl acetate, 4-
(4-methoxybenzylidene) -2,5-dioxo3
-Octyl-1-imidazolidine vinyl acetate, 4-(3
,4-dimethoxybenzylidene) -2,5-dioxo-1-methyl-3-imidazolidine vinyl acetate, 4-(
4-methoxybenzylidene) -2,5-dioxo-1
-Methyl-3-imidazolidine vinyl acetate, 4-(3,
4-dimethoxybenzylidene)-2゜5-dioxo-1
-ethyl-3-imidazolidine vinyl acetate, 4-(4-
methoxybenzylidene)-2,5-dioxo-1-ethyl-3-imidazolidine vinyl acetate, 4-(3,4-dimethoxybenzylidene)2,5-dioxo-1-octyl-3-imidazolidine vinyl acetate, 4- (4-methoxybenzylidene)-2,5-dioxo-1-octyl-
3-Imidazolidine vinyl acetate, 4-(4-methoxybenzylidene)-2,5-dioxo-3-vinyl-1-imidazolidine vinyl acetate, 1-(3,4-dimethoxybenzylidene)-2,5-dioxo- 1-vinyl-3-
Vinyl imidazolidine propionate, 4-(4-methoxybenzylidene)-2,5-dioxo-1-vinyl-3-vinyl imidazolidine propionate, 4-(3,
4-dimethoxybenzylidene) -2,5-dioxo-
1-vinyl-3-imidazolidine vinyl acetate, 4-(4
-methoxybenzylidene) -2,5-dioxo-1-
Vinyl-3-imidazolidine Vinyl acetate, 4-(3,4
-dimethoxybenzylidene)-25-dioxo-3-vinyl-1-imidazolidine vinyl propionate, 4-(
4-methoxybenzylidene)-2,5-dioxo-3-
Vinyl-1-imidazolidine propionate, or 4-(3,4 dimethoxybenzylidene) -2,5-
Various vinyl esters such as dioxo-3-vinyl-1-imidazolidine vinyl acetate, as well as alkyl p-N-vinylaminobenzoates with structures similar to these (here, alkyl refers to C1 to C2 ), p-vinylcinnamate alkyl, o-N-vinylaminobenzoate alkyl, ■-vinyl-5-urocanate alkyl or 1
-Various vinyl alkyl esters such as alkyl vinyl-4-urocanate; or (meth)acrylic esters; furthermore, 1-(3-vinyl)phenyl-3-
(3-methyl)phenyl-1,3-propanedione, 2
- (N,N-dimethyl)amino-5-vinyl-1,3
-Indanedione, 2-(3-vinyl)hengylidene-
In addition to 5-(3-isopropyl)henzylidene-cyclopentanone, 4-(4-methoxybenzylidene)
-2,5-dioxo-3-vinyl-1-imidazolidine octyl acetate, 4-(4-methoxybenzylidene) -
2,5-dioxo-3-vinyl-■-imidazolidine ethyl acetate, 4-(3,4-dimethoxybenzylidene)-
Octyl 2,5-dioxo-1-vinyl-3-imidazolidinepropionate, 4-(3,4-dimethoxybenzylidene)-ethyl 2,5-dioxo-1-vinyl-3-imidazolidinepropionate, 4-( 3,4-dimethoxybenzylidene)2,5-dioxo-I-vinyl-
3-Imidazolidine octyl acetate, 4-(3,4-dimethoxybenzylidene)-2,5-dioxo-1-vinyl-3-imidazolidine ethyl acetate, 4-(4-methoxybenzylidene)-2,5-dioxo- 1-vinyl-3-
Octyl imidazolidine propionate, 4-(4-methoxybenzylidene) -2,5-dioxo-1-vinyl-3-imidapridine ethyl propionate, 4(4-methoxybenzylidene) -2,5-dioxo-1-vinyl -3-Imidazolidine octyl acetate, 4-(4-methoxybenzylidene) -2,5-dioxo-1-vinyl-3-imidazolidine ethyl acetate, 4-(3,4-dimethoxybenzylidene) -2,5-dioxo -3-vinyl-1-imidapridine octyl propionate, 4-
Ethyl (3,4-dimethoxybenzylidene)-2,5-dioxo-3-vinyl-1-imidazolidinepropionate, 4-(3,4-dimethoxybenzylidene') -2
,5-dioxo-3-vinyl-1-imidazolidine octyl acetate, 4-(3,4-dimethoxybenzylidene)
-2,5-dioxo-3-vinyl-1-imidazolidine ethyl acetate, 4-(4methoxybenzylidene) -2,
Octyl 5-dioxo-3-vinyl-1-imidazolidinepropionate or ethyl 4-(4-methoxybenzylidene)-2゜5-dioxo-3-vinyl-1-imidazolidinepropionate, etc. , 4-dimethoxybenzylidene)-2,5-dioxo-imidazolidine-1-acrylamide, 4-(4-methoxybenzylidene)-2,5-dioxo-imidazolidine 1-acrylamide, 4-(3,4-dimethoxybenzylidene) )-2,5-dioxo-imidazolidine-1-methacrylamide, 4-(4-methoxybenzylidene)-2,5
-dioxo-imidazolidine-1 methacrylamide, 4
-(3,4-dimethoxybenzylidene)-2,5-dioxo-imidazolidine-3-acrylamide, 4-(4
-methoxybenzylidene)-2,5-dioxo-imidazolidine-3-acrylamide, 4-(3,4-dimethoxybenzylidene) -2,5-dioxo-imidazolidine-3-methacrylamide, 4-(4-methoxybenzylidene) ) 2,5-dioxo-imidazolidine-3-
Methacrylamide, 4-(3,4-dimethoxybenzylidene)25-dioxo-imidazolidine-1,3-diacrylamide, 4-(4-methoxybenzylidene)-2
, 5-dioxo-imidazolidine-1,3-diacrylamide, 1-(3,4-dimethoxybenzylidene)2.
5-dioxo-imidazolidine-1,3-dimethacrylamide, 4-(4-methoxybenzylidene)-2,5-
Dioxo-imidazolidine-1,3-dimethacrylamide, 4-(3,4-dimethoxybenzylidene)2.5-
Dioxo-3-methylimidazolidine-1-acrylamide, 4-(4-methoxybenzylidene)-2,5-dioxo-3-methylimidazolidine-1-acrylamide, 4-(3,4-dimethoxybenzylidene)-2,5
-dioxo-1-methylimidazolidine-3-acrylamide, 4-(4-methoxybenzylidene) -2,5
-dioxo-1-methylimidapridine-3-acrylamide, 4-(3,4-dimethoxybenzylidene)
-2,5-dioxo3-methylimidazolidine-1-methacrylamide, 4-(4-methoxybenzylidene)
-2,5-dioxo-3-methylimidazolidine-1-methacrylamide, 4-(3,4-dimethoxybenzylidene)-"2,5-dioxo-1-methylimidazolidine-3-methacrylamide, or 4-(4 -methoxybenzylidene) -2,5-dioxo-1-methylimidazolidine-3-methacrylamide.

