JP2006225358A - Siloxane ester compound, oil component for skin care preparation or hair cosmetic, and skin care preparation or hair cosmetic prepared by compounding the oil component - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an oil component for a skin care preparation or for a hair cosmetic, which is excellent in refreshed sense of use and is suitable for dissolving a hardly soluble ultraviolet absorber or drug; and a skin care preparation or a hair cosmetic prepared by compounding the oil component. <P>SOLUTION: The oil component for a skin care preparation or for a hair cosmetic consists of [methylbis(trimethylsiloxy)silyl]propyl benzenecarboxylate represented by general formula (1). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a novel siloxane ester compound, a skin external preparation oil or hair cosmetic oil comprising the siloxane ester compound, and a skin external preparation or hair cosmetic containing the same. More specifically, the present invention relates to a skin external preparation oil or hair cosmetic oil excellent in a refreshing feeling of use and suitable for dissolving a sparingly soluble ultraviolet absorber and drug, and a skin external preparation or hair cosmetic containing the same. .

  Many silicone oils having a refreshing feeling of use have been developed and have been blended into skin external preparations. However, since silicone oil has poor solubility of UV absorbers and drugs, hydrocarbon oils with good solubility of drugs and UV absorbers have been desired. However, hydrocarbon oils have good solubility in drugs and ultraviolet absorbers, but tend to be sticky as the amount is increased.

（式中、Ｒは炭素数８〜１０の直鎖若しくは分岐のアルキル基を示す） On the other hand, the inventor of the present application has researched and developed an alkylbenzoate compound represented by the following general formula as a skin external preparation oil component having a refreshing feeling of use and excellent solubility in ultraviolet absorbers and drugs (patent) Reference 1).

(Wherein R represents a linear or branched alkyl group having 8 to 10 carbon atoms)

JP 2003-327505 A

  An object of the present invention is to develop a further skin external preparation oil or hair cosmetic oil, which has a refreshing feeling of use like silicone oil, and can be stably incorporated with drugs and ultraviolet absorbers. It is to provide an external preparation for skin or a hair cosmetic containing a suitable oil.

式中、Ｒ¹は炭素数１〜４のアルキル基またはフェニル基またはトリメチルシロキシ基、Ｒ²はすくなくとも２個の炭素原子を有する二価の炭化水素基（複素原子Ｏを有するものを含む）、Ｘは水素、ヒドロキシル基、アルコキシ基、ｎは０〜３の整数、aは１〜５の整数を表す。

式中、Ｒ³は炭素数１〜４のアルキル基またはフェニル基またはトリメチルシロキシ基、ｍは０〜３の整数を表す。 That is, the present invention is a siloxane having at least one unit represented by the following general formula (1), wherein other units present in the siloxane are represented by the general formula (2). A siloxane ester compound is provided.

In the formula, R ¹ is an alkyl group having 1 to 4 carbon atoms, a phenyl group or a trimethylsiloxy group, R ² is a divalent hydrocarbon group having at least 2 carbon atoms (including those having a heteroatom O), X represents hydrogen, a hydroxyl group, an alkoxy group, n represents an integer of 0 to 3, and a represents an integer of 1 to 5.

In the formula, R ³ represents an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a trimethylsiloxy group, and m represents an integer of 0 to 3.

The present invention also provides benzenecarboxylic acid [methylbis (trimethylsiloxy) silyl] propyl represented by the following formula (3).

  Moreover, this invention provides the skin external preparation oil part or hair cosmetic oil part which consists of a siloxane ester compound comprised by the said General formula (1) and General formula (2).

  Furthermore, this invention provides the skin external preparation oil component or hair cosmetic oil component which consists of benzenecarboxylic acid [methylbis (trimethylsiloxy) silyl] propyl shown by the said Formula (3).

  Furthermore, this invention provides the skin external preparation or hair cosmetics characterized by containing said skin external preparation oil content or hair cosmetic oil content.

  Moreover, this invention provides said skin external preparation or hair cosmetics characterized by containing a ultraviolet absorber further.

  The skin external preparation oil or hair cosmetic oil of the present invention has a refreshing feeling of use, and can be stably blended with a poorly soluble ultraviolet absorber and a hardly soluble drug. In addition, it has a chemical structure with excellent safety as an oil component. Therefore, if the oil of the present invention is used, a desired amount of UV absorber or drug can be blended. And the skin external preparation or hair cosmetics which have the outstanding usability | use_condition can be provided.

  Hereinafter, the present invention will be described in detail.

式中、Ｒ¹は炭素数１〜４のアルキル基またはフェニル基またはトリメチルシロキシ基、Ｒ²はすくなくとも２個の炭素原子を有する二価の炭化水素基（複素原子Ｏを有するものを含む）、Ｘは水素、ヒドロキシル基、アルコキシ基、ｎは０〜３の整数、aは１〜５の整数を表す。

式中、Ｒ³は炭素数１〜４のアルキル基またはフェニル基またはトリメチルシロキシ基、ｍは０〜３の整数を表す。 The siloxane ester compound of the present invention is a siloxane having at least one unit represented by the following general formula (1), and other units present in the siloxane are represented by the general formula (2). It is a characteristic siloxane ester compound.

In the formula, R ¹ is an alkyl group having 1 to 4 carbon atoms, a phenyl group or a trimethylsiloxy group, R ² is a divalent hydrocarbon group having at least 2 carbon atoms (including those having a heteroatom O), X represents hydrogen, a hydroxyl group, an alkoxy group, n represents an integer of 0 to 3, and a represents an integer of 1 to 5.

In the formula, R ³ represents an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a trimethylsiloxy group, and m represents an integer of 0 to 3.

Specific examples of R ¹ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, phenyl group, trimethylsiloxy group and the like. For reasons such as easy availability of raw materials, the methyl group or a part thereof is preferably a phenyl group or a trimethylsiloxy group. n represents the number of substitutions of R ¹ .

R ² is a linear or branched alkylene group having 2 to 6 carbon atoms, and preferred specific examples are shown below.

In addition, hexylene, cyclohexylene, decylene group and the like can be mentioned.
R ² is preferably an alkylene group having 2 to 4 carbon atoms. In particular, since the side reaction of the hydrosilylation reaction is relatively small, the following structure is preferable.

  Specific examples of X include, for example, methoxy group, ethoxy group, isopropoxy group and the like. In either case, there is no significant difference in the solubility and refreshing usability of the poorly soluble drug or the UV absorber, but hydrogen is particularly preferable because of the availability of the reagent. a represents the number of substitutions of X.

Specific examples of R ³ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, phenyl group, trimethylsiloxy group and the like. For reasons such as availability of raw materials, it is preferable that the methyl group or a part thereof is a phenyl group or a trimethylsiloxy group. m is the number of substitutions of R ³ .

  The above siloxane ester compound has excellent properties as a liquid oil component having a benzoate skeleton described in Patent Document 1, and is produced from a benzoyl chloride and a trisiloxane compound by a known esterification synthesis reaction. I can do it. Preferred specific compounds are compounds of the following formulas (3) and (4), and specific production methods are described in the examples.

Among the siloxane ester compounds composed of the above general formulas (1) and (2), a compound that can be an excellent oil component particularly used in a skin external preparation or a hair cosmetic is a benzenecarboxylic acid [methyl bis] of the following formula (3). (Trimethylsiloxy) silyl] propyl.
That is, in the general formula (1), X is hydrogen, a is 5, R ² is a propyl group (—CH ₂ CH ₂ CH ₂ —), R ¹ is a methyl group, n is 1, and the general formula (2 ) Is a siloxane ester compound in which m is 3 and R ³ is a methyl group.

