JP6383141B2 - Surface-treated powder and skin external preparation containing the surface-treated powder - Google Patents

Description

  The present invention relates to a surface-treated powder, and also relates to a skin external preparation containing the surface-treated powder.

  Cosmetics, especially makeup cosmetics, are required to have a good feeling of use, such as covering skin troubles such as spots and freckles, making the skin color healthy, and feeling refreshed when applied. Yes. In order to obtain an excellent make-up effect, it is necessary that the colored pigments responsible for these effects are uniformly dispersed in the make-up cosmetic and the dispersion state is maintained for a long time. Moreover, in order to obtain a good feeling of use, similar characteristics are required.

  As an attempt to improve the dispersibility and dispersion stability of colored pigments and extender pigments, by incorporating a pigment coated with an acrylic polymer having a polysiloxane chain in the side chain into an emulsifier type cosmetic, A technique is known in which the dispersibility of the pigment is improved, and an excellent makeup and a refreshing feeling of use can be obtained (see, for example, Patent Documents 1 and 2).

  Moreover, the dispersibility of the pigment is improved by blending the pigment coated with the acrylic polymer having a polysiloxane chain in the side chain into the emulsified cosmetic blended with the ultraviolet absorbers in the A region and the B region. In addition, a technique is known in which an emulsified cosmetic material having excellent makeup protection and an ultraviolet protection effect in the A region and the B region is obtained (see, for example, Patent Document 3).

JP-A-5-339125 JP 2003-48814 A JP 2013-28556 A

However, in these techniques, there has been a problem that the dispersibility of the pigment may deteriorate when stored for a long period of time.
This invention makes it a subject to provide the skin external preparation excellent in the dispersion stability of powder in which the favorable dispersibility is maintained over a long period in the skin external preparation which mix | blended the ultraviolet absorber.

  The inventors of the present invention have studied to solve the above-mentioned problems, and in the conventionally proposed technology, since the dispersion stability of the contained pigment is not yet sufficient, the makeup effect and the feeling of use are further improved. I knew I would get it. Then, in order to improve the dispersion stability of powders such as pigments, a surface treatment method for powders was studied. (A) Reactive organopolysiloxane having a specific structure, and (b) at least one phenyl group. The present invention has been completed by finding that the above-mentioned problems can be solved by treating the powder surface with an organopolysiloxane having bismuth.

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）に記載の粉体。

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）に記載の粉体。

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）前記粉体は、金属酸化物、無機有色顔料、体質顔料、及び無機光輝性顔料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粉体。 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 A powder having an average primary particle diameter of 100 nm or more.
(2) The powder 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 powder according to (2), wherein the powder is selected from an alkyl group of the following formula, 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 powder according to (2) or (3), which is selected from the group represented by the formula (1) 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 powder according to any one of (1) to (4), wherein the powder includes at least one selected from metal oxides, inorganic colored pigments, extender pigments, and inorganic bright pigments.

The second embodiment of the present invention is as follows.
(6) A skin external preparation containing the powder 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.

  ADVANTAGE OF THE INVENTION According to this invention, the skin external preparation which was excellent in the dispersion stability of the powder in which favorable dispersibility is maintained over a long period can be provided in the skin external preparation which mix | blended the ultraviolet absorber. In addition, the powder blended in the external preparation for skin of the present invention has good dispersibility in an oil agent, the powder does not aggregate over time, and is not likely to be recommended. The external preparation does not deteriorate the make-up effect and the feeling of use over time.

The first embodiment of the present invention is a powder surface-treated with two types of organopolysiloxanes.
The powder used in this embodiment may be any powder that has a primary particle size of usually 100 nm or more as observed by an electron microscope and can be blended in a skin external preparation. Examples of powders include metal oxides such as titanium oxide, zinc oxide, zirconium oxide and cerium oxide; colored inorganic pigments such as bengara, yellow iron oxide, black iron oxide, chromium oxide and chromium hydroxide; barium sulfate and talc And extender pigments such as sericite, kaolin, mica, silicic anhydride, boron nitride and alumina; and inorganic bright pigments such as titanium mica. The surface of these powders 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 powder used in this embodiment has a primary particle diameter of 100 nm or more as observed with an electron microscope, and is distinguished from fine particles in the cosmetics field. The average primary particle size of the powder used in this embodiment is preferably 150 nm or more, more preferably 200 nm or more, and usually 10 μm or less, preferably 5 μm or less, more preferably 3 μm or less.
As the powder used in this embodiment, since it plays a role of giving a make-up effect and good usability, colored inorganic such as titanium oxide, bengara, yellow iron oxide, black iron oxide, chromium oxide, chromium hydroxide, etc. Pigments, talc, sericite and mica are preferred.

