JP2000290154A - Sunscreen cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject cosmetic excellent in dispersibility of an ultraviolet scattering agent and good in effects on protection against ultraviolet rays, preservation stability and feeling of use by including a specific long-chain alkyl- modified acrylic-silicone-based graft copolymer and titanium oxide and/or zinc oxide having a specified average particle diameter. SOLUTION: This cosmetic comprises (A) an organopolysiloxane compound having a radically polymerizable group at one terminal of the molecular chain, preferably a long-chain alkyl-modified acrylic-silicone-based graft copolymer prepared by copolymerizing a compound represented by the formula (R1 is methyl or H; R2 is a 1-10C bivalent saturated hydrocarbon; R is methyl or butyl; 1 is 3-300) and a radically polymerizable monomer consisting essentially of a 12-30C alkyl (meth)acrylate [e.g. stearyl (meth)acrylate] and (B) titanium oxide and/or zinc oxide having 0.01-0.10 μm average particle diameter in (1:1) to (1:50) formulation weight ratio of the ingredients A to B.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sunscreen cosmetic which is excellent in dispersibility of an ultraviolet light scattering agent, and has good ultraviolet protection effect, storage stability and feeling of use.

[0002]

2. Description of the Related Art Conventionally, in sunscreen cosmetics, various ultraviolet scattering agents have been used in order to impart an ultraviolet protection effect. As an example, titanium oxide, zinc oxide, iron oxide, zirconium oxide, aluminum oxide, and the like can be mentioned, and further, those in which these are made into fine particles, those in which they are compounded, and the like are blended. Among them, titanium oxide or zinc oxide is widely used.

[0003]

However, although the above-mentioned titanium oxide and zinc oxide are excellent in the ultraviolet scattering effect, they have a strong cohesive force of the powder. And the feeling of use becomes worse. In order to solve this problem, technical studies have been made to improve the dispersibility of titanium oxide and zinc oxide using various dispersants. For example, attempts have been made to use trimethylsiloxysilicic acid or polyoxyalkylene-modified silicone as a powder dispersant, but none of them has been able to satisfy the dispersion stability and feeling of use. Therefore, excellent dispersibility and dispersion stability of the ultraviolet scattering agent,
In addition, development of a sunscreen cosmetic having a good feeling of use has been desired.

[0004]

Means for Solving the Problems In view of the above circumstances, the present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, by using a specific long-chain alkyl-modified acryl-silicone graft copolymer. It has been found that the dispersibility of titanium oxide and zinc oxide is remarkably improved, and as a result, a sunscreen cosmetic with excellent transparency of the coating film, excellent ultraviolet protection effect, storage stability and feeling of use can be obtained. The invention has been completed.

That is, the present invention relates to the following components (A) and (B): (A) an organopolysiloxane compound having a radical polymerizable group at one end of a molecular chain, and an alkyl (meth) acrylate having 12 to 30 carbon atoms. (B) titanium oxide and / or zinc oxide having an average particle diameter of 0.01 to 0.10 μm obtained by copolymerizing a radical polymerizable monomer mainly composed of And the compounding weight ratio of component (A) and component (B) is (A) :( B) = 1: 1 to 1:
It is a sunscreen cosmetic characterized by being 50. Hereinafter, the present invention will be described in detail.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The long-chain alkyl-modified acryl-silicone graft copolymer of the component (A) used in the present invention comprises an organopolysiloxane compound having a radical polymerizable group at one end of a molecular chain and a carbon It is obtained by radically polymerizing radically polymerizable monomers mainly composed of alkyl (meth) acrylates of several 12 to 30. For example, an organopolysiloxane compound having radical polymerizability at one end of a molecular chain is represented by the following general formula (1)

[0007]

Embedded image

R ¹ : methyl group or hydrogen atom R ² : carbon atom having a linear or branched carbon chain optionally interrupted by one or two ether bonds
Ten divalent saturated hydrocarbon groups R ³ : a group represented by methyl group or butyl group 1: 3 to 300 are exemplified.

On the other hand, a radical polymerizable monomer mainly composed of acrylate and / or methacrylate means a compound having one radical polymerizable unsaturated bond in a molecule. An alkyl (meth) acrylate of the number 12 to 30 is an essential component, and examples thereof include stearyl (meth) acrylate and behenyl (meth) acrylate. In addition, alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate; Hydroxyalkyl (meth) acrylates such as hydroxypropyl (meth) acrylate, perfluoroalkyl (meth) acrylates having a fluorocarbon chain of 1 to 10, cholesteryl (meth) acrylate, alkyl cholesteryl (meth) acrylate, (meth) acrylamide Can be used. Further, in the radical polymerizable monomer mainly composed of acrylate and / or methacrylate in the present invention, various polymerizable monomer compounds other than the above-mentioned acrylate and / or methacrylate can be used as needed. These compounds include styrene,
Substituted styrene, vinyl acetate, (meth) acrylic acid, maleic anhydride, maleic ester, fumaric ester,
Vinyl chloride, vinylidene chloride, ethylene, propylene,
Butadiene, acrylonitrile, fluorinated olefin, N
-Vinylpyrrolidone and the like. The copolymerization of the dimethylpolysiloxane compound (A) having a radical polymerizable group at one end of the molecular chain with the radical copolymerizable monomer (B) mainly composed of acrylate and / or methacrylate has a polymerization ratio ((A) / (B)): 1 / 19-
In the range of 2/1, the reaction is carried out in the presence of a usual radical polymerization initiator such as benzoyl peroxide, lauroyl peroxide, azobisisobutyronitrile, etc. Any of the bulk polymerization methods can be applied. KP561 as a commercial product
(Manufactured by Shin-Etsu Chemical Co., Ltd.).

The titanium oxide and / or zinc oxide of the component (B) used in the present invention has an average particle diameter of 0.01 to 0.1.
It is essential that the thickness is 1 μm, and any shape such as a sphere, a plate, a spindle, and a needle can be used. When the average particle diameter of titanium oxide and zinc oxide is less than 0.01 μm, the powder is agglomerated to deteriorate the ultraviolet protection effect and usability, and when the particle diameter is larger than 0.1 μm, transparency is impaired. In addition, the UV protection effect is deteriorated. Among these titanium oxides and zinc oxides, in order to suppress the surface activity, those treated with an inorganic substance such as aluminum oxide, silicon oxide, and zirconium oxide, those treated with an organic substance such as stearic acid, and the like can be used. Can be used. Further, those obtained by subjecting the surface-treated titanium oxide or zinc oxide to a hydrophobic treatment such as a silicone treatment, a fatty acid treatment, a metal soap treatment, a fluorine treatment, or a hydrophilic treatment such as a polyacrylic acid treatment may also be used. can do.

In the sunscreen cosmetic of the present invention, the above-mentioned alkyl-modified acrylic silicone-based graft copolymer of the component (A) and the titanium oxide and / or the component (B) are used.
Or, the mixing weight ratio of zinc oxide is (A) :( B) = 1: 1.
１ ： 1: 50 is essential, and more preferably (A) :( B) = 1: 10 to 1:40. If the compounding weight ratio of the component (B) to the component (A) exceeds 50, good dispersibility cannot be obtained, and if the weight ratio is less than 1, the sticky feeling and the weight of elongation may be reduced. There are disadvantages in feel.

[0012] The sunscreen cosmetic of the present invention can obtain a higher ultraviolet protection effect by blending an organic ultraviolet absorber in addition to the above essential components. Examples of the organic ultraviolet absorber used in the present invention include benzyl paramethoxycinnamate, 2-ethylhexyl paramethoxycinnamate, 2-ethoxyethyl paramethoxycinnamate, glyceryl mono-2-ethylhexanoate diparamethoxycinnamate, and paramethoxycinnamate Cinnamic acid-based ultraviolet absorbers such as isopropyl acid / diisopropyl cinnamate mixture, hydroxymethoxybenzophenone, hydroxymethoxybenzophenonesulfonic acid, sodium hydroxymethoxybenzophenonesulfonate, dihydroxymethoxybenzophenone, sodium dihydroxymethoxybenzophenonedisulfonate, dihydroxybenzophenone, Benzophenone UV absorbers such as tetrahydroxybendiphenone and urocanic acids such as urocanic acid and ethyl urocanate External ray absorbent, paraaminobenzoic acid, ethyl paraaminobenzoate, glyceryl paraaminobenzoate, amyl paradimethylaminobenzoate, octyl paradimethylaminobenzoate, 4- [N, N-di (2-hydroxypropyl) amino] benzoic acid Benzoic acid ester ultraviolet absorbers such as ethyl, salicylic acid ultraviolet absorbers such as ethylene glycol salicylate, phenyl salicylate, octyl salicylate, benzyl salicylate, p-tert-butylphenyl salicylate, and homomenthyl salicylate;
-Tert-butyl-4'-methoxybenzoylmethane, oxybenzone, 2,4,6-trianilino-p-
(Carbo-2'-ethylhexyl-1'-oxy)-
1,3,5-triazine, menthyl anthranilate, 2
-(2-hydroxy-5-methylphenyl) benzotriazole and the like, and one or more of these can be appropriately selected and blended. The preferred amount is
It is not more than 20% by weight (hereinafter simply referred to as "%"), more preferably 0.1 to 10%.

Further, the sunscreen cosmetic of the present invention is a water-in-oil (W / O) emulsion cosmetic containing a polyoxyalkylene-modified silicone and / or a polyoxyalkylene-modified silicone containing a long-chain alkyl. More usability,
A product having an excellent ultraviolet protection effect and stability can be obtained. Examples of the polyoxyalkylene-modified silicone and the long-chain alkyl-containing polyoxyalkylene-modified silicone used in the present invention include those represented by the following general formulas (2) and (3).

[0014]

Embedded image [In the formula (2), R ¹ represents an alkyl group having 1 to 5 carbon atoms or a phenyl group. R ² represents —Q ¹ —O— (C ₂ H
_{4 O) m- (C 3 H} 6 O) n-R 3 ( where, ^{Q 1} represents a divalent hydrocarbon group having 1 to 5 carbon atoms, ^{R 3} is a hydrogen atom, C1-5 Represents an alkyl group or an acetyl group.
m is an integer of 1 or more, and n is 0 or an integer of 1 or more. ). G ¹ and G ² may be the same or different and each represents R ¹ or R ² . a and b each represent 0 or an integer of 1 or more. However, when b = 0, at least one of G ¹ and G ² is R ² . ]

R ¹ _a R ² _b R ³ _c SiO _{(4-abc) / 2} (3) [In the formula (3), R ¹ is an alkyl group having 1 to 10 carbon atoms;
It represents an aryl group, an aralkyl group or a fluorine-substituted alkyl group. R ² _{is, -C m H 2m -O- (C} 2 H 4 O) d
_(C 3 _H 6 O) organic group represented by ^{e-R 4, R 3} is -
_{C n H 2n -O- (C 2} H 4 O) f (C 3 H 6 O) g-
The organic group represented by R ⁵ (where, ^{R 4} is an alkyl group or ^R 6 a hydrogen atom or a C1-5 - (CO) - organic group represented by, ^{R 6} is alkyl of 1 to 5 carbon atoms Represents a group, d is an integer of 2 to 200, e is an integer of 0 to 200, and d + e is 3 to 200, f is an integer of 0 to 50, g is an integer of 0 to 50, and f + g is 0 to 50, and m and n are each an integer of 0 to 5.)
a, b, and c are 1.0 ≦ a ≦ 2.5 and 0.00, respectively.
1 ≦ b ≦ 1.5 and 0.001 ≦ c ≦ 1.5. ]

The content of the polyoxyalkylene-modified silicone and / or the long-chain alkyl-containing polyoxyalkylene-modified silicone used in the present invention is 0.5 to 30.
0% is preferable, and more preferably, it is 1.0 to 10.0%. By using in this range, a water-in-oil type sunscreen cosmetic having excellent usability and stability can be obtained.

The sunscreen cosmetic of the present invention may contain, in addition to the above components, components generally used in cosmetics as long as the effects of the present invention are not impaired. Such components include, for example, fats, waxes, hydrocarbons, fatty acids,
Oil materials such as alcohols, ester oils, ether oils, silicone oils, fluorine compounds, powder materials other than component (B), metal soaps, surfactants, silicone surfactants, polyhydric alcohols, antioxidants Agents, polymer compounds, fragrances, preservatives, UV protection agents, humectants, pH
Modifiers, cosmetic ingredients, pigments, fragrances, and the like.

[0018]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.

Production Example 1 Acrylic-silicone graft copolymer 1 The following composition formula (4)

[0020]

Embedded image

50 g of dimethyl polysiloxane substituted with methacrylate at one end, methyl methacrylate 10
g, stearyl methacrylate 40 g, toluene 100
g of azobisisobutyronitrile 1.5
After adding and dissolving g, the mixture was reacted for 5 hours in a temperature range of 80 to 90 ° C. with stirring to obtain a viscous solution. The solution was poured into methanol to precipitate the graft polymer. The precipitate was separated by filtration and dried to obtain a polymer.

Production Example 2 Acrylic-Silicone Graft Copolymer 2 The following compositional formula (5)

[0023]

Embedded image

A mixture of 60 g of dimethyl polysiloxane substituted with methacrylate at one end, 5 g of n-butyl methacrylate, 25 g of stearyl methacrylate, 10 g of behenyl methacrylate and 100 g of toluene, and then 1.5 g of azobisisobutyronitrile were added and dissolved. After the reaction, the mixture was reacted for 5 hours in a temperature range of 80 to 90 ° C. with stirring to obtain a viscous solution. The solution was poured into methanol to precipitate the graft polymer. The precipitate was separated by filtration and dried to obtain a polymer.

Examples 1 to 3 and Comparative Examples 1 to 3 Water-in-oil type (W / O type) according to the composition shown in Table 1 and the following production method
Sunscreen cosmetics were prepared and evaluated for usability (good spreadability, non-stickiness, lack of whiteness of the coating film), ultraviolet protection effect, and dispersibility using the following test methods.

[0026]

[Table 1]

(Production method) A: Components 1 to 8 are kneaded with three rollers. B: Components 9 to 13 are mixed and dissolved. C: B was injected into A while stirring, emulsified, and defoamed to obtain a water-in-oil type sunscreen cosmetic.

(Evaluation method) (A) Usability and UV protection test Using the sunscreen cosmetics of Examples 1 to 3 and Comparative Examples 1 to 3, a use test was conducted by a 10-person expert evaluation panel.
Good spreadability, non-stickiness, lack of whiteness of the coating film, and ultraviolet protection effect were evaluated according to the following evaluation criteria, and the average was evaluated according to the following criteria. [Evaluation criteria] 5 points: Very good. 4 points: good. 3 points: Normal. 2 points: bad. 1 point: very bad. [Judgment Criteria] ：: Average score of 4.5 or more ○: Average score of 3.5 or more and less than 4.5 Δ: Average score of 2.5 or more and less than 3.5 ×: Average score of less than 2.5

(B) Dispersibility test In general, it is known that, when the dispersibility of the fine particle powder is improved, the hiding power is reduced and the transparency is improved. In the present invention, the dispersibility of the powder was evaluated based on the transparency of the coating film. Using the sunscreen cosmetics of Examples 1 to 3 and Comparative Examples 1 to 3 as samples, each sample was tested for hiding power test paper (JI
SK5101) was spread using a 4 mil doctor blade, and the transparency was visually evaluated according to the following criteria. [Judgment Criteria] A: Very good. ：: good. Δ: Somewhat poor. X: Poor. The results obtained are shown in Table 1.

As is evident from the results in Table 1, Examples 1 to 3 according to the present invention have good usability and an ultraviolet protection effect, and are excellent in powder dispersibility. I was satisfied. On the other hand, in Comparative Examples 1 to 3, none satisfying all the evaluation items was obtained.

Example: 4 Water-in-oil type (W / O type) sunscreen cosmetic (component) (%) 1. Cross-linked polyether-modified silicon 3.0 2. Methylpolysiloxane 7.0 Decamethylpentacyclopolysiloxane 10.0 4. 4. Isotridecyl isononanoate 10.0 5. Methylphenyl polysiloxane 5.0 Acrylic-silicone graft copolymer (Production Example 2) 2.0 7. 7. Stearic acid-treated titanium oxide (average particle diameter 0.03 μm) 10.0 8. Zinc oxide (average particle size 0.02 μm) 5.0 Purified water balance 10. Sodium chloride 0.5 11.1,3-butylene glycol 8.0 12. 12. Methyl paraoxybenzoate 0.2 Appropriate amount of fragrance

(Preparation method) Components 1 to 8 are kneaded with three rollers. The components 9 to 12 mixed and dissolved therein were added with stirring and emulsified, and the components 13 were added and deaerated to obtain a water-in-oil type sunscreen cosmetic. Example 4 was a water-in-oil type sunscreen cosmetic having good dispersibility of powder and excellent usability.

Example 5 Oil-in-Water (O / W Type) Sunscreen Cosmetic (Component) (%) Decamethylpentacyclopolysiloxane 10.02. 2. Glyceryl tri-2-ethylhexanoate 10.0 Methylphenyl polysiloxane 5.0 4. Acrylic-silicone graft copolymer (Production Example 1) 2.05. 5. Stearic acid-treated titanium oxide (average particle diameter 0.01 μm) 10.0 6. Zinc oxide (average particle diameter 0.03 μm) 5.0 Stearic acid 2.0 8. Cetanol 1.0 9. Glyceryl monostearate 0.5 10. Purified water balance 11. Triethanolamine 1.0 12.1,3-butylene glycol 8.0 13. 13. Methyl paraoxybenzoate 0.2 Carboxyvinyl polymer 0.1 15. Appropriate amount of fragrance

(Preparation method) Components 1 to 9 are kneaded with three rollers. This was added to the homogeneously mixed components 10 to 14 while stirring to emulsify, and the components 15 were added and deaerated to obtain an oil-in-water sunscreen cosmetic. Example 5 was an oil-in-water sunscreen cosmetic having good powder dispersibility and excellent usability.

Example 6 Oily Sunscreen Cosmetic (Component) (%) Cross-linked methylpolysiloxane 10.0 2. Methyl polysiloxane 10.0 3. 3. Decamethylpentacyclopolysiloxane remaining amount 4. Isotridecyl isononanoate 10.0 5. Methylphenyl polysiloxane 5.0 Acrylic-silicone graft copolymer (Production Example 1) 1.0 7. 7. Acrylic-silicone graft copolymer (Production Example 2) 1.0 Glyceryl tribehenate 3.0 3.0 9. 10. Stearic acid-treated titanium oxide (average particle diameter 0.05 μm) 10.0 10. Zinc oxide (average particle diameter 0.03 μm) 10.0 11. Siliconized sericite 20.0 Appropriate amount of fragrance

(Preparation method) Components 1 to 11 are kneaded with three rollers. Component 12 was added to the mixture and the mixture was degassed to obtain an oily sunscreen cosmetic. Example 6 was an oily sunscreen cosmetic having good powder dispersibility and excellent usability.

[0037]

As described in detail above, the sunscreen cosmetics of the present invention have good usability and UV protection effect,
Moreover, it is excellent in powder dispersibility.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4C083 AB211 AB212 AB241 AB242 AB332 AB432 AC072 AC102 AC122 AC242 AC342 AC352 AC392 AC422 AC482 AC542 AD092 AD152 AD161 AD162 AD172 BB46 CC05 CC19 DD31 DD32 DD33 EE17

Claims (4)

[Claims] 1. The following components (A) and (B): (A) mainly comprising an organopolysiloxane compound having a radical polymerizable group at one end of a molecular chain and an alkyl (meth) acrylate having 12 to 30 carbon atoms. A long-chain alkyl-modified acrylic-silicone-based graft copolymer obtained by copolymerizing a radically polymerizable monomer (B) containing titanium oxide and / or zinc oxide having an average particle diameter of 0.01 to 0.10 μm, And the compounding weight ratio of the component (A) and the component (B) is (A) :( B) = 1: 1 to 1:
50. A sunscreen cosmetic characterized by being 50. 2. A sunscreen cosmetic comprising an ultraviolet absorber in addition to the component according to claim 1. 3. A sunscreen characterized by containing one or more selected from polyoxyalkylene-modified silicones and long-chain alkyl-containing polyoxyalkylene-modified silicones in addition to the components described in claim 1 or 2. Cosmetics. 4. The sunscreen cosmetic according to claim 1, which is a water-in-oil emulsion cosmetic.