JP2011173852A - Cosmetic containing silicone phosphoric acid triester - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To develop a novel silicone phosphoric acid triester, and to apply it as a cosmetic. <P>SOLUTION: The novel silicone phosphoric acid triester is a compound shown by formula (I), when this is used for a cosmetic, it excels in a treatment effect, smooth feeling of use, or a cosmetic persistent effect. The cosmetic may include a silicone phosphoric acid diester and/or a silicone phosphoric acid monoester. In the formula, each R<SB>1</SB>respectively, denotes a 1-4C alkyl group; R denotes a 2-7C divalent hydrocarbon group which may have at least one sort chosen from -O- and -CO-, and n denotes an integer of either one of 5-40. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a cosmetic containing a novel silicone phosphate triester.

Conventionally, a modified organo (poly) siloxane is blended in cosmetics. For example, there are organo (poly) siloxanes such as amino modification, epoxy modification, carboxylic acid modification, and phosphate ester modification.
Among these, regarding phosphate ester-modified organo (poly) siloxane, for example, Patent Document 1 discloses that at least one silicon atom of organo (poly) siloxane has the following formula:

[Wherein, R ¹ represents a linear or branched alkylene group having 2 to 20 carbon atoms, and R ² represents a linear or branched alkylene group having 1 to 20 carbon atoms which may be substituted by a hydroxyl group. , R ³ and R ⁴ are the same or different and each represents a linear or branched alkyl group having 1 to 22 carbon atoms, p represents a number from 0 to 20, and a, b and c are each bonded to a phosphorus atom. The number of groups in parentheses is shown, a + b + c = 3, a is 1 or 2, and b and c are 0 or 1. However, when p = 0, R ² has 9 to 20 carbon atoms. A phosphate triester modified organo (poly) siloxane modified with a phosphate triester group represented by the formula:

  Further, in Patent Document 2, as a surface treatment agent for a cosmetic powder, at least one silicon atom of an organo (poly) siloxane is represented by the following formula as a phosphate ester-modified organo (poly) siloxane.

[R ¹ and R ² represent a C2-20 alkylene group, R ³ represents an optionally substituted C1-20 alkylene group, R ⁴ represents a C1-22 alkyl group, M Represents H or a monovalent cation, p and q represent numbers from 0 to 200, a, b and c represent the number of groups in parentheses bonded to a phosphorus atom, a + b + c = 3, a and c Is 1 or 2, and b is 0 or 1. A phosphate ester-modified organo (poly) siloxane modified with a phosphate group represented by the formula:

Patent Document 3 discloses that at least one silicon atom of an organo (poly) siloxane has the following formula [{—CH ₂ CH ₂ —R ² — (OR ¹ ) _p —O} ₃ P═O] _1/3
[In the formula, in the trivalent group in the square brackets, 3p R ^{1 s} are the same or different and represent a linear or branched alkylene group having 2 to 20 carbon atoms, and three R ² are the same or different. And a hydroxyl group may be a linear or branched alkylene group having 7 to 20 carbon atoms which may be substituted, and three ps are the same or different and represent a number of 0 to 20. All three terminal carbon atoms are bonded to silicon atoms of the same or two or three different organo (poly) siloxane molecules. A phosphoric ester triester-modified organo (poly) siloxane modified with a group represented by the formula:

However, Patent Documents 1 and 2 describe that a silicone phosphate triester used in the present invention, that is, a triester body in which three organo (poly) siloxanes are bonded to phosphoric acid, is blended in cosmetics. However, in Patent Document 3 described above, although a triester body in which three organo (poly) siloxanes are bonded to phosphoric acid is described, organo (poly) siloxane and phosphoric acid are —CH ₂ CH ₂ They are bonded via a —R ² — (OR ¹ ) _p — group, and the group has a long chain of 9 or more carbon atoms.

In Patent Document 3, a phosphate triester-modified organo (poly) siloxane is substituted with an organopolysiloxane having at least one hydrogen atom bonded to a silicon atom by the following formula {CH ₂ = CH-R ^2- (OR ¹ ) _{p -O}} 3 _P = O
[Wherein, 3p R ^{1 s} are the same or different and represent a linear or branched alkylene group having 2 to 20 carbon atoms, and three R ² are the same or different and may be substituted with a hydroxyl group] A linear or branched alkylene group having a number of 7 to 20 is shown, and three p's are the same or different and represent a number of 0 to 20. In the method, the —CH ₂ CH ₂ —R ² — (OR ¹ ) _p — group is short as in the present invention. In some cases, synthesis was difficult.