Further, the amount of the reactive ultraviolet absorber used is as follows. That is, the amount dissolved in 100 parts by weight of the radically polymerizable monomer constituting the non-film-forming resin emulsion is 0.01 to 50 parts by weight, more preferably 0.05 parts by weight.
~30 parts by weight is suitable.

On the other hand, as the radically polymerizable monomer, the following monomers may be used alone or in any mixture.

(1) As the carboxyl group-containing monovinyl monomer,
Examples include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, and fumaric acid. (2) Examples of hydroxyl group-containing monovinyl monomers include 2-hydroxyethyl acrylate, hydroxypropyl acrylate, 2- Hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, allyl alcohol, methalyl alcohol, etc. may be mentioned. (3) As the monovinyl monomer containing amiF group or its N-methylol group or its alkoxy group, for example Examples include meth)acrylic acid amide or N-methylolated (meth)acrylic acid amide, and (4) nitrile group-containing monovinyl monomers include:
Examples of the nitrogen-containing alkyl group-containing monovinyl monomer include dimethylaminoethyl acrylate and dimethylaminoethyl methacrylate; (6) sulfonic acid groups or their Examples of the base-containing monovinyl monomer include vinyl sulfonic acid, styrene sulfonic acid, or salts thereof, and (7) (meth)acrylic acid alkyl esters include:
For example, methyl-, ethyl-, propyl n-butyl-1
t-butyl-1n-amyl-amyl-hexyl-,
Octyl-, nonyl-, decyl-F decyl-, octadecylcyclohexyl-, phenyl-, and hensyl (
Examples of the monovinyl ester (8) include vinyl acetate, vinyl propionate, vinyl butyralate, and vinyl hersate.

(9) Examples of monovinyl ether include methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, t-
Butyl vinyl ether, n-pentyl vinyl ether,
Alkyl vinyl ethers or substituted alkyl vinyl ethers such as n-hexyl vinyl ether, n-octyl vinyl ether, 2-ethylhexyl vinyl ether, chloromethyl vinyl ether, chloroethyl vinyl ether, benzyl vinyl ether or phenylethyl vinyl ether; such as cyclopentyl vinyl ether, cyclohexyl vinyl ether or methylcyclohexyl vinyl ether Cycloalkyl vinyl ethers; or trifluoromethyl vinyl ether, pentafluoroethyl vinyl ether, tetrafluoroethyl vinyl ether, tetrafluoropropyl vinyl ether, hephtafluoropropyl vinyl ether (
(bar) fluoroalkyl vinyl ethers; 00) Other monovinyl monomers include vinyl halides such as vinyl chloride or vinylidene chloride; or dialkyl esters of maleic acid, fumaric acid, or itaconic acid. unsaturated dibasic acid dialkyl esters such as; styrenes such as styrene or vinyltoluene; monoenes and dienes such as ethylene and butadiene; silane group-containing monovinyl monomers such as vinyltrichlorosilane and vinyltriethoxysilane; Examples of monovinyl monomers containing a glycidyl group such as methyl) glycidyl (meth)acrylate, and examples of (10 polyfunctional crosslinkable monomers) include monovinyl monomers having two or more polymerizable unsaturated bonds in the molecule. Ethylene glycol dimethacrylate, 1.3-butylene glycol dimethacrylate, 1.4-butylene glycol dimethacrylate, propylene glycol dimethacrylate, sivinylhenzen, trivinylhenzen, diallyl phthalate, ethylene glycol diacrylate, 1.3 -butylene glycol diacrylate and the like.

In addition, when the reactive ultraviolet absorber is a vinyl ester, the above monovinyl ether monomer (9) can be used as
Its use is effective because it has high reactivity with this and reduces the amount of unreacted monomer in the system. The amount used in this case is preferably equivalent to or more than the amount of the vinyl ester ultraviolet absorber. In addition, the amount of the polyfunctional crosslinking monomer (l 1) mentioned above should be less than 50% by weight, preferably 0.5% by weight based on the total monomers, from the viewpoint of solvent resistance of the final resin. A range of 1 to 30% by weight is suitable.

The non-film-forming resin emulsion obtained by the method of the present invention can be obtained by emulsion copolymerizing various reactive ultraviolet absorbers and radically polymerizable monomers as listed above, or by the following method. The resulting core/shell type non-film-forming resin emulsion having small pores inside may be used.