  There is no particular difficulty in obtaining the powder used in this embodiment, and a commercially available powder may be used as appropriate.

The powder 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 have improved the dispersibility in a dispersion medium containing an ultraviolet absorber by coating the powder with the above-mentioned two types of (a) and (b) organopolysiloxanes. In addition, it was conceived that the make-up effect was sustained and the feeling of use was good because of excellent dispersion stability of the powder.

(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 standpoint of reactivity and the like, 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 making the degree of polymerization within this range, the usability when blended into a cosmetic and the reactivity with the powder 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. is there. 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 powder with the organopolysiloxanes (a) and (b) may be performed according to a conventional method. For example, the powder and the organopolysiloxane are mixed with a mixer such as a Henschel mixer, if necessary, using a solvent. And a method of heating the mixture. 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 powder according to this embodiment, the coating amount of the organopolysiloxanes (a) and (b) is usually 0.5% by mass or more, preferably 1% by mass or more, respectively, with respect to the powder after the surface treatment. Moreover, it is 15 mass% or less normally, Preferably it is 10 mass% or less. By making the coating amount with the organopolysiloxane within this range, the dispersibility of the powder according to the present embodiment becomes better, and the dispersion stability of the powder when blended into the external preparation for skin is improved. Will continue and the feeling will 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 powder according to the first embodiment and an ultraviolet absorber.
In the external preparation for skin according to this embodiment, the blending amount of the powder according to the first embodiment is not particularly limited and can be appropriately set depending on the type of cosmetic, but is usually 1 for the total amount of external preparation for skin. It is at least mass%, preferably at least 2 mass%, and is usually at most 70 mass%, preferably at most 50 mass%, more preferably at most 30 mass%.
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 compounding quantity of a ultraviolet absorber is not specifically limited, It is 0.01 mass% or more normally with respect to the skin external preparation whole quantity, Preferably it is 0.1 mass% or more, and is 25 mass% or less normally, Preferably it is 20 mass. % 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, it is particularly preferable to apply the makeup cosmetic having an ultraviolet absorption Osamuko fruit.

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, pantothenic acid, panthetin, pyrroloquinoline quinone and other vitamins;
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 Pigment Grade Titanium Dioxide
85 g of pigment grade titanium dioxide (average primary particle size 0.3 μm), α-triethoxypolymethylpolysiloxane (polymerization degree 30, molecular weight dispersity 1.19, one terminal ethoxy group) 8.0 g as reactive polyorganosiloxane A solution of 7.0 g of silicone having phenyl group (“silicone KF54” manufactured by Shin-Etsu Chemical Co., Ltd.) 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 a silicone- coated pigment grade titanium dioxide 1 of the present invention.

<Examples 2 to 6> Production example 1 of silicone-coated inorganic colored pigment and extender pigment
A silicone-coated inorganic colored pigment and extender listed in Table 1 were obtained in the same manner as in Example 1 except that the pigment grade titanium dioxide in Example 1 was changed to the inorganic colored pigment and extender shown in Table 1. The average primary particle diameter of each powder was yellow iron oxide: 0.3 μm, bengara 0.3 μm, black iron oxide 0.3 μm, talc 5 μm, and sericite 5 μm.

<Example 7> Production example 2 of silicone-coated pigment-grade titanium dioxide
85 g of pigment grade titanium dioxide (average primary particle size 0.3 μm), α-monohydroxypolysiloxane as a reactive polyorganosiloxane (polymerization degree 35, molecular weight dispersion degree 1.21, one end group is a monosilanol group) 7.5 g In addition, a solution in which 7.5 g of silicone having a phenyl group (“silicone KF56” manufactured by Shin-Etsu Chemical Co., Ltd.) 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 pigment-grade titanium dioxide 2 of the present invention.

<Examples 8 to 12> Production example 2 of silicone-coated inorganic colored pigment and extender pigment
Except having changed the pigment grade titanium dioxide in Example 7 into the inorganic colored pigment and extender pigment shown in Table 2, the same operation as in the Example was carried out to obtain the silicone-coated inorganic colored pigment and extender pigment described in Table 2. In addition, the average primary particle diameter of each powder is the same as that of Production Example 1 of the silicone-coated inorganic colored pigment and extender pigment.

<Comparative Examples 1-6> Production Example 3 of Silicone-Coated Inorganic Colored Pigment and Extender Pigment
A solution obtained by dissolving 85 g of the pigment of Table 3 and 15.0 g of α-triethoxypolymethylpolysiloxane (polymerization degree 30, molecular weight dispersity 1.19, one-terminal ethoxy group) as reactive polyorganosiloxane in 50 ml of isopropyl alcohol. The mixture was stirred and mixed in a Henschel mixer.
This mixture was heat-treated at 150 ° C. for 8 hours to obtain a silicone-coated inorganic colored pigment and extender pigment. In addition, the average primary particle diameter of each powder is the same as that of Production Example 1 of the silicone-coated inorganic colored pigment and extender pigment.

<Comparative Examples 7-12> Production Example 4 of Silicone-Coated Inorganic Colored Pigment and Extender Pigment
A solution obtained by dissolving 85 g of the pigment of Table 4 and 15.0 g of a phenyl group-containing silicone (“Silicone KF54” manufactured by Shin-Etsu Chemical Co., Ltd.) 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 a silicone-coated inorganic colored pigment and extender pigment. In addition, the average primary particle diameter of each powder is the same as that of Production Example 1 of the silicone-coated inorganic colored pigment and extender pigment.

<Manufacture example 1> Preparation of a pigment base The silicone coating powder prepared above was mixed in the ratio of Table 5 in the Henschel mixer, and the pigment bases 1-4 were prepared. For the pigment base 1, only one of the above silicone-coated powders was used. Hereinafter, pigment bases 2 to 4 were similarly prepared. The numbers in the table represent parts by weight.

<Test Example 1> Dispersion stability based on silicone-coated pigment 26.85 g of a mixed oil obtained by mixing glyceryl tri-2-ethylhexanoate and dimethicone (20 cs) at a mass ratio of 7: 3, 0.15 g of hexyl diethylaminohydroxybenzoylbenzoate and 3.0 g of each of the silicone-coated pigment bases 1 to 4 prepared above was 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 pigment base was observed with the naked eye. The results are shown in Table 6.

<Examples 13 to 16, Comparative Examples 13 to 14>
According to the formulation shown in Table 7, 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 7 represent mass%.

<Test Example 2> Evaluation of storage stability After the sunscreen cosmetics of Examples 13 to 16 and Comparative Examples 13 to 14 were stored at 50 ° C for 3 months, the state was observed with the naked eye. The results are shown in Table 8.

<Test Example 3> Evaluation of dispersion state Thin films of sunscreen cosmetics of Examples 13 to 16 and Comparative Examples 13 to 14 were formed on a slide glass using a 0.5 mil doctor blade. The total transmittance of this thin film at 560 nm was measured using a spectrophotometer with an integrating sphere. The same measurement was performed after storage at 50 ° C. for 3 months. The results are shown in Table 8. The smaller the transmittance, the better the dispersion state of the powder.

<Test Example 4> Evaluation of finish uniformity Sensory evaluation was performed on the feeling of use when the sunscreen cosmetics of Examples 13 to 16 and Comparative Examples 13 to 14 were applied by five skilled evaluators. The uniformity of the finish 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 8.
Compared to Comparative Example 13 where the finish uniformity was just after preparation:
5 points, which are considerably more uniform 4 points, which are slightly more uniform 4 points, equivalent 3 points, slightly inferiority 2 points, 1 point, which is considerably inferior 1

<Test Example 5> Evaluation of feeling on the skin Sensory evaluation was performed on the feeling when the sunscreen cosmetics of Examples 13 to 16 and Comparative Examples 13 to 14 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 8.
Compared to Comparative Example 13 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 8, the external preparation for skin of the present invention has good dispersion stability of the powder, and as a result, has excellent use feeling and make-up effect.

<Examples 17-20, Comparative Examples 15-16>
According to the formulation shown in Table 9, 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 9 represent mass%. In addition, the sunscreen cosmetics of Examples 17 to 20 and Comparative Examples 15 to 16 were evaluated in the same manner as in Test Examples 2 to 5, for storage stability, dispersion state, finish uniformity, and feeling on the skin. . The results are shown in Table 10.

As is apparent from Table 10, it was proved that the skin external preparation of the present invention was excellent in dispersion stability of the powder even in the oil-in-water dosage form, and as a result, had excellent usability and make-up effect.

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

Claims (7)

A skin external preparation containing a powder coated with the following (a) and (b) having an average primary particle diameter of 100 nm or more 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. , A linear reactive organopolysiloxane having at least one selected from the group consisting of a halogen atom, an amino group and an imino group (b) an organopolysiloxane having at least one phenyl group 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 external preparation for skin according to any one of claims 1 to 4, wherein the powder contains at least one selected from metal oxides, inorganic colored pigments, extender pigments, and inorganic bright pigments.   The skin external preparation according to any one of claims 1 to 5, comprising an ultraviolet absorber that absorbs ultraviolet rays in the A region and an ultraviolet absorber that absorbs ultraviolet rays in the B region. The external preparation for skin according to any one of claims 1 to 6, which is a cosmetic.