^{_{Therefore, -CH 2 CH 2 -R 2 -}} (OR 1) p - for (also referred to as silicone phosphate triester) group is short phosphoric acid triester modified organo (poly) siloxanes, which have utility as substrates for cosmetics Whether or not it was not known at all.

JP 09-048855 A JP 09-136815 A Japanese Patent Laid-Open No. 09-157397

An object of the present invention is different from the silicone phosphate triester described in Patent Document ^{_{3, -CH 2 CH 2 -R 2}} - (OR 1) p - group is developing a short silicone phosphotriester, it Is applied as a cosmetic.

The present inventors used a silicone phosphate triester compound having a short —CH ₂ CH ₂ —R ² — (OR ¹ ) _p — group, which could not be synthesized in Patent Document 3, as a base material for cosmetics. Then, it discovered that it was excellent in the treatment effect, the smooth feeling of use, and the makeup lasting effect, and completed this invention.

That is, the present invention
(1) Formula (I)

(In the formula, each R ₁ independently represents an alkyl group having 1 to 4 carbon atoms, and R may have at least one selected from —O— and —CO—.) A cosmetic containing 1 type or 2 types or more of silicone phosphoric acid triesters represented by the divalent hydrocarbon group of -7, n represents any integer of 5-40,
(2) Formula (I)

(In the formula, each R ₁ independently represents an alkyl group having 1 to 4 carbon atoms, and R may have at least one selected from —O— and —CO—.) 1 to 2 or more of 60 to 100% by mass of a silicone phosphoric acid triester represented by a divalent hydrocarbon group of ˜7, and n represents an integer of 5 to 40),
Formula (II)

(Wherein R ₁ , R and n are the same as defined in the above formula (I)), one or more silicone phosphate diesters represented by 0 to 35% by mass, and
Formula (III)

(Wherein R ₁ , R and n are the same as defined in the above formula (I)), a silicone phosphate ester mixture composed of 0 to 5% by mass of one or more of the silicone phosphate monoesters represented by the formula (I) The cosmetic according to (1) above, characterized by containing, and
(3) The cosmetic according to (1) or (2), further comprising an oil.

  Since the silicone phosphate triester used in the present invention is excellent in adhesion to keratin substances such as skin and hair, a cosmetic compounded with this is particularly excellent in treatment effect, smooth use feeling and makeup sustaining effect. .

Details of the present invention will be described below.
(Silicone phosphate triester)
The silicone phosphate triester used in the present invention has the formula (I)

It is represented by
In the formula, each R ₁ independently represents an alkyl group having 1 to 4 carbon atoms, and R 2 may have at least one selected from —O— and —CO—. 7 represents a divalent hydrocarbon group, and n represents an integer of 5 to 40.

Examples of the “alkyl group having 1 to 4 carbon atoms” in R ₁ include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, i-butyl group, and t-butyl. Groups. Of these, methyl is preferred as R ₁ .
“Divalent hydrocarbon group having 2 to 7 carbon atoms” of “Divalent hydrocarbon group having 2 to 7 carbon atoms which may have at least one selected from —O— and —CO—” in R Examples of "" include ethylene chain, propylene chain, methylethylene chain, butylene chain, 1,2-dimethylethylene chain, pentylene chain, 1-methylbutylene chain, 2-methylbutylene chain, hexylene chain, heptylene chain and the like.