すなわち、一般式（１）において、Ｘはヒドロキシル基、ａは１、Ｒ²がプロピル基(-CH₂CH₂CH₂-)、Ｒ₁がメチル基(CH₃)、ｎが１、であり、一般式（２）の部分がｍが３、Ｒ³がメチル基に相当するシロキサンエステル化合物である。 In addition, the following (4) 2-hydroxybenzenecarboxylic acid [methylbis (trimethylsiloxy) silyl] propyl is also an excellent oil used in a skin external preparation or hair cosmetic.

That is, in the general formula (1), X is a hydroxyl group, a is 1, R ² is a propyl group (—CH ₂ CH ₂ CH ₂ —), R ₁ is a methyl group (CH ₃ ), and n is 1. In the general formula (2), m is 3, and R ³ is a siloxane ester compound corresponding to a methyl group.

  Said siloxane ester compound can be preferably used for the skin external preparation oil component or the hair cosmetic oil component. The blending amount as oil is not particularly limited. It is 0.001-50 mass% normally with respect to the skin external preparation whole quantity, Preferably it is 0.1-30.0 mass%. If it is less than 0.001% by mass, the effect of the blending is not exhibited, and if it exceeds 50.0% by mass, stickiness may be felt after use.

  The skin external preparation or hair cosmetic of the present invention is produced by blending the above siloxane ester compound into the skin external preparation or hair cosmetic base. In addition to the oils described above, the external preparation for skin or hair cosmetic of the present invention has other components that are usually used in external preparations for skin or cosmetics for hair, such as powder components, liquid fats and oils, solid fats and oils, waxes, hydrocarbons, high grades. Fatty acids, higher alcohols, esters, silicones, anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, humectants, water-soluble polymers, thickeners, film agents, UV absorbers, metals Sequestrants, lower alcohols, polyhydric alcohols, sugars, amino acids, organic amines, polymer emulsions, pH adjusters, skin nutrients, vitamins, antioxidants, antioxidant aids, fragrances, water, etc. as needed It can mix | blend suitably and can be manufactured by a conventional method according to the target dosage form. Specific ingredients that can be blended are listed below, and the skin external preparation or hair cosmetic composition of the present invention can be prepared by blending the above essential blending ingredients and any one or more of the following ingredients.

Examples of the ultraviolet absorber include the following ultraviolet absorbers.
1) Triazine ultraviolet absorbers For example, bisresorcinyl triazine.
More specifically, bis {[4- (2-ethylhexyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) 1,3,5-triazine,
2,4,6-tris {4- (2-ethylhexyloxycarbonyl) anilino} 1,3,5-triazine and the like.
2) Benzoic acid UV absorbers, for example, paraaminobenzoic acid (hereinafter abbreviated as PABA), PABA monoglycerin ester, N, N-dipropoxy PABA ethyl ester, N, N-diethoxy PABA ethyl ester, N, N-dimethyl PABA Ethyl ester, N, N-dimethyl PABA butyl ester, N, N-dimethyl PABA ethyl ester and the like.
3) Anthranilic acid ultraviolet absorbers such as homomenthyl-N-acetylanthranilate.
4) Salicylic acid ultraviolet absorbers such as amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, p-isopropanol phenyl salicylate, and the like.
5) Cinnamic acid UV absorbers For example, octylcinnamate, ethyl-4-isopropylcinnamate, methyl-2,5-diisopropylcinnamate, ethyl-2,4-diisopropylcinnamate, methyl-2,4-diisopropyl Cinnamate, propyl-p-methoxycinnamate, isopropyl-p-methoxycinnamate, isoamyl-p-methoxycinnamate, octyl-p-methoxycinnamate (2-ethylhexyl-p-methoxycinnamate), 2-ethoxyethyl -p-methoxycinnamate, cyclohexyl-p-methoxycinnamate, ethyl-α-cyano-β-phenylcinnamate, 2-ethylhexyl-α-cyano-β-phenylcinnamate, glyceryl mono-2-ethylhexanoyl- Diparamethoxycinnamate etc.
6) Other UV absorbers For example, 3- (4'-methylbenzylidene) -d, l-camphor, 3-benzylidene-d, l-camphor, 2-phenyl-5-methylbenzoxazole, 2,2 ' -Hydroxy-5-methylphenylbenzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenylbenzotriazole), dibenzalazine, dianisoylmethane 4-methoxy-4′-t-butyldibenzoylmethane, 5- (3,3-dimethyl-2-norbornylidene) -3-pentan-2-one and the like.

  Examples of the powder component include inorganic powders (for example, talc, kaolin, mica, sericite, muscovite, phlogopite, synthetic mica, saucite, biotite, permiculite, magnesium carbonate, calcium carbonate, silicic acid. Aluminum, barium silicate, calcium silicate, magnesium silicate, strontium silicate, metal tungstate, magnesium, silica, zeolite, barium sulfate, calcined calcium sulfate (baked gypsum), calcium phosphate, fluorine apatite, hydroxyapatite, ceramic powder , Metal soap (eg, zinc myristate, calcium palmitate, aluminum stearate), boron nitride, etc .; organic powder (eg, polyamide resin powder (nylon powder), polyethylene powder, polymethyl methacrylate powder, polystyrene Powder, copolymer resin powder of styrene and acrylic acid, benzoguanamine resin powder, polytetrafluoroethylene powder, cellulose powder, etc.); inorganic white pigment (eg, titanium dioxide, zinc oxide, etc.); inorganic red pigment (eg, Iron oxide (Bengara), iron titanate, etc .; Inorganic brown pigments (eg, γ-iron oxide, etc.); Inorganic yellow pigments (eg, yellow iron oxide, loess, etc.); Inorganic black pigments (eg, black oxide) Iron, low-order titanium oxide, etc.); inorganic purple pigments (eg, manganese violet, cobalt violet, etc.); inorganic green pigments (eg, chromium oxide, chromium hydroxide, cobalt titanate, etc.); inorganic blue pigments (eg, Pearl pigments (eg, titanium oxide coated mica, titanium oxide coated bismuth oxychloride, titanium oxide coated talc, colored acid) Titanium coated mica, bismuth oxychloride, fish scale foil, etc.); metal powder pigments (eg, aluminum powder, copper powder, etc.); organic pigments such as zirconium, barium or aluminum lake (eg, red 201, red 202, red 204) No., Red No. 205, Red No. 220, Red No. 226, Red No. 228, Red No. 405, Orange No. 203, Orange No. 204, Yellow No. 205, Yellow No. 401 and Blue No. 404; , Red 104, Red 106, Red 227, Red 230, Red 401, Red 505, Orange 205, Yellow 4, Yellow 5, Yellow 202, Yellow 203, Green 3 and Blue No. 1 etc.); natural pigments (for example, chlorophyll, β-carotene, etc.) and the like.

  Examples of liquid oils include avocado oil, camellia oil, turtle oil, macadamia nut oil, corn oil, mink oil, olive oil, rapeseed oil, egg yolk oil, sesame oil, persic oil, wheat germ oil, southern castor oil, castor oil, linseed oil , Safflower oil, cottonseed oil, eno oil, soybean oil, peanut oil, tea seed oil, kaya oil, rice bran oil, cinnagiri oil, Japanese kiri oil, jojoba oil, germ oil, triglycerin and the like.

  Examples of the solid fat include cacao butter, coconut oil, hardened coconut oil, palm oil, palm kernel oil, owl kernel oil, hardened oil, owl, and hardened castor oil.

  Examples of the wax include beeswax, candelilla wax, cotton wax, carnauba wax, bayberry wax, ibota wax, whale wax, montan wax, nuka wax, lanolin, kapok wax, lanolin acetate, liquid lanolin, sugar cane wax, lanolin fatty acid isopropyl, hexyl laurate, reduced lanolin, Examples include jojoba wax, hard lanolin, shellac wax, POE lanolin alcohol ether, POE lanolin alcohol acetate, POE cholesterol ether, lanolin fatty acid polyethylene glycol, and POE hydrogenated lanolin alcohol ether.

  Examples of the hydrocarbon oil include liquid paraffin, ozokerite, squalane, pristane, paraffin, ceresin, squalene, petrolatum, microcrystalline wax, and the like.

  Examples of higher fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, undecylenic acid, tall oil fatty acid, isostearic acid, linoleic acid, linolenic acid, eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA) etc. are mentioned.

  Examples of higher alcohols include linear alcohols (eg, lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, cetostearyl alcohol); branched chain alcohols (eg, monostearyl glycerin ether (batyl alcohol) ), 2-decyltetradecinol, lanolin alcohol, cholesterol, phytosterol, hexyl decanol, isostearyl alcohol, octyldodecanol and the like.

  Examples of ester oils include isopropyl myristate, cetyl octanoate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, hexyl decyl dimethyloctanoate, cetyl lactate, lactic acid Myristyl, lanolin acetate, isocetyl stearate, isocetyl isostearate, cholesteryl 12-hydroxystearate, ethylene glycol di-2-ethylhexanoate, dipentaerythritol fatty acid ester, N-alkyl glycol monoisostearate, neopentyl glycol dicaprate, Diisostearyl malate, glycerin di-2-heptylundecanoate, trimethylolpropane tri-2-ethylhexanoate, trime triisostearate Roll propane, penta-2-ethylhexanoate pentaerythritol, glycerol tri-2-ethylhexanoate, glyceryl trioctanoate, glyceryl triisopalmitate, trimethylolpropane triisostearate, cetyl 2-ethylhexanoate, 2-ethylhexyl Palmitate, glyceryl trimyristate, tri-2-heptylundecanoic acid glyceride, castor oil fatty acid methyl ester, oleyl oleate, acetoglyceride, 2-heptylundecyl palmitate, diisobutyl adipate, N-lauroyl-L-glutamic acid 2-octyldodecyl ester, di-2-heptylundecyl adipate, ethyl laurate, di-2-ethylhexyl sebacate, 2-hexyldecyl myristate, 2-hexyldecyl palmitate, 2-hexyl adipate Decyl, diisopropyl sebacate, 2-ethylhexyl succinate, and triethyl citrate.

  Examples of the silicone oil include linear polysiloxanes (for example, dimethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane, etc.); cyclic polysiloxanes (for example, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexyl). And silicone resins that form a three-dimensional network structure, various modified polysiloxanes (amino-modified polysiloxane, polyether-modified polysiloxane, alkyl-modified polysiloxane, fluorine-modified polysiloxane, etc.) It is done.

  Anionic surfactants include, for example, fatty acid soaps (eg, sodium laurate, sodium palmitate, etc.); higher alkyl sulfates (eg, sodium lauryl sulfate, potassium lauryl sulfate, etc.); alkyl ether sulfates (eg, POE-lauryl sulfate triethanolamine, POE-sodium lauryl sulfate, etc.); N-acyl sarcosine acids (eg, sodium lauroyl sarcosine, etc.); higher fatty acid amide sulfonates (eg, sodium N-myristoyl-N-methyl taurate, palm Oil fatty acid methyl tauride sodium, lauryl methyl tauride sodium, etc .; phosphate ester salt (POE-oleyl ether sodium phosphate, POE-stearyl ether phosphate, etc.); sulfosuccinate (eg, di-2-ethylhexyl sulfo) Sodium succinate, monolauroyl monoethanolamide sodium polyoxyethylene sulfosuccinate, sodium lauryl polypropylene glycol sulfosuccinate, etc.); alkyl benzene sulfonates (eg, sodium linear dodecyl benzene sulfonate, triethanol amine linear dodecyl benzene sulfonate, linear dodecyl) Higher fatty acid ester sulfates (eg, hydrogenated coconut oil fatty acid sodium glycerol sulfate); N-acyl glutamate (eg, monosodium N-lauroyl glutamate, disodium N-stearoyl glutamate, N-myristoyl) -L-glutamic acid monosodium, etc.); sulfated oil (eg funnel oil); POE-alkyl ether carboxylic acid; POE-alkyl allyl ether Α-olefin sulfonates; higher fatty acid ester sulfonates; secondary alcohol sulfates; higher fatty acid alkylolamide sulfates; lauroyl monoethanolamide sodium succinate; N-palmitoyl aspartate ditriethanolamine ; Sodium caseinate and the like.

  Examples of the cationic surfactant include alkyltrimethylammonium salts (eg, stearyltrimethylammonium chloride, lauryltrimethylammonium chloride, etc.); alkylpyridinium salts (eg, cetylpyridinium chloride, etc.); distearyldimethylammonium dialkyldimethylammonium chloride; Poly (N, N'-dimethyl-3,5-methylenepiperidinium chloride); alkyl quaternary ammonium salt; alkyldimethylbenzylammonium salt; alkylisoquinolinium salt; dialkyl morpholinium salt; POE-alkylamine; Examples include alkylamine salts; polyamine fatty acid derivatives; amyl alcohol fatty acid derivatives; benzalkonium chloride; benzethonium chloride and the like.

  Examples of amphoteric surfactants include imidazoline-based amphoteric surfactants (eg, 2-undecyl-N, N, N- (hydroxyethylcarboxymethyl) -2-imidazoline sodium, 2-cocoyl-2-imidazolinium hydroxide). Side-1-carboxyethyloxy disodium salt, etc.); betaine surfactants (for example, 2-heptadecyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, lauryldimethylaminoacetic acid betaine, alkylbetaine, amide betaine) , Sulfobetaine, etc.).

  Examples of the lipophilic nonionic surfactant include sorbitan fatty acid esters (for example, sorbitan monooleate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquioleate, Sorbitan trioleate, diglycerol sorbitan penta-2-ethylhexylate, diglycerol sorbitan tetra-2-ethylhexylate); glycerin polyglycerin fatty acids (eg mono cottonseed oil fatty acid glycerin, monoerucic acid glycerin, sesquioleate glycerin, monostearin) Glycerin acid, α, α'-oleic acid pyroglutamate glycerin, monostearic acid glycerin malic acid, etc.); propylene glycol fatty acid esters (eg monostearies) Propylene glycolate, etc.); hardened castor oil derivative; glycerin alkyl ether, etc.

  Examples of hydrophilic nonionic surfactants include POE-sorbitan fatty acid esters (for example, POE-sorbitan monooleate, POE-sorbitan monostearate, POE-sorbitan monooleate, POE-sorbitan tetraoleate, etc.); POE sorbite fatty acid esters (eg, POE-sorbite monolaurate, POE-sorbite monooleate, POE-sorbite pentaoleate, POE-sorbite monostearate, etc.); POE-glycerin fatty acid esters (eg, POE-glycerin) Monostearate, POE-glycerol monoisostearate, POE-monooleate such as POE-glycerol triisostearate, etc.); POE-fatty acid esters (for example, POE-distearate, POE-monodiolate, ethylene glycol distearate, etc.); POE-alkyl ethers (eg POE- Uril ether, POE-oleyl ether, POE-stearyl ether, POE-behenyl ether, POE-2-octyldodecyl ether, POE-cholestanol ether, etc.); Pluronic type (for example, Pluronic, etc.); POE / POP-alkyl ether (For example, POE / POP-cetyl ether, POE / POP-2-decyltetradecyl ether, POE / POP-monobutyl ether, POE / POP-hydrogenated lanolin, POE / POP-glycerin ether, etc.); Tetra POE / tetra POP-ethylenediamine condensates (eg Tetronic, etc.); POE-castor oil hardened castor oil derivatives (eg POE-castor oil, POE-hardened castor oil, POE-hardened castor oil monoisostearate, POE-hardened castor Oil triisostearate, POE-hardened castor oil monopyroglutamic acid monoisostearic acid diester, POE-hardened castor oil maleic acid, etc.); PO E-beeswax lanolin derivatives (eg POE-sorbite beeswax); alkanolamides (eg coconut oil fatty acid diethanolamide, lauric acid monoethanolamide, fatty acid isopropanolamide, etc.); POE-propylene glycol fatty acid ester; POE-alkylamine POE-fatty acid amide; sucrose fatty acid ester; alkyl ethoxydimethylamine oxide; trioleyl phosphate and the like.

  Examples of humectants include polyethylene glycol, propylene glycol, glycerin, 1,3-butylene glycol, xylitol, sorbitol, maltitol, chondroitin sulfate, hyaluronic acid, mucoitin sulfate, caronic acid, atelocollagen, cholesteryl-12-hydroxystearate. Sodium lactate, bile salt, dl-pyrrolidone carboxylate, short-chain soluble collagen, diglycerin (EO) PO adduct, Izayoi rose extract, yarrow extract, merirot extract and the like.

  Examples of natural water-soluble polymers include plant-based polymers (for example, gum arabic, gum tragacanth, galactan, guar gum, carob gum, caraya gum, carrageenan, pectin, agar, quince seed (malmello), alge colloid (guckweed extract), starch (Rice, corn, potato, wheat), glycyrrhizic acid); microbial polymers (eg, xanthan gum, dextran, succinoglucan, bullulan, etc.); animal polymers (eg, collagen, casein, albumin, gelatin, etc.), etc. Is mentioned.

  Semi-synthetic water-soluble polymers include, for example, starch polymers (eg, carboxymethyl starch, methylhydroxypropyl starch, etc.); cellulose polymers (methylcellulose, ethylcellulose, methylhydroxypropylcellulose, hydroxyethylcellulose, sodium cellulose sulfate) Hydroxypropylcellulose, carboxymethylcellulose, sodium carboxymethylcellulose, crystalline cellulose, cellulose powder and the like); alginic acid polymers (for example, sodium alginate, propylene glycol alginate, etc.) and the like.

  Synthetic water-soluble polymers include, for example, vinyl polymers (eg, polyvinyl alcohol, polyvinyl methyl ether, polyvinyl pyrrolidone, carboxyvinyl polymer); polyoxyethylene polymers (eg, polyethylene glycol 20,000, 40,000, 60,000). Polyoxyethylene polyoxypropylene copolymer, etc.); acrylic polymers (for example, sodium polyacrylate, polyethyl acrylate, polyacrylamide, etc.); polyethyleneimine; cationic polymers, and the like.

  Examples of thickeners include gum arabic, carrageenan, caraya gum, gum tragacanth, carob gum, quince seed (malmello), casein, dextrin, gelatin, sodium pectate, sodium alginate, methylcellulose, ethylcellulose, CMC, hydroxyethylcellulose, hydroxypropyl Cellulose, PVA, PVM, PVP, sodium polyacrylate, carboxyvinyl polymer, locust bean gum, guar gum, tamarind gum, cellulose dialkyldimethylammonium sulfate, xanthan gum, magnesium aluminum silicate, bentonite, hectorite, AlMg silicate (Beegum), Examples thereof include laponite and silicic anhydride.

  Examples of the sequestering agent include 1-hydroxyethane-1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid tetrasodium salt, disodium edetate, trisodium edetate, and tetrasodium edetate. Sodium citrate, sodium polyphosphate, sodium metaphosphate, gluconic acid, phosphoric acid, citric acid, ascorbic acid, succinic acid, edetic acid, trisodium ethylenediaminehydroxyethyl triacetate and the like.

  Examples of the lower alcohol include ethanol, propanol, isopropanol, isobutyl alcohol, t-butyl alcohol and the like.

  Examples of the polyhydric alcohol include divalent alcohols (for example, ethylene glycol, propylene glycol, trimethylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, tetramethylene glycol, 2,3-butylene glycol, Pentamethylene glycol, 2-butene-1,4-diol, hexylene glycol, octylene glycol, etc.); trivalent alcohol (eg, glycerin, trimethylolpropane, etc.); tetravalent alcohol (eg, 1,2,6) Pentaerythritol such as hexanetriol); pentahydric alcohol (eg, xylitol, etc.); hexavalent alcohol (eg, sorbitol, mannitol, etc.); polyhydric alcohol polymer (eg, diethylene glycol, dipropylene glycol, triethylene glycol, polypropylene Glycol, tetraethylene glycol, diglycerin, polyethylene glycol, triglycerin, tetraglycerin, polyglycerin, etc.); divalent alcohol alkyl ethers (for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene) Glycol monophenyl ether, ethylene glycol monohexyl ether, ethylene glycol mono 2-methylhexyl ether, ethylene glycol isoamyl ether, ethylene glycol benzyl ether, ethylene glycol isopropyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, etc.) ; Dihydric alcohol alkyl ester Tellurium (for example, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol butyl ether, diethylene glycol methyl ethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether , Propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol isopropyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol butyl ether, etc.); divalent alcohol Ether esters (eg, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, ethylene glycol diazinate, ethylene glycol disuccinate, diethylene glycol monoethyl ether acetate, diethylene glycol) Monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monophenyl ether acetate, etc .; glycerin monoalkyl ethers (for example, Kimyl alcohol, Serakir al Sugar alcohol (eg, sorbitol, maltitol, maltotriose, mannitol, sucrose, erythritol, glucose, fructose, amylolytic sugar, maltose, xylitolose, amylolytic sugar reducing alcohol, etc.); Solid; tetrahydrofurfuryl alcohol; POE-tetrahydrofurfuryl alcohol; POP-butyl ether; POP / POE-butyl ether; tripolyoxypropylene glycerin ether; POP-glycerin ether; POP-glycerin ether phosphate; POP / POE-pentaneerythritol Examples include ether and polyglycerin.

  Monosaccharides include, for example, tricarbon sugars (eg, D-glyceryl aldehyde, dihydroxyacetone, etc.); tetracarbon sugars (eg, D-erythrose, D-erythrulose, D-treose, erythritol, etc.); pentose sugars (eg, , L-arabinose, D-xylose, L-lyxose, D-arabinose, D-ribose, D-ribulose, D-xylulose, L-xylulose, etc .; hexose (eg, D-glucose, D-talose, D) -Bucicose, D-galactose, D-fructose, L-galactose, L-mannose, D-tagatose, etc.); pentose sugar (eg, aldheptose, heproose, etc.); octose sugar (eg, octulose, etc.); For example, 2-deoxy-D-ribose, 6-deoxy-L-galactose, 6-deoxy-L-mannose, etc .; amino sugar (eg, D-glucosamine, D-galactosamine, shea Acid, Aminouron acid, muramic acid); uronic acid (e.g., D- glucuronic acid, D- mannuronic acid, L- guluronic acid, D- galacturonic acid, L- iduronic acid) and the like.

  Examples of the oligosaccharide include sucrose, umbelliferose, lactose, planteose, isolicnose, α, α-trehalose, raffinose, lycnose, umbilicin, stachyose verbus course, and the like.

  Examples of the polysaccharide include cellulose, quince seed, chondroitin sulfate, starch, galactan, dermatan sulfate, glycogen, gum arabic, heparan sulfate, hyaluronic acid, tragacanth gum, keratan sulfate, chondroitin, xanthan gum, mucoitin sulfate, guar gum, dextran, kerato sulfate. , Locust bingham, succinoglucan, caronic acid and the like.

  Examples of amino acids include neutral amino acids (eg, threonine, cysteine, etc.); basic amino acids (eg, hydroxylysine, etc.) and the like. Examples of amino acid derivatives include acyl sarcosine sodium (lauroyl sarcosine sodium), acyl glutamate, acyl β-alanine sodium, glutathione, and pyrrolidone carboxylic acid.

  Examples of the organic amine include monoethanolamine, diethanolamine, triethanolamine, morpholine, triisopropanolamine, 2-amino-2-methyl-1,3-propanediol, and 2-amino-2-methyl-1-propanol. Is mentioned.

  Examples of the polymer emulsion include an acrylic resin emulsion, a polyethyl acrylate emulsion, an acrylic resin liquid, a polyacryl alkyl ester emulsion, a polyvinyl acetate resin emulsion, and a natural rubber latex.

  Examples of the pH adjuster include buffers such as lactic acid-sodium lactate, citric acid-sodium citrate, and succinic acid-sodium succinate.

  Examples of vitamins include vitamins A, B1, B2, B6, C, E and derivatives thereof, pantothenic acid and derivatives thereof, biotin and the like.

  Examples of the antioxidant include tocopherols, dibutylhydroxytoluene, butylhydroxyanisole, gallic acid esters and the like.

  Examples of the antioxidant assistant include phosphoric acid, citric acid, ascorbic acid, maleic acid, malonic acid, succinic acid, fumaric acid, kephalin, hexametaphosphate, phytic acid, and ethylenediaminetetraacetic acid.

  Other components that can be blended include, for example, preservatives (ethyl paraben, butyl paraben, etc.); anti-inflammatory agents (eg, glycyrrhizic acid derivatives, glycyrrhetinic acid derivatives, salicylic acid derivatives, hinokitiol, zinc oxide, allantoin, etc.); whitening agents (for example, Extract, placenta extract, saxifrage extract, arbutin, etc.); various extracts (eg, buckwheat, auren, shikon, peonies, assembly, birch, sage, loquat, carrot, aloe, mallow), iris, grape, yokuinin, loofah, lily , Saffron, nematode, ginger, hypericum, onionis, garlic, capsicum, chimpi, toki, seaweed, etc.), activator (eg, royal jelly, photosensitizer, cholesterol derivative, etc.); blood circulation promoter (eg, benzyl nicotinate, nicotine β-butoxyethyl ester, capsaicin, gingerone, cantalis tincture, ictamol, tannic acid, α-borneol, tocopherol nicotinate, inositol hexanicotinate, cyclandrate, cinnarizine, trazoline, acetylcholine, verapamil, cephalanthin, γ-oryzanol, etc. ); Antiseborrheic agents (eg, sulfur, thianthol, etc.); anti-inflammatory agents (eg, tranexamic acid, thiotaurine, hypotaurine, etc.) and the like.

The skin external preparation or hair cosmetic composition of the present invention can stably contain an ultraviolet absorber or a drug. Therefore, it is preferable to blend a poorly soluble ultraviolet absorber or a poorly soluble drug, which has not been able to obtain high solubility with conventional oils and has been difficult to blend stably.
Examples of the ultraviolet absorber that is preferably blended in the external preparation for skin or hair cosmetic of the present invention include triazine-based ultraviolet absorbers that are difficult to dissolve in conventional oils. For example, an ultraviolet absorber such as bisresorcinyltriazine is preferably blended. More specifically,
2,4-bis {[4- (2-ethylhexyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) 1,3,5-triazine or octylreazone 2,4,6-tris {4- (2-ethylhexyloxycarbonyl) anilino} 1,3,5-triazine is preferably blended.

The dosage form of the external preparation for skin or hair cosmetic of the present invention is arbitrary, and includes any of solution system, solubilization system, emulsion system, powder dispersion system, water-oil two-layer system, water-oil-powder three-layer system, etc. Such a dosage form may be used. Moreover, the product form of the external preparation for skin or hair cosmetics of this invention is also arbitrary. Facial cosmetics such as lotions, emulsions, creams and packs, makeup cosmetics such as foundations, lipsticks and eye shadows, body cosmetics, aromatic cosmetics, cleansing agents, skin external preparations such as ointments, various types of hair nourishing agents, etc. It can be produced by a conventional method by blending the above oil into hair cosmetics.
In addition, when mix | blending a ultraviolet absorber and a chemical | medical agent, an emulsion and a cream-like emulsion composition are preferable from a usability point.

  Next, the present invention will be described more specifically with reference to examples. The present invention is not limited thereby. First, synthesis examples of the siloxane ester compound of the present invention will be described.

"Synthesis Example 1: Benzenecarboxylic acid [methylbis (trimethylsiloxy) silyl] propyl"
Toluene (special grade Wako Reagent) (30 mL) was placed in a 300 mL three-necked flask purged with argon, benzoyl chloride (Tokyo Kasei) (5.8 mL, 0.05 mol) was added, and the mixture was stirred at room temperature. Furthermore, under ice-cooling at 0 ° C., heptamethyl-3- (3-hydroxypropyl) trisiloxane (Shin-Etsu Chemical Co., Ltd.) (15.7 mL, 0.05 mol) and pyridine (Nacalai Tesque) (4.4 mL, 0.055 mol), toluene (20 mL) Was added dropwise and stirred for 3 hours while gradually warming to room temperature. Add 50 mL of water to quench unreacted benzoyl chloride, wash with 50 mL of 5% hydrochloric acid, 50 mL of saturated aqueous sodium bicarbonate, and 50 mL of saturated aqueous sodium chloride, dry over sodium sulfate, and remove the solvent under reduced pressure. Was distilled off. The obtained colorless oily product was subjected to column chromatography to obtain the desired compound as a colorless odorless oil in a yield of 90%.
This compound was identified by 1H-NMR (JEOL JNM-ECP400) and confirmed to be benzenecarboxylic acid [methylbis (trimethylsiloxy) silyl] propyl represented by the following formula (3). The spectrum of 1H-NMR is shown in FIG. 1 (the upper part of the figure is an enlarged view of each spectrum). The spectrum is assigned as follows.
1H-NMR (400 MHz CDCl ₃ ) spectrum assignment: δ 8.03 (2H, dd), 7.52 (1H, tt), 7.42 (2H, tt), 4.26 (2H, t), 1.77 (2H, m), 0.55 (2H, m), 0.08 (18H, s), 0.05 (3H, s)

