JP6366241B2 - Fine particle metal oxide and external preparation for skin containing the fine particle metal oxide - Google Patents

Description

  The present invention relates to a fine particle metal oxide having improved dispersibility in a dispersion medium, and also relates to a skin external preparation containing the fine particle metal oxide.

  Cosmetics, particularly makeup cosmetics, are required to have a high UV protection effect. In order to impart a high UV protection effect to cosmetics, so-called UV-A absorbers that absorb 320 to 400 nm wavelength (A region) UV rays and 290 to 320 nm wavelength (B region) UV rays are absorbed in cosmetics. So-called UV-B absorbers are blended. These ultraviolet absorbents are highly viscous oils, and when a high concentration of the ultraviolet absorbent is blended in order to obtain a high ultraviolet protective effect, there is a problem that the feeling of use of the cosmetic is impaired.

  As an attempt to improve the feeling of use of a cosmetic containing a high concentration of an ultraviolet absorber, it has been studied to add a particulate metal oxide. In cosmetics containing fine metal oxides, it is necessary to uniformly disperse the fine metal oxides in the cosmetics in order to exert a high UV absorption effect. Have been proposed (see, for example, Patent Documents 1 and 2).

JP 2011-093826 A JP 2009-191033 A

  This invention makes it a subject to provide the skin external preparation which has a sufficient ultraviolet-ray protective effect and has a favorable usability in the skin external preparation which mix | blended the ultraviolet absorber.

  The inventors of the present invention have studied to solve the above-described problems. As a result, the conventionally proposed technique does not have sufficient dispersibility of the fine particle metal oxide, so that the ultraviolet absorption effect is not sufficient, and the skin It was thought that the feeling of use when using an external preparation was not sufficient. Then, in order to improve the dispersibility of the fine particle metal oxide, the surface treatment method of the fine particle metal oxide was examined. As a result, (a) a reactive organopolysiloxane having a specific structure, and (b) at least one phenyl group. The present inventors have found that the above-mentioned problems can be solved by treating the surface of the fine-particle metal oxide with an organopolysiloxane having the present invention.

上記式（３）中、Ｒ_３は独立して、水素、炭素数１〜３のアルキル基、及び炭素数１〜３のアルコキシ基から選択される。Ｒ_４は独立して水素、炭素数１〜３のアルキル基、下記一般式（４）で表される基及びフェニル基から選択されるとともに、フェニル基を有するユニットを少なくとも１つ有する。ｎは整数である。

上記式（４）中Ｒ_５は独立して炭素数１〜３のアルキル基を表す。
（３）前記式（３）において、Ｒ_３は独立して、炭素数１〜３のアルキル基、及び炭素数１〜３のアルコキシ基から選択され、Ｒ_４は独立して炭素数１〜３のアルキル基、下記一般式（４）で表される基及びフェニル基から選択されるとともに、フェニル基を有するユニットを少なくとも１つ有する、（２）に記載の微粒子金属酸化物。

上記式（４）中Ｒ_５は独立して炭素数１〜３のアルキル基を表す。
（４）前記式（３）において、Ｒ_３は独立して、炭素数１〜３のアルキル基から選択され、Ｒ_４は独立して炭素数１〜３のアルキル基、下記一般式（４）で表される基及びフェニル基から選択されるとともに、フェニル基を有するユニットを少なくとも１つ有する、（２）または（３）に記載の微粒子金属酸化物。

上記式（４）中Ｒ_５は独立して炭素数１〜３のアルキル基を表す。
（５）前記微粒子金属酸化物が微粒子酸化チタン、及び微粒子酸化亜鉛から選択される少なくとも１種を含む、（１）〜（４）のいずれかに記載の微粒子金属酸化物。 The first embodiment of the present invention is as follows.
(1) (a) The degree of polymerization is 25 or more and 100 or less, the ratio Mw / Mn between the weight average molecular weight Mw and the number average molecular weight Mn is 1 or more and 1.3 or less, and at least one molecular chain terminal is alkoxylated A linear reactive organopolysiloxane having at least one selected from the group consisting of a group, a hydroxyl group, a halogen atom, an amino group and an imino group, and (b) an organopolysiloxane having at least one phenyl group. Coated, particulate metal oxide.
(2) The fine particle metal oxide according to (1), wherein (b) the organopolysiloxane having at least one phenyl group is represented by the following general formula (3).

In the formula (3), _{R 3} is independently hydrogen, are selected from alkyl groups having 1 to 3 carbon atoms, and alkoxy group having 1 to 3 carbon atoms. R ₄ is independently selected from hydrogen, an alkyl group having 1 to 3 carbon atoms, a group represented by the following general formula (4), and a phenyl group, and has at least one unit having a phenyl group. n is an integer.

In the above formula (4), R ₅ independently represents an alkyl group having 1 to 3 carbon atoms.
(3) In the formula (3), R ₃ is independently selected from an alkyl group having 1 to 3 carbon atoms and an alkoxy group having 1 to 3 carbon atoms, and R ₄ is independently selected from 1 to 3 carbon atoms. The fine-particle metal oxide according to (2), which is selected from an alkyl group of the above, a group represented by the following general formula (4), and a phenyl group, and having at least one unit having a phenyl group.

In the above formula (4), R ₅ independently represents an alkyl group having 1 to 3 carbon atoms.
(4) In the formula (3), R ₃ is independently selected from an alkyl group having 1 to 3 carbon atoms, R ₄ is independently an alkyl group having 1 to 3 carbon atoms, and the following general formula (4) The fine particle metal oxide according to (2) or (3), which is selected from the group represented by formula (I) and a phenyl group, and has at least one unit having a phenyl group.

In the above formula (4), R ₅ independently represents an alkyl group having 1 to 3 carbon atoms.
(5) The particulate metal oxide according to any one of (1) to (4), wherein the particulate metal oxide contains at least one selected from particulate titanium oxide and particulate zinc oxide.

The second embodiment of the present invention is as follows.
(6) A skin external preparation containing the particulate metal oxide according to any one of (1) to (5) and an ultraviolet absorber.
(7) The skin external preparation described in (6), which contains an ultraviolet absorber that absorbs ultraviolet rays in the A region and an ultraviolet absorber that absorbs ultraviolet rays in the B region.
(8) The external preparation for skin according to (6) or (7), which is a cosmetic.

According to the present invention, high it has ultraviolet ray defense effect, and can provide a skin external preparation which does not impair the feeling. Moreover, the fine particle metal oxide contained in such a skin external preparation can be provided.

The first embodiment of the present invention is a particulate metal oxide surface-treated with two types of organopolysiloxanes.
The type of the particulate metal oxide is not particularly limited as long as it is a metal oxide that can be blended into the external preparation for skin. Examples of metal oxides include titanium dioxide, zinc oxide, zirconium oxide, cerium oxide and the like. The surface of these metal oxides may be coated with an inorganic compound such as silica or alumina, or an organic compound such as fatty acid metal soap or silicone.

The fine particle metal oxide has a particle size referred to as a fine particle in the technical field. For example, the primary particle size by electron microscope observation is usually 5 nm or more, preferably 10 nm or more, and usually 100 nm or less, preferably 80 nm. It is as follows.
The fine particle metal oxide used in this embodiment preferably has at least one selected from the group consisting of fine particle titanium dioxide and fine particle zinc oxide because of its excellent ultraviolet absorption effect.

  The fine particle metal oxide used in the present embodiment can be prepared by a conventional method such as thermal decomposition of the corresponding metal salt in the gas phase, but there are many commercially available products. It can also be used as it is. Specific examples of such commercially available products include “MTY-110M3S” (manufactured by Teica), “MTY-02” (manufactured by Teica), “MT-100TV” ( (Taika Corporation), “MT-500HSA” (Taika Corporation), “MT-100T” (Taika Corporation), “MT-01” (Taika Corporation), “MT-10EX” ”(Manufactured by Teika),“ MT-05 ”(manufactured by Teika),“ MT-100Z ”(manufactured by Teica),“ MT-150EX ”(manufactured by Teica),“ MT -100AQ "(manufactured by Teika)," MT-100WP "(manufactured by Teika)," MT-100SA "(manufactured by Teica)," MT-500B "(manufactured by Teica), “MT-500SA” (manufactured by Teika Co., Ltd., “MT-600B”) ) "MT-500SAS" (manufactured by Teika Co., Ltd.), "Taipeke CR-50" (manufactured by Ishihara Sangyo Co., Ltd.), "Taipeke TTO-M-1" (Ishihara Sangyo Co., Ltd.) "Taipaque TTO-V4" (Ishihara Sangyo Co., Ltd.), "ST-455" (Titanium Industry Co., Ltd.), "STT-65C-S" (Titanium Industry Co., Ltd.), "STT- 30EHS "(manufactured by Titanium Industry Co., Ltd.)," Bayer Titanium R-KB-1 "(manufactured by Bayer) and the like.

  Further, as fine particle zinc oxide, “MZ-300” (manufactured by Teika), “MZY-303S” (manufactured by Teika), “MZ-306X” (manufactured by Teica), “MZ-500”. "(Manufactured by Teica)," MZY-505S "(manufactured by Teika)," MZ-506X "(manufactured by Teica)," MZ-510HPSX "(manufactured by Teica)," WSX -MZ-700 "(manufactured by Teika Co., Ltd.)," SAMT-UFZO-450 "(manufactured by Miyoshi Kasei Co., Ltd.)," SAMT-UFZO-500 "(manufactured by Miyoshi Kasei Co., Ltd.)," FZO-50 " (Manufactured by Ishihara Sangyo Co., Ltd.), “Maxlite ZS-032” (manufactured by Showa Denko KK), “Maxlite ZS-032D” (manufactured by Showa Denko KK) and the like.

The particulate metal oxide according to this embodiment is coated with (a) a reactive organopolysiloxane having a specific structure, and (b) an organopolysiloxane having at least one phenyl group.
The present inventors improved the dispersibility of the particulate metal oxide in the dispersion medium containing the ultraviolet absorber by coating the particulate metal oxide with the above-mentioned two types of organopolysiloxanes (a) and (b). It was conceived that when it was used as an external preparation for skin, it exhibited a sufficient ultraviolet absorption effect and had a good usability.

(A) The organopolysiloxane is a linear reactive organopolysiloxane having a degree of polymerization of 25 to 100 and a ratio Mw / Mn of the weight average molecular weight Mw to the number average molecular weight Mn of 1 to 1. 3 or less, and at least one molecular chain terminal has at least one selected from the group consisting of an alkoxy group, a hydroxyl group, a halogen atom, an amino group, and an imino group.
The reactive group selected from the group consisting of an alkoxy group, a hydroxyl group, a halogen atom, an amino group and an imino group may be present at at least one molecular chain end, and may be present at both molecular chain ends. From the viewpoint of reactivity with oxides, etc., at least one of these reactive groups may be present at only one molecular chain end.
As an alkoxy group, a C1-C5 thing is preferable and a C1-C3 thing, ie, a methoxy group, an ethoxy group, and a propoxy group are more preferable.
As the halogen atom, chlorine, bromine, iodine and the like are preferable.

The degree of polymerization of the (a) reactive organopolysiloxane used in this embodiment is 25 or more and 100 or less. Preferably it is 30 or more. Moreover, it is preferable that it is 60 or less, and it is more preferable that it is 50 or less.
By setting the degree of polymerization within this range, the usability when blended in a cosmetic and the reactivity with the fine particle metal oxide are improved.

  The (a) reactive organopolysiloxane used in this embodiment has a ratio Mw / Mn (hereinafter also referred to as molecular weight dispersity) of the weight average molecular weight Mw and the number average molecular weight Mn of 1 or more and 1.3 or less. It is. When the value of Mw / Mn is within this range, the molecular weight distribution becomes sharp, and it is easy to obtain a good feeling when used in cosmetics. The weight average molecular weight and the number average molecular weight can be determined by GPC (gel permeation chromatography), for example.

Specific examples of the (a) reactive organopolysiloxane used in this embodiment include polyorganosiloxanes represented by the following general formulas (1) and (2).

In the above formulas (1) and (2), R ₁ is independently selected from alkyl groups having 1 to 3 carbon atoms. A C1-C3 alkyl group is a methyl group, an ethyl group, and a propyl group.
In the above formula (1), R ₂ is independently selected from the group consisting of an alkyl group, an alkoxy group, a hydroxyl group, a halogen atom, an amino group, and an imino group, and at least one of R ₂ is an alkoxy group, a hydroxyl group , A reactive group selected from the group consisting of a halogen atom, an amino group and an imino group. As an alkoxy group, it is preferable that it is a C1-C3 alkoxy group, and a methoxy group, an ethoxy group, and a propoxy group are preferable. As the halogen atom, chlorine, bromine and iodine are preferable.
R is independently selected from a single bond and a divalent hydrocarbon group, and when it is a divalent hydrocarbon group, the hydrogen atom is a hydroxyl group, a methoxy group, an ethoxy group, a methyl group, or an ethyl group May be substituted. Examples of the divalent hydrocarbon group include a methylene group, an ethylene group, and a propene group.
m is usually 25 or more, preferably 30 or more, and is usually 100 or less, preferably 60 or less, more preferably 50 or less.

As further specific examples of the above-mentioned (a) reactive organopolysiloxane, for example, dimethylpolysiloxysilazane, α-monohydroxysiloxane, α, ω-dihydroxypolydimethylsiloxane, α-monoalkoxypolydimethylsiloxane, α-di Alkoxypolydimethylsiloxane, α-trialkoxypolydimethylsiloxane, α, ω-dialkoxydimethylpolysiloxane, α, ω-hexaalkoxypolydimethylpolysiloxane, dimethylpolysiloxane chloride, dimethylpolysiloxybromide, and dimethylpolysiloxy iodide Etc.
Among them, α-monoalkoxypolydimethylsiloxane, α-dialkoxypolydimethylsiloxane and α-trialkoxypolydimethylsiloxane (for example, α-triethoxypolydimethylsiloxane) have very good reactivity. This is preferable because it provides a smooth feel.

  The (b) organopolysiloxane is an organopolysiloxane having a phenyl group. (B) As long as the organopolysiloxane has a phenyl group, the type thereof is not particularly limited, and examples thereof include organopolysiloxanes represented by the following general formula (3).

上記式（４）中Ｒ_５は独立して炭素数１〜３のアルキル基を表す。 In the formula (3), _{R 3} is independently hydrogen, are selected from alkyl groups having 1 to 3 carbon atoms, and alkoxy group having 1 to 3 carbon atoms. Preferably, R ₃ is independently selected from an alkyl group having 1 to 3 carbon atoms and an alkoxy group having 1 to 3 carbon atoms, and more preferably, R ₃ is independently alkyl having 1 to 3 carbon atoms. Selected from the group.
R ₄ is independently selected from hydrogen, an alkyl group having 1 to 3 carbon atoms, a group represented by the following general formula (4), and a phenyl group, and has at least one unit having a phenyl group. Preferably, R ₄ is independently selected from an alkyl group having 1 to 3 carbon atoms and a phenyl group, and has at least one unit having a phenyl group.
n is an integer and is usually 3 or more, preferably 5 or more, and usually 600 or less, preferably 400 or less.

In the above formula (4), R ₅ independently represents an alkyl group having 1 to 3 carbon atoms.

Preferable specific examples contained in the (b) organopolysiloxane include monophenyl dimethicone, diphenyl dimethicone, diphenylsiloxyphenyl trimethicone, trimethylsiloxyphenyl dimethicone and the like. These can be prepared according to conventional methods, but commercially available products may also be used.
Examples of commercially available products include “silicone KF54” (manufactured by Shin-Etsu Chemical Co., Ltd.), “silicone KF56” (manufactured by Shin-Etsu Chemical Co., Ltd.), “BELSEL PDM 1000” (manufactured by Asahi Kasei Wacker Silicone Co., Ltd.), and the like.
The number average molecular weight of the (b) organopolysiloxane is not particularly limited, but is usually 500 or more, preferably 800 or more, and usually 100,000 or less, preferably 80000 or less.

  The surface treatment of the fine metal oxide with the organopolysiloxanes (a) and (b) may be performed according to a conventional method. For example, if necessary, the fine metal oxide is mixed with a mixer such as a Henschel mixer using a solvent. And organopolysiloxane are mixed and the mixture is heated. Further, the order of the treatment with the organopolysiloxanes (a) and (b) is not particularly limited, but after the surface treatment with the organopolysiloxane (a), the treatment with the organopolysiloxane (b) is performed. Thus, the effect of the present invention becomes more remarkable and preferable.

In the particulate metal oxide according to this embodiment, the coating amount of the organopolysiloxanes (a) and (b) above is usually 0.5% by mass or more, preferably with respect to the particulate metal oxide after the surface treatment. It is 1 mass% or more, and is usually 25 mass% or less, preferably 20 mass% or less. By making the coating amount with the organopolysiloxane within this range, the dispersibility of the fine particle metal oxide according to the present embodiment becomes better, and when it is blended into a skin external preparation, it exhibits a sufficient ultraviolet absorption effect and feels to be used. Will also be good.

  Moreover, the ratio of the coating amount of the organopolysiloxane (a) and (b) is not particularly limited, and is usually (a) :( b) = 95: 5 to 5:95, preferably 80: 20-20; 80, more preferably 70: 30-30: 70.

The second embodiment of the present invention is a skin external preparation containing the particulate metal oxide according to the first embodiment and an ultraviolet absorber.
In the external preparation for skin according to this embodiment, the blending amount of the fine particle metal oxide according to the first embodiment is not particularly limited and can be appropriately set according to the type of cosmetic, It is usually 1% by mass or more, preferably 2% by mass or more, and usually 70% by mass or less, preferably 50% by mass or less, more preferably 30% by mass or less.
The ultraviolet absorber is not particularly limited as long as it is an ultraviolet absorber that can be blended into a skin external preparation, but UV-A that absorbs ultraviolet rays having a wavelength of 320 to 400 nm (A region) in order to absorb ultraviolet rays having a wide range of wavelengths. It is preferable to include an absorber and a UV-B absorber that absorbs ultraviolet rays having a wavelength of 290 to 320 nm (B region).
The blending amount of the ultraviolet absorber is not particularly limited, and is usually 0.01% by mass or more, preferably 0.1% by mass or more, and usually 15% by mass or less, preferably 10% by mass with respect to the total amount of the external preparation for skin. % Or less.

  Examples of UV-A absorbers include 2-hydroxy-4-methoxybenzophenone, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, dimethoxybenzylidenedioxoimidazolidinepropionate 2-ethylhexyl, and bis (reslucinyl). Examples include triazine, methylenebisbenzotriazolyltetramethylbutylphenol, hexyl diethylaminohydroxybenzoyl benzoate, t-butylmethoxybenzoylmethane, and the like. Among these, diethylaminohydroxybenzoyl hexyl benzoate and t-butylmethoxybenzoylmethane are particularly preferable because of their excellent ultraviolet absorbing ability. Since these compounds have commercial products, commercial products can be used as they are. Specific commercial products include “Ubinal A Plus Granular” (diethylaminohydroxybenzoyl hexyl benzoate manufactured by BASF) and “Pulsol 1789” (manufactured by t-butylmethoxybenzoylmethane DSM).

  The content of the UV-A absorber is usually 0.01% by mass or more, preferably 0.1% by mass or more, and usually 5% by mass or less, preferably 3% by mass or less, based on the total amount of the external preparation for skin. It is.

Specific examples of the UV-B absorber include 2-methoxyhexyl paramethoxycinnamate, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, dimethicodiethylbenzalmalonate, 2,4,6-trianilino Examples include -p- (carbo-2'-ethylhexyl-1'-oxy) -1,3,5-triazine, 2-hydroxy-4-methoxybenzophenone, homomenthyl salicylate, octyl salicylate and the like. Since these compounds have commercial products, commercial products can be used as they are. Specific commercial products include “Ubinal MC80” (2-ethylhexyl paramethoxycinnamate, manufactured by BASF), “Ubinal T150” (2,4,6-trianilino-p- (carbo-2′-ethylhexyl-1′-). Oxy) -1,3,5-triazine (made by BASF), “Ubinal M40” (made by 2-hydroxy-4-methoxybenzophenone BASF), “Pulsol SLX” (made by dimethicodiethylbenzalmalonate DSM), “Pulsol 340” (2-ethylhexyl 2-cyano-3,3-diphenylacrylate, manufactured by DSM), “Pulsol HMS” (homomothyl salicylate, manufactured by DSM), “Pulsol EMS” (made by octyl salicylate, DSM) can be exemplified. .

  The content of the UV-B absorber is usually 0.1% by mass or more, preferably 0.5% by mass or more, and usually 10% by mass or less, preferably 7% by mass or less, based on the total amount of the external preparation for skin. It is. With the content in the above range, the ultraviolet absorption effect can be exhibited better.

The skin external preparation according to this embodiment is not particularly limited as long as it is externally administered to the skin, and examples thereof include cosmetics including quasi-drugs, and skin external goods. More preferably, it is used as a cosmetic.
The external preparation for skin according to this embodiment may take any of the conventionally known emulsion dosage forms, essence dosage forms, cream dosage forms, and powder-containing dosage forms. The cosmetics, basic cosmetics, hair cosmetics, but any such makeup cosmetics can be applied, since the ultraviolet absorption Osamuko result is good, it is particularly preferable to apply the sunscreen.

In the external preparation for skin according to this embodiment, in addition to the above-described components, optional components that are usually used in cosmetics and external preparations for skin can be contained. Such optional ingredients include, for example: macadamia nut oil, avocado oil, corn oil, olive oil, rapeseed oil, sesame oil, castor oil, safflower oil, cottonseed oil, jojoba oil, palm oil, palm oil, liquid lanolin, hydrogenated coconut oil Oils such as hardened oil, mole, hardened castor oil, beeswax, candelilla wax, carnauba wax, ibotarou, lanolin, reduced lanolin, hard lanolin, jojoba wax, waxes;
Hydrocarbons such as liquid paraffin, squalane, pristane, ozokerite, paraffin, ceresin, petrolatum, microcrystalline wax;
Higher fatty acids such as oleic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, undecylenic acid;
Higher alcohols such as cetyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, octyldodecanol, myristyl alcohol, cetostearyl alcohol;
Cetyl isooctanoate, isopropyl myristate, hexyl decyl isostearate, diisopropyl adipate, di-2-ethylhexyl sebacate, cetyl lactate, diisostearyl malate, ethylene glycol di-2-ethylhexanoate, neopentyl glycol dicaprate, Synthetic esters such as glycerin di-2-heptylundecanoate, glyceryl tri-2-ethylhexanoate, trimethylolpropane tri-2-ethylhexanoate, trimethylolpropane triisostearate, pentane erythritol tetra-2-ethylhexanoate Oils;
Linear polysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane, cyclic polysiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexanesiloxane, amino-modified polysiloxane, polyether-modified poly Oil agents such as silicone oil such as siloxane, alkyl-modified polysiloxane, and modified polysiloxane such as fluorine-modified polysiloxane;
Anionic surfactants such as fatty acid soap (sodium laurate, sodium palmitate, etc.), potassium lauryl sulfate, alkylsulfuric acid triethanolamine ether;
Cationic surfactants such as stearyltrimethylammonium chloride, benzalkonium chloride, laurylamine oxide;
Betaine surfactants (alkyl betaines, amide betaines, sulfobetaines, etc.), imidazoline amphoteric surfactants (such as 2-cocoyl-2-imidazolinium hydroxide-1-carboxyethyloxy disodium salt), acylmethyl taurine Amphoteric surfactants such as;
Sorbitan fatty acid esters (such as sorbitan monostearate and sorbitan sesquioleate), glycerin fatty acids (such as glyceryl monostearate), propylene glycol fatty acid esters (such as propylene glycol monostearate), hydrogenated castor oil derivatives, glycerin alkyl ether POE sorbitan fatty acid esters (POE sorbitan monooleate, polyoxyethylene sorbitan monostearate, etc.), POE sorbite fatty acid esters (POE-sorbitol monolaurate, etc.), POE glycerin fatty acid esters (POE-glycerin monoisosteare) Rate), POE fatty acid esters (polyethylene glycol monooleate, POE distearate, etc.), POE alkyl ethers (POE2-octyl) Decyl ether, etc.), POE alkylphenyl ethers (POE nonylphenyl ether, etc.), pluronic types, POE / POP alkyl ethers (POE / POP2-decyltetradecyl ether, etc.), tetronics, POE castor oil / cured castor Nonionic surfactants such as oil derivatives (POE castor oil, POE hydrogenated castor oil, etc.), sucrose fatty acid esters, alkyl glucosides;
Polyethylene glycol, glycerin, 1,3-butylene glycol, erythritol, sorbitol, xylitol, maltitol, propylene glycol, dipropylene glycol, diglycerin, isoprene glycol, 1,2-pentanediol, 2,4-hexylene glycol, 1 Polyhydric alcohols such as 1,2-hexanediol and 1,2-octanediol;
Moisturizing ingredients such as sodium pyrrolidonecarboxylate, lactic acid, sodium lactate;
Gua gum, quince seed, carrageenan, galactan, arabic gum, pectin, mannan, starch, xanthan gum, curdlan, methylcellulose, hydroxyethylcellulose, carboxymethylcellulose, methylhydroxypropylcellulose, chondroitin sulfate, dermatan sulfate, glycogen, heparan sulfate, hyaluronic acid, Sodium hyaluronate, gum tragacanth, keratan sulfate, chondroitin, mucoitin sulfate, hydroxyethyl guar gum, carboxymethyl guar gum, dextran, kerato sulfate, locust bean gum, succinoglucan, carolinic acid, chitin, chitosan, carboxymethyl chitin, agar, polyvinyl alcohol , Polyvinylpyrrolidone, carboxyvinyl polymer, alkyl-modified carboxyl Vinyl polymers, sodium polyacrylate, polyethylene glycol, bentonite thickener;
Powders such as mica, talc, kaolin, synthetic mica, calcium carbonate, magnesium carbonate, anhydrous silicic acid (silica), aluminum oxide, barium sulfate, etc. whose surface may be treated;
Inorganic pigments such as bengara, yellow iron oxide, black iron oxide, cobalt oxide, ultramarine, bitumen, titanium oxide, zinc oxide, the surface of which may be treated;
Pearl agents such as titanium mica, fish phosphorus foil, bismuth oxychloride, etc. whose surface may be treated;
Red 202, Red 228, Red 226, Yellow 4, Blue 404, Yellow 5, Red 505, Red 230, Red 223, Orange 201, Red 213 which may be raked Organic dyes such as Yellow No. 204, Yellow No. 203, Blue No. 1, Green No. 201, Purple No. 201, Red No. 204;
Organic powders such as polyethylene powder, polymethyl methacrylate, nylon powder, organopolysiloxane elastomer;
Paraaminobenzoic acid UV absorbers, anthranilic acid UV absorbers, salicylic acid UV absorbers, cinnamic acid UV absorbers, benzophenone UV absorbers, sugar UV absorbers, 2- (2'-hydroxy-5 ' UV absorbers such as -t-octylphenyl) benzotriazole, 4-methoxy-4'-t-butyldibenzoylmethane;
Lower alcohols such as ethanol and isopropanol;
Vitamin A or a derivative thereof, vitamin B ₆ hydrochloride, vitamin B ₆ tripalmitate, vitamin B ₆ dioctanoate, vitamin B ₂ or a derivative thereof, vitamin B ₁₂ such as vitamin B ₁₂ , vitamin B ₁₅ or a derivative thereof, α-tocopherol , Β-tocopherol, γ-tocopherol, vitamin E such as vitamin E acetate, vitamin D, vitamin H,
Vitamins such as pantothenic acid, panthetin, pyrroloquinoline quinone;
Etc. can be preferably exemplified.

EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example, it cannot be overemphasized that this invention is not limited only to a following example.
<Example 1> Production example 1 of silicone-coated fine particle titanium dioxide
85 g of fine particle titanium dioxide (“Taipeku TTO-M-2” manufactured by Ishihara Sangyo Co., Ltd.), α-triethoxypolymethylpolysiloxane as a reactive polyorganosiloxane (polymerization degree 30, molecular weight dispersity 1.19, single-terminal ethoxy group) Group) 8.0 g of a silicone having a phenyl group (“silicone KF54” manufactured by Shin-Etsu Chemical Co., Ltd.) 7.0 g dissolved in 50 ml of isopropyl alcohol was stirred and mixed in a Henschel mixer.
The mixture was heated for 8 hours treatment with 0.99 ° C., to obtain a silicone down the covering particles of titanium dioxide of the present invention.

<Example 2> Production example 2 of silicone-coated fine particle titanium dioxide
6. 85 g of fine particle titanium dioxide (“MT-100T” manufactured by Teica Co., Ltd.), α-monohydroxypolysiloxane as a reactive polyorganosiloxane (polymerization degree 35, molecular weight dispersity 1.21, one end group is a monosilanol group) 5 g of silicone having a phenyl group ("silicone KF56" manufactured by Shin-Etsu Chemical Co., Ltd.) 7.5 g of isopropyl alcohol 50
The solution dissolved in ml was stirred and mixed in a Henschel mixer.
The mixture was heated for 8 hours treatment with 0.99 ° C., to obtain a silicone down the covering particles of titanium dioxide 2 of the present invention.

Comparative Example 1 Production Example 3 of Silicone-Coated Fine Particle Titanium Dioxide
85 g of fine particle titanium dioxide (“Taipeku TTO-M-2” manufactured by Ishihara Sangyo Co., Ltd.), α-triethoxypolymethylpolysiloxane as a reactive polyorganosiloxane (polymerization degree 30, molecular weight dispersity 1.19, single-terminal ethoxy group) Base) A solution in which 15.0 g was dissolved in 50 ml of isopropyl alcohol was stirred and mixed in a Henschel mixer.
The mixture was heated for 8 hours treatment with 0.99 ° C., to obtain a silicone down the covering fine particulate titanium dioxide 3.

Comparative Example 2 Production Example 4 of Silicone-Coated Fine Particle Titanium Dioxide
15. Fine particle titanium dioxide (“Taipeke TTO-M-2” manufactured by Ishihara Sangyo Co., Ltd.) 85 g, phenyl group silicone (“Silicone KF54” manufactured by Shin-Etsu Chemical Co., Ltd.)
A solution prepared by dissolving 0 g in 50 ml of isopropyl alcohol was stirred and mixed in a Henschel mixer.
The mixture was heated for 8 hours treatment with 0.99 ° C., to obtain a silicone down the covering particles of titanium dioxide 4.

<Example 3> Production example 1 of silicone- coated fine particle zinc oxide
85 g of fine particle zinc oxide (“Maxlite ZS-032”, Showa Denko KK), α-triethoxypolymethylpolysiloxane as a reactive polyorganosiloxane (polymerization degree 30, molecular weight dispersity 1.19, single-terminal ethoxy group) ) 8.0 g and a phenyl group-containing silicone (“silicone KF54” manufactured by Shin-Etsu Chemical Co., Ltd.) 7.0 g in 50 ml of isopropyl alcohol was stirred and mixed in a Henschel mixer.
The mixture was heated for 8 hours treatment with 0.99 ° C., silicone down the covering zinc oxide particles 1 of the present invention
Got.

<Example 4> Production example 2 of silicone- coated fine particle zinc oxide
85 g of fine particle zinc oxide (“FZO50” manufactured by Ishihara Sangyo Co., Ltd.), α-monohydroxypolysiloxane (polymerization degree 35, molecular weight dispersity 1.2) as reactive polyorganosiloxane
1. A solution prepared by dissolving 7.5 g of a silicone having a phenyl group (monosilanol group at one end group) and 7.5 g of “silicone KF56” manufactured by Shin-Etsu Chemical Co., Ltd. in 50 ml of isopropyl alcohol was stirred and mixed in a Henschel mixer. .
The mixture was heated for 8 hours treatment with 0.99 ° C., silicone down the covering zinc oxide particles 2 of the present invention
Got.

Comparative Example 3 Production Example 3 of Silicone-Coated Fine Particle Zinc Oxide
85 g of fine particle zinc oxide (“Maxlite ZS-032” manufactured by Showa Denko KK), α-triethoxypolymethylpolysiloxane as a reactive polyorganosiloxane (polymerization degree 30, molecular weight dispersity 1.19, single-terminal ethoxy group) ) A solution of 15.0 g dissolved in 50 ml of isopropyl alcohol was stirred and mixed in a Henschel mixer.
The mixture was heated for 8 hours treatment with 0.99 ° C., to obtain a silicone down the covering zinc oxide particles 3.

Comparative Example 4 Production Example 4 of Silicone-Coated Fine Particle Zinc Oxide
85 g of fine particle zinc oxide (“Maxlite ZS-032” manufactured by Showa Denko KK), phenyl-containing silicone (“Silicone KF54” manufactured by Shin-Etsu Chemical Co., Ltd.) 15.0
A solution prepared by dissolving g in 50 ml of isopropyl alcohol was stirred and mixed in a Henschel mixer.
This mixture was heat-treated at 150 ° C. for 8 hours to obtain silicone-coated fine particle zinc oxide 4.

<Test Example 1> Dispersion stability of silicone-coated fine particle titanium dioxide and zinc oxide 26.85 g of a mixed oil prepared by mixing glyceryl tri-2-ethylhexanoate and dimethicone (20 cs) at a mass ratio of 7: 3, hexyl diethylaminohydroxybenzoyl benzoate 0.15 g and 3.0 g of the silicone-coated fine particle titanium dioxide 1 to 4 and the silicone-coated fine particle zinc oxide 1 to 4 prepared above were each placed in a 50 ml glass screw bottle and subjected to ultrasonic treatment for 10 minutes to be uniformly dispersed. This dispersion was allowed to stand for 24 hours, and the dispersion state of the silicone-coated fine particle titanium dioxide and zinc oxide was observed with the naked eye. The results are shown in Table 1.

  As is apparent from Table 1, the silicone-coated fine particle metal oxide of the present invention has excellent dispersion stability in an oil containing a UV absorber.

<Production example 1> Preparation of silicone-coated fine particle titanium dioxide paste 1 50 g of silicone-coated fine particle titanium dioxide 1 of Example 1, 46 g of decamethylcyclopentasiloxane, and 4 g of sorbitan sesquiisostearate were placed in a coball mill (manufactured by Shinko Pantech Co., Ltd.). The mixture was pulverized for 4 hours to obtain a silicone-coated fine particle titanium dioxide paste 1.

<Production Example 2> Preparation of Silicone-Coated Fine Particle Zinc Oxide Paste 50 g of silicone-coated fine particle zinc oxide 1 of Example 3, 46 g of decamethylcyclopentasiloxane, and 4 g of sorbitan sesquiisostearate were taken in a coball mill (made by Shinko Pantech Co., Ltd.). The mixture was pulverized for 4 hours to obtain a silicone-coated fine particle zinc oxide paste 1.

<Examples 5-8, Comparative Examples 5-6>
According to the formulation shown in Table 2, a water-in-oil sunscreen cosmetic and a comparative water-in-oil sunscreen cosmetic, which are emulsified cosmetics of the present invention, were prepared. That is, component (a) was heated to 75 ° C. and mixed with stirring. Next, the component (b) was added to the component (a), and the mixture was stirred for 4 minutes at 5000 rpm using a disper while continuing the heating, so that the component (b) was uniformly dispersed in the component (a). Furthermore, the component (c) was heated to 75 ° C. and mixed with stirring, and while maintaining the temperature at 75 ° C., the component (c) was added to the mixture of the component (a) and the component (b) with stirring to perform emulsification. Thereafter, it was cooled to room temperature to obtain a water-in-oil sunscreen cosmetic. The numbers in Table 2 represent mass%.

<Test Example 2> Measurement of SPF Value The SPF value was measured when the sunscreen cosmetics of Examples 5 to 8 and Comparative Examples 5 to 6 were applied by the method of ISO 24444. The results are shown in Table 3.

<Test Example 3> Evaluation of UVAPF Value The UVAPF value was evaluated when the sunscreen cosmetics of Examples 5 to 8 and Comparative Examples 5 to 6 were applied according to the test method of ISO24442. The results are shown in Table 3.

Test Example 4 Storage Stability Evaluation After the sunscreen cosmetics of Examples 5 to 8 and Comparative Examples 5 to 6 were stored at 50 ° C. for 3 months, the SPF value and UVAPF value were determined by the methods of Test Examples 1 and 2. It was measured. The ratio of the measured value after storage to the measured value immediately after application before storage, that is, the maintenance ratio was calculated. The closer the maintenance rate is to 100%, the less the ultraviolet protective effect is reduced by storage. The results are shown in Table 3.

<Test Example 5> Evaluation of feeling on the skin Sensory evaluation was performed on the feeling when the sunscreen cosmetics of Examples 5 to 8 and Comparative Examples 5 to 6 were applied by five skilled evaluators. The refreshing feeling was evaluated based on the following evaluation criteria. In the evaluation, the average value of 5 persons was obtained and used as the score of the sunscreen cosmetic. The same evaluation was performed after storage at 50 ° C. for 3 months. The results are shown in Table 3.
Compared with Comparative Example 5 immediately after preparation, the refreshing feeling:
There are quite 5 points Somewhat 4 points Equivalent 3 points Somewhat not 2 Points Not quite 1 point

  As is apparent from Table 3, the external preparation for skin of the present invention is excellent in a refreshing feeling during use and has a high protective effect against ultraviolet rays in the A region and the B region. Moreover, these excellent functions are maintained even after a long period of severe storage.

<Examples 9-12, Comparative Examples 7-8>
According to the formulation shown in Table 4, an oil-in-water sunscreen cosmetic and a comparative oil-in-water sunscreen cosmetic, which are emulsified cosmetics of the present invention, were prepared. That is, component (a) was heated to 75 ° C. and mixed with stirring. Next, the component (b) was added to the component (a), and the mixture was stirred for 4 minutes at 5000 rpm using a disper while continuing the heating, so that the component (b) was uniformly dispersed in the component (a). Furthermore, the component (c) was heated to 75 ° C. and mixed with stirring, and while maintaining the temperature at 75 ° C., the component (c) was added to the mixture of the component (a) and the component (b) with stirring to perform emulsification. Thereafter, the mixture was cooled to room temperature to obtain an oil-in-water sunscreen cosmetic. The numbers in Table 4 represent mass%. Moreover, about the sunscreen cosmetics of Examples 9-12 and Comparative Examples 7-8, similarly to Test Examples 2-4, measurement of SPF value and UVAPF value immediately after application, measurement of SPF value and PFA value after storage The maintenance rate of SPF value and UVAPF value was calculated. Moreover, the refreshing feeling at the time of use was evaluated similarly to Test Example 5. The results are shown in Table 5.

  As is apparent from the results in Table 5, the external preparation for skin of the present invention has a refreshing feeling when used, and has a high protective effect against ultraviolet rays in the A region and B region. It was also confirmed in the oil-in-water dosage form that it was maintained even after passing.

  The present invention can be used for sunscreen cosmetics and the like.

Claims (7)

A skin external preparation containing a particulate metal oxide coated with the following (a) and (b) and an ultraviolet absorber.
(A) The degree of polymerization is 25 or more and 100 or less, and the ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn is 1 or more and 1.3 or less. , halogen atom, organopolysiloxane down with a linear reactive organopolysiloxane emissions (b) at least one phenyl group having at least one selected from the group consisting of amino groups and imino groups The external preparation for skin according to claim 1, wherein the organopolysiloxane (b) having at least one phenyl group is represented by the following general formula (3).

In the formula (3), _{R 3} is independently hydrogen, are selected from alkyl groups having 1 to 3 carbon atoms, and alkoxy group having 1 to 3 carbon atoms. R ₄ is independently selected from hydrogen, an alkyl group having 1 to 3 carbon atoms, a group represented by the following general formula (4), and a phenyl group, and has at least one unit having a phenyl group. n is an integer.

In the above formula (4), R ₅ independently represents an alkyl group having 1 to 3 carbon atoms. In the formula (3), R ₃ is independently selected from an alkyl group having 1 to 3 carbon atoms and an alkoxy group having 1 to 3 carbon atoms, and R ₄ is independently an alkyl group having 1 to 3 carbon atoms. The skin external preparation according to claim 2, which is selected from a group represented by the following general formula (4) and a phenyl group, and has at least one unit having a phenyl group.

In the above formula (4), R ₅ independently represents an alkyl group having 1 to 3 carbon atoms. In the formula (3), R ₃ is independently selected from alkyl groups having 1 to 3 carbon atoms, R ₄ is independently an alkyl group having 1 to 3 carbon atoms, represented by the following general formula (4). The skin external preparation of Claim 2 or 3 which has at least 1 unit which has a unit which has a phenyl group while being selected from a group and a phenyl group.

In the above formula (4), R ₅ independently represents an alkyl group having 1 to 3 carbon atoms. The skin external preparation according to any one of claims 1 to 4, wherein the particulate metal oxide contains at least one selected from particulate titanium oxide and particulate zinc oxide. The skin external preparation of any one of Claims 1-5 containing the ultraviolet absorber which absorbs the ultraviolet-ray of A area | region, and the ultraviolet absorber which absorbs the ultraviolet-ray of B area | region. The skin external preparation of any one of Claims 1-6 which is cosmetics.