The “C2-C7 divalent hydrocarbon group having at least one selected from —O— and —CO—” has one or more of —O— or —CO—. For example, —CH ₂ —O— (CH ₂ ) ₂ —, — (CH ₂ ) ₂ —O— (CH ₂ ) ₂ —, — (CH ₂ ) ₃ —O— (CH ₂ ) ₂ —, _{- (CH 2) 4 -O- (} CH 2) 2 -, - (CH 2) 2 -O (CH 2) 2 -O- (CH 2) 2 -, - (CH 2) 2 -O- (CH _{2) 4 -, - (CH} 2) 2 -O- (CH 2) 5 -, - (CH 2) 3 -O-CH 2 -, - CH 2 -CO- (CH 2) 2 -, - (CH ₂ ) _2- CO— (CH ₂ ) ₂ —, — (CH ₂ ) ₃ —CO— (CH ₂ ) ₂ —, — (CH ₂ ) ₄ —CO— (CH ₂ ) ₂ —, — (CH ₂ ) ₂ —CO— (CH ₂ ) ₄ —, — (CH ₂ ) ₂ —CO— (CH ₂ ) ₅ —, — (CH ₂ ) ₃ —CO—CH ₂ — and the like.
“C2-C7 divalent hydrocarbon group optionally having at least one selected from —O— and —CO—” includes — (CH ₂ ) ₃ O (CH ₂ ) _2- is preferred.

  Specific examples of silicone phosphate triesters include the following. However, n is an integer in any one of 5-40.

  These can be used singly or in a mixture of two or more.

(Method for producing silicone phosphate triester)
The silicone phosphate triester of the present invention can be produced, for example, by the method shown in the following reaction formula.

(Wherein R ₁ , R and n are the same as defined in the above formula (I))

One-terminal carbinol-modified silicone represented by the formula (IV) is reacted with phosphorus oxychloride represented by the formula (V) in the presence of a base in a solvent.
As a solvent used in carrying out the above reaction, polar solvents such as tetrahydrofuran, dimethyl sulfoxide, N, N-dimethylformamide, acetone, diethyl ether and acetonitrile can be used.
Examples of the base include alkylamines such as diethylamine and triethylamine, heterocyclic amines such as piperazine and imidazole, quaternary ammonium salts such as benzyltriethylammonium chloride and methyltrioctylammonium chloride, n-butyllithium, lithium diisopropylamide and the like. Organic metals can be used.
The reaction temperature is usually about 25 ° C. to 50 ° C., and the reaction time is usually about 2 hours to 20 hours, although it varies depending on the silicone chain length.

  Although the silicone phosphoric acid triester represented by the formula (I) is obtained by the above reaction, as a by-product, the silicone phosphoric acid diester represented by the formula (II), the silicone phosphoric acid represented by the formula (III) Monoesters are produced. Although these by-products can be used as a silicone phosphate ester mixture, the product is purified by a conventional method to obtain substantially only the silicone phosphate triester represented by the formula (I). May be used.

(Cosmetics)
The cosmetic of the present invention may be one or more of the silicone phosphate triesters represented by the above formula (I) and, if necessary, the formula (II)

(Wherein R ₁ , R and n are the same as defined in the above formula (I)) and / or two or more types of silicone phosphate diesters represented by formula (III)

(Wherein R ₁ , R and n are the same as defined in the above formula (I)), one or more of silicone phosphoric acid monoesters are contained.

The compounding ratio of the silicone phosphate triester represented by the formula (I), the silicone phosphate diester represented by the formula (II) and the silicone phosphate monoester represented by the formula (III) is represented by the formula (I): The silicone phosphate triester represented is not particularly limited as long as the silicone phosphate triester has an effect as a base material for cosmetics. Preferably, the silicone phosphate triester represented by the formula (I) is 60 to 100% by mass, the formula ( The silicone phosphate diester represented by II) is 0 to 35% by mass, and the silicone phosphate monoester represented by the formula (III) is 0 to 5% by mass.
The blending ratio of these silicone phosphate esters in the cosmetic is 1 to 50% by mass, preferably 5 to 30% by mass.

Components that can be blended according to the type can be blended appropriately in the cosmetic.
For example, oils, surfactants, alcohols, water, humectants, gelling agents and thickeners, powders, UV absorbers, preservatives, antibacterial agents, antioxidants, skin beautifying agents (whitening agents, cell activation agents) Agents, anti-inflammatory agents, blood circulation promoters, skin astringents, antiseborrheic agents, etc.), vitamins, amino acids, nucleic acids, hormones, and the like.
Among these, it is preferable to use with an oil agent, and it will not specifically limit if it is an oil agent which can melt | dissolve the said silicone phosphate ester. By blending the silicone phosphate ester, there is an effect that the compatibility between the polar oil such as ester oil and the nonpolar oil such as silicone oil is increased, and the entire oil agent can be dissolved uniformly.