That is, the radically polymerizable monomer is emulsion polymerized (first step reaction), and then in the presence of this emulsion polymer emulsion, the contact angle of water is 5% compared to the polymer of the emulsion.
When performing emulsion polymerization by adding a radically polymerizable monomer that can form a polymer with a high temperature of ~110° (second stage reaction), the radically polymerizable monomer of the first stage reaction and/or second stage reaction is added. Said - Formulas (1) to (III) or [■]
This is a method in which emulsion copolymerization is carried out by adding a reactive ultraviolet absorber represented by ~[■] or structural formula [IV].

In such a core/shell type non-film-forming resin emulsion, radically polymerizable monomers constituting the emulsion polymer emulsion (seed particle emulsion) resulting from the first stage reaction,
The radically polymerizable monomer to be added later can be arbitrarily selected as long as it satisfies the above conditions, but the radical polymers constituting the seed particle emulsion include hydrophilic vinyl monomers, (meth)acrylic monomers, Preferably, it contains an 01-C4 alkyl ester of an acid, a polyfunctional crosslinking monomer,
Post-added polymerizable monomers (second-stage forming monomers) include relatively hydrophobic olefins such as styrene or vinyltoluene; monoenes and dienes such as ethylene and butadiene; or polyfunctional crosslinkable monomers. Preferably, it contains a monomer.

In addition, the polymer produced by the post-added radically polymerizable monomer (including reactive ultraviolet absorbers) has lower hydrophilicity than the polymer of the emulsion polymer emulsion of the seed particles, and the catalytic angle of water is Usually the angle does not exceed 120°.

Here, the contact angle of water on a polymer is defined as the contact angle between the water droplet and the film or sheet when a drop of water is dropped onto the film or sheet of the polymer in a state where the polymer does not substantially contain additives such as emulsifiers. It is shown in terms of the contact angle.

The contact angle is described, for example, in [Medical Materials and Living Organisms, edited by Manabu Seno, Yukio Imanishi, and Yoshi Takemoto, Hisashi Sakurai, and published by Kodansha.

In addition, the emulsion polymer emulsion (seed particle emulsion) used in producing a core/shell type resin emulsion usually contains the above-mentioned monomer (which may also contain a reactive ultraviolet absorber), an emulsifier, a catalyst, etc. It is preferable to use resin particles synthesized using 5 to 65% solid content of resin particles having a particle diameter of 0.01 to 1.0 μm.

Furthermore, the amount of such seed particle emulsion to be used is as follows:
The polymerization ratio of the solid content/post-added radically polymerizable monomer (which may contain a reactive ultraviolet absorber) is 0, 1/
99.9 to 90/10, preferably 0.5/99.5
A range of ˜60/40 is appropriate.

In the core/shell type non-film-forming emulsion produced by the above method, when a radically polymerizable monomer is added and polymerized, the polymer particles (seed particles) in the seed particle emulsion are swollen with the monomer, Next, by emulsion polymerization, due to the difference in hydrophilicity of each polymer, the polymer of the emulsion polymer emulsion and the polymer that will be produced later are reversed, resulting in non-film-forming resin particles having small pores inside. It is assumed that a maelsion of

When producing the ultraviolet absorber copolymerizable non-film-forming resin emulsion of the present invention, including the core/shell type described above, an emulsifier and a catalyst are usually used. Examples of such emulsifiers include anionic emulsifiers, nonionic emulsifiers, and cationic emulsifiers, as well as reactive emulsifiers, acrylic oligomers, and other substances with surfactant ability, and these can be used alone or in combination of two or more. . Among these, nonionic and anionic emulsifiers are preferred because they produce less aggregates during polymerization and provide stable emulsions. As the nonionic emulsifier, any commercially available nonionic emulsifier such as polyoxyethylene alkyl phenol ether, polyoxyethylene alkyl ether, polyoxyethylene higher fatty acid ester or ethylene oxide-propylene oxide block copolymer can be used, Further, as the anionic emulsifier, any of commercially available anionic emulsifiers such as alkylbenzene sulfonic acid alkali metal salts, alkyl sulfate alkali metal salts, or polyoxyethylene alkylphenol sulfate alkali metal salts can be used. Furthermore, it is also possible to use water-soluble oligomers in place of or in combination with the above-mentioned anionic emulsifiers, and in particular, those consisting of polycarboxylic acids or sulfonates are commercially available. It is readily available, and it is thereby also possible to obtain so-called soap-free emulsion compositions. Furthermore, protective colloids often used in emulsion polymerization can also be used. Examples of protective colloids include water-soluble polymeric substances such as polyvinyl alcohol and hydroxyethyl cellulose. When these protective colloids are used in emulsion polymerization, their adhesion to the skin decreases, so when used, the amount should be 5 parts by weight or less, preferably 2 parts by weight or less, based on 100 parts by weight of the total monomer. Should.

In addition, in obtaining a core/shell type resin emulsion, an emulsifier is always used during the production of the emulsion polymer emulsion that serves as the seed particles, but in the subsequent polymerization, it is not necessary to add it even if it is newly added. However, it is usually preferable not to add it. The amount of emulsifier used is not particularly limited, but is usually 0.1 to 10 parts by weight per 100 parts by weight of the total monomer.

In addition, as a catalyst, any catalyst commonly used in emulsion polymerization may be used; representative examples include various water-soluble inorganic catalysts such as hydrogen peroxide and ammonium persulfate. oxides or persulfates; various effective peroxides such as cumene hydroperoxide and benzoyl peroxide; or azo compounds such as azobisisobutyronitrile;
It is used as a seed or a mixture of two or more types.

The amount used may be about 0.1 to 2% based on the total weight of the monomers.

Of course, it is also possible to use a method generally known as redox polymerization, which uses these catalysts together with metal ions and reducing agents.

Furthermore, the various monomers described above may be added all at once, in portions, or continuously by dropwise addition.
In the presence of the above-mentioned catalyst, 0 to 100°C1Practically,
Polymerization is carried out at temperatures ranging from 30 to 90°C.

The resin particles in the ultraviolet absorber copolymerized resin emulsion obtained by the method of the present invention are resins with a glass transition temperature (calculated value) of 40°C or higher, preferably 50°C or higher, and have UV absorption in the polymerized resin matrix. These are so-called non-film-forming resin particles, which have a copolymerized agent and do not have film-forming ability at room temperature. Also,
This may or may not have small pores (microvoids) inside. Such non-film-forming resin particles are usually 0.05 to 5. Own, preferably 0.1-1.
If the particles have a diameter within the range of 0 μm and have small pores inside, the small pores (microvoids) are usually
0.01-1.0μm, preferably 0.02-0.5μm
It has a diameter within the range m. The small pores may be hollow or may contain water, and if water is present, the water will be volatilized during drying.

The solid content concentration of the ultraviolet absorber copolymerized non-film-forming resin emulsion obtained by the method of the present invention is not particularly limited, but is generally 5 to 70% by weight, preferably 20 to 6% by weight.
A range of 0% by weight is appropriate.

In addition, it can be easily confirmed whether the resin particles of the ultraviolet absorption side copolymerizable non-film-forming resin maulsion have small pores. For example, such pores can be seen in their own transmission and scanning electron microscopy observations. In addition, it is also possible to measure the specific gravity of the emulsion.

According to the present invention, the ultraviolet absorber copolymerized non-film-forming resin emulsion described above can be powdered by drying. Such powdering can be carried out by any commonly used emulsion powdering method, such as spray drying at a temperature of 135 to 155°C, or 50 to 70°C.
This can be carried out by tray drying in a hot air atmosphere or fluidized bed drying at a temperature of . The solid content concentration of the maelsion before drying is preferably about 20 to 60% by weight.

The primary particle diameter of the UV-absorbing side copolymerizable non-film-forming resin powder thus obtained is approximately the same as the particle diameter of the emulsion used. Such powder can be redispersed in water by adding various dispersants such as emulsifiers and protective colloids, if necessary.

Furthermore, in order to increase the safety of the resin emulsion obtained by the method of the present invention in practical use, low-boiling components including unreacted monomers may be distilled off by distillation under reduced pressure or steam distillation. It is also possible to extract with supercritical gas.

In addition, if necessary, dry powdered non-film-forming resin fine powder may be treated with a poorly soluble solvent for the particles and an easily soluble solvent for low boiling point components including unreacted additives. For example 1. A method of washing with a non-polar solvent such as hexane or cyclohexane and then re-drying is also a very effective means for increasing safety.

The thus obtained ultraviolet absorber copolymerizable non-film-forming resin into which a reactive ultraviolet absorber typified by an ultraviolet absorbing vinyl monomer has been introduced can be stored in an emulsion state or in a powder state. It can be used as is or incorporated into cosmetics, which are the objects of the present invention.

At that time, the content or blending amount based on the resin powder is the total weight of the prescription ingredients in the cosmetic of the present invention,
That is, based on the weight of the so-called resin composition,
Usually within the range of 1 to 90% by weight, preferably 5% by weight.
A range of 60% by weight is suitable.

If it is less than 1% by weight, the ability to absorb and block ultraviolet rays will inevitably decrease;
If it exceeds 0% by weight, the cosmetic will inevitably have a powdery feel, which in either case tends to be undesirable in terms of use.

The cosmetic composition of the present invention is prepared by a conventional method using, for example, the ultraviolet absorber copolymerizable non-film-forming resin obtained by the method of the present invention as described above together with ordinary raw materials for cosmetic compositions. be able to.

Accordingly, the cosmetic composition of the present invention may contain oily components, moisturizing agents, surfactants, extender pigments, fragrances, preservatives, water-soluble polymeric substances, and the like, if necessary.

The cosmetics of the present invention include, for example, sunscreen lotions, sunscreen creams, sunoils, suncut pressed powders, sun protection lipsticks,
Alternatively, it is useful as a sun cut cake foundation.

[Effects of the Invention] The ultraviolet absorber copolymerized non-film-forming resin emulsion and its powder obtained by the method of the present invention can be applied to the skin by variously changing the reactive ultraviolet absorber to be copolymerized. Not only does it protect the skin by absorbing harmful UV-A and UV-B UV rays, but by copolymerizing the UV absorber into the resin, it can prevent skin irritation from the UV absorber itself. It has great advantages in that it protects against temporary skin irritation caused by UV absorbers that absorb light energy, is highly safe, and improves the stability of UV absorbers, especially storage stability. It has the following.

Furthermore, the resin emulsion and its powder obtained by the method of the present invention are close to a monodisperse system, have small and uniform particle diameters, have excellent adhesion to the skin, and have excellent ultraviolet absorption and shielding effects. Use on skin to increase irritation. In addition, when the resin particles obtained by the method of the present invention have a hollow structure with small pores inside, visible light etc. is diffusely reflected within the hollow structure.
It has an appropriate concealing power, can correct skin color appropriately, and is elastic.

On the other hand, since the cosmetic of the present invention contains such an ultraviolet absorber copolymerized non-film-forming resin emulsion or its resin powder, it does not contain UV-A that has a harmful effect on the skin. It protects the skin by absorbing ultraviolet rays in the UV and UVB ranges, preventing melasma, freckles, skin aging, degeneration of skin elastic fibers, and induction of photosensitivity. can do.

In addition, since resin emulsions obtained by copolymerizing ultraviolet absorbers into resins and their I fat powders are used, skin irritation due to ultraviolet absorption itself and ultraviolet absorbers that have absorbed light energy may occur. It protects against temporary skin irritation caused by the skin, and is also highly safe.

〔Example〕

Next, the present invention will be specifically explained using Examples and Comparative Examples. In the following, all parts and percentages are based on weight unless otherwise specified.

All polymerization reactions were carried out in an atmosphere of an inert gas such as nitrogen gas, and the absorption and shielding effects of ultraviolet rays were evaluated using SPF (Sun Protection Factor).
It was evaluated using the value ``Factor)''.

Here, the SPF value refers to the amount of water on the backs of the three panelists.
The ratio of the minimum erythema-forming energy Ea when a cosmetic sample of 2 cm per 1 cJ is uniformly applied to the minimum erythema-forming energy Ec when the sample is not applied at all, SPF value = E a / E The SPF value was measured using a clothing ultraviolet irradiation device called "rM-DM l type" manufactured by Toshiba Apparel Co., Ltd., and "Toshiba FL-20SE-30" [
Toshiba tube equipment ■ product] Connect 5 lamps, 1
This was done by irradiating from a distance of 5 cm, and the irradiation energy was measured using rUVR-305/365J C
The measurements were carried out using an ultraviolet intensity meter manufactured by Toshiba Optical Machinery.

The definition of this SRF value is r FederalR
egister”43, (166), PP, 3
8206-38269 (1978).

For each cosmetic shown in each Example and Comparative Example, evaluations were made of the adhesion on the skin, spreadability, coverage, durability of cosmetic effect, and natural finish characteristics. , which was examined by three professional inspectors.

Each effect characteristic was expressed as the average score of the following evaluation points.

“Very good” −・・−・−・・−・−−−−−−5 points “Good” −・・−−−−−・−・・−・−4 points “Excellent
Through J－－－－－－－・・・－・－・－・・－3 points
-・・−・−・−2 points “Very bad” −・−・−・−・−1 point Example 1 (
Example of Preparation of Ultraviolet Absorber Copolymerization Type Non-Film-Forming Resin Emulsion) In a reaction vessel equipped with a stirrer, reflux condenser, dropping funnel, and thermometer, 140 parts of water, [Emulgen 950J (
1.5 parts of emulsifier manufactured by Kao ■ and [Levenol W
1.5 parts of ZJ (same as above) (all calculated in terms of solid content) were added and stirred well.

Next, the reactor was kept at 70°C and the reactive ultraviolet absorber p
-A mixture of 20 parts of vinyl N,N-dimethylaminobenzoate, 50 parts of methyl methacrylate, 25.8 parts of styrene, 15 parts of hydroxybutyl vinyl ether, 2 parts of methacrylic acid, and 3 parts of divinylbenzene, and 0.40 parts of potassium persulfate. and 13 parts water.
The mixture was injected over a period of time to react, and was further aged for 45 minutes. Thereafter, it was cooled and a 25% ammonia aqueous solution was added to adjust the pn.

The obtained emulsion had a solid content concentration of 42% and a viscosity of 1
5 cps (value of BM type rotational viscometer, rotor No. 1, rotation speed 60 rpm I11, temperature 25°C; the same applies hereinafter) PI (
6,5, the average particle diameter measured with a submicron particle analyzer (Coulter N-4) was 0.3 μm. This emulsion is designated as A-1.

Examples 2 to 4 (same as above) A resin emulsion was prepared in exactly the same manner as in Example 1, except that the reactive ultraviolet absorbers used and the radically polymerizable monomers copolymerized with them were shown in Table 1. Obtained. These emulsions are designated as A-2 to A-4, and their properties are shown in Table 1.

Example 5 [Preparation example of ultraviolet absorber copolymerizable non-film-forming resin emulsion having small pores inside] In a reaction vessel similar to A-1 above, 150 parts of water and "Emulgen 931J" were added.
0.5 part of Emulsifier (manufactured by Kao ■) and 1.0 part of "Hitenol N-08" manufactured by Daiichi Kogyo Seiyaku ■ were added and stirred well.Then, the internal temperature of the reaction vessel was lowered. A mixture of a reactive ultraviolet absorber and a radically polymerizable monomer to be copolymerized with them in the numbers shown in Table 1, 0.15 parts of ammonium persulfate, and 10 parts of water was maintained at 70°C. were injected for 1 hour each to react.
The mixture was further aged for 1 hour (first stage reaction completed). Thereafter, while maintaining the internal temperature at 70°C, a mixture of the monomer mixture shown in Table 1, 0.25 parts of ammonium persulfate, and 15 parts of water was injected over a period of 2 hours. The reaction was then carried out for 45 minutes (second stage reaction completed).
.

After that, cool it down, add 25% ammonia aqueous solution, and p
H was adjusted. This emulsion was designated as A-5, and its properties are shown in Table 1.

Example 6 (same as above) A resin emulsion was obtained in exactly the same manner as in Example 5, except that the reactive ultraviolet absorbers used and the radically polymerizable monomers copolymerized with them were shown in Table 1. Ta. This emulsion was designated as A-6, and its properties are shown in Table 1.

Examples 7 to 10 Resin emulsions were obtained in exactly the same manner as in Example 1, except that the reactive ultraviolet absorbers used and the radically polymerizable monomers copolymerized with these were shown in Table 1. . These emulsions were designated as A-7 to A-10, and their properties are shown in Table 1.

Comparative Example 1 Except that the reactive ultraviolet absorber used in Example 1, PN, vinyl N-dimethylaminobenzoate, was replaced with octyl P-N,N-dimethylaminobenzoate as the ultraviolet absorber. A resin emulsion was obtained in exactly the same manner as in Example 1. This emulsion is A'-
1, and its properties are shown in Table 1.

Comparative Example 2 Completely the same as Example 2 except that the same amount of p-methoxycinnamic acid was used as the ultraviolet absorber instead of vinyl p-methoxycinnamic acid, the reactive ultraviolet absorber used in Example 2. A resin emulsion was obtained in the same manner. This emulsion was designated as A'-2, and its properties are shown in Table 1.

Comparative Example 3 A resin emulsion was obtained in the same manner as in Example 2 without using vinyl p-methoxycinnamate as a reactive ultraviolet absorber. 102.8 parts of this resin emulsion were cold blended with 20 parts of P-methoxycinnamic acid dissolved in 50 m2 of tetrahydrofuran. This emulsion was designated as A'-3, and its properties are shown in Table 1.

Comparative Examples 4 to 6 Resin emulsions were obtained according to Examples 4 to 6, except that those shown in Table 1 were used as ultraviolet absorbers. This emulsion was prepared as A'-4 to A'-6 (!:), and its properties are shown in Table 1.

/ Note l) Composition of ultraviolet absorber and copolymerizable monomer p-MC
V...p-methoxyvinyl cinnamate p-DABV...
p-N,N-vinyl dimethylaminobenzoate p-MCA...p-methoxycinnamic acid p-0AOB...p-N,N-octyl dimethylaminobenzoate DBMV...1-(2-vinyloxy carbonyl) phenyl-3-(4'-methoxy) phenyl-1,3-propanedione IPV...4-(3,4-dimethoxybenzylidene)
2.5-Dioxo-1-imidazolidine propionate vinyl phylum A...Methyl methacrylate, St...Styrene, HBVE...Hydroxybutyl vinyl ether, MA
8...methacrylic acid, DVB...divinylbenzene, BA...n-butyl acrylate, CHVE...cyclohexyl vinyl ether, EGD
M...Ethylene glycol dimethacrylate, IBVE...Isobutyl vinyl ether, IBMA.
... Isobutyl methacrylate 2) Contact angle DI = Contact angle of first-stage copolymer polymer Contact angle of water droplets on solid surface D2 ... Contact angle of second-stage copolymer polymer of water droplets on solid surface Contact angle 3) D, -D,: Difference in the contact angle of a water droplet on the polymer solid surface between the second stage copolymer polymer and the first stage copolymer polymer Catalytic angle of water droplet: Polymer solid surface The contact angle θ of the water droplet was measured using an ermagoniometer type contact angle measuring device based on the following vector.

Contact angle θ and vector of each energy component per unit area T- = Surface tension of water Ts: Surface free energy of solid Ts-: Interfacial free energy between solid surface and water 4) Particle size: Scanning electron microscope Measured from the photo.

5) Small pore (microvoid) diameter: The emulsion was frozen in liquid nitrogen, and the maximum diameter of the small pores was determined from a scanning electron micrograph of the fractured surface and was expressed using this value.

From Table 1, in Examples 1 to 10 of the present invention, non-film-forming resin emulsions copolymerized with a reactive ultraviolet absorber were able to be produced. The particle diameter was 0.1 to 0.6 μm, showing monodispersity with uniform particle diameter.

On the other hand, in Comparative Examples 1 to 2 and 4 to 6, a non-reactive ultraviolet absorber was encapsulated, but it was difficult to completely encapsulate the ultraviolet absorber.

Furthermore, simply blending a non-reactive ultraviolet absorber as in Comparative Example 3 does not allow encapsulation, which is undesirable as lumps and lumps occur.

Examples 11 to 16 [Method for powderizing non-film-forming emulsions] 5. of each emulsion A-1 to A-6 prepared in the above examples. After distilling off low boiling point components under reduced pressure from O40 to 160 mmHg and 60 to 80''C, the inlet temperature was reduced to 150 to 200℃ using a spray dryer (Mobil Minor model for small research and development, manufactured by Ashizawa Niro Atomizer ■). A resin powder was prepared in about 3 hours under conditions of a dropping rate of 2.01/hr.

Comparative Examples 7 to 12 Resin powders were prepared from the emulsions A'-1 to A'6 synthesized in Comparative Examples 1 to 6 in the same manner as in Examples 11 to 16.

Table 2 compares the characteristics of each resin powder obtained in Examples and Comparative Examples and the characteristics when applied to the skin.

Example 17 (Example of preparation of cosmetics - example of sunscreen lotion) A. Prescription ■ Ultraviolet absorber copolymerized non-film forming 21 parts resin emulsion (A-1) ■ Ethanol 0.5 part ■
Liquid paraffin 5.0 parts■ Methyl paraoxybenzoate 0.1 part■ Diisopropaturamine 0.4 parts■ Pure water
61.6 parts ■ Carboxyl vinyl polymer 0.4 parts ■ Edetate disodium 0.1 parts [Phase] Glycerin
5.5 parts B, Preparation method The above ingredients ~ [phase] are uniformly dispersed and dissolved (
Solution l). On the other hand, the above-mentioned components (1) to (2) are uniformly dispersed and dissolved (dissolution 2). Next, Solution 2 was added to this Solution 1 while stirring it with a homomixer, and component (2) was then uniformly dispersed to obtain the desired sunscreen lotion.

The sunscreen lotion thus obtained is a white emulsion, and has excellent spreadability to the skin (average score = 5.0 points), coverage (average score = 4.8 points), and adhesion (average score = 5.0 points). 5.0 points), and the ultraviolet absorption/shielding effect (SPF value) was 4, confirming that this effect is sustained. Moreover,
The finish after application was also good (same as above = 5 points) and smooth.

Example 18 (same as above) Except that 10.03 parts of resin emulsion (A-5) was used instead of resin emulsion (A-1), and the amount of pure water used was changed to 72.57 parts. A desired sunscreen lotion was obtained in the same manner as in Example 7.

Similar to Example 7, this had excellent efficacy characteristics.

Examples 19 to 21 and Comparative Examples 13 and 14 (same as above - example of "Suncut Pressed Powder") Suncut pressed powders were prepared separately according to the formulations shown in Table 3.

First, A was mixed with a Henschel mixer, and then pulverized with an atomizer. While stirring this with a Henschel mixer, B was added thereto and mixed for 10 minutes. The resulting mixture was made homogeneous using a blower sifter and filled into a mold container.
A suncut pressed powder was obtained by stamping. Their properties are shown in Table 4.

As is clear from this, the cosmetics of the present invention have excellent adhesion, spreadability, and coverage on the skin, and therefore have excellent ultraviolet absorption and shielding effects (SPF value), long-lasting cosmetic effects, and natural appearance. The finish quality is further improved.

/・F Example 22 and Comparative Examples 15 and 16 (same as above - examples of sunscreen creams) According to the formulation shown in Table 5, the ultraviolet absorber p-
A sunscreen cream of the present invention was prepared using the resin powder (B2) copolymerized with MCV, and this was designated as Example 22.

For comparison purposes, an ultraviolet absorber: P-MCA was blended as it was, and this was designated as Comparative Example 15.
Example 2 of the invention described in Publication No.-120514
20 parts of p-MCA to 100 parts of resin
Spherical porous resin powder (average particle size =
Comparative Example 16 was prepared by blending a sample with a diameter of 5 μm (having no hollow portion).

As polymerizable monomers, MMA and EGDM were used,
In addition to using cumene peroxide (cumene hydroperoxide) as a polymerization initiator, toluene was used as a solvent, and an anionic emulsifier was used.
A spherical porous resin powder was prepared according to Example 2 of the invention described in JP-A-120514.

/ / / / / / / Each of the above-mentioned components ① to ② is uniformly dissolved at 80°C (dissolution 1). On the other hand, the above-mentioned components (1) to (2) are uniformly dissolved at 80°C (solution 2).

Next, add this solution 1 to a homomixer while stirring.
Add Solution 2, then add each of the above components [phase] ~■
After mixing with Henschel mixer, at 60℃,
The respective powders (component ①) and the above-mentioned component [phase] were added and uniformly dispersed, and the mixture was cooled to 30°C to obtain respective sunscreen creams.

Table 6 summarizes the characteristics of each cream.
Shown below.

From these results, the cosmetic sunscreen cream of the present invention has superior ultraviolet absorption and shielding effects, as well as better spreadability, coverage, and adhesion to the skin, compared to the comparative sunscreen cream. It was confirmed that

Furthermore, the finish after application was smooth and the makeup effect was long lasting.

/ 2' / Example 23 (same as above - example of "Sun Protect Lipstick") A. Prescription ■ Carnauba wax ■ Cambrella wax ■ Solid paraffin ■ Lanolin ■ Castor oil 2 parts 5 parts 10 parts 25 parts 21.58 parts ■ Ultraviolet absorber copolymer type hollow 23 parts Resin powder (B-6) ■ Red No. 204 3 parts ■ Red No. 223 0.4 parts [Phase] Orange No. 201 0.02 parts B, Preparation method The above ingredients ■ ~ ■ After melting at 80℃, the components
phase] and mix evenly. Next, after kneading with a roller, the mixture was poured into a mold and molded to obtain the desired sun protection lipstick.

This product has an ultraviolet absorption/shielding effect (SPF value) of 6.
”, extensibility (4, 6 points) and coverage (4, 6 points) for the lips.
It was found that the product had good adhesion (4 and 9 points), did not turn white like regular sun protection lipsticks, and had good finish and durability.

In particular, the lips do not have melanin pigment, so they must be protected from strong ultraviolet rays. Therefore, the present invention is very useful.

Example 24 (Same as above - example of "sun oil") A. Prescription ■ Liquid paraffin 74 parts ■ Jojoba oil 6 parts ■ Dextrin fatty acid ester 4 parts ■ Ultraviolet absorption side copolymerization type 8 parts Resin powder (B-1 ) ■ Ultraviolet absorber copolymerized hollow 8-part resin powder (B-6) B. Preparation method Each of the above components ■ to ■ is dissolved at about 80°C.
Cool to 0°C. Next, components (1) and (2) were uniformly dispersed therein to obtain the desired sun oil.

This product has an SPF value of IO, has good skin coverage (4.7 points) and adhesion (5.0 points), and has a long lasting makeup effect (4.9 points). was also good.

Claims (1)

[Claims] 1. A radically polymerizable monomer having a polymerizable unsaturated bond, the following general formula [I] to [III] or [V] to [
VIII] or at least one reactive ultraviolet absorber represented by formula [IV] is added and emulsion copolymerized. ▲There are mathematical formulas, chemical formulas, tables, etc.▼... [I] [However, Q_1 in the formula is -CH=CH_2, -C(CH
_3)=CH_2, or an alkyl group having 1 to 20 carbon atoms, and R_1 is -H, -OCH_3, or -
CH=CH_2, and Q_1 is 1 to 2.
Only when it is an alkyl group having 0 carbon atoms, R
It is assumed that _1 takes -CH=CH_2. ] ▲There are mathematical formulas, chemical formulas, tables, etc.▼... [II] [However, Q_1 in the formula is as described above, and R_2 is -NH_2, -N(CH_3)_2, -N
H (-CH=CH_2), or -N(C_3H_6O
H)_2 shall be represented, but only when Q_1 is an alkyl group having 1 to 20 carbon atoms, R_2 shall be -NH (-CH=CH_2). ▲There are mathematical formulas, chemical formulas, tables, etc.▼... [III] [However, Q_1 in the formula shall be as described above, and R_3 shall represent -H or -CH=CH_2. , Q_1 is an alkyl group having 1 to 20 carbon atoms, R_3 is -CH=CH_2. ] ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[IV] ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[V] [However, R_4 in the formula is -COOCH=CH_2 or -CH=CH_2 , and R_5 and R_6 may be the same or different, -H, -
CH_3, -CH(CH_3)_2, -C(CH_3)
_4 or -OCH_3. ] ▲There are mathematical formulas, chemical formulas, tables, etc.▼... [IV] [However, R_7 in the formula represents -COOCH=CH_2 or -CH=CH_2, and R_8 and R_9 may each be the same, even if they are the same. May be different, -H, -
Let it represent CH_3 or -CH=CH_2. ] ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[VII] [However, R_1_0 in the formula represents -COOCH=CH_2 or -CH=CH_2, and R_1_1 represents -H, -
CH_3, -CH(CH_3)_2, -C(CH_3)
_3 or -OCH_3. or ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[VIII] [However, R_1_2 and R_1_3 in the formula are respectively -H, -CH=CH_2, an alkyl group having 1 to 20 carbon atoms, or a carbon an alkoxyl group having a number of 1 to 20, and R_1_4 and R_1_5 are each
-H, -CH=CH_2, an alkyl group having 1 to 20 carbon atoms, -COOQ_1, -CH_2COOQ_1, or -CH_2CH_2COOQ_1 (provided that Q_1 is as described above). However, R_1_2, R_1_3, R_1_4, R_1_4
Or, at least one of Q_1 must necessarily contain an ethylenically unsaturated double bond. 2. Emulsion polymerization of radically polymerizable monomers (first stage reaction)
Then, in the presence of the emulsified polymer emulsion thus obtained, a radical polymer monomer capable of forming a polymer having a water contact angle 5 to 110° C. higher than that of the polymer of the emulsion is added and emulsified. During polymerization (second stage reaction),
In each of the radically polymerizable monomers in the first stage reaction and/or second stage reaction, the following general formula [I
] ~ [III] or [V] ~ [VIII] or formula [IV]
A method for producing an ultraviolet absorber copolymerizable non-film-forming resin emulsion having small pores inside the emulsion, the method comprising adding at least one reactive ultraviolet absorber represented by the following formula and carrying out emulsion copolymerization. ▲There are mathematical formulas, chemical formulas, tables, etc.▼... [I] [However, Q_1 in the formula is -CH=CH_2, -C(CH
_3)=CH_2, or an alkyl group having 1 to 20 carbon atoms, and R_1 is -H, -OCH_3, or -
CH=CH_2, and Q_1 is 1 to 2.
Only when it is an alkyl group having 0 carbon atoms, R
It is assumed that _1 takes -CH=CH_2. ] ▲There are mathematical formulas, chemical formulas, tables, etc.▼... [II] [However, Q_1 in the formula is as described above, and R_2 is -NH_2, -N(CH_3)_2, -N
H (-CH=CH_2), or -N(C_3H_6O
H)_2 shall be represented, but only when Q_1 is an alkyl group having 1 to 20 carbon atoms, R_2 shall be -NH (-CH=CH_2). ]▲There are mathematical formulas, chemical formulas, tables, etc.▼... [III] [However, Q_1 in the formula shall be as described above, and R_3 shall represent -H or -CH=CH_2 However, only when Q_1 is an alkyl group having 1 to 20 carbon atoms, R_3 is -CH=CH_2. ] ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[IV] ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[V] [However, R_4 in the formula is -COOCH=CH_2 or -CH=CH_2 , and R_5 and R_6 may be the same or different, -H, -
CH_3, -CH(CH_3)_2, -C(CH_3)
_3 or -OCH_3. ] ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[VI] [However, R_7 in the formula represents -COOCH=CH_2 or -CH=CH_2, and R_8 and R_9 may each be the same, even if they are the same. May be different, -H, -
Let it represent CH_3 or -CH=CH_2. ] ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[VII] [However, R_1_0 in the formula represents -COOCH=CH_2 or -CH=CH_2, and R_1_1 represents -H, -
CH_3, -CH(CH_3)_2, -C(CH_3)
_3 or -OCH_3. ] or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼... [VIII] [However, R_1_2 and R_1_3 in the formula are respectively -H, -CH=CH_2, an alkyl group having 1 to 20 carbon atoms, or R_1_4 and R_1_5 each represent an alkoxyl group having 1 to 20 carbon atoms;
-H, -CH=CH_2, an alkyl group having 1 to 20 carbon atoms, -COOQ_1, -CH_2COOQ_1, or -CH_2CH_2COOQ_1 (provided that Q_1 is as described above). However, R_1_2, R_1_3, R_1_4, R_1_4
Or, at least one of Q_1 must necessarily contain an ethylenically unsaturated double bond. 3. The method according to claim 1 or 2, wherein the reactive ultraviolet absorber has a vinyl group. 4. The low-boiling components contained in the ultraviolet absorber copolymerized non-film-forming resin emulsion obtained by the production method according to claim 1 or 2 are distilled off under reduced pressure or by steam distillation. A method for purifying the resin emulsion, characterized by: 5. Powder of the resin emulsion, which is characterized in that the ultraviolet absorber copolymerized non-film-forming resin emulsion obtained by the production method according to claim 1 or 2 is purified, if necessary, and then powdered. cation law. 6. A cosmetic containing at least one type of ultraviolet absorber copolymerizable non-film-forming resin obtained by the production method according to claim 1, 2 or 5.