すなわち、上記式（４）化合物は、一般式（１）において、Ｘはヒドロキシル基、ａは１、Ｒ²がプロピル基(-CH₂CH₂CH₂-)、Ｒ¹がメチル基(CH₃)、ｎが１、であり、一般式（２）の部分が、ｍが３、Ｒ³がメチル基に相当するシロキサンエステル化合物である。 “Synthesis Example 2: 2-hydroxybenzenecarboxylic acid [methylbis (trimethylsiloxy) silyl] propyl”
Chloroform (Wako Special Grade) (100 mL) was placed in a 500 mL three-neck flask purged with argon, salicylic acid (Nacalai Tesque) (3.7 g, 26.5 mmol) was added, and the mixture was stirred at room temperature. Furthermore, after adding carbonylbisimidazole (Tokyo Kasei) (5.15 g, 31.8 mmol) at room temperature and stirring for 1 hour, heptamethyl-3- (3-hydroxypropyl) trisiloxane (10.0 mL, 31.8 mmol) was dripped. Stir for 24 hours. The extract was washed with 50 mL of 0.1% aqueous ammonium chloride solution, 50 mL of saturated aqueous sodium hydrogen carbonate solution and 100 mL of saturated aqueous sodium chloride solution in that order, dried over sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained colorless oily product was subjected to column chromatography to obtain a colorless and odorless oily compound in a yield of 88%.
This compound was identified by 1H-NMR (JEOL JNM-ECP400) and confirmed to be 2-hydroxybenzenecarboxylic acid [methylbis (trimethylsiloxy) silyl] propyl represented by the following formula (4). The spectrum of 1H-NMR is shown in FIG. 2 (the upper part of the figure is an enlarged view of each spectrum). The spectrum is assigned as follows.
Assignment of 1H-NMR (400 MHz CDCl ₃ ) spectrum: δ10.85 (1H, s), 7.84 (1H, dd), 7.43 (1H, dt), 6.96 (1H, dd), 6.86 (1H, dt) 4.28 ( 2H, t), 1.78 (2H, m), 0.54 (2H, m), 0.08 (18H, s), 0.02 (3H, s)

That is, the compound of the above formula (4) has the general formula (1), wherein X is a hydroxyl group, a is 1, R ² is a propyl group (—CH ₂ CH ₂ CH ₂ —), and R ¹ is a methyl group (CH ₃ ), N is 1, and the portion of the general formula (2) is a siloxane ester compound in which m is 3 and R ³ is a methyl group.

"Solubility of poorly soluble UV absorbers in oils obtained in Synthesis Examples 1 and 2"
Solubility of triazine derivative (2,4-bis {[4- (2-ethylhexyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) 1,3,5-triazine) as a poorly soluble ultraviolet absorber It was investigated.
Compared with the solubility of cosmetic general-purpose silicone oil and various oils.
Solubility represented the density | concentration (mass percentage) in the saturated solution in 0 degreeC.
As the alkyl benzoate having 12 to 15 carbon atoms, a commercially available product (Clodamol AB; Croda Inc.) was used. This oil is a mixture of alkyl benzoates having an alkyl group having 12 to 15 carbon atoms.
It can be seen that the silicone ester derivatives used in the external preparation for skin or hair cosmetics of the present invention have significantly improved solubility of poorly soluble drugs compared to silicone oils. Further, it has excellent solubility comparable to that of dioctyl succinate and pentaerythrityl tetraoctanoic acid having excellent solubility. Furthermore, the compounds of Synthesis Examples 1 and 2 were excellent oils having no odor.

  Next, examples of the external preparation for skin containing the oil of the above synthesis example will be described. The siloxane ester compound obtained in the above synthesis example was blended into a skin external preparation and evaluated. The blending amounts in the examples are% (mass percentage) unless otherwise specified. First, test methods and evaluation methods will be explained.

“Evaluation (1): Refreshing skin”
An actual use test was conducted by 10 expert panelists on the freshness of the skin during use. The evaluation criteria are as follows.
A: More than 8 professional panelists recognized that the skin feels refreshed during use.
○: 6 or more and less than 8 professional panelists recognized that the skin feels refreshed during use.
Δ: 3 or more and less than 6 panelists recognized that the skin was refreshing during use.
X: Less than 3 professional panelists recognized that there was a refreshing feeling during use.

"Evaluation (2): No stickiness on the skin"
An actual use test was conducted by 10 expert panelists on the non-stickiness of the skin during and after use. The evaluation criteria are as follows.
A: Eight or more professional panelists recognized that there was no stickiness on the skin during and after use.
○: 6 or more professional panelists recognized that there was no stickiness on the skin during and after use.
Δ: 3 or more specialist panelists and less than 6 people recognized that there was no stickiness on the skin during and after use.
X: Less than 3 professional panelists recognized that there was no stickiness on the skin during and after use.

"Stability"
The sample was put in each thermostat of 50 degreeC, 25 degreeC, and -5 degreeC, and the state after 3 months was observed with the microscope and visual observation.
A: No abnormality by microscope and visual inspection.
○: No abnormality is visually observed, but slight separation or crystal precipitation is observed by microscopic observation.
Δ: Slight separation or crystal precipitation is observed by visual observation or microscopic observation.
X: Separation or crystal precipitation is clearly seen visually.

"Ultraviolet ray prevention effect test"
This was performed using a high-precision in vitro SPF measurement system (a system capable of measuring SPF and PFA values with high accuracy) described in JP-A-7-167781.
Specifically, a solar simulator (Solar Ultraviolet Simulator Model 600: Solar Light Co.) was used as a light source. The test product was uniformly applied at a coating amount of 2.0 mg / cm ^{2 to} the applied transpore tape TM (3M Co.) and irradiated with ultraviolet rays. The transmitted ultraviolet spectrum was calculated and the SPF value and the PFA value were calculated.

Next, the sunscreen cosmetics of the water-in-oil emulsion compositions of Examples and Comparative Examples shown in “Table 5” and “Table 6” were produced and evaluated as follows. The blending amount is mass% unless otherwise specified.
"Production Method"
(1) to (11) are mixed and stirred to obtain a uniform oil phase. Next, (12) and (13) are added to this oil phase and stirred uniformly with a homomixer to obtain an oil phase part. Finally, (14), in which (15) is dissolved, is gradually added to the oil phase stirred with a homomixer and emulsified at room temperature (20 ° C.) to obtain a sunscreen cosmetic (cream type). It was.

＊１：アラセルP135 ユニケマ製
＊２：Decaglyn 5-IS 日本サーファクタント工業株式会社製
＊３：商品名：ＫＦ６０１７、デカメチルシクロペンタシロキサンの５０％溶液、信越化学工業株式会社製
＊４：商品名：チノソーブＳ、チバ・スペシャリティー・ケミカルズ株式会社製
＊５：商品名：ＫＦ７３１２Ｊ、信越化学工業株式会社製

* 1: Aracel P135 made by Unikema * 2: Decaglyn 5-IS made by Nippon Surfactant Industries * 3: Product name: KF6017, 50% solution of decamethylcyclopentasiloxane, manufactured by Shin-Etsu Chemical Co., Ltd. * 4: Product name: Chinosorb S, manufactured by Ciba Specialty Chemicals Co., Ltd. * 5: Product name: KF7312J, manufactured by Shin-Etsu Chemical Co., Ltd.

＊１：アラセルP135 ユニケマ製
＊２：Decaglyn 5-IS 日本サーファクタント工業株式会社製
＊３：商品名：ＫＦ６０１７、信越化学工業株式会社製
＊４：商品名：チノソーブＳ、チバ・スペシャリティー・ケミカルズ株式会社製
＊５：商品名：ＫＦ７３１２Ｊ、信越化学工業株式会社製

* 1: Allercel P135 made by Unikema * 2: Decaglyn 5-IS Nippon Surfactant Industries * 3: Product name: KF6017, Shin-Etsu Chemical Co., Ltd. * 4: Product name: Chinosorb S, Ciba Specialty Chemicals shares * 5: Product name: KF7312J, manufactured by Shin-Etsu Chemical Co., Ltd.

From the above results, it can be seen that the external preparation for skin of the present invention has excellent effects in all evaluation items.
That is, the specific siloxane ester compound used in the present invention is excellent in a refreshing feeling and non-stickiness as a conventional silicone oil as an oil component to be blended in a skin external preparation. Furthermore, since the solubility in a poorly soluble ultraviolet absorber is high, it is possible to provide a skin external preparation capable of stably blending a desired amount in a skin external preparation containing a poorly soluble ultraviolet absorber or drug. . It functions as an excellent skin external preparation oil without odor.
In addition, since it can be formulated stably with a poorly soluble UV absorber, it has a high sunscreen effect, its usability is refreshing, non-sticky, and excellent in stability. It became clear that it could be provided. In addition, the same result is obtained even if it mix | blends with hair cosmetics as a hair cosmetic oil component.

  Other examples of the present invention will be given below.

Example 14 Sunscreen Emulsion Oil phase volatile cyclic silicone 27.0%
(Decamethylcyclopentanesiloxane)
Silicone hydrophobized titanium dioxide 10.0
Silicone hydrophobized zinc oxide 10.0
Silicone hydrophobized talc 4.0
Compound of Synthesis Example 1 10.0
Octyl methoxycinnamate 5.0
4-Methoxy-4'-t-butyldibenzoylmethane 2.0
2,4-bis {[4- (2-ethylhexyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) 1,3,5-triazine 3.0
Organically modified montmorillonite 0.5
Preservative appropriate amount perfume appropriate amount B. Water phase purified water Residual dipropylene glycol 7.0
(Manufacturing method and evaluation)
The oil phase part and the water phase part are mixed and dissolved. In the oil phase part, the titanium dioxide is sufficiently dispersed, and the water phase part is added and emulsified using a homogenizer. The resulting sunscreen emulsion is refreshing. In addition, the dissolution stability of 2,4-bis {[4- (2-ethylhexyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) 1,3,5-triazine, a poorly soluble ultraviolet absorber Also excellent in properties.

Example 15 Sunscreen Cream Oil phase Stearic acid 10.0%
Stearyl alcohol 4.0
Butyl stearate 8.0
Stearic acid monoglycerin ester 2.0
Vitamin E acetate 0.5
Vitamin A palmitate 0.1
Compound of Synthesis Example 1 10.0
2,4-bis {[4- (2-ethylhexyloxy) -2-hydroxy] phenyl}
-6- (4-methoxyphenyl) 1,3,5-triazine
3.0
Macadamia nut oil 1.0
Tea oil 3.0
Fragrance 0.4
Preservative appropriate amount Aqueous phase Glycerin 4.0
1,2 pentanediol 3.0
Sodium hyaluronate 1.0
Potassium hydroxide 2.0
Magnesium ascorbate phosphate 0.1
L-arginine hydrochloride 0.01
Edetate trisodium 0.05
Purified water residue (production method and evaluation)
The oil phase part of A and the aqueous phase part of B are each heated to 70 ° C. and completely dissolved. Add Phase A to Phase B and emulsify with an emulsifier. The emulsion is cooled by a heat exchanger to obtain a cream. This cream has excellent smoothness, does not feel sticky, and has a moisturizing effect. In addition, the dissolution stability of 2,4-bis {[4- (2-ethylhexyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) 1,3,5-triazine, a poorly soluble ultraviolet absorber Also excellent in properties.

Example 16 Cream A. Oil phase Cetanol 4.0%
Vaseline 7.0
Isopropyl myristate 8.0
Squalane 10.0
Compound of Synthesis Example 1 10.0
2,4-bis {[4- (2-ethylhexyloxy) -2-hydroxy] phenyl}
-6- (4-methoxyphenyl) 1,3,5-triazine
3.0
Stearic acid monoglycerol ester 2.2
POE (20) sorbitan monostearate 2.8
3,7-dimethyloctylbenzoate (Synthesis Example 1) 20.0
Vitamin E Nicotinate 2.0
Fragrance 0.3
Antioxidant appropriate amount Preservative appropriate amount Aqueous phase Glycerin 10.0
Sodium hyaluronate 0.02
Dipropylene glycol 4.0
Sodium pyrrolidonecarboxylate 1.0
Edetate disodium 0.01
Purified water residue (production method and evaluation)
The oil phase part of A and the aqueous phase part of B are each heated to 70 ° C. and completely dissolved. Add Phase A to Phase B and emulsify with an emulsifier. The emulsion is cooled by a heat exchanger to obtain a cream. This cream has excellent smoothness, does not feel sticky, and has a moisturizing effect. In addition, the dissolution stability of 2,4-bis {[4- (2-ethylhexyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) 1,3,5-triazine, a poorly soluble ultraviolet absorber Also excellent in properties.

Example 17 Foundation A. Oil phase Cetanol 3.5%
Deodorized lanolin 4.0
Jojoba oil 5.0
Vaseline 2.0
Squalane 6.0
Stearic acid monoglycerin ester 2.5
POE (60) hydrogenated castor oil 1.5
POE (20) cetyl ether 1.0
Compound of Synthesis Example 1 2.0
Pyridoxine tripalmitate 0.1
Preservative appropriate amount Fragrance 0.3
B. Aqueous phase Propylene glycol 10.0
Formulated powder 12.0
Ethylenediamine hydroxyethyl triacetate trisodium 1.0
Purified water residue (production method and evaluation)
The oil phase part of A and the aqueous phase part of B are each heated to 70 ° C. and completely dissolved. Add Phase A to Phase B and emulsify with an emulsifier. The emulsion is cooled by a heat exchanger to obtain an emulsion foundation. This emulsification foundation is a cream that is excellent in smoothness, has no stickiness, has a refreshing feeling, and maintains a moisturizing effect. In addition, the dissolution stability of 2,4-bis {[4- (2-ethylhexyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) 1,3,5-triazine, a poorly soluble ultraviolet absorber Also excellent in properties.

Example 18 Water-in-oil type sunscreen cosmetic (milky lotion type)%
(Oil phase)
(1) Octyl paramethoxycinnamate 5.0
(2) Oxybenzone 3.0
(3) 4-tertbutyl-4′-methoxybenzoylmethane 1.0
(4) Silicone hydrophobized titanium dioxide 6.0
(5) Silicone hydrophobized zinc oxide 6.0
(6) Squalane 10.0
(7) Compound of Synthesis Example 1 23.0
(8) Octamethylcyclotetrasiloxane 5.0
(9) Glycerin diisostearate 2.0
(10) Polyethylene glycol dipolyhydroxystearate 1.0
(11) Bisresorcinyl triazine 3.0
(Product name: Chinosorb S, manufactured by Ciba Specialty Chemicals Co., Ltd.)
(Water phase)
(12) Methylparaben 0.1
(13) Phenoxyethanol 0.1
(14) Ion exchange water 29.8
(15) 1,3-butylene glycol 5.0
(Manufacturing method)
Each component of the oil phase part and the water phase part is heated to 70 ° C. and dissolved. In the oil phase part, the aqueous phase part is added while sufficiently dispersing titanium dioxide and performing a homogenizer treatment. The emulsified composition is cooled using a heat exchanger to obtain an emulsion-type water-in-oil sunscreen cosmetic with a viscosity of 8000 mPa · s. The obtained sunscreen cosmetic is refreshing, non-sticky, has an SPF value of 50.1, a PFA value of 8.8, and is kept in a constant temperature bath at −5 ° C., 25 ° C., and 50 ° C. (3 months (Standing), but there is no abnormality in stability.

Example 19 Water-in-oil type sunscreen cosmetic (cream type)%
(Oil phase)
(1) Fatty acid dextrin hydrophobized titanium dioxide 7.0
(2) Silicone hydrophobized zinc oxide 10.0
(3) Decamethylcyclopentasiloxane 10.0
(4) Compound of Synthesis Example 1 25.0
(5) Liquid paraffin 10.0
(6) Glycerin diisostearate 3.0
(7) Tetraglycerin pentastearate 4.0
(8) Butylparaben 0.2
(9) Fragrance 0.1
(10) Octyl methoxycinnamate 5.0
(11) Bisresorcinyl triazine 1.5
(Product name: Chinosorb S, manufactured by Ciba Specialty Chemicals Co., Ltd.)
(Water phase)
(12) Ion exchange water 21.7
(13) 1,3-butylene glycol 2.5
(Manufacturing method)
Each component of the oil phase part and the water phase part is heated to 70 ° C. and dissolved. In the oil phase part, titanium dioxide is sufficiently dispersed, and the water phase part is added while homomixing. This emulsion composition is cooled using a heat exchanger to obtain a water-in-oil type sunscreen cosmetic with a viscosity of 55000 mPa · s.
The obtained sunscreen cosmetics are refreshing, non-sticky, have an SPF value of 49.2 and a PFA value of 8.3, and are kept under constant temperature baths of −5 ° C., 25 ° C. and 50 ° C. (3 months (Standing), but there is no abnormality in stability.

Example 20 Water-in-oil type sunscreen cosmetic (milky lotion)%
(Oil phase)
(1) Dimethylpolysiloxane 6 mPa · s 12.0
(2) Compound of Synthesis Example 1 25.0
(3) Liquid paraffin 1.5
(4) Octyl methoxycinnamate 7.0
(5) Ethylparaben 0.2
(6) Fragrance 0.1
(7) Fatty acid dextrin hydrophobized zinc oxide 6.0
(8) Polyethylene glycol dipolyhydroxystearate 1.5
(Water phase)
(9) Ion exchange water 39.7
(10) Propylene glycol 5.0
(11) Sodium glutamate 1.5
(12) Sodium chloride 0.5
(Manufacturing method)
Each component of the oil phase part and the water phase part is heated to 70 ° C. and dissolved. In the oil phase part, the titanium dioxide is sufficiently dispersed, and the water phase part is added while performing the homogenizer treatment. The emulsified composition is cooled using a heat exchanger to obtain an emulsion-type water-in-oil sunscreen cosmetic with a viscosity of 2000 mPa · s. The obtained sunscreen cosmetics are not refreshing and have a SPF value of 42.4 and a PFA value of 6.8. In addition, no abnormality is observed in stability even in a constant temperature bath at −5 ° C., 25 ° C., and 50 ° C. (left for 3 months).

Example 21 Hair Conditioner
(mass%)
(1) Isopentyldiol 5.0
(2) Sorbitol 5.0
(3) Dimethicone (1 million cSt) 1.5
(4) Dimethicone (20 cSt) 2.0
(5) Stearyl alcohol 3.0
(6) Behenyl alcohol 2.0
(7) Stearyl trimonium chloride 1.5
(8) Compound of Synthesis Example 2 1.0
(9) Arginine 0.01
(10) PEG-90M 0.02
(11) Stearyl dihydroxypropyl dimonium oligosaccharide 0.05
(12) Citric acid 0.07
(13) Appropriate amount of phenoxyethanol (14) Appropriate fragrance Appropriate amount (15) Soy lecithin 0.1
(16) Hydrolyzed wheat protein / hydrolyzed wheat starch 0.02
(17) N-lauroyl glutamic acid
Di (phytosteryl / 2-octyldodecyl) 0.1
(18) Purified water residue (production method)
Emulsify by a conventional method.

Example 22 Hair Oil
(mass%)
(1) Light liquid isoparaffin 85
(2) Compound 2 of Synthesis Example 1
(3) Octylmethoxine namate 1
(4) Methylphenylpolysiloxane 5
(5) Perfume appropriate amount (production method)
After mixing (1) to (4), (5) is added to make uniform.

Example 23 Hair Spray
(mass%)
(1) Volatile isoparaffin 16
(2) Dimethylpolysiloxane 7
(3) Propylene glycol 5
(4) Ethanol appropriate amount (5) Purified water 2
(6) Octyl methoxycinnamate 4
(7) Compound of Synthesis Example 1 (8) Poly (oxyethylene / oxypropylene) / methylpolysiloxane copolymer
4
(9) Perfume appropriate amount (10) LPG residue (production method)
After emulsification by a conventional method, (9) is added to make uniform, and then the hair spray container is filled together with (10).

Example 24 Hair Cream (Prescription) (mass%)
(1) Volatile isoparaffin 10
(2) Dimethylpolysiloxane 1
(3) Ethanol 10
(4) 1,3-butylene glycol 5
(5) POE (14) POP (7) Dimethyl ether 1
(6) Isostearic acid 0.5
(7) Polyoxyethylene hydrogenated castor oil 0.1
(8) 2-alkyl-N-carboxymethyl 1
-N-hydroxyethylimidazolinium betaine (9) sodium hydroxide 0.3
(10) Compound 5 of Synthesis Example 1
(11) Octyl methoxycinnamate 4
(12) Carboxyvinyl polymer 0.8
(13) Paraoxybenzoic acid ester appropriate amount (14) edetate trisodium appropriate amount (15) purified water residue (16) perfume appropriate amount (production method)
Emulsify by a conventional method.

The novel siloxane ester compound of the present invention is useful as a skin external preparation oil component or hair cosmetic oil component that is excellent in a refreshing feel and is hardly soluble and is suitable for dissolving a drug.
With the oil of the present invention, it is possible to provide a skin external preparation or a hair cosmetic that is excellent in a refreshing feeling of use and that can be easily blended with a poorly soluble ultraviolet absorber or drug.
The skin external preparation or hair cosmetic of the present invention can be stably blended with a high-polarity ultraviolet absorber, and is preferably used as a sunscreen cosmetic.

2 is a 1H-NMR spectrum of the compound of Synthesis Example 1. 2 is a 1H-NMR spectrum of the compound of Synthesis Example 2.

Claims (6)

A siloxane ester compound, which is a siloxane having at least one unit represented by the following general formula (1), wherein another unit present in the siloxane is represented by the general formula (2).

In the formula, R ¹ is an alkyl group having 1 to 4 carbon atoms, a phenyl group or a trimethylsiloxy group, R ² is a divalent hydrocarbon group having at least 2 carbon atoms (including those having a heteroatom O), X represents hydrogen, a hydroxyl group, an alkoxy group, n represents an integer of 0 to 3, and a represents an integer of 1 to 5.

In the formula, R ³ represents an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a trimethylsiloxy group, and m represents an integer of 0 to 3. Benzenecarboxylic acid [methylbis (trimethylsiloxy) silyl] propyl represented by the following formula (3).

  A skin external preparation oil or hair cosmetic oil comprising the siloxane ester compound according to claim 1.   A skin external preparation oil or hair cosmetic oil comprising the benzenecarboxylic acid [methylbis (trimethylsiloxy) silyl] propyl according to claim 2.   A skin external preparation or hair cosmetic comprising the skin external preparation oil or hair cosmetic oil according to claim 3 or 4. The skin external preparation or hair cosmetic according to claim 5, further comprising an ultraviolet absorber.

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