  Although the compounding quantity of an oil agent is not specifically limited, 1-30 mass% is preferable, and also 5-20 mass% is more preferable.

Examples of oils include solid oils, semi-solid oils, liquid oils, and examples include natural animal and vegetable oils and semi-synthetic oils, hydrocarbon oils, ester oils, glyceride oils, silicone oils, higher alcohols, higher fatty acids, and organic solvents. Is done.
Solid oils include carnauba wax, candelilla wax, cotton wax, shellac wax, natural waxes such as hardened oil, mineral waxes such as ozokerite, ceresin, paraffin wax, microcrystalline wax, polyethylene wax, Fischer-Tropsch wax, ethylene propylene copolymer And the like, synthetic alcohols such as behenyl alcohol, cetyl alcohol, stearyl alcohol, cholesterol and phytosterols, higher fatty acids such as stearic acid and behenic acid, and the like.
Liquid oils, including natural animal and vegetable oils and semi-synthetic oils, specifically avocado oil, linseed oil, almond oil, ibotarou, eno oil, olive oil, kaya oil, liver oil, kyounin oil, wheat germ oil, sesame oil, rice germ oil , Rice bran oil, sasanqua oil, safflower oil, cinnamon oil, cinnamon oil, turtle oil, soybean oil, tea seed oil, camellia oil, evening primrose oil, corn oil, rapeseed oil, Japanese kiri oil, nukarou, germ oil, permanent oil , Palm oil, palm kernel oil, castor oil, sunflower oil, grape oil, jojoba oil, macadamia nut oil, cottonseed oil, palm oil, tricoconut oil fatty acid glyceride, peanut oil, lanolin, liquid lanolin, reduced lanolin, lanolin alcohol, lanolin acetate, Lanolin fatty acid isopropyl, POE lanolin alcohol ether, POE lanolin alcohol acetate , Lanolin fatty acid polyethylene glycol, POE hydrogenated lanolin alcohol ether, yolk oil, and the like.
Examples of the hydrocarbon oil include squalane, squalene, liquid paraffin, pristane, polyisobutylene and the like.
As ester oils, diisobutyl adipate, 2-hexyldecyl adipate, di-2-heptylundecyl adipate, monoisostearic acid-N-alkyl glycol, isocetyl isostearate, trimethylolpropane triisostearate, 2-ethylhexane Cetyl acid, ethylene glycol di-2-ethylhexanoate, neopentyl glycol di-2-ethylhexanoate, trimethylolpropane tri-2-ethylhexanoate, pentaerythritol tetra-2-ethylhexanoate, cetyl octanoate, octyl Dodecyl gum ester, oleyl oleate, octyldodecyl oleate, decyl oleate, neopentyl glycol dicaprate, triethyl citrate, 2-ethylhexyl succinate, amyl acetate, ethyl acetate Butyl acetate, isocetyl stearate, butyl stearate, diisopropyl sebacate, di-2-ethylhexyl sebacate, cetyl lactate, myristyl lactate, isopropyl palmitate, 2-ethylhexyl palmitate, 2-hexyldecyl palmitate, palmitic acid 2-heptylundecyl, cholesteryl 12-hydroxystearylate, dipentaerythritol fatty acid ester, isopropyl myristate, 2-octyldodecyl myristate, 2-hexyldecyl myristate, myristyl myristate, hexyldecyl dimethyloctanoate, ethyl laurate Hexyl laurate, N-lauroyl-L-glutamic acid-2-octyldodecyl ester, diisostearyl malate and the like.
Examples of glyceride oil include acetoglyceride, triisooctanoic acid glyceride, triisostearic acid glyceride, triisopalmitic acid glyceride, tri-2-ethylhexanoic acid glyceride, monostearic acid glyceride, di-2-heptylundecanoic acid glyceride, and trimyristic acid. A glyceride etc. are mentioned.
Silicone oils include dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, tetramethyltetrahydrogencyclotetrasiloxane, alkyl-modified silicone. Etc.
Examples of higher alcohols include oleyl alcohol, lauryl alcohol, stearyl alcohol, isostearyl alcohol, and 2-octyldodecanol. Examples of higher fatty acids include oleic acid, palmitic acid, myristic acid, stearic acid, and isostearic acid.
Organic solvents include hydrocarbons such as n-hexane and cyclohexane, aromatic compounds such as benzene, toluene and xylene, non-aromatic compounds such as ethyl acetate and butyl acetate, chlorine compounds such as chloroform, dichloromethane and dichloroethane, and dioxane. And ether compounds such as tetrahydrofuran, 2-propanol, benzyl alcohol, phenoxyethanol, carbitols, cellosolves, polybutene, spindle oil and the like.

The surfactant is not particularly limited as long as it is usually used in cosmetics, and any surfactant can be used. Examples of the surfactant include an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant. These may be used alone or in combination of two or more as required. be able to.
Specific examples of anionic surfactants include fatty acid soaps such as sodium stearate and triethanolamine palmitate, alkyl ether carboxylic acids and salts thereof, carboxylates such as condensation of amino acids and fatty acids, alkyl sulfonic acids, and alkene sulfones. Acid salts, sulfonates of fatty acid esters, sulfonates of fatty acid amides, sulfonates of alkyl sulfonates and their formalin condensates, alkyl sulfate esters, secondary higher alcohol sulfates, alkyl and allyl ether sulfates Ester salts, fatty acid ester sulfates, fatty acid alkylolamide sulfates, polyoxyethylene alkyl sulfates, sulfate salts such as funnel oil, alkyl phosphates, ether phosphates, alkyl allyl ether phosphates A Dorin salts, such as N- acylamino acid-based active agents.
Cationic surfactants include long chain alkyltrimethylammonium salts, dilong chain alkyldimethylammonium salts, long chain alkyldimethylbenzylammonium salts, dipolyoxyethylene alkylmethylammonium salts, dipolyoxyethylene alkyl ether dimethylammonium salts, poly Alkyl quaternary ammonium salts such as oxypropylene methyl diethyl ammonium salt and aromatic quaternary ammonium salts, pyridinium salts such as alkyl pyridinium salts, imidazoline salts such as alkyl dihydroxyethyl imidazoline salts, N-acyl basic amino acid lower alkyl esters And amine salts such as alkylamine salts, polyamines, amino alcohol fatty acid derivatives and the like.
Nonionic surfactants include sorbitan fatty acid ester, glycerin fatty acid ester, polyglycerin fatty acid ester, propylene glycol fatty acid ester, polyethylene glycol fatty acid ester, sucrose fatty acid ester, polyoxyethylene alkyl ether, polyoxypropylene alkyl ether, polyoxy Ethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene propylene glycol fatty acid ester, polyoxyethylene castor oil, polyoxyethylene cured Castor oil, polyoxyethylene hydrogenated castor oil fatty acid ester, polyoxyethylene N-phytostanol ether, polyoxyethylene phytosterol ether, polyoxyethylene cholestanol ether, polyoxyethylene cholesteryl ether, polyoxyalkylene-modified organopolysiloxane, polyoxyalkylene / alkyl co-modified organopolysiloxane, alkanolamide, sugar ether, sugar Examples include amides.
Examples of amphoteric surfactants include carbobetaine-type amphoteric surfactants such as alkyldimethylaminoacetic acid betaine, fatty acid amidopropyldimethylaminoacetic acid betaine, alkyldihydroxyethylaminoacetic acid betaine, and sulfobetaine-type amphoteric surfactants such as alkylsulfobetaine, N -Amidoamine type (imidazoline type) amphoteric surfactants such as fatty acid acyl-N-carboxymethyl-N-hydroxyethylethylenediamine salt, N-fatty acid acyl-N-carboxymethoxyethyl-N-carboxymethylethylenediamine di-salt, N- [ Amino acid type amphoteric surfactants such as 3-alkyloxy-2-hydroxypropyl] arginine salt, and alkyliminodicarboxylate type amphoteric surfactants.

Specific examples of alcohols include lower alcohols such as ethanol and isopropanol, glycerin, diglycerin, polyglycerin, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1,3-butylene glycol, and erythritol. Examples thereof include sugar alcohols such as monohydric alcohol, sorbitol, maltose, xylitol and maltitol.
Examples of the humectant include urea, hyaluronic acid, chondroitin sulfate, pyrrolidone carboxylate and the like.

  Aqueous gum, tragacanth gum, galactan, carob gum, guar gum, caraya gum, carrageenan, pectin, agar, quince seed (malmello), starch (rice, corn, potato, wheat), alge colloid, tolant gum Plant polymers such as locust bean gum, microbial polymers such as xanthan gum, dextran, succinoglucan, pullulan, animal polymers such as collagen, casein, albumin, gelatin, carboxymethyl starch, methylhydroxypropyl starch, etc. Starch-based polymers, methylcellulose, ethylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, hydroxymethylcellulose, hydroxypropylcellulose, nito Cellulose, cellulose sulfate sodium, sodium carboxymethyl cellulose, crystalline cellulose, cellulose-based cellulose polymer, alginic acid-based polymers such as sodium alginate, propylene glycol alginate, polyvinyl methyl ether, carboxyvinyl polymer, alkyl-modified carboxyvinyl polymer, etc. Vinyl polymer, polyoxyethylene polymer, polyoxyethylene polyoxypropylene copolymer polymer, acrylic polymer such as sodium polyacrylate, polyethyl acrylate, polyacrylamide, bentonite, magnesium aluminum silicate, laponite Inorganic thickeners such as hectorite and silicic anhydride, polyethyleneimine, and cationic polymers. Also included are film forming agents such as polyvinyl alcohol and polyvinyl pyrrolidone.

  Examples of oil gelling agents include metal soaps such as aluminum stearate, magnesium stearate, zinc myristate, amino acid derivatives such as N-lauroyl-L-glutamic acid, α, γ-di-n-butylamine, dextrin palmitate, Dextrin fatty acid esters such as dextrin stearic acid ester, dextrin 2-ethylhexanoic acid palmitic acid ester, sucrose fatty acid esters such as sucrose palmitic acid ester, sucrose stearic acid ester, benzylidene of sorbitol such as monobenzylidene sorbitol, dibenzylidene sorbitol Examples thereof include organically modified clay minerals such as derivatives, dimethylbenzyl dodecyl ammonium montmorillonite clay, and dimethyl dioctadecyl ammonium montmorillonite clay.

Examples of powders include inorganic powders, organic powders, metal soap powders, colored pigments, pearl pigments, metal powders, tar dyes, natural dyes, etc., and their particle shapes (spherical, needle, plate, etc.) and particles Any one can be used regardless of the diameter (smoke, fine particles, pigment grade, etc.) and the particle structure (porous, non-porous, etc.).
Specific inorganic powders include titanium oxide, zirconium oxide, zinc oxide, cerium oxide, magnesium oxide, barium sulfate, calcium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, talc, mica, kaolin, sericite, muscovite , Synthetic mica, phlogopite, saucite, biotite, lithia mica, silicic acid, anhydrous silicic acid, aluminum silicate, magnesium silicate, magnesium aluminum silicate, calcium silicate, barium silicate, strontium silicate, tungstic acid Metal salts, hydroxyapatite, vermiculite, hydrite, bentonite, montmorillonite, hectorite, zeolite, ceramic powder, dicalcium phosphate, alumina, aluminum hydroxide, boron nitride, boron nitride, silica, etc. It is.
Organic powders include polyamide powder, polyester powder, polyethylene powder, polypropylene powder, polystyrene powder, polyurethane, benzoguanamine powder, polymethylbenzoguanamine powder, tetrafluoroethylene powder, polymethylmethacrylate powder, cellulose powder, silk powder, nylon powder ( 12 nylon, 6 nylon), styrene / acrylic acid copolymer powder, divinylbenzene / styrene copolymer powder, vinyl resin powder, urea resin powder, phenol resin powder, fluororesin powder, silicon resin powder, acrylic resin powder, melamine Resin powder, epoxy resin powder, polycarbonate resin powder, microcrystalline fiber powder powder, comedemp And lauroyl lysine.
Examples of metal soap powder (surfactant metal salt powder) include zinc stearate, aluminum stearate, calcium stearate, magnesium stearate, zinc myristate, magnesium myristate, zinc cetyl phosphate, calcium cetyl phosphate, and sodium zinc cetyl phosphate. Each powder is mentioned.
As colored pigments, inorganic red pigments such as iron oxide, iron hydroxide and iron titanate, inorganic brown pigments such as γ-iron oxide, inorganic yellow pigments such as yellow iron oxide and loess, black iron oxide, carbon black, etc. Lake inorganic black pigments, inorganic purple pigments such as manganese violet and cobalt violet, inorganic green pigments such as chromium hydroxide, chromium oxide, cobalt oxide and cobalt titanate, inorganic blue pigments such as bitumen and ultramarine blue, and tar dyes And those obtained by lacquering natural pigments and composite powders obtained by combining these powders.
Examples of pearl pigments include titanium oxide-coated mica, titanium oxide-coated mica, bismuth oxychloride, titanium oxide-coated bismuth oxychloride, titanium oxide-coated talc, fish scale foil, titanium oxide-coated glass flakes, and titanium oxide-coated colored mica. Examples of the metal powder include aluminum powder, copper powder, and stainless steel powder.
The tar pigments are red No. 3, red No. 104, red No. 106, red No. 201, red No. 202, red No. 204, red No. 205, red No. 220, red No. 226, red No. 227, red No. 228 and red 230. No., red 401, red 505, yellow 4, yellow 5, yellow 202, yellow 203, yellow 204, yellow 401, blue 1, blue 2, blue 201, blue 404, Green No. 3, Green No. 201, Green No. 204, Green No. 205, Orange No. 201, Orange No. 203, Orange No. 204, Orange No. 206, Orange No. 207 and the like, and natural pigments include carminic acid, lacaic acid, Examples include calsamine, bradylin, and crocin.
These powders may be used as they are, but these powders may be combined, or may be used after surface treatment with an oil agent, silicone, fluorine compound or the like.
The said powder can be used 1 type or in combination of 2 or more type as needed.

  As UV absorbers, benzoic acid UV absorbers such as paraaminobenzoic acid, anthranilic acid UV absorbers such as methyl anthranilate, salicylic acid UV absorbers such as methyl salicylate, and cinnamic acids such as octyl paramethoxycinnamate And benzophenone ultraviolet absorbers such as 2,4-dihydroxybenzophenone, and urocanic acid ultraviolet absorbers such as ethyl urocanate.

  As preservatives and antibacterial agents, paraoxybenzoic acid esters, benzoic acid, sodium benzoate, sorbic acid, potassium sorbate, phenoxyethanol, salicylic acid, coalic acid, sorbic acid, parachlorometacresol, hexachlorophene, benzalkonium chloride, chlorhexidine chloride , Trichlorocarbanilide, photosensitizer, isopropylmethylphenol and the like.

  Tocopherol, butylhydroxyanisole, dibutylhydroxytoluene and the like as antioxidants, and lactic acid, lactate, citric acid, citrate, glycolic acid, succinic acid, tartaric acid, malic acid, potassium carbonate, sodium bicarbonate as pH adjusters , Ammonium bicarbonate, etc., as a chelating agent alanine, sodium edetate, sodium polyphosphate, sodium metaphosphate, phosphate, hydroxyethane diphosphone, etc., as a refreshing agent, L-menthol, camphor, light cargo oil, peppermint oil Examples of anti-inflammatory agents such as eucalyptus oil include allantoin, glycyrrhetinate, glycyrrhetin derivatives, tranexamic acid, azulene and the like.

  As skin beautifying ingredients, whitening agents such as arbutin, glutathione, and yukinoshita extract, royal jelly, photosensitizer, cholesterol derivatives, cell activators such as calf blood extract, skin roughening agent, nonyl acid wallenyl amide, nicotinic acid benzyl ester, Nicotinic acid β-butoxyethyl ester, capsaicin, gingerone, cantalis tincture, ictamol, caffeine, tannic acid, α-borneol, tocopherol nicotinate, inositol hexanicotinate, cyclandrate, cinnarizine, trazoline, acetylcholine, verapamil, cephalanthin , Blood circulation promoