WO2013031825A1

WO2013031825A1 - Uv-shielding gel composition, method for producing same, and cosmetic material

Info

Publication number: WO2013031825A1
Application number: PCT/JP2012/071826
Authority: WO
Inventors: 千明片山; 浩和松下; 真吾細田
Original assignee: 住友大阪セメント株式会社
Priority date: 2011-08-30
Filing date: 2012-08-29
Publication date: 2013-03-07
Also published as: JP2013049641A; JP5708377B2

Abstract

The present invention provides a UV-shielding gel composition, a method for producing same, and a cosmetic material, whereby resin particles having a UV-shielding function can be applied not only to water-in-oil (W/O) and oil-in-water (O/W) cosmetic materials, but also to water-based cosmetic materials, and furthermore whereby quality can be stabilized over a long period of time. This UV-shielding gel composition contains 0.01-5 mass% of a polyacrylic acid polymer, 30-80 mass% of water, 0.1-5 mass% of an emulsion silicone, 1-50 mass% of UV-shielding-agent-containing resin particles, and 1-40 mass% of alcohol.

Description

UV shielding gel composition, method for producing the same, and cosmetics

The present invention relates to an ultraviolet shielding gel-like composition, a method for producing the same, and a cosmetic. More specifically, the present invention relates to various cosmetics such as skin care cosmetics, makeup cosmetics, and body care cosmetics, in particular, whitening of skin care cosmetics that require UV shielding ability, base makeup for makeup cosmetics, and sun of body care cosmetics. The present invention relates to an ultraviolet shielding gel-like composition suitable for use in a screen, a method for producing the same, and a cosmetic containing the ultraviolet shielding gel-like composition.
This application claims priority based on Japanese Patent Application No. 2011-187531 filed in Japan on August 30, 2011, the contents of which are incorporated herein by reference.

Polyacrylic acid polymers are widely used as gel cosmetics because they do not have a sticky feeling and can provide a refreshing feeling, freshness, refreshing feeling and the like.
Conventionally, in order to impart an ultraviolet shielding function to cosmetics using such gel cosmetics, organic ultraviolet absorbers and inorganic ultraviolet shielding agents have been used, and are properly used depending on the application.
Since these inorganic ultraviolet shielding agents and organic ultraviolet absorbers have different wavelengths of ultraviolet rays that can be shielded according to their types, it is preferable to prescribe cosmetics by appropriately combining them.

By the way, since the organic ultraviolet absorber is insoluble in water, it is necessary to dissolve it in a specific solvent in order to exert its ultraviolet absorption effect, and there is a problem that the degree of freedom of cosmetic formulation is lowered. It was.
Among inorganic ultraviolet shielding agents, in particular, zinc oxide, which is added to the sunscreen and exhibits its effect, has the property of being dissolved in water in a small amount because it is an amphoteric oxide. Therefore, the inorganic UV screening agent is sometimes used as a deodorant or astringent that absorbs the body odor component due to the action of the eluted zinc ions, and at the same time, the oil agent in which the eluted zinc ions are other components of cosmetics. There is a risk of reacting with a fragrance, a colorant, an organic ultraviolet absorber, a water-soluble polymer, etc. to change the viscosity, generate a strange odor, or induce discoloration, coloring or gelation. For this reason, the content of water in the cosmetic cannot be increased, and therefore there is a problem that the degree of freedom of formulation as a cosmetic is reduced.

In addition, when an inorganic ultraviolet shielding agent and an organic ultraviolet absorber are used in combination, the organic ultraviolet absorber is recrystallized due to the influence of metal ions, causing deterioration of the cosmetics, discoloration, a decrease in feeling of use, etc. However, there is a problem that cosmetics cannot be formulated by freely mixing inorganic ultraviolet shielding agents and organic ultraviolet absorbers.

Therefore, in order to solve the above problems, a spherical resin powder having an ultraviolet shielding function containing 1 to 80% by mass of an inorganic ultraviolet shielding agent out of the total weight and having a particle size of 30 μm or less (Patent Document 1) In addition, a resin powder (Patent Document 2) obtained by dispersing a metal oxide having an ultraviolet shielding function in a resin monomer and performing suspension polymerization or emulsion polymerization has been proposed. These formulate cosmetics that can prevent inorganic UV shielding agents from coming into direct contact with organic UV absorbers and other ingredients of cosmetics by including inorganic UV shielding agents in the resin powder. can do.
In addition, cosmetics that do not need to be dissolved in a specific solvent have been proposed by using organic ultraviolet absorbers as microcapsules (Patent Document 3).

Japanese Patent No. 3469641 Japanese Patent No. 3205249 Japanese Patent Application Laid-Open No. 07-267841

However, when trying to apply conventional resin particles and microcapsules to gel cosmetics, foaming is severe when mixing the components of gel cosmetics such as polyacrylic acid polymer and resin particles, microcapsules, etc. It was not possible to mix well. Therefore, there has been a problem that a gel-like cosmetic material having a high ultraviolet-shielding ability cannot be obtained because a UV-shielding agent cannot be sufficiently added to the gel-like cosmetic material.
Further, when forcibly mixed, there is a problem that the obtained cosmetics are liable to deteriorate in quality and cannot be stabilized over a long period of time.

This invention is made | formed in view of the said situation, Comprising: The resin particle which has an ultraviolet-ray shielding function is used for the water-in-oil type (W / O type) and oil-in-water type (O / W type) cosmetics. Of course, it is possible to provide an ultraviolet shielding gel-like composition that can be applied to water-based cosmetics and can stabilize the quality over a long period of time, a method for producing the same, and a cosmetic. Objective.

As a result of intensive studies in order to solve the above problems, the present inventors, as a result, include ultraviolet ray shielding agent-containing resin particles including organic ultraviolet absorbers and metal oxide particles having ultraviolet ray shielding ability, and a polyacrylic acid polymer. When mixing, by adding emulsion type silicone and alcohol, it was found that foaming at the time of mixing was suppressed, and an ultraviolet shielding gel-like composition having good usability and excellent quality stability was obtained. It came to be completed.

That is, the ultraviolet shielding gel-like composition of the present invention has a polyacrylic acid polymer of 0.01% by mass to 5% by mass, water of 30% by mass to 80% by mass, and an emulsion type silicone of 0.1% by mass. % Or more and 5% by mass or less, 1% by mass or more and 50% by mass or less of ultraviolet shielding agent-containing resin particles, and 1% by mass or more and 40% by mass or less of alcohol.

Furthermore, it is preferable to contain 0.01% by mass or more and 5% by mass or less of a water-soluble polymer other than the polyacrylic acid polymer.
The emulsion type silicone is 10 mass% or more and 50 mass% or less of silicone resin, 0.5 mass% or more and 5 mass% or less of sorbitan fatty acid ester, and 0.5 mass% or more and 5 mass% or less of glycerin fatty acid ester. The sucrose fatty acid ester is preferably contained in an amount of 0.1% by mass to 1% by mass.

The ultraviolet shielding agent-containing resin particles contain one or both of an organic ultraviolet absorber and metal oxide particles having ultraviolet shielding ability in the resin particles, and have an average particle diameter of 0.05 μm or more and 5 μm. The metal oxide particles contain one or more selected from the group consisting of zinc oxide, titanium oxide, cerium oxide, and iron oxide, and have an average particle diameter of 0.003 μm or more and 0 0.1 μm or less of the particles, and the ultraviolet shielding agent-containing resin particles have a content of the organic ultraviolet absorber of 0.1% by mass to 80% by mass, and a content of the metal oxide particles of 1% by mass. % Or more and 80% by mass or less is preferable.
The organic ultraviolet absorber is preferably one or more selected from the group consisting of dibenzoylmethane compounds, benzophenone derivatives, paraaminobenzoic acid derivatives, methoxycinnamic acid derivatives, and salicylic acid derivatives.

The production method of the ultraviolet shielding gel composition of the present invention is such that the polyacrylic acid polymer is 0.01% by mass or more and 5% by mass or less, the water is 30% by mass or more and 80% by mass or less, and the emulsion type silicone is 0.1%. These are mixed to form a mixture such that the ultraviolet shielding agent-containing resin particles are 1% by mass to 50% by mass and the alcohol is 1% by mass to 40% by mass, Next, the hydrogen ion index of the mixture is adjusted to 6 or more and 8 or less.

The cosmetic of the present invention is characterized by containing the ultraviolet shielding gel composition of the present invention.

According to the ultraviolet shielding gel-like composition of the present invention, since the emulsion type silicone and alcohol are added to the polyacrylic acid polymer and the ultraviolet shielding agent-containing resin particles, the polyacrylic acid polymer and the ultraviolet shielding agent-containing resin particles, There is no foaming and it can be mixed well.
Therefore, it is possible to provide an ultraviolet shielding gel-like composition that has an excellent ultraviolet shielding function and a feeling of use and is excellent in quality stability.

According to the method for producing an ultraviolet shielding gel composition of the present invention, after mixing polyacrylic acid polymer, water, emulsion type silicone, ultraviolet shielding agent-containing resin particles and alcohol to obtain a mixture, the hydrogen ion index of this mixture Is adjusted to 6 or more and 8 or less, the polyacrylic acid polymer and the ultraviolet shielding agent-containing resin particles can be sufficiently mixed without foaming.
Accordingly, it is possible to easily obtain an ultraviolet shielding gel-like composition that is excellent in ultraviolet shielding function and feeling of use and excellent in quality stability.

According to the cosmetic of the present invention, since it contains the ultraviolet shielding gel-like composition of the present invention, it provides a cosmetic that is excellent in ultraviolet shielding function, transparency, and feeling of use, and excellent in quality stability and safety. be able to.

FIG. 3 is a graph showing the spectral transmittance of each ultraviolet shielding gel composition of Examples 1 to 5 of the present invention. It is a figure which shows the spectral transmission factor of the coating film formed by apply | coating the ultraviolet-ray shielding gel-like composition of Example 5 of this invention. FIG. 3 is a graph showing the spectral transmittance of each of the moisture gels of Reference Examples 1 to 3 of the present invention.

The form for implementing the ultraviolet-ray shielding gel-like composition of this invention, its manufacturing method, and cosmetics is demonstrated.
The following embodiments are specifically described for better understanding of the gist of the invention, and do not limit the present invention unless otherwise specified.

[Ultraviolet shielding gel-like composition]
The ultraviolet shielding gel-like composition of the present embodiment comprises a polyacrylic acid polymer of 0.01% by mass to 5% by mass, water of 30% by mass to 80% by mass, and an emulsion type silicone of 0.1% by mass. It is a gel composition comprising 5% by mass or less, 1% by mass to 50% by mass of resin particles containing ultraviolet shielding agent, and 1% by mass to 40% by mass of alcohol.
In this case, it is necessary to adjust the content of each component so that the total content of each component of polyacrylic acid polymer, water, emulsion-type silicone, ultraviolet shielding agent-containing resin particles, and alcohol does not exceed 100% by mass. There is.
This gel composition may contain a pH adjuster, an antioxidant, a preservative and the like as appropriate.

Next, each component of the ultraviolet shielding gel-like composition will be described in detail.
"Polyacrylic acid polymer"
The polyacrylic acid polymer has a structure represented by the following formula (1), and is not particularly limited as long as it can be used as a cosmetic.
For example, a carbomer which is a polymer of acrylic acid crosslinked with pentaerythrityl allyl ether, sucrose allyl ether or propylene allyl ether, one or more monomers consisting of acrylic acid, methacrylic acid or esters thereof and alkyl acrylate (C10 And (-30) a cross-polymer (acrylates / alkyl acrylate (C10-30)) cross-linked with an allyl ether of sucrose or an allyl ether of pentaerythritol.

The average molecular weight of this polyacrylic acid polymer is preferably 500,000 to 10 million, particularly preferably 1,000,000 to 5 million.
Here, when the average molecular weight is less than 500,000, the viscosity becomes insufficient, and a gel having a desired viscosity cannot be obtained. On the other hand, when the average molecular weight exceeds 10 million, It is not preferable because it may agglomerate and settle.
Examples of such polyacrylic acid polymers include B.I. F. Carbopol (registered trademark) series (Carbopol 934, Carbopol 940, Carbopol 950, Carbopol 980, Carbopol 951, Carbopol 981, Carbopol Ultrez10, Carbopol ETD2020, Carbopol 1382, Carbopol 1342) manufactured by Goodrich can be used.

The content of this polyacrylic acid polymer with respect to the total amount of the ultraviolet shielding gel-like composition is preferably 0.01% by mass or more and 5% by mass or less.
Here, when the content of the polyacrylic acid polymer is less than 0.01% by mass, it is not preferable because viscosity as a gel cannot be obtained. This is not preferable because there is no sticky effect and coagulation sedimentation may occur.

"water"
The content of water with respect to the total amount of the ultraviolet shielding gel-like composition is preferably 30% by mass or more and 80% by mass or less.
Here, when the water content is less than 30% by mass, it is not preferable because the refreshing feeling, freshness, refreshing feeling and the like that are characteristic of the polyacrylic acid polymer are lost. If it exceeds 80% by mass, it is difficult to formulate ingredients other than water, and the degree of freedom in formulating is reduced, which is not preferable.
The water is not particularly limited as long as it is generally used in cosmetics. Pure water, ion-exchanged water, distilled water, purified water, ultrapure water, natural water, alkaline ionized water, deep layer Any of water and the like may be used.

"Emulsion type silicone"
The emulsion type silicone is not particularly limited as long as it is obtained by emulsifying a silicone resin in an O / W type with a nonionic surfactant or the like.
As such an emulsion type silicone, for example, an emulsion type silicone in which a sorbitan fatty acid ester, a glycerin fatty acid ester and a sucrose fatty acid ester (oil-soluble gelling agent) are added and emulsified to a silicone resin can be used. .

As such an emulsion type silicone, for example, the silicone resin is 10% by mass or more and 50% by mass or less, the sorbitan fatty acid ester is 0.5% by mass or more and 5% by mass or less, and the glycerin fatty acid ester is 0.5% by mass or more. And it is preferable to contain 5 mass% or less and sucrose fatty acid ester 0.1 mass% or more and 1 mass% or less. It is preferable to produce an emulsion type silicone within the above range because stability as an emulsion is easily obtained.
Specific examples of such an emulsion type silicone include emulsion type silicone KM-72F (composition: silicone resin 30% by mass, sorbitan fatty acid ester 3% by mass, glycerin fatty acid ester 1% by mass, sucrose fatty acid ester 0.5% by mass). Water, 65.5% by mass; viscosity (25 ° C.): 1000 to 3000 mPa · s).

The content of the emulsion type silicone with respect to the total amount of the ultraviolet shielding gel-like composition is preferably 0.1% by mass or more and 5% by mass or less.
Here, if the content of the emulsion-type silicone is less than 0.1% by mass, the defoaming effect cannot be obtained, and it is not preferable. Therefore, excessive emulsion-type silicone is wasted, and the refreshing feeling, freshness, and refreshing feeling characteristic of the polyacrylic acid polymer are lost.
By adding this emulsion type silicone within the above range, the defoaming effect is exhibited, foaming due to stirring during mixing is suppressed, the dispersibility of the ultraviolet shielding agent-containing resin particles is improved, and ultraviolet shielding after gelation is achieved. The usability of the gel composition can be prevented from being impaired.

"Ultraviolet shielding agent-containing resin particles"
The ultraviolet shielding agent-containing resin particles have an average particle diameter of 0.05 μm or more, wherein the resin particles contain one or both of an organic ultraviolet absorber and metal oxide particles having ultraviolet shielding ability. Particles of 5 μm or less.
The ultraviolet shielding agent-containing resin particles are (1) ultraviolet shielding agent-containing resin particles containing an organic ultraviolet absorber (hereinafter abbreviated as organic ultraviolet absorber-containing resin particles), and (2) ultraviolet shielding ability. Ultraviolet shielding agent-containing resin particles containing metal oxide particles (hereinafter abbreviated as metal oxide particle-containing resin particles), (3) ultraviolet rays containing organic ultraviolet absorbers and metal oxide particles having ultraviolet shielding ability Any form of shielding agent-containing resin particles (hereinafter abbreviated as organic-inorganic ultraviolet absorber-containing resin particles) may be used. The ultraviolet shielding agent-containing resin particles may be in the form of ultraviolet shielding agent-containing resin particles made of a mixture containing (4) organic ultraviolet absorber-containing resin particles and metal oxide particle-containing resin particles.
Furthermore, in another embodiment, instead of the above-described ultraviolet shielding agent-containing resin particles, an organic ultraviolet absorber-containing resin containing an organic ultraviolet absorber in the resin, and the resin contains metal oxide particles. An ultraviolet shielding agent-containing resin deposit formed by adhering the resulting metal oxide particle-containing resin may be used. Such a resin deposit includes (5) a structure in which one or more organic ultraviolet absorber-containing resin particles and one or more metal oxide particle-containing resin particles are adhered to each other, and (6) organic ultraviolet absorber-containing resin particles. A structure in which one or more of the other resin particles are attached to the periphery of any one of the resin particles and the metal oxide particle-containing resin particles; Any form of a structure in which one or more resin particles are attached may be used.
Further, as another form of the ultraviolet shielding agent-containing resin deposit, (8) a core material part is formed by either one of the organic ultraviolet absorber-containing resin particles and the metal oxide particle-containing resin particles. A structure in which the material part is partially or completely covered with either one or both of the organic ultraviolet absorber-containing resin and the metal oxide particle-containing resin, (9) around the structure of (8), Further, it may be in any form of a double-coated structure that is partially or completely covered with either one or both of an organic ultraviolet absorber-containing resin and an inorganic-containing resin.
Hereinafter, each form of said ultraviolet shielding agent containing resin particle and ultraviolet shielding agent containing resin deposit | attachment is demonstrated.

(1) Organic ultraviolet absorber-containing resin particles The organic ultraviolet absorber-containing resin particles are resin particles containing an organic ultraviolet absorber in a resin.
The average particle diameter of the organic ultraviolet absorber-containing resin particles is preferably 0.05 μm or more and 5 μm or less, more preferably 0.1 μm or more and 3 μm or less, and further preferably 0.2 μm or more and 1 μm or less.
Here, when the average particle diameter of the organic ultraviolet absorber-containing resin particles is less than 0.05 μm, the resin particles tend to aggregate with each other, and therefore, the dispersibility decreases when the resin particles are dispersed in the dispersion medium. However, it is not preferable because the ultraviolet ray shielding function cannot be sufficiently exhibited. On the other hand, when the average particle diameter exceeds 5 μm, when used as a cosmetic, elongation and slippage in the skin are reduced, resulting in a feeling of roughness and the like, and the feeling of use is deteriorated. It is not preferable.
Here, the average particle diameter of the organic ultraviolet absorber-containing resin particles is 5% by mass of the organic ultraviolet absorber-containing resin particles, and 10% by mass of polyether-modified silicone (manufactured by Toray Dow Corning Co., Ltd., SH3775M). Decamethylcyclopentasiloxane (manufactured by Toray Dow Corning Co., Ltd., SH245) was dispersed with a sand mill at 2500 rpm for 3 hours, and a dynamic light scattering particle size distribution analyzer (manufactured by Horiba Ltd., LB- 550) means that the cumulative volume particle size distribution when the dispersed particle size is measured is 50% by volume (D50).
In addition, the dispersed particle diameter of D50 obtained by the above measurement method substantially matches the primary particle diameter of the resin particles when the organic ultraviolet absorbent-containing resin particles are observed with a scanning electron microscope. Therefore, the average primary particle diameter of the organic ultraviolet absorbent-containing resin particles may be measured as the average particle diameter of the organic ultraviolet absorbent-containing resin particles.

(resin)
The resin is not particularly limited as long as it is a resin monomer capable of dissolving an organic ultraviolet absorber and having a high transparency of the polymer and usable as a raw material for cosmetics.
Examples of such resin monomers include (meth) acrylic resins, acrylic esters, methacrylic esters, acrylic styrene copolymers, acrylamide copolymers, acrylic epoxy copolymers, acrylic urethane copolymers, acrylic polyester copolymers. Monomers such as a polymer, a silicon acrylic copolymer, a vinyl acetate resin, a polyamide resin, an epoxy resin, a urethane resin, a polyester resin, and a silicone resin can be used. Among these, a monomer of (meth) acrylic resin is preferable in that it is excellent in transparency.

(Meth) acrylic resin monomers include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, acrylic acid Dodecyl, lauryl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methyl α-chloroacrylate, trifluoroethyl acrylate, tetrafluoropropyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate , N-butyl methacrylate, isobutyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, lauryl methacrylate, methacrylic acid Allyl, and the like.

Resin monomers that can be polymerized in combination with this (meth) acrylic resin monomer include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, pt-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonyl Styrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, vinyl acetate, vinyl propionate, vinyl benzoate, butyric acid Vinyl, N-vinylpyrrolidone, vinylidene fluoride, tetrafluoroethylene, hex Hexafluoropropylene, butadiene, isoprene, and the like.
These resin monomers may be used by polymerizing only one kind alone or in combination of two or more kinds. For example, when a (meth) acrylic resin monomer and other resin monomers are combined, the content of the (meth) acrylic resin monomer in the resin monomer may be 10% by mass or more from the viewpoint of transparency. Preferably, it is more preferably 30% by mass or more.

(Organic UV absorber)
The organic ultraviolet absorber is not particularly limited as long as it can be dissolved in the resin monomer, and examples thereof include dibenzoylmethane compounds, benzophenone derivatives, paraaminobenzoic acid derivatives, and methoxycinnamic acid derivatives. And salicylic acid derivatives. These organic ultraviolet absorbers may be used alone or in combination of two or more.

The content of the organic ultraviolet absorber in the organic ultraviolet absorber-containing resin particles is preferably 0.1% by mass or more and 80% by mass or less, more preferably 0.5% by mass or more and 50% by mass or less, More preferably, it is 1 mass% or more and 30 mass% or less.
Here, if the content of the organic ultraviolet absorber in the organic ultraviolet absorber-containing resin particles is less than 0.1% by mass, the amount of the organic ultraviolet absorber is too small, and the ultraviolet rays that the organic ultraviolet absorber has. As a result, it becomes impossible to fully develop the shielding function, and as a result, a large amount of resin particles containing organic ultraviolet absorbers are required to fully develop the ultraviolet shielding function. Is not preferable because it becomes extremely difficult. On the other hand, when the content exceeds 80% by mass, the amount of the organic ultraviolet absorber becomes relatively high with respect to the resin, and as a result, the dispersibility of the organic ultraviolet absorber in the resin decreases, Since uniformity is impaired, it is not preferable.

If necessary, the organic ultraviolet absorber-containing resin particles may be surface-treated with 1% by mass or more and 20% by mass or less of organosiloxane based on the organic ultraviolet absorber-containing resin particles.
Examples of the organosiloxane include a dialkylalkoxysilane compound. Among them, an organopolysiloxane or an organopolysiloxane selected from the group consisting of an alkyl group, an isocyanate group, an epoxy group, an acrylic group, and an alkyl silicon compound or Modified organopolysiloxanes modified by two or more types are preferably used, and in particular, dimethylpolysiloxane (silicone oil) and modified dimethylpolysiloxane (modified silicone oil) modified from dimethylpolysiloxane (silicone oil) are preferably used. It is done.
By treating the surface of the resin particles with organosiloxane, it is possible to further suppress the elution of the organic ultraviolet absorbent, which is a component of the organic ultraviolet absorbent-containing resin particles, into a solvent such as pure water. .

(Method for producing organic ultraviolet absorbent-containing resin particles)
The method for producing the organic ultraviolet absorbent-containing resin particles includes the above-mentioned organic ultraviolet absorbent in the resin monomer, and the organic ultraviolet absorbent content is 0.1% by mass or more and 80% by mass or less. The resin monomer solution is then dissolved in an amount of 0.1% by mass to 10% by mass with respect to the total mass of the resin monomer solution, and 0%. . Suspended or emulsified in pure water containing 1% by mass or more and 10% by mass or less of a crosslinking agent to form a suspension or emulsion, and then the suspension or emulsion was added to the suspension or emulsion. Addition of 0.01% by mass or more and 1% by mass or less of a polymerization initiator with respect to the total mass of resin monomers in the liquid to perform suspension polymerization or emulsion polymerization to produce organic ultraviolet absorber-containing resin particles Is the method.

When producing small organic ultraviolet absorber-containing resin particles having an average particle size of 5 μm or less, 0.01 mass% or more of the resin monomer solution is added to the resin monomer solution. And 5 mass% or less of silicone type antifoaming agents may be added.

Here, the manufacturing method of this organic type ultraviolet absorber containing resin particle is demonstrated in detail.
First, an organic ultraviolet absorber is dissolved in a resin monomer to obtain a resin monomer solution.
In addition, in order to increase the emulsion film strength of the suspension or emulsion described later and increase the polymerization efficiency of the suspension polymerization or emulsion polymerization, it is 1% by mass or more and 50% by mass with respect to the total mass of the resin monomer solution. The following dispersants may be added.
The dispersant is recognized as a raw material for cosmetics, and preferably has a high affinity with a resin monomer and is highly hydrophobic.

Examples of such a dispersant include carboxylic acids such as sodium carboxymethyl cellulose or salts thereof, sulfonic acids such as sodium alkanesulfonate or salts thereof, sulfate esters such as polyoxyethylene nonylphenyl ether sodium sulfate or salts thereof, Examples thereof include phosphoric acid esters such as oxyethylene alkylphenyl ether phosphoric acid and polyoxyethylene alkyl ether phosphoric acid or salts thereof, and phosphonic acids such as sodium lauryl phosphate or salts thereof.

The addition amount of the dispersant is preferably 1% by mass or more and 50% by mass or less with respect to the total mass of the resin monomer solution. The reason is that when the addition amount is less than 1% by mass, the emulsion film strength of the suspension or emulsion described later does not increase, and as a result, the polymerization efficiency of suspension polymerization or emulsion polymerization decreases. If it exceeds 50% by mass, the polymerization efficiency cannot be improved even if the addition amount is increased further, and the dispersant is wasted.

The method for dissolving the organic ultraviolet absorber in the resin monomer is not particularly limited as long as the organic ultraviolet absorber is dissolved in the resin monomer, and the compatibility between the organic ultraviolet absorber and the resin monomer is taken into consideration. Thus, a mixing method may be selected as appropriate.
What is necessary is just to mix until the precipitation of solid content is not recognized when visually observing as a grade of mixing. As a mixing apparatus used for this mixing process, a magnetic stirrer, a stirrer, etc. are mentioned, for example.
As described above, a resin monomer solution in which an organic ultraviolet absorber is dissolved in a resin monomer can be obtained.

Next, the resin monomer solution is suspended or emulsified in pure water containing a suspension protective agent and a crosslinking agent.
Suspension protectants include nonionic surfactants such as polyoxyethylene alkyl ethers and polyoxyethylene alkylphenyl ethers, or anionic interfaces such as alkylbenzene sulfonates, alkyl sulfates, and alkylphenyl sulfates. An anionic surfactant is preferable among these, and an alkylbenzene sulfonate is preferable as this anionic surfactant.
The addition amount of the suspension protective agent is preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.1% by mass or more and 2% by mass or less, based on the total mass of the resin monomer solution. is there.

The crosslinking agent is not particularly limited as long as it is a monomer having two or more unsaturated double bonds, but is not limited to a polyfunctional vinyl monomer or a polyfunctional (meth) acrylic acid ester derivative. Etc. can be appropriately selected and used.
More specifically, divinylbenzene, divinylbiphenyl, divinylnaphthalene, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, (poly) tetramethylene glycol di (meth) acrylate, etc. (Poly) alkylene glycol type | system | group di (meth) acrylate is mentioned.

1,6-hexanediol di (meth) acrylate, 1,8-octanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, 2,4-diethyl-1,5-pentanediol di (meth) acrylate, butylethylpropanediol Examples include alkanediol-based di (meth) acrylates such as di (meth) acrylate, 3-methyl-1,7-octanediol di (meth) acrylate, and 2-methyl-1,8-octanediol di (meth) acrylate. .

Also, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, ethoxylated cyclohexanedi Methanol di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) acrylate, 1,1,1-trishydroxymethylethane Di (meth) acrylate, 1,1,1-trishydroxymethylethane tri (meth) acrylate, 1,1,1-trishydroxymethylpropane triacrylate, diary Phthalate and its isomers, triallyl isocyanurate and derivatives thereof may be mentioned.
Among these, (poly) ethylene glycol di (meth) acrylate is particularly preferable.

The addition amount of the crosslinking agent is preferably 0.1% by mass or more and 10% by mass or less, more preferably 1% by mass or more and 10% by mass or less, based on the total mass of the resin monomer solution.
The pure water is not particularly limited as long as it is water generally used in cosmetics, and includes ion exchange water, distilled water, purified water, ultrapure water, natural water, alkali ion water, deep water and the like. Pure water may be added so as to be 40% by mass or more and 80% by mass or less, preferably 50% by mass or more and 70% by mass or less with respect to the total amount of the suspension or emulsion.

Here, when producing resin particles of 5 μm or less, a silicone-based antifoaming agent is added to the above resin monomer solution, and this silicone-based antifoaming agent-added resin monomer solution is used as a suspension protective agent and a crosslinking agent. Is suspended or emulsified in pure water containing a suspension or emulsion having an average dispersed particle size of 0.05 μm or more and 5 μm or less.

Examples of the silicone-based antifoaming agent include an oil type, an oil compound type, a solution type, a powder type, a solid type, an emulsion type, and a self-emulsifying type. Among these, an oil compound type is preferable.
The addition amount of the silicone antifoaming agent is preferably 0.01% by mass or more and 5% by mass or less, more preferably 0.1% by mass or more and 1% by mass with respect to the total mass of the resin monomer solution. It is as follows.

By adding 0.01% by mass or more and 5% by mass or less of a silicone-based antifoaming agent to the resin monomer solution, the stirring speed of a mixer, stirrer, homomixer, homogenizer, etc. is greatly increased. As a result, the resin particles can be reduced to about 50 nm.
Therefore, it is possible to provide a cosmetic material that is superior in transparency and excellent in feeling of use with no roughness.
In addition, the stirring speed of mixers, stirrers, homomixers, homogenizers, etc. can be greatly increased, and as a result, the production efficiency and yield of organic UV absorber-containing resin particles can be improved. Cost can be greatly reduced.

Subsequently, a polymerization initiator is added to said suspension or emulsion, and suspension polymerization or emulsion polymerization is performed.
Polymerization initiators include persulfates such as potassium persulfate and ammonium persulfate, hydrogen peroxide, benzoyl peroxide, lauroyl peroxide, t-butyl hydroperoxide, benzoyl peroxide, cumene hydroperoxide, and other organic peroxides. Azo initiators such as azobisdiisobutyronitrile, 2,2-azobis (2-amidinopropane) dihydrochloride, and the like. Among these, persulfuric acid is used because polymerization can be performed quickly. Salts are preferred.
The addition amount of the polymerization initiator is preferably 0.01% by mass or more and 1% by mass or less, more preferably 0.05% by mass or more and 0.5% by mass or less with respect to the above suspension or emulsion. is there.

As a polymerization method, a suspension or emulsion to which a polymerization initiator is added is heated while stirring in a nitrogen atmosphere to a predetermined temperature, and polymerization is started at the predetermined temperature. Is preferred.
The temperature at which this polymerization is initiated is preferably 50 ° C. or higher and 80 ° C. or lower. In addition, the holding time at this temperature is preferably about 1 to 5 hours, and an appropriate time may be selected in consideration of the time when the unreacted residual monomer is minimized, the polymerization state, and the production cost.
Thereafter, the polymerization reaction is stopped by cooling with ice, water or natural cooling.

Here, when a silicone-based antifoaming agent is added to the suspension or emulsion, the content of these suspension protective agent, crosslinking agent, silicone-based antifoaming agent and polymerization initiator is within the above range. By limiting, the average particle diameter of the obtained organic ultraviolet absorber-containing resin particles can be controlled to 0.05 μm or more and 5 μm or less.

Next, in order to remove the remaining monomers, the crosslinking agent, the suspension protective agent such as a surfactant, the polymerization initiator and the like from the obtained polymerized product, washing is performed with pure water. In this washing step, in order to improve the washing efficiency, washing with alcohol or the like may be performed before washing with pure water.
The alcohol is not particularly limited as long as it is soluble in pure water and can be easily washed away. Examples thereof include ethanol, 2-propanol and the like, and 2-propanol is particularly preferable in terms of cleaning efficiency.
The washing method is not particularly limited as long as residual monomers and the like can be removed, but pressure filtration, suction filtration, filter press, centrifugation, ultrafiltration, decantation, and the like are preferable.
When washing with alcohol, the degree of washing may be such that only a small amount of alcohol remains. For example, when washing with 2-propanol, the 2-propanol densitometer does not exceed 1%. Perform to a level of 20 μS / cm or less with a rate meter.

After completion of washing, the obtained polymer is dried at 80 ° C. or higher and 100 ° C. or lower to remove alcohol or pure water.
The drying method is not particularly limited as long as it is a method capable of removing alcohol and pure water, and examples thereof include drying in atmospheric pressure and vacuum drying.

Next, the obtained dried product is crushed.
The crushing method is not particularly limited, and a pin mill, a hammer mill, a jet mill, an impeller mill, or the like can be used.
In particular, in order to obtain higher transparency when blended in a cosmetic, it is preferable to crush the obtained dried product into particles of 0.05 μm or more and 5 μm or less. By passing through this crushing step, each particle aggregated by drying can be crushed and the usability when used in a cosmetic can be improved.
As described above, the organic ultraviolet absorbent-containing resin particles can be produced.

(2) Metal Oxide Particle-Containing Resin Particles The metal oxide particle-containing resin particles are resin particles obtained by containing metal oxide particles having ultraviolet shielding ability in the resin.

The average particle size of the metal oxide particle-containing resin particles is preferably 0.05 μm or more and 5 μm or less, more preferably 0.1 μm or more and 3.0 μm or less, and further preferably 0.2 μm or more and 1.0 μm or less. is there.
Here, when the average particle size of the metal oxide particle-containing resin particles is less than 0.05 μm, the metal oxide particle-containing resin particles are likely to aggregate with each other. Therefore, when the resin particles are dispersed in a dispersion medium This is not preferable because the dispersibility is lowered and the ultraviolet ray shielding function cannot be sufficiently exhibited. On the other hand, when the average particle diameter exceeds 5 μm, when used as a cosmetic, elongation and slippage in the skin are reduced, resulting in a feeling of roughness and the like, and the feeling of use is deteriorated. It is not preferable.
Here, the average particle size of the metal oxide particle-containing resin particles is 5% by mass of the metal oxide particle-containing resin particles, polyether-modified silicone (Toray Dow Corning Co., Ltd.), like the organic ultraviolet absorber-containing resin particles. ) SH3775M) A dispersion obtained by dispersing 10% by mass of decamethylcyclopentasiloxane (manufactured by Toray Dow Corning Co., Ltd., SH245) with a sand mill at 2500 rpm for 3 hours, a dynamic light scattering particle size distribution analyzer (Horiba, Ltd.) LB-550), and the dispersed particle size is measured, and the cumulative volume particle size distribution means a particle size of 50 volume% (D50).
In addition, the dispersed particle diameter of D50 obtained by the above measurement method substantially coincides with the primary particle diameter of the resin particles when the metal oxide particle-containing resin particles are observed with a scanning electron microscope. Therefore, you may measure the average primary particle diameter of a metal oxide particle containing resin particle as an average particle diameter of a metal oxide particle containing resin particle.

In the metal oxide particle-containing resin particles, as in the case of (1) the organic ultraviolet absorber-containing resin particles described above, 1% by mass or more and 20% by mass with respect to the metal oxide particle-containing resin particles as necessary. The surface treatment may be performed with the following organosiloxane.
By treating the surface of the resin particles with organosiloxane, it is possible to further suppress the elution of the metal oxide particles that are components of the resin particles into a solvent such as pure water.

(resin)
As the resin, similar to the resin used in the above-mentioned (1) organic ultraviolet absorber-containing resin particles, the metal oxide particles can be dispersed, and the transparency of the polymer is high. Any resin monomer may be used.
Since this resin monomer has already been described in the column of (1) Resin of the organic ultraviolet absorbent-containing resin particles described above, the description thereof will be omitted.

(Metal oxide particles)
The metal oxide particles are particles having an ultraviolet shielding ability containing one or more selected from the group consisting of zinc oxide, titanium oxide, cerium oxide, and iron oxide, and the average particle diameter is 0.003 μm or more and It is preferably 0.1 μm or less, more preferably 0.01 μm or more and 0.05 μm or less, and still more preferably 0.02 μm or more and 0.04 μm or less.
Here, when the average particle diameter of the metal oxide particles is less than 0.003 μm, the degree of crystallinity is lowered and the ultraviolet shielding function is not exhibited. Since the scattering coefficient of the oxide particles with respect to visible light is increased, the transparency is remarkably lowered, and as a result, the light transmittance with respect to visible light is lowered and the transparency is deteriorated.

The metal oxide particles may be those that have been surface-treated with one or more selected from the group consisting of silica, alumina, and organosiloxane. When the metal oxide particles are surface-treated with one or more selected from the group consisting of silica, alumina and organopolysiloxane, the dispersion stability when dispersed in the monomer is improved.
Examples of the organosiloxane include a dialkylalkoxysilane compound. Among them, an organopolysiloxane or an organopolysiloxane selected from the group consisting of an alkyl group, an isocyanate group, an epoxy group, an acrylic group, and an alkyl silicon compound is used. Modified organopolysiloxanes modified with more than one species are preferably used. Particularly, dimethylpolysiloxane (silicone oil) and modified dimethylpolysiloxane (modified silicone oil) obtained by modifying this dimethylpolysiloxane (silicone oil) are preferably used. .
By treating the surface of the metal oxide particles with organosiloxane, it is possible to further suppress elution of metal ions, which are components of the metal oxide particles, into a solvent such as pure water.

The content of the metal oxide particles in the resin particles containing metal oxide particles is preferably 1% by mass or more and 80% by mass or less, more preferably 30% by mass or more and 80% by mass or less, and further preferably 50% by mass or more. And it is 80 mass% or less.
Here, if the content of the metal oxide particles in the resin particles is less than 1% by mass, the amount of the metal oxide particles is too small to fully express the ultraviolet shielding function of the metal oxide particles, Therefore, in order to sufficiently exhibit the ultraviolet shielding function, a large amount of metal oxide particle-containing resin particles are required, and material design when producing a cosmetic becomes extremely difficult. On the other hand, when the content exceeds 80% by mass, the amount of the metal oxide particles becomes too high relative to the resin, and as a result, the dispersibility of the metal oxide particles in the resin is reduced, and the composition This is not preferable because the uniformity of is impaired.

When this metal oxide particle-containing resin particle is used in a water-based cosmetic, it is preferable that the metal oxide particle is dispersed in the resin particle without being exposed on the surface of the resin particle.
That is, the metal oxide particles dispersed in the resin particles are completely embedded in the resin particles to be in an encapsulated state, and the surface of the composite particles is completely covered with the resin. It is preferred that no oxide particles are exposed.
For example, when zinc oxide fine particles are used as the metal oxide particles, since the zinc oxide fine particles are completely embedded in the resin particles and are in an encapsulated state, zinc can be prevented from being eluted into the cosmetic, The quality stability of water-based cosmetics can be increased.

On the other hand, even when this metal oxide particle-containing resin particle is used for cosmetics of W / O type, O / W type, etc., when the amount of water is small, or even if a small amount of zinc is eluted, the cosmetics In the case where the quality stability is not affected, the zinc oxide particles do not have to be completely embedded in the resin particles to be in an encapsulated state.

(Method for producing metal oxide particle-containing resin particles)
In the method for producing the resin particles containing metal oxide particles, the metal oxide particles having ultraviolet shielding ability are contained in a resin monomer containing a dispersant of 1% by mass to 50% by mass with respect to the metal oxide particles. The resin monomer dispersion is dispersed to obtain a resin monomer dispersion, and then the resin monomer dispersion is added in an amount of 0.1% by mass to 10% by mass with respect to the total mass of the resin monomer dispersion, and 0.1% by mass. % Or more and 10% by mass or less of a crosslinking agent suspended or emulsified in pure water to form a suspension or emulsion, and then into this suspension or emulsion, This is a method for producing metal oxide particle-containing resin particles by adding 0.01% by mass or more and 1% by mass or less of a polymerization initiator with respect to the total mass of the resin monomer to perform suspension polymerization or emulsion polymerization.

In the case of producing small metal oxide particle-containing resin particles having an average particle size of 5 μm or less, the resin monomer dispersion is added to 0.01% by mass or more based on the total mass of the resin monomer dispersion and What is necessary is just to add a 5 mass% or less silicone type antifoamer.

Here, the manufacturing method of this metal oxide particle containing resin particle is demonstrated in detail.
First, metal oxide particles having an ultraviolet shielding ability with an average particle diameter of 0.003 μm or more and 0.1 μm or less are dispersed in a resin monomer containing a dispersant to obtain a resin monomer dispersion.
As the dispersant, a material that can be used as a raw material for cosmetics, has high affinity with a resin monomer, and is highly hydrophobic is preferable. That is, the dispersing agent promotes dispersion to the resin monomer by coating the metal oxide particles, and at the same time, the metal oxide particles are almost monodispersed in a relatively short time, and the average dispersed particle size is 0.003 μm or more and 0.1 μm or less.
Further, since the dispersant imparts hydrophobicity to the metal oxide particles, the metal oxide particles do not go out of the polymer and do not migrate to the aqueous phase, and help to be taken into the resin.
As such a dispersing agent, it is possible to use the same dispersing agent as that used when the above-mentioned (1) organic ultraviolet absorber-containing resin particles are produced.

The addition amount of the dispersing agent is preferably 1% by mass or more and 50% by mass or less with respect to the total mass of the metal oxide particles. If the addition amount is less than 1% by mass, the amount of the metal oxide particles is too small to cover the surface of the metal oxide particles, and the metal oxide particles cannot be sufficiently dispersed. Even if the addition amount is increased further, the dispersibility of the metal oxide particles is not further improved, and the dispersant is wasted, which is not preferable.

The dispersion apparatus used is not particularly limited as long as it can impart sufficient dispersion energy to the dispersion system, and examples thereof include a ball mill, a sand mill, an ultrasonic disperser, and a homogenizer. It is done.
The dispersion time is preferably about 30 minutes to 3 hours, but an appropriate time may be selected in consideration of the dispersion state and production cost.

As described above, a resin monomer having an average dispersed particle size of metal oxide particles of 0.003 μm or more and 0.1 μm or less, preferably 0.003 μm or more and 0.05 μm or less, more preferably 0.003 μm or more and 0.03 μm or less. A dispersion can be obtained.
Here, when the average dispersed particle size of the metal oxide particles in the resin monomer dispersion exceeds 0.1 μm, the scattering coefficient for visible light of the resin particles containing metal oxide particles increases, and as a result, transparency decreases. In some cases, however, there is a risk of devitrification, which is not preferable.

After the step of suspending or emulsifying this resin monomer dispersion in pure water containing a suspension protective agent and a crosslinking agent to obtain a suspension or emulsion, the above-described (1) organic ultraviolet absorber-containing resin particles are used. In this production method, since the resin monomer dispersion liquid is used in place of the resin monomer solution, the description is omitted.
By the above, the metal oxide particle containing resin particle can be produced.

(3) Organic-inorganic ultraviolet absorbent-containing resin particles These organic-inorganic ultraviolet absorbent-containing resin particles are resin particles containing an organic ultraviolet absorbent and metal oxide particles having ultraviolet shielding ability in the resin. It is.
About these resin, organic type ultraviolet absorber, and metal oxide particle which has ultraviolet-ray shielding ability, in the column of said (1) organic type ultraviolet absorber containing resin particle and (2) metal oxide particle containing resin particle. Since it is described in detail, the description is omitted here.

The organic ultraviolet absorber content in the organic-inorganic ultraviolet absorber-containing resin particles is preferably 0.1% by mass or more and 80% by mass or less, and the content of the metal oxide particles is 1% by mass or more and 80% by mass. The following is preferred.
By setting it as the said range, the material design at the time of producing cosmetics becomes easy, and the uniformity of a composition can be maintained.

The average particle size of the organic-inorganic ultraviolet absorbent-containing resin particles is preferably 0.05 μm or more and 5 μm or less, more preferably 0.1 μm or more and 3 μm or less, and further preferably 0.2 μm or more and 1 μm or less.
Here, when the average particle size of the organic-inorganic ultraviolet absorber-containing resin particles is less than 0.05 μm, the average particle size of the metal oxide particles having ultraviolet shielding ability is 0.003 μm or more and 0.1 μm or less. Since it becomes difficult to disperse the metal oxide particles in the resin particles without being exposed on the surface of the resin particles, it is not preferable. On the other hand, when the average particle diameter exceeds 5 μm, This is not preferable since the feeling of use may be deteriorated, such as a decrease in elongation and slipping, resulting in a feeling of roughness and a deterioration in the touch.

In the case of the organic-inorganic ultraviolet absorbent-containing resin particles, as in the above-mentioned columns of (1) organic ultraviolet absorbent-containing resin particles and (2) metal oxide particle-containing resin particles, the surface thereof may be It is good also as what processed with 1 to 20 mass% organosiloxane with respect to the resin particle.
By treating the surface of the organic-inorganic ultraviolet absorber-containing resin particles with organosiloxane, the metal oxide particles or the organic ultraviolet absorber, which are components of the organic-inorganic ultraviolet absorber-containing resin particles, such as pure water Elution into the solvent can be further suppressed.

As described in the section (2) above, the metal oxide particles are preferably not exposed on the surface of the resin particles, but may be exposed as long as they do not significantly affect the quality of the cosmetic. There may be something.

These organic ultraviolet absorbers and metal oxide particles may be used in appropriate combination in consideration of the wavelength band that each material can absorb or shield.
For example, zinc oxide is an n-type metal oxide semiconductor, and the band gap energy Eg in its band structure is 3.2 eV. Therefore, when the zinc oxide is irradiated with light having energy equal to or higher than the band gap energy Eg, the electrons absorb the light energy and are excited from the valence band to the conduction band. Since the absorption edge of zinc oxide is around 380 nm, zinc oxide can absorb the wavelength band from long-wavelength ultraviolet (UVA) to medium-wavelength ultraviolet (UVB).
Therefore, with respect to zinc oxide that can absorb the wavelength band from long wavelength ultraviolet rays (UVA) to medium wavelength ultraviolet rays (UVB), organic ultraviolet absorbers that can block long wavelength ultraviolet rays (UVA) and medium It is preferably used in combination with an organic ultraviolet absorber capable of shielding ultraviolet rays (UVB).

Titanium oxide has a band gap energy Eg of 3.0 eV to 3.2 eV in its band structure, but since the excitation of electrons in titanium oxide is an indirect transition, the absorption wavelength assumed from the value of the energy gap. Light absorption starts from around 320 nm which is a much lower wavelength side. Thus, since titanium oxide has a strong effect of shielding the wavelength band of medium wavelength ultraviolet light (UVB), it is preferably used in combination with an organic ultraviolet absorber that can shield long wavelength ultraviolet light (UVA).

As an example of a combination of metal oxide particles and an organic ultraviolet absorber, a combination of zinc oxide capable of shielding a wavelength band of 380 nm or less and dibenzoylmethane having a maximum absorption in a wavelength band of 358 nm to 360 nm Can be mentioned.
When these zinc oxide and dibenzoylmethane are simply mixed in a monomer, an ultraviolet ray shielding function appears from around 400 nm, which is preferable.

The following reasons can be considered as reasons why such an effect appears.
That is, when light is transmitted through the resin particles, the light travels while being scattered or reflected by the metal oxide particles in the resin particles, so that the distance is longer than when transmitting through the resin particles not including the metal oxide particles. Will proceed. Therefore, when the metal oxide particles and the organic ultraviolet absorber are mixed and mixed, the organic ultraviolet absorber in the resin particles is lighter than when the organic ultraviolet absorber is mixed alone. It is considered that the time for contact with the liquid becomes longer, and the absorption effect thereof becomes higher.

In particular, when the average particle diameter of the resin particles is 0.05 μm or more and 5 μm or less, the metal oxide particles and the organic ultraviolet absorber are close to each other in a narrow region. By repeating the scattering and reflection and the absorption by the organic ultraviolet absorber more frequently, a higher ultraviolet absorption effect can be obtained.

(Method for producing organic-inorganic ultraviolet absorbent-containing resin particles)
The organic-inorganic ultraviolet absorber-containing resin particle production method includes a resin monomer containing a metal oxide particle having an ultraviolet shielding ability and a dispersant of 1% by mass to 50% by mass with respect to the metal oxide particle. The resin monomer dispersion is dispersed into the resin monomer dispersion, and then the organic UV absorber is dissolved in the resin monomer dispersion by 0.1 to 80% by mass to obtain a resin monomer solution. The solution is suspended in pure water containing 0.1 to 10% by weight of a suspension protectant and 0.1 to 10% by weight of a crosslinking agent with respect to the resin monomer solution. The suspension or emulsion is made turbid or emulsified, and then 0.01% by mass or more and 1% by mass or less of the polymerization initiator is added to the suspension or emulsion. Add and hang Perform polymerization or emulsion polymerization, organic - a method of producing an inorganic ultraviolet absorber-containing resin particles.
When producing small resin particles of 5 μm or less, a silicone-based antifoaming agent is added to the resin monomer dispersion in an amount of 0.01% by mass to 5% by mass with respect to the resin monomer dispersion. Good.

Here, a method for producing the organic-inorganic ultraviolet absorbent-containing resin particles will be described.
First, metal oxide particles having an ultraviolet shielding ability having an average particle diameter of 0.003 μm or more and 0.1 μm or less are dispersed in a resin monomer containing a dispersant to obtain a resin monomer dispersion.
The method for preparing this resin monomer dispersion is exactly the same as the manufacturing method in the column of (2) Metal Oxide Particle-Containing Resin Particles described above, and a description thereof will be omitted.

Next, a resin monomer solution can be obtained by dissolving the organic ultraviolet absorber in the resin monomer dispersion so as to be 0.1% by mass or more and 80% by mass or less. The method for dissolving the organic ultraviolet absorber is exactly the same as the method described in the column of (1) Method for producing organic ultraviolet absorber-containing resin particles described above, and the description thereof is omitted.

Next, the resin monomer solution is suspended or emulsified in pure water containing a suspension protective agent and a crosslinking agent to form a suspension or emulsion, and then a polymerization initiator is added to the suspension or emulsion. Then, suspension polymerization or emulsion polymerization is performed to produce organic-inorganic ultraviolet absorber-containing resin particles.
In this step, instead of the resin monomer solution in the column of (1) organic ultraviolet absorber-containing resin particles, a resin monomer solution in which an organic ultraviolet absorber is dissolved in the resin monomer dispersion is used. Except for the above, the description is omitted because it is exactly the same as the description in the column of the method for producing (1) organic ultraviolet absorbent-containing resin particles.
Thus, organic-inorganic ultraviolet absorbent-containing resin particles can be produced.

Examples of the resin particles other than the ultraviolet shielding agent-containing resin particles described above include, for example, organic-inorganic resin particles having a two-layer structure in which metal oxide particle-containing resin particles are coated with an organic ultraviolet absorber-containing resin, or organic ultraviolet rays. Examples thereof include organic-inorganic resin particles having a two-layer structure in which absorbent resin-containing resin particles are coated with metal oxide particle-containing resin.
The two-layer structure such as the organic-inorganic resin particles is also preferable because the ultraviolet shielding function is exhibited from around 400 nm due to the interaction between the inorganic oxide particles and the organic ultraviolet absorber. The form of such a two-layer structure will be described in detail in (5 to 9) Deposits of organic ultraviolet absorber-containing resin and metal oxide particle-containing resin described later.

In addition, even when one or more of metal oxide particle-containing resin particles and organic ultraviolet absorber-containing resin particles are mixed and used, the ultraviolet shielding function is achieved by the interaction between the inorganic oxide particles and the organic ultraviolet absorber. Is preferable since it is expressed from around 400 nm.
Further, in order to further suppress the elution of metal oxide particles and organic ultraviolet absorbers into water, a resin-only layer may be coated on the outermost layer of the resin particles. The mode of mixing such resin particles will be described in detail in the following (4) Mixture of organic ultraviolet absorber-containing resin particles and metal oxide particle-containing resin particles.

(4) Mixture of Organic UV Absorber-Containing Resin Particles and Metal Oxide Particle-Containing Resin Particles This mixture, which is an ultraviolet shielding agent-containing resin particle, contains an organic ultraviolet absorber and contains first resin particles (hereinafter referred to as “organic”). And a second resin particle containing metal oxide particles having an ultraviolet shielding ability (hereinafter sometimes abbreviated as metal oxide particle-containing resin particles). It contains ultraviolet shielding agent-containing resin particles.
In particular, the preferred form of this mixture has the ultraviolet ray shielding ability and the first resin particles (ultraviolet absorber-containing resin particles) containing an organic ultraviolet absorber and having an average particle diameter of 0.1 μm or more and 1 μm or less. UV-shielding agent-containing resin particles comprising metal oxide particles and second resin particles (ultraviolet absorber-containing resin particles) having an average particle diameter of 0.1 μm or more and 1 μm or less, wherein the organic ultraviolet light The absorbent and the metal oxide particles have a mass ratio of 1:45 to 3: 1.

The first resin particles (ultraviolet absorber-containing resin particles) containing an organic ultraviolet absorber and the second resin particles (metal oxide particle-containing resin particles) containing metal oxide particles having ultraviolet shielding ability are: The organic ultraviolet absorbent and the metal oxide particles are mixed in a mass ratio of 1:45 to 3: 1, preferably 1: 6 to 3: 1. By mixing within this range, a synergistic effect of the ultraviolet shielding effect of the organic ultraviolet absorber-containing resin particles and the metal oxide particle-containing resin particles can be obtained, and the wavelength of 380 nm to more than when these resin particles are used alone. The ultraviolet shielding effect of 400 nm is enhanced.

"Organic UV absorber-containing resin particles (first resin particles)"
The average particle diameter of the organic ultraviolet absorbent-containing resin particles of the present embodiment is 0.1 μm or more and 1 μm or less, preferably 0.1 μm or more and 0.6 μm or less, and more preferably 0.1 μm or more and 0.4 μm or less. More preferred. Here, by setting the average particle diameter of the resin particles in the above range, a synergistic effect of the ultraviolet shielding effect of the organic ultraviolet absorber-containing resin particles and the metal oxide particle-containing resin particles can be obtained. Compared with the case of using UV, the ultraviolet shielding effect with a wavelength of 380 nm to 400 nm is enhanced.

Regarding the content and type of the organic ultraviolet absorber used in the organic ultraviolet absorber-containing resin particles, the type of resin, and the surface treatment of the organic ultraviolet absorber-containing resin particles, the above (1) organic ultraviolet rays Since it is described in detail in the column of the absorbent-containing resin particles, the description is omitted here.

“Metal oxide particle-containing resin particles (second resin particles)”
The average particle diameter of the metal oxide particle-containing resin particles of the present embodiment is 0.1 μm or more and 1 μm or less, preferably 0.1 μm or more and 0.6 μm or less, more preferably 0.1 μm or more and 0.4 μm or less. preferable. Here, by setting the average particle size of the metal oxide particle-containing resin particles in the above range, a synergistic effect of the ultraviolet shielding effect of the organic ultraviolet absorber-containing resin particles and the metal oxide particle-containing resin particles can be obtained, Therefore, the ultraviolet shielding effect of 380 nm to 400 nm is enhanced as compared with the case of using these resin particles.

The content of the metal oxide particles in the resin particles is preferably 1% by mass or more and 80% by mass or less, more preferably 5% by mass or more and 70% by mass or less, and further preferably 10% by mass or more and 60% by mass or less. It is.

Here, when the content of the metal oxide particles in the resin particles is less than 1% by mass, the amount of the metal oxide particles is too small to fully develop the ultraviolet shielding function of the metal oxide particles. . Therefore, in order to sufficiently exhibit the ultraviolet shielding function, a large amount of metal oxide particle-containing resin particles is required, and it becomes extremely difficult to design a material when producing a cosmetic. On the other hand, when the content exceeds 80% by mass, the amount of the metal oxide particles becomes relatively high with respect to the resin, and as a result, the dispersibility of the metal oxide particles in the resin decreases, and the metal oxide particles Since the uniformity of the composition of the contained resin particles is impaired, it is not preferable.

The type of resin used for the metal oxide particle-containing resin particles is described in detail in the column of (1) Organic ultraviolet absorber-containing resin particles, and the metal oxide used for the metal oxide particle-containing resin particles. Since the particle size of the product particles, the type and surface treatment thereof, and the surface treatment of the metal oxide particle-containing resin particles are described in detail in the column of (2) Metal oxide particle-containing resin particles, Description is omitted.

The organic ultraviolet absorber and the metal oxide particles are considered in the wavelength region that can be absorbed or shielded by each material, as described in detail in the section of (3) Resin particles containing organic-inorganic ultraviolet absorber. And may be used in appropriate combinations.

Examples of combinations of organic ultraviolet absorbers and metal oxide particles include a combination of zinc oxide capable of shielding a wavelength region of 380 nm or less and avobenzone having a maximum absorption at a wavelength of 358 nm to 360 nm. Can do.

In the present embodiment, organic ultraviolet absorber-containing resin particles (first resin particles) containing an organic ultraviolet absorber having an average particle size of 0.1 μm or more and 1 μm or less, and an average particle size of 0.1 μm A metal oxide particle-containing resin particle (second resin particle) containing metal oxide particles having an ultraviolet shielding ability of 1 μm or less, an organic ultraviolet absorber and metal oxide particles contained therein Are mixed so as to have a predetermined mass ratio (1:45 to 3: 1), the effect of shielding ultraviolet rays having a wavelength of 380 nm to 400 nm is enhanced as compared with the case where they are used alone. The details of the mechanism for obtaining such an effect are unknown, but are considered as follows.

First, in the case of the ultraviolet shielding agent-containing resin particles containing only the organic ultraviolet absorber-containing resin particles, the ultraviolet rays are absorbed by the organic ultraviolet absorber in the organic ultraviolet absorber-containing resin particles, but light is absorbed in the resin particles. Therefore, it is considered that ultraviolet rays having a wavelength of 380 nm to 400 nm cannot be sufficiently shielded.

On the other hand, in the case of the ultraviolet shielding agent-containing resin particles containing only the metal oxide particle-containing resin particles, the ultraviolet rays are shielded while being reflected and scattered by the metal oxide particles. Therefore, compared with the ultraviolet shielding agent-containing resin particles containing only the organic ultraviolet absorber-containing resin particles, the time during which the ultraviolet rays pass through the resin particles is relatively long, and the time during which the metal oxide particles and the ultraviolet rays are in contact with each other. Is also relatively long. However, since the metal oxide particles themselves have a low ability to shield ultraviolet rays in the range of 380 nm to 400 nm, they cannot be shielded sufficiently.

In contrast to the above, in the case of ultraviolet shielding agent-containing resin particles containing both organic ultraviolet absorber-containing resin particles and metal oxide particle-containing resin particles, the incident light is reflected by the metal oxide particle-containing resin particles.・ It is scattered and absorbed by the organic ultraviolet absorber-containing resin particles. The light reflected by the metal oxide particle-containing resin particles reaches the organic ultraviolet absorber-containing resin particles and is absorbed. By repeating this, in the ultraviolet shielding agent-containing resin particles of the present embodiment, shielding with metal oxide particles and absorption with an organic ultraviolet absorber are performed many times. That is, the number of times that ultraviolet rays pass through the resin particles due to scattering and reflection of the metal oxide particles is larger than when the organic ultraviolet absorber-containing resin particles are used alone, and it is considered that more ultraviolet rays can be shielded. . These effects are considered to provide a synergistic effect of ultraviolet shielding by the organic ultraviolet absorber and the metal oxide particles.

And since the space | gap which arises between resin particles becomes small because the average particle diameter of each resin particle shall be 1 micrometer or less, the distance of the metal oxide particle in a resin particle and an organic type ultraviolet absorber is also near relatively. Become. Therefore, it is considered that the absorption of ultraviolet rays by the organic ultraviolet absorber and the shielding of ultraviolet rays by the metal oxide particles are more easily performed, and the synergistic effect of ultraviolet shielding is more easily obtained.

Furthermore, by setting the mass ratio of the organic ultraviolet absorber to the metal oxide particles to 1:45 to 3: 1, the balance between the absorption effect by the organic ultraviolet rays and the shielding effect, scattering and reflection effect by the metal oxide particles is achieved. It is considered that a synergistic effect of ultraviolet shielding can be easily obtained by taking off.
Due to the above effects, it is presumed that the ultraviolet shielding agent-containing resin particles of the present embodiment can enhance the ultraviolet shielding effect at a wavelength of 380 nm to 400 nm, rather than using each resin particle alone.

The ultraviolet shielding agent-containing resin particles of the present embodiment may contain the organic ultraviolet absorber or the metal oxide particles separately depending on the application. For example, in the case of oil-based cosmetics such as a water-in-oil type (W / O type), an organic ultraviolet absorber can be added to the ultraviolet shielding agent-containing resin particles of this embodiment by adding an organic ultraviolet absorber. The addition amount of the absorbent-containing resin particles can be reduced, and a cosmetic with higher transparency can be obtained.

"Production Method of UV Screening Agent-Containing Resin Particles"
The ultraviolet shielding agent-containing resin particles of the present embodiment include a step of producing metal oxide particle-containing resin particles, a step of producing organic ultraviolet absorber-containing resin particles, an organic ultraviolet absorber-containing resin particle and metal oxide particles. It is obtained by the step of mixing the containing resin particles.

(Process for producing metal oxide particle-containing resin particles)
In the method for producing metal oxide particle-containing resin particles of the present embodiment, first, metal oxide particles having ultraviolet shielding ability are added to a dispersant in an amount of 1% by mass to 50% by mass with respect to the metal oxide particles. A resin monomer dispersion is prepared by dispersing in the resin monomer.
Next, the resin monomer dispersion is added to the resin monomer dispersion by 0.1 to 10% by weight of a suspension protectant and 0.01 to 5% by weight of a silicone-based polymer. A suspension or emulsion having an average dispersed particle size of 0.1 μm or more and 1.2 μm or less by being suspended or emulsified in pure water containing a foaming agent and 0.1% by mass or more and 10% by mass or less of a crosslinking agent. And
Next, by adding 0.01% by mass or more and 1% by mass or less of a polymerization initiator to the suspension or emulsion, suspension polymerization or emulsion polymerization is performed. Then, resin particles containing metal oxide particles are produced.

Since each step in the method for producing the metal oxide particle-containing resin particles is described in detail in the column of (2) Metal oxide particle-containing resin particles, the description thereof is omitted here.
Subsequently, in order to remove the remaining monomer, polymerization initiator, and surfactant from the obtained polymer, it is washed with pure water and dried, and the resulting resin particles are crushed. Since this step is exactly the same as the washing, drying and crushing step in the column of (1) Organic ultraviolet absorber-containing resin particles described above, description thereof is omitted.
As described above, the metal oxide particle-containing resin particles can be generated.

(Process for producing organic ultraviolet absorber-containing resin particles)
In the method for producing organic ultraviolet absorbent-containing resin particles of the present embodiment, first, an organic ultraviolet absorbent is used as a resin monomer, and the content of the organic ultraviolet absorbent is 0.1% by mass or more and 80% by mass or less. To obtain a resin monomer solution.
Next, the resin monomer solution is added to the resin monomer solution in an amount of 0.1% by mass to 10% by mass of a suspension protective agent, 0.01% by mass to 5% by mass of a silicone-based antifoaming agent. Suspension or emulsification in pure water containing an agent and 0.1% by mass or more and 10% by mass or less of a crosslinking agent to obtain a suspension or emulsion.
Next, suspension polymerization or emulsion polymerization is carried out by adding 0.01% by mass or more and 1% by mass or less of a polymerization initiator to the suspension or emulsion to the suspension or emulsion.

Since each manufacturing process of the organic ultraviolet absorber-containing resin particles has been described in detail in the column of (1) Organic ultraviolet absorber-containing resin particles, description thereof is omitted here.

Subsequently, in order to remove the remaining monomer, polymerization initiator, and surfactant from the obtained polymer, it is washed with pure water and dried, and the resulting resin particles are crushed. Since this step is exactly the same as the washing, drying and crushing step in the column of (1) Organic ultraviolet absorber-containing resin particles described above, description thereof is omitted.
As described above, the organic ultraviolet absorbent-containing resin particles can be generated.

The organic ultraviolet absorber-containing resin particles and the metal oxide particle-containing resin particles obtained above are adjusted so that the mass ratio of the organic ultraviolet absorber and the metal oxide particles is 1:45 to 3: 1. Mix.
The method of mixing is not particularly limited, and dry powder resin particles may be mixed, and as described later, organic ultraviolet absorber-containing resin particles and metal oxide particle-containing resin particles are mixed in a solvent. Also good.

Moreover, the polymer in the middle of the production of the metal oxide particle-containing resin particles and the polymer in the middle of the production of the organic ultraviolet absorber-containing resin particles are mixed so as to be in the above range, and the same as above. It can also be mixed by washing, drying and crushing.

Through the above steps, the ultraviolet shielding agent-containing resin particles of this embodiment can be obtained.

(5-9) Adhesive of Organic Ultraviolet Absorber-Containing Resin and Metal Oxide Particle-Containing Resin In this embodiment, the resin contains an organic ultraviolet absorber in place of the above-described ultraviolet shielding agent-containing resin particles. This is an ultraviolet shielding agent-containing resin adhering material obtained by adhering an organic ultraviolet absorber-containing resin and a metal oxide particle-containing resin containing metal oxide particles to the resin.

Here, an organic ultraviolet absorber-containing resin containing an organic ultraviolet absorber in a resin and a metal oxide particle-containing resin containing a metal oxide particle in a resin are attached. The structure is not particularly limited as long as the organic ultraviolet absorber-containing resin and the metal oxide particle-containing resin are attached to each other.

As such a structure, for example, (5) the organic ultraviolet absorber-containing resin is formed into particles to form organic ultraviolet absorber-containing resin particles, and the metal oxide particle-containing resin is formed into particles. A structure having both an ultraviolet absorption function and an ultraviolet shielding function by attaching one or more of these organic ultraviolet absorber-containing resin particles and metal oxide particle-containing resin particles to each other. Examples include the body.

(6) A structure in which one or more of the other resin particles are attached around one of the resin particles including the organic ultraviolet absorber-containing resin particles and the metal oxide particle-containing resin particles. ) A structure or the like in which at least one or both of the resin particles are attached around the deposit (6).

Furthermore, (8) a core material part is formed from either one of the organic ultraviolet absorber-containing resin particles and the metal oxide particle-containing resin particles, and the core material part is contained in the ultraviolet absorber-containing resin and the metal oxide particles. Structures partially or completely covered with either one or both of the resins, (9) (8) around the structure, and double covering partially or completely covered with either or both Examples include structures.

Among such structures, a core material part is formed from either one of the organic ultraviolet absorber-containing resin particles and the metal oxide particle-containing resin particles, and the core material part is made of an organic ultraviolet absorber-containing resin and A structure (hereinafter also referred to as a core-shell structure) that is partially or completely covered with either one of the metal oxide particle-containing resins is preferable.
Such a core-shell structure is characterized in that the absorption effect of the organic ultraviolet absorber and the ultraviolet shielding effect of the metal oxide particles act efficiently and a synergistic effect is easily obtained.

In the case of the core-shell structure, the absorption effect of the organic ultraviolet absorber can be enhanced by the scattering effect of the metal oxide particles. Therefore, the metal oxide particles are not limited to those having ultraviolet shielding ability, and metal oxide particles having a refractive index of 1.9 or more may be used.
That is, in the case of the core-shell structure, the metal oxide particles are selected from the group consisting of zinc oxide, titanium oxide, cerium oxide, iron oxide, zirconium oxide, tin oxide, copper oxide and the like having a refractive index of 1.9 or more. Particles containing one kind or two or more kinds can be used.

The average particle size in these structures is preferably 0.1 μm or more and 5 μm or less, and more preferably 0.1 μm or more and 1 μm or less.

In these structures, when the average particle size is less than 0.1 μm, it is difficult to uniformly disperse the metal oxide particles in the resin. On the other hand, when the average particle size exceeds 5 μm, When blended in cosmetics and the like, the transparency is impaired, which is not preferable.

Particularly, in the case of a core-shell structure in which the core part is partially or completely covered, the average particle diameter of the core part is preferably 0.05 μm or more and 4.8 μm or less, more preferably 0.05 μm or more and 0.8 μm or less. preferable.
Here, when the average particle diameter of the core material portion is less than 0.05 μm, the ultraviolet shielding effect may be insufficient, which is not preferable. On the other hand, when the average particle diameter exceeds 4.8 μm, Further, the thickness of the coating layer becomes thin, and as a result, the ultraviolet shielding effect in the coating layer may not be sufficiently exhibited, which is not preferable.

Further, the thickness of the coating layer that partially or completely covers the core part is preferably 0.01 μm or more and 0.5 μm or less, and more preferably 0.01 μm or more and 0.2 μm or less.
Here, when the thickness of the coating layer is less than 0.01 μm, the effect of the coating layer covering the core part becomes insufficient, and the ultraviolet shielding effect in the coating layer may not be sufficiently exhibited, which is not preferable. On the other hand, when the thickness of the coating layer exceeds 0.5 μm, the coating layer becomes too thick and the average particle diameter of the core material portion becomes relatively small. This is not preferable because it may not be able to fully exhibit.

The ratio (Mv: Mm) of the mass (Mv) of the organic ultraviolet absorber-containing resin to the mass (Mm) of the metal oxide particle-containing resin in the ultraviolet shielding agent-containing resin deposit is 1: 9 to 5: 5. A range is preferable, and a range of 2: 8 to 4: 6 is more preferable.
By setting the ratio (Mv: Mm) in the range of 1: 9 to 5: 5, the absorption effect of the organic ultraviolet absorber and the ultraviolet shielding effect of the metal oxide particles act efficiently, and the synergy of the ultraviolet shielding effect. The effect is easily obtained.

If necessary, the surface of the ultraviolet shielding agent-containing resin deposit is treated with 1% by mass or more and 20% by mass or less of organosiloxane based on the total amount of the ultraviolet shielding agent-containing resin deposit. Also good.
By treating the surface of this ultraviolet shielding agent-containing resin deposit with organosiloxane, for example, when zinc oxide is used as the metal oxide particles, the zinc oxide can be prevented from eluting to the outside.

Examples of the organosiloxane include a dialkylalkoxysilane compound. Among them, an organopolysiloxane or an organopolysiloxane selected from the group consisting of an alkyl group, an isocyanate group, an epoxy group, an acrylic group, and an alkyl silicon compound or Modified organopolysiloxanes modified by two or more types are preferably used, and in particular, dimethylpolysiloxane (silicone oil) and modified dimethylpolysiloxane (modified silicone oil) obtained by modifying this dimethylpolysiloxane (silicone oil) are preferable. .

Next, each of the organic ultraviolet absorber-containing resin and the metal oxide particle-containing resin constituting the ultraviolet shielding agent-containing resin deposit will be described in detail.

"Organic UV absorber-containing resin"
The organic ultraviolet absorber-containing resin is a resin containing an organic ultraviolet absorber, and when the resin forms particles, the average particle diameter of the resin particles is preferably 0.05 μm or more and 5 μm or less. .

Here, when the average particle diameter of the resin particles is less than 0.05 μm, the resin particles easily aggregate with each other. Therefore, when the resin particles are dispersed in the dispersion medium, the dispersibility is lowered and the ultraviolet ray shielding function is reduced. This is not preferable because it cannot be fully expressed. On the other hand, when the average particle diameter exceeds 5 μm, when used as a cosmetic, elongation and slippage in the skin are reduced, resulting in a feeling of roughness and the like, and the feeling of use is deteriorated. It is not preferable.

The content and type of the organic ultraviolet absorber used in the organic ultraviolet absorber-containing resin, and the type of resin are described in detail in the column of (1) Organic ultraviolet absorber-containing resin particles. Therefore, explanation is omitted here.

"Metal oxide particle-containing resin"
The metal oxide particle-containing resin is a resin containing metal oxide particles, and when the resin forms particles, the average particle diameter of the resin particles is preferably 0.05 μm or more and 5 μm or less. More preferably, it is not less than 05 μm and not more than 1 μm.

Here, when the average particle diameter of the resin particles is less than 0.05 μm, the resin particles are easily aggregated. Therefore, when the resin particles are dispersed in the dispersion medium, the dispersibility is lowered and the ultraviolet rays are shielded. This is not preferable because the function cannot be sufficiently expressed. On the other hand, when the average particle diameter exceeds 5 μm, when used as a cosmetic, elongation and slippage in the skin are reduced, resulting in a feeling of roughness and the like, and the feeling of use is deteriorated. It is not preferable.

The content of the metal oxide particles in the metal oxide particle-containing resin is preferably 1% by mass or more and 80% by mass or less, more preferably 5% by mass or more and 70% by mass or less, and further preferably 10% by mass or more. And it is 60 mass% or less.
Here, when the content of the metal oxide particles in the resin is less than 1% by mass, the amount of the metal oxide particles is too small to fully develop the ultraviolet shielding function of the metal oxide particles. On the other hand, when the content exceeds 80% by mass, the amount of the metal oxide particles is relatively high with respect to the resin, and as a result, the dispersibility of the metal oxide particles in the resin is reduced. Since the uniformity of composition is impaired, it is not preferable.

The type of resin used for the metal oxide particle-containing resin particles is described in detail in the column of (1) Organic ultraviolet absorber-containing resin particles, and the metal oxide used for the metal oxide particle-containing resin particles. Since the average particle diameter and surface treatment of the product particles are described in detail in the column of (2) Resin particles containing metal oxide particles, the description thereof is omitted here.

In this ultraviolet shielding agent-containing resin deposit, as described in detail in the column of (3) Organic-inorganic ultraviolet absorber-containing resin particles, the metal oxide particles contained in the metal oxide particle-containing resin, and the organic ultraviolet rays In consideration of the wavelength range in which each of the organic ultraviolet absorbers contained in the absorbent-containing resin can be absorbed or shielded, the metal oxide particle-containing resin and the organic ultraviolet absorber-containing resin are used in appropriate combinations. preferable.

The reason why the ultraviolet shielding effect is enhanced by adopting a structure in which an organic ultraviolet absorber-containing resin and a metal oxide particle-containing resin are adhered is considered as follows.
When light passes through the ultraviolet shielding agent-containing resin deposit of this embodiment, since the organic ultraviolet absorber-containing resin and the metal oxide particle-containing resin are adhered, they enter the organic ultraviolet absorber-containing resin. In some cases, the ultraviolet light is absorbed again by being incident on the metal oxide particle-containing resin and being scattered and reflected. In addition, since the metal oxide particles transmit ultraviolet light through the ultraviolet shielding agent-containing resin particles while being repeatedly scattered and reflected, they pass through the ultraviolet shielding agent-containing resin deposit not having the metal oxide particle-containing resin. The possibility that ultraviolet rays are absorbed by the organic ultraviolet absorber is increased. That is, the light is absorbed more by both the absorption effect by the organic ultraviolet absorber and the ultraviolet shielding effect by the metal oxide particles, and the synergistic effect is that the ultraviolet ray in the wavelength region of 380 nm to 400 nm can be shielded more than when used alone. It is thought that an effect is acquired.

In particular, in the case of the core-shell structure, ultraviolet rays are first shielded by the resin covering the core part, then ultraviolet rays are shielded by the resin of the core part, and ultraviolet rays are again shielded by the resin covering the core part. Since it is shielded, it is considered that the synergistic effect of the shielding effect of the organic ultraviolet absorbent and the metal oxide particles is further enhanced.
In particular, a core-shell structure in which resin particles containing zinc oxide are coated on the core material with a resin containing a dibenzoylmethane-based compound (abovobenzone) is preferable.

"Production method for UV-shielding agent-containing resin deposits"
As a manufacturing method of the ultraviolet shielding agent containing resin deposit of this embodiment, (A) The manufacturing method of the ultraviolet shielding agent containing resin deposit of a core-shell structure, (B) The manufacturing method of the ultraviolet shielding agent containing resin deposit of an adhesion type structure Will be described in order.

(A) Method for Producing Ultraviolet Screening Agent-Containing Resin Deposit with Core / Shell Structure This production method comprises a step of dispersing metal oxide particles in a resin monomer containing a dispersant to obtain a resin monomer dispersion, A step of adding a resin-based ultraviolet absorber and a dispersant to dissolve it into a resin monomer solution, and the resin monomer dispersion or resin monomer solution contains a suspension protective agent, a silicone-based antifoaming agent, and a crosslinking agent. A step of suspending or emulsifying in pure water to obtain a suspension or emulsion, and adding a polymerization initiator to the suspension or emulsion to perform suspension polymerization or emulsion polymerization. Alternatively, a core resin particle dispersion preparation step for preparing a resin particle dispersion containing metal oxide particles and the above resin monomer dispersion or resin monomer solution suspended in pure water containing a polymerization initiator Or the coating resin suspension emulsification step to be emulsified to give a suspension or emulsion, and the suspension or emulsion obtained in this step, the dispersion obtained in the above core resin particle dispersion preparation step It is constituted by a core-shell structure manufacturing step in which mixing and suspension polymerization or emulsion polymerization are performed.

The manufacturing method of this core shell structure ultraviolet shielding agent containing resin deposit is demonstrated in detail.
Here, for convenience of explanation, a case will be described in which resin particles containing metal oxide particles are used as a core material portion, and the core material portion is covered with a resin containing an organic ultraviolet absorber.
When the core part is formed with resin particles containing an organic ultraviolet absorber and the core part is covered with a resin containing metal oxide particles, the monomer dispersion and the monomer solution are interchanged. It is sufficient to implement it.

(1 Preparation of resin monomer dispersion)
First, metal oxide particles are dispersed in a resin monomer containing a dispersant to obtain a resin monomer dispersion.
The metal oxide particles having an ultraviolet shielding ability are the same as the metal oxide particles described in the column of (2) Metal oxide particle-containing resin particles, and thus the description thereof is omitted.

When the metal oxide particles are dispersed in the resin monomer, the average dispersed particle size is preferably 0.1 μm or less.
Here, when the average dispersion particle size of the metal oxide particles in the resin monomer exceeds 0.1 μm, the scattering coefficient of the resin powder with respect to visible light increases, so that the transparency is significantly lowered. The transparency is lowered, and in some cases, the glass may be devitrified.

Since the dispersing agent, the dispersing device and the dispersing time to be used are described in detail in the column of (2) Resin particles containing metal oxide particles, the description is omitted here.

Thus, a resin monomer dispersion having an average dispersed particle size of metal oxide particles of 0.003 μm or more and 0.1 μm or less can be obtained.

(2 Preparation of resin monomer solution)
First, an organic ultraviolet absorber is dissolved in a resin monomer to obtain a resin monomer solution.
Since the organic ultraviolet absorber is exactly the same as the organic ultraviolet absorber described in the column of (1) Organic ultraviolet absorber-containing resin particles, the description thereof is omitted.

Next, 1% by mass or more and 50% by mass or less of a dispersant is mixed with the resin monomer solution. The dispersant to be used is exactly the same as the dispersant described in the column of (1) Organic UV absorber-containing resin particles, and therefore the description thereof is omitted.
By the above, the resin monomer solution containing an organic ultraviolet absorber can be obtained.

(3 Production of core part)
First, the above resin monomer dispersion is suspended or emulsified in pure water containing a suspension protective agent, a silicone-based antifoaming agent, and a crosslinking agent, and a suspension having an average dispersed particle diameter of 0.05 μm to 5 μm or Emulsified.

The suspension protective agent, silicone antifoaming agent, cross-linking agent, and pure water are described in detail in the column of (1) Organic ultraviolet absorber-containing resin particles, and thus the description thereof is omitted here.

Subsequently, a polymerization initiator is added to said suspension or emulsion, and suspension polymerization or emulsion polymerization is performed.
Since the polymerization initiator and the polymerization method are described in detail in the column of (1) Organic ultraviolet absorber-containing resin particles, the description is omitted here.

Thereafter, ice-cooling or natural cooling is performed to stop the polymerization reaction, thereby obtaining a dispersion liquid containing a core part composed of resin particles containing metal oxide particles.

As described above, the average particle diameter of the obtained core material part, that is, the metal oxide particle-containing resin particles can be controlled to 0.05 μm or more and 5 μm or less.

(4 Suspension emulsification of coating resin)
The resin monomer solution is suspended or emulsified in pure water containing 0.01% by mass or more and 1% by mass or less of the polymerization initiator with respect to the resin monomer solution to suspend the coating resin. Liquid or emulsion.
Since the polymerization initiator and pure water are exactly the same as those described in the above “polymerization initiator” and “pure water”, the description thereof is omitted.

(5 Fabrication of core-shell structure)
An ultraviolet shielding agent-containing resin having a core-shell structure is prepared by mixing a suspension or emulsion of the coating resin and a dispersion containing the core part, and then polymerizing, washing, drying, and crushing. A deposit can be obtained.

The mixing ratio of the resin monomer solution and the dispersion containing the core material is such that the organic ultraviolet absorber and the metal oxide particles are mixed in a mass ratio of 1: 9 to 5: 5. preferable.
By mixing the resin monomer solution and the dispersion containing the core part in the above range, a synergistic effect of the ultraviolet shielding ability of the organic ultraviolet absorber and the metal oxide particles can be obtained.
Since the polymerization method is exactly the same as the polymerization method of the above suspension or emulsion, description thereof will be omitted.

Next, the obtained polymer is washed with pure water. Thereby, the monomer, polymerization initiator, and surfactant remaining in the polymer are removed. In this washing step, in order to improve the washing efficiency, washing with alcohol or the like may be performed before washing with pure water.
The alcohol is not particularly limited as long as it is soluble in pure water and can be easily washed away, and examples thereof include ethanol and 2-propanol. 2-propanol is particularly preferable.
The washing method is not particularly limited as long as residual monomers and the like can be removed, but pressure filtration, suction filtration, filter press, centrifugation, ultrafiltration, decantation, and the like are preferable.

After completion of washing, the polymer obtained is dried at 80 ° C. to 100 ° C. to remove alcohol and pure water remaining in the polymer. The drying method is not particularly limited as long as it is a method capable of removing alcohol and pure water, and examples thereof include drying in atmospheric pressure and vacuum drying.

Next, the dried polymer is crushed. The crushing method is not particularly limited as long as it can crush each particle, and examples thereof include a pin mill, a hammer mill, a jet mill, and an impeller mill.
As described above, an ultraviolet shielding agent-containing resin deposit having a core-shell structure can be generated.
This ultraviolet shielding agent-containing resin deposit can improve the feeling of use when it is used in cosmetics by crushing each particle aggregated by drying through a crushing step.

(B) Method for Producing Ultraviolet Screening Agent-Containing Resin Deposit with Adhesive Structure This production method comprises a step of dispersing metal oxide particles in a resin monomer containing a dispersant to form a resin monomer dispersion, A step of adding an organic ultraviolet absorber and a dispersant to dissolve it to obtain a resin monomer solution, and a suspension or emulsification of the resin monomer by suspending or emulsifying it in pure water containing a polymerization initiator. Step, and then mixing and polymerizing the above suspension or emulsion, resin monomer dispersion, and resin monomer solution, and then polymerizing resin particles containing metal oxide particles, and organic ultraviolet absorption It is comprised by the process of coat | covering the resin particle containing an agent with the layer only of resin.

According to this production method, the adhesive particle-containing ultraviolet shielding agent containing resin particles containing metal oxide particles and resin particles containing an organic ultraviolet absorber are covered with a resin-only layer. Resin deposits can be obtained.
In addition, the monomer dispersion and the monomer solution are each made into the core resin particle dispersion, and the mixture of these dispersions is washed and dried in the same manner as described above, so that an adhesion type ultraviolet shielding agent-containing resin deposit is obtained. Can be obtained.

"alcohol"
Examples of the alcohol include monohydric alcohols or polyhydric alcohols having 1 to 6 carbon atoms, such as ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, glycerin, 1,3-butylene glycol, propylene glycol, and sorbitol. Among them, monohydric alcohols, particularly ethanol is preferable.
The content of the alcohol in the ultraviolet shielding gel-like composition is preferably 1% by mass or more and 40% by mass or less, more preferably 10% by mass or more and 30% by mass or less.
By making the content rate of alcohol into the said range, the dispersibility and quality stability of the ultraviolet shielding agent-containing resin particles in the ultraviolet shielding gel-like composition can be improved.

In the ultraviolet shielding gel-like composition of the present embodiment, the water-soluble polymer other than the polyacrylic acid polymer is 0.01% by mass or more and 5% by mass or less, more preferably 0.1% by mass or more and 3% by mass. It is good also as containing below. In this case, the total content of each component of the polyacrylic acid polymer, water, emulsion type silicone, ultraviolet shielding agent-containing resin particles, alcohol, and water-soluble polymer should not exceed 100% by mass. It is necessary to adjust the content rate.

The water-soluble polymer other than the polyacrylic acid polymer is not particularly limited as long as it can be used for cosmetics. Carboxymethyl starch, agar, xanthan gum, quince seed, guar gum, collagen, gelatin, cellulose, dextran, dextrin, tragacanth gum, hydroxyethyl cellulose, hydroxypropyl cellulose, sodium hyaluronate pectin, pullulan, methyl cellulose, methyl hydroxypropyl cellulose, etc. . These water-soluble polymers may be used alone or in combination of two or more.
The water-soluble polymer has a role as a dispersant and a viscosity modifier, and when added, the dispersibility and dispersion stability of the ultraviolet shielding agent-containing resin particles in the polyacrylic acid polymer are also improved.

When the ultraviolet shielding gel-like composition of the present embodiment contains a water-soluble polymer, the alcohol content is preferably 1% by mass to 40% by mass, more preferably 10% by mass to 30% by mass. is there.
Here, the reason why the alcohol content when the ultraviolet shielding gel-like composition of the present embodiment contains a water-soluble polymer is 1% by mass or more and 40% by mass or less is that the content is less than 1% by mass, Since the alcohol content is too small, the water-soluble polymer cannot uniformly infiltrate into the alcohol and swells non-uniformly with moisture. As a result, the dispersibility of the UV shielding agent-containing resin particles decreases. Therefore, handling becomes difficult, and further, dispersion stability is lowered, which is not preferable. On the other hand, if the content exceeds 40% by mass, the viscosity of the ultraviolet shielding gel-like composition as a whole is increased, so that the dispersibility of the ultraviolet shielding agent-containing resin particles is lowered and the dispersion stability is also lowered.

[Method for producing UV-shielding gel composition]
The production method of the ultraviolet shielding gel-like composition of the present embodiment is such that the polyacrylic acid polymer is 0.01% by mass or more and 5% by mass or less, the water is 30% by mass or more and 80% by mass or less, and the emulsion type silicone is 0.00%. These are mixed to form a mixture such that the amount of the ultraviolet shielding agent-containing resin particles is 1% by mass to 50% by mass and the alcohol is 1% by mass to 40% by mass. Then, the hydrogen ion exponent (pH) of this mixture is adjusted to 6 or more and 8 or less.
In this case, the content of each component is adjusted so that the total content of each component of the polyacrylic acid polymer, water, emulsion type silicone, ultraviolet shielding agent-containing resin particles, and alcohol does not exceed 100 mass%. There is a need.

The mixing is not particularly limited as long as it is a method that can sufficiently disperse the above-described ultraviolet shielding agent-containing resin particles in the ultraviolet shielding gel-like composition. For example, a homogenizer, a homomixer, a mixer, a stirrer, etc. Can be used.

In order to adjust the hydrogen ion index (pH) of the mixture to 6 or more and 8 or less, an alkaline agent that can be used for cosmetics may be added to the mixture.
Examples of the alkali agent include inorganic alkali agents such as an aqueous sodium hydroxide solution and organic alkali agents such as an aqueous triethanolamine solution.
By setting the hydrogen ion exponent (pH) of this mixture to 6 or more and 8 or less, an ultraviolet shielding gel-like composition equivalent to the skin pH can be obtained.

[Cosmetics]
The cosmetic of the present embodiment is a cosmetic comprising the above-described ultraviolet shielding gel-like composition, and is excellent in ultraviolet shielding function, feeling of use, and quality stability.
In this cosmetic, the elution of the metal oxide is suppressed by blending the ultraviolet shielding gel-like composition described above into a water-based cosmetic such as skin lotion or sunscreen gel, which has conventionally been difficult to formulate. In addition, it is possible to obtain a water-based cosmetic excellent in ultraviolet shielding ability, transparency and use feeling.

By using this cosmetic as a cosmetic ingredient, it is possible to provide various cosmetics such as skin care cosmetics, makeup cosmetics, body care cosmetics and the like excellent in ultraviolet shielding ability, transparency, and feeling of use. In particular, it is suitable for whitening skin care cosmetics that require UV shielding ability, base makeup for makeup cosmetics, sunscreens for body care cosmetics, and the like.

As described above, according to the ultraviolet shielding gel composition of the present embodiment, the emulsion type silicone and the alcohol are added to the polyacrylic acid polymer and the ultraviolet shielding agent-containing resin particles. The agent-containing resin particles can be easily and uniformly mixed. Therefore, it is possible to provide an ultraviolet shielding gel-like composition that has an excellent ultraviolet shielding function and a feeling of use and is excellent in quality stability.
Further, when a water-soluble polymer other than the polyacrylic acid polymer is contained, the dispersibility and dispersion stability of the ultraviolet shielding agent-containing resin particles in the ultraviolet shielding gel-like composition can be further improved.

When the emulsion type silicone contains a silicone resin, a sorbitan fatty acid ester, a glycerin fatty acid ester and a sucrose fatty acid ester, the stability as an emulsion can be further improved.
When the ultraviolet shielding agent-containing resin particles contain one or both of an organic ultraviolet absorbent and metal oxide particles having ultraviolet shielding ability in the resin particles, these organic ultraviolet absorbents In addition, either or both of the metal oxide particles having an ultraviolet shielding ability are immobilized in the resin, and thus metal ions and organic ultraviolet absorbers may be eluted in water by contact with water. Disappear. Therefore, it is possible to prevent deterioration, discoloration, and deterioration in feeling of use due to elution of metal ions and organic ultraviolet absorbers, and the quality can be stabilized.
Since the average particle diameter of the ultraviolet shielding agent-containing resin particles is 0.05 μm or more and 5 μm or less, the transparency when applied to the skin is excellent, and there is no roughness and the usability is excellent.

When (meth) acrylic resin is used as the resin, more excellent transparency can be maintained.
In particular, when a metal oxide particle having an ultraviolet shielding ability such as zinc oxide and an organic ultraviolet absorbent capable of shielding long wavelength ultraviolet rays (UVA) are combined to form an organic-inorganic ultraviolet absorbent-containing resin particle Compared with the case where the organic ultraviolet absorbent-containing resin particles and the metal oxide particle-containing resin particles are simply mixed, ultraviolet rays (UV) can be shielded from the long wavelength side.

According to the method for producing an ultraviolet shielding gel composition of the present embodiment, the pH of the mixture obtained by mixing polyacrylic acid polymer, water, emulsion type silicone, ultraviolet shielding agent-containing resin particles and alcohol is 6 or more and Since it adjusts to 8 or less, a polyacrylic acid polymer and an ultraviolet shielding agent containing resin particle can be mixed easily and uniformly. Accordingly, it is possible to easily obtain an ultraviolet shielding gel-like composition that is excellent in ultraviolet shielding function and feeling of use and excellent in quality stability.
Moreover, since the dispersibility of the ultraviolet shielding agent-containing resin particles in the ultraviolet shielding gel-like composition can be improved, it is possible to obtain an excellent feeling after use.

According to the cosmetic of the present embodiment, since it contains the ultraviolet shielding gel composition described above, skin care cosmetics and makeup cosmetics excellent in ultraviolet shielding function, transparency, feeling of use, quality stability and safety. Various cosmetics such as body care cosmetics can be provided.
Especially when used for skin care cosmetic whitening, makeup cosmetic base makeup, body care cosmetic sunscreen, etc. that require UV shielding ability, it has excellent UV shielding ability, transparency, usability and safety. Cosmetics can be provided.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

[Example 1]
"Preparation of resin monomer solution"
12 parts by mass of dibenzoylmethane (Avobenzone, Pulsol (registered trademark) 1789) was added to 108 parts by mass of methyl methacrylate, and completely dissolved to prepare a resin monomer solution A.

"Preparation of emulsion"
In 105 parts by mass of the above resin monomer solution A, 229.5 parts by mass of pure water, 0.5 parts by mass of sodium dodecylbenzenesulfonate, 14.0 parts by mass of ethylene glycol dimethacrylate, 1.0 part by mass of a silicone-based antifoaming agent Were mixed and stirred using a homogenizer to prepare an emulsion.

"Production of resin particles"
320.0 parts by mass of the above emulsion, 79.856 parts by mass of pure water, and 0.144 parts by mass of potassium persulfate were mixed, transferred to a reactor equipped with a stirrer and a thermometer, and replaced with nitrogen for 1 hour. It was.
Next, the nitrogen-substituted reaction solution was heated to 65 ° C. and held at 65 ° C. for 3 hours to conduct a polymerization reaction. Thereafter, the polymerization reaction was stopped by cooling with ice.
The obtained polymer is washed with 2-propanol and pure water and then dried at 90 ° C. to produce organic ultraviolet absorber-containing resin particles made of polymethyl methacrylate (PMMA) containing 10% by mass of dibenzoylmethane. did. The average particle diameter of the obtained organic ultraviolet absorber-containing resin particles was 323.7 nm.

"Preparation of UV shielding gel-like composition"
1 part by weight of emulsion type silicone KM-72F (manufactured by Shin-Etsu Chemical Co., Ltd.), 68.6 parts by weight of pure water, 10 parts by weight of the above-mentioned organic ultraviolet absorber-containing resin particles, and polyacrylic acid polymer Carbopol Ultrez 10 (manufactured by BF Goodrich) was mixed with 0.4 parts by mass and 20 parts by mass of ethanol, and stirred at 10,000 rpm for 10 minutes using a homogenizer to obtain a polyacrylic acid polymer dispersion.
Subsequently, the obtained polyacrylic acid polymer dispersion was adjusted to pH 7 with a 10% by mass aqueous sodium hydroxide solution to obtain an ultraviolet shielding gel-like composition of Example 1.

Subsequently, the spectral transmittance of the ultraviolet shielding gel-like composition was measured using Spectrophotometer V-570 UV / VIS / NIR (manufactured by JASCO Corporation). The spectral transmittance of this ultraviolet shielding gel-like composition is shown in FIG.
When this ultraviolet shielding gel-like composition was applied to the skin, there was no stickiness and a refreshing feeling was obtained.

[Example 2]
Except for changing the pure water from 68.6 parts by mass to 77.6 parts by mass and the organic ultraviolet absorber-containing resin particles from 10 parts by mass to 1 part by mass when preparing the ultraviolet shielding gel-like composition. Prepared the ultraviolet shielding gel-like composition of Example 2 according to Example 1.
Subsequently, the spectral transmittance of the ultraviolet shielding gel-like composition was measured according to Example 1. The spectral transmittance of this ultraviolet shielding gel-like composition is shown in FIG.
When this ultraviolet shielding gel-like composition was applied to the skin, there was no stickiness and a refreshing feeling was obtained.

[Example 3]
Except for changing the pure water from 68.6 parts by mass to 73.6 parts by mass and the organic ultraviolet absorber-containing resin particles from 10 parts by mass to 5 parts by mass when preparing the ultraviolet shielding gel-like composition. Prepared the ultraviolet shielding gel-like composition of Example 3 according to Example 1.
Subsequently, the spectral transmittance of the ultraviolet shielding gel-like composition was measured according to Example 1. The spectral transmittance of this ultraviolet shielding gel-like composition is shown in FIG.
When this ultraviolet shielding gel-like composition was applied to the skin, there was no stickiness and a refreshing feeling was obtained.

[Example 4]
Except for changing the pure water from 68.6 parts by mass to 63.6 parts by mass and the organic ultraviolet absorber-containing resin particles from 10 parts by mass to 15 parts by mass when preparing the ultraviolet shielding gel-like composition. Produced the ultraviolet shielding gel-like composition of Example 4 according to Example 1.
Subsequently, the spectral transmittance of the ultraviolet shielding gel-like composition was measured according to Example 1. The spectral transmittance of this ultraviolet shielding gel-like composition is shown in FIG.
When this ultraviolet shielding gel-like composition was applied to the skin, there was no stickiness and a refreshing feeling was obtained.

[Example 5]
Except for changing the pure water from 68.6 parts by mass to 58.6 parts by mass and the organic ultraviolet absorber-containing resin particles from 10 parts by mass to 20 parts by mass when preparing the ultraviolet shielding gel-like composition. Prepared the ultraviolet shielding gel-like composition of Example 5 according to Example 1.
Subsequently, the spectral transmittance of the ultraviolet shielding gel-like composition was measured according to Example 1. The spectral transmittance of this ultraviolet shielding gel-like composition is shown in FIG.
When this ultraviolet shielding gel-like composition was applied to the skin, there was no stickiness and a refreshing feeling was obtained.

Next, this ultraviolet shielding gel-like composition was applied to a quartz plate in an amount of ² mg / cm ² , and the spectral transmittance and SPF value of this coating film were measured using SPF analyzer UV-1000S (manufactured by Labsphere, USA). It was measured. This spectral transmittance is shown in FIG. The SPF value was 39.3.
Moreover, it was 40,000 mPa * s when the viscosity of this ultraviolet-ray shielding gel-like composition was measured using the B-type viscosity meter (made by Toki Sangyo Co., Ltd.). Furthermore, this ultraviolet shielding gel-like composition was allowed to stand at 25 ° C. for 2 weeks, and then its viscosity was measured using a B-type viscometer (manufactured by Toki Sangyo Co., Ltd.), which was 40,000 mPa · s. It was confirmed that the viscosity did not change even when allowed to stand at room temperature, and the dispersion stability was excellent.

[Comparative Example 1]
Except that the emulsion type silicone KM-72F was changed to an oil compound type silicone KS-66 (manufactured by Shin-Etsu Chemical Co., Ltd.) when producing the ultraviolet shielding gel-like composition, An ultraviolet shielding gel-like composition was prepared.
This UV-shielding gel-like composition started to foam during stirring, and when stirred at a rotational speed of 10,000 rpm, it could only be stirred for 5 minutes, but the appearance was uniform.
When this ultraviolet shielding gel-like composition was applied to the skin, it was a little sticky on the skin and an oily feeling remained, so a refreshing feeling was not obtained.
Moreover, when the organic ultraviolet absorber containing polyacrylic acid polymer dispersion before adjusting to pH 7 with a 10 mass% sodium hydroxide aqueous solution was allowed to stand at room temperature for 3 hours, the water component and the resin particles were separated.

[Comparative Example 2]
The ultraviolet ray of Comparative Example 2 was prepared according to Example 1 except that the emulsion type silicone KM-72F was changed to an oil type silicone KF-96 (manufactured by Shin-Etsu Chemical Co., Ltd.) when the ultraviolet ray shielding gel-like composition was prepared. A shielding gel composition was prepared.
This UV-shielding gel-like composition started to foam during stirring, and when stirred at a rotational speed of 10,000 rpm, it could only be stirred for 5 minutes, but the appearance was uniform.
When this ultraviolet shielding gel-like composition was applied to the skin, it was a little sticky on the skin and an oily feeling remained, so a refreshing feeling was not obtained.
Moreover, when the organic ultraviolet absorber containing polyacrylic acid polymer dispersion before adjusting to pH 7 with a 10 mass% sodium hydroxide aqueous solution was allowed to stand at room temperature for 3 hours, the water component and the resin particles were separated.

[Comparative Example 3]
Example 1 except that 19.6 parts by mass of the emulsion-type silicone KM-72F and 68.6 parts by mass of pure water were used instead of 69.6 parts by mass of pure water when producing the ultraviolet shielding gel-like composition. When an attempt was made to produce the ultraviolet shielding gel composition of Comparative Example 3 according to the above, foaming occurred immediately after stirring, and uniform mixing was not possible.

[Comparative Example 4]
Instead of using 1 part by weight of emulsion type silicone KM-72F and 68.6 parts by weight of pure water when preparing the ultraviolet shielding gel-like composition, the phosphate type dispersant phosphine is added to 68.6 parts by weight of pure water. An attempt was made to produce an ultraviolet shielding gel-like composition of Comparative Example 4 according to Example 1 except that a mixture obtained by mixing 1 part of Phanol RS-610 (manufactured by Toho Chemical Co., Ltd.) was used. Immediately after foaming, uniform mixing was not possible.

[Reference Example 1]
[Moisture gel containing both inorganic resin particles and organic resin particles]

“Production of zinc oxide-containing resin particles (inorganic resin particles)”
200 parts by mass of zinc oxide fine particles (manufactured by Sumitomo Osaka Cement Co., Ltd., average primary particle size: 0.02 μm), 188 parts by mass of methyl methacrylate, and 12 parts by mass of a phosphoric acid ester type surfactant are mixed, and a sand mill is used. Dispersion treatment was performed for 2 hours to obtain a monomer dispersion liquid in which zinc oxide fine particles were dispersed in methyl methacrylate.

Next, 105.0 parts by mass of the obtained monomer (MMA) dispersion, 229.5 parts by mass of pure water, 0.5 parts by mass of sodium dodecylbenzenesulfonate, 14.0 parts by mass of ethylene glycol dimethacrylate, silicone-based antifoaming 1.0 part by mass of the agent was mixed and stirred at 6000 rpm for 10 minutes using a homogenizer to obtain an emulsion having a dispersed particle size D50 of 0.6 μm.

Next, 320.0 parts by mass of the obtained emulsion, 79.856 parts by mass of pure water, and 0.144 parts by mass of potassium persulfate were mixed, transferred to a reactor equipped with a stirrer and a thermometer, and replaced with nitrogen at room temperature. It went for 1 hour. Subsequently, it heated up at 65 degreeC and hold | maintained for 3 hours, and the polymerization reaction was performed. Next, the polymerization reaction was stopped by cooling with ice, and the resulting polymer was washed with 2-propanol, further washed with pure water, and dried at 90 ° C. The dried product thus obtained was crushed with a hammer mill to obtain resin particles containing zinc oxide fine particles having an average particle size of 0.5 μm. The obtained resin particles were measured with TG-DTA (Thermo Plus 2 TG8120, manufactured by Rigaku Corporation), and it was confirmed that the resin particles contained 50% by mass of zinc oxide.

[Aqueous dispersion containing zinc oxide-containing resin particles]
25 parts by mass of the zinc oxide-containing resin particles obtained above, 7.5 parts by mass of ethanol, and 17.5 parts by mass of pure water were mixed to obtain an aqueous dispersion containing zinc oxide-containing resin particles.

“Preparation of avobenzone-containing resin particles (organic resin particles)”
Avobenzone (manufactured by DSM Nutrition Japan Co., Ltd., Pulsol (registered trademark) 1789) and 5 parts by mass of a phosphate ester type surfactant are added to and mixed with 85 parts by mass of methyl methacrylate, and a resin monomer solution is added. Produced.
Next, 105 mass parts of this resin monomer solution was added to 229.5 mass parts of pure water, 0.5 mass parts of sodium dodecylbenzenesulfonate, 14.0 mass parts of ethylene glycol dimethacrylate, 1.0 mass of silicone antifoaming agent. The parts were mixed and stirred at 10,000 rpm for 10 minutes using a homogenizer to prepare an emulsion.

320.0 parts by mass of the above emulsion, 79.856 parts by mass of pure water, and 0.144 parts by mass of potassium persulfate were mixed, transferred to a reactor equipped with a stirrer and a thermometer, and replaced with nitrogen for 1 hour. It was.
Next, the temperature of the reaction solution after nitrogen substitution was raised to 65 ° C. and held at 65 ° C. for 3 hours to carry out a polymerization reaction. Thereafter, the polymerization reaction was stopped by cooling with ice, and the resulting polymer was washed with 2-propanol and pure water and then dried at 90 ° C. The dried product thus obtained was crushed with a hammer mill to obtain resin particles containing avobenzone having an average particle size of 0.3 μm.
The mass of the recovered resin particles substantially coincided with the total mass of methyl methacrylate, avobenzone, and phosphate ester surfactant used for preparing the resin particles. Therefore, the following compounding was performed on the assumption that 10% by mass of avobenzone was contained in the resin particles.

"Aqueous dispersion containing avobenzone-containing resin particles"
25 parts by mass of the avobenzone-containing resin particles obtained above, 7.5 parts by mass of ethanol, and 17.5 parts by mass of pure water were mixed to obtain an aqueous dispersion containing avobenzone-containing resin particles.

"Moisture gel containing both inorganic resin particles and organic resin particles"
20 parts by mass of the aqueous dispersion containing the zinc oxide-containing resin particles obtained above, 20 parts by mass of the aqueous dispersion containing the avobenzone-containing resin particles obtained above, and 1.5 parts by mass of sodium carboxymethylcellulose Parts, ethanol (6.0 parts by mass) and glycerin (2.5 parts by mass) were mixed. Next, the mixture was heated and stirred at 70 ° C. for 10 minutes to obtain a moisture gel containing zinc oxide-containing resin particles and avobenzone-containing resin particles (organic ultraviolet absorber: zinc oxide = 1: 5).

The obtained moisture gel was applied to a quartz plate in an amount of ² mg / cm ² , and the spectral transmittance and SPF value were measured using SPF analyzer UV-1000S (manufactured by Labsphere, USA). This spectral transmittance is shown in FIG. The SPF value was 66.8.

[Reference Example 2]
"Moisture gel containing only inorganic resin particles"
20 parts by mass of the aqueous dispersion containing the zinc oxide-containing resin particles obtained in Reference Example 1, 1.5 parts by mass of sodium carboxymethylcellulose, 6.0 parts by mass of ethanol, and 2.5 parts by mass of glycerin were mixed. . Next, the mixture was heated and stirred at 70 ° C. for 10 minutes to prepare a moisture gel containing zinc oxide-containing resin particles.

The SPF value and the spectral transmittance were measured in the same manner as in Reference Example 1. This spectral transmittance is shown in FIG. The SPF value was 33.0.

[Reference Example 3]
"Moisture gel containing only organic resin particles"
20 parts by mass of the aqueous dispersion containing the avobenzone-containing resin particles obtained in Reference Example 1, 1.5 parts by mass of sodium carboxymethylcellulose, 6.0 parts by mass of ethanol, and 2.5 parts by mass of glycerin were mixed. Next, the mixture was heated and stirred at 70 ° C. for 10 minutes to obtain a moisture gel containing avobenzone-containing resin particles.

The SPF value and the spectral transmittance were measured in the same manner as in Reference Example 1. This spectral transmittance is shown in FIG. The SPF value was 40.5.

From FIG. 3, the moisture gel containing both the zinc oxide-containing resin particles and the avobenzone-containing resin particles of Reference Example 1 has an ultraviolet shielding rate with a wavelength of 380 nm to 400 nm as compared with the moisture gel containing individual resin particles. Excellent. Further, the SPF value was the highest in Reference Example 1, and it was confirmed that the UV shielding ability was excellent.

According to the ultraviolet shielding gel-like composition of the present invention, since the emulsion type silicone and alcohol are added to the polyacrylic acid polymer and the ultraviolet shielding agent-containing resin particles, the polyacrylic acid polymer and the ultraviolet shielding agent-containing resin particles, There is no foaming and it can be mixed well. Therefore, the present invention can be suitably used for an ultraviolet shielding gel composition.

Further, according to the method for producing an ultraviolet shielding gel composition of the present invention, after mixing polyacrylic acid polymer, water, emulsion type silicone, ultraviolet shielding agent-containing resin particles and alcohol to obtain a mixture, Since the ion index is adjusted to 6 or more and 8 or less, the polyacrylic acid polymer and the ultraviolet shielding agent-containing resin particles can be sufficiently mixed without foaming. Therefore, this invention can be used suitably for the manufacturing method of a ultraviolet shielding gel-like composition.

Further, according to the cosmetic of the present invention, since it contains the ultraviolet shielding gel-like composition of the present invention, a cosmetic that is excellent in ultraviolet shielding function, transparency, and feeling of use, and excellent in quality stability and safety. Can be provided. Therefore, this invention can be used suitably for cosmetics.

Claims

0.01% to 5% by weight of polyacrylic acid polymer, 30% to 80% by weight of water, 0.1% to 5% by weight of emulsion type silicone, UV shielding agent-containing resin An ultraviolet shielding gel-like composition comprising 1% by mass to 50% by mass of particles and 1% by mass to 40% by mass of alcohol.
The ultraviolet shielding gel-like composition according to claim 1, further comprising 0.01% by mass to 5% by mass of a water-soluble polymer other than the polyacrylic acid polymer.
The emulsion type silicone is 10 mass% or more and 50 mass% or less of silicone resin, 0.5 mass% or more and 5 mass% or less of sorbitan fatty acid ester, and 0.5 mass% or more and 5 mass% or less of glycerin fatty acid ester. The ultraviolet shielding gel-like composition according to claim 1, wherein the composition contains 0.1% by mass or more and 1% by mass or less of sucrose fatty acid ester.
The ultraviolet shielding agent-containing resin particles contain one or both of an organic ultraviolet absorber and metal oxide particles having ultraviolet shielding ability in the resin particles, and have an average particle diameter of 0.05 μm or more and 5 μm. The following particles:
The metal oxide particles include one or more selected from the group consisting of zinc oxide, titanium oxide, cerium oxide, and iron oxide, and particles having an average particle diameter of 0.003 μm or more and 0.1 μm or less. Yes,
The ultraviolet shielding agent-containing resin particles have a content of the organic ultraviolet absorber of 0.1% by mass to 80% by mass and a content of the metal oxide particles of 1% by mass to 80% by mass. The ultraviolet shielding gel-like composition according to any one of claims 1 to 3, wherein the composition is an ultraviolet shielding gel-like composition.
The organic ultraviolet absorber is one or more selected from the group consisting of dibenzoylmethane compounds, benzophenone derivatives, paraaminobenzoic acid derivatives, methoxycinnamic acid derivatives, and salicylic acid derivatives. 4. The ultraviolet shielding gel-like composition according to 4.
A method for producing an ultraviolet shielding gel composition according to any one of claims 1 to 5,
Polyacrylic acid polymer is 0.01% by weight to 5% by weight, water is 30% by weight to 80% by weight, emulsion type silicone is 0.1% by weight to 5% by weight, UV shielding agent-containing resin These are mixed so that the particles are 1% by mass to 50% by mass and the alcohol is 1% by mass to 40% by mass, and then the hydrogen ion index of this mixture is 6 to 8%. A method for producing an ultraviolet shielding gel-like composition, wherein
A cosmetic comprising the ultraviolet shielding gel-like composition according to any one of claims 1 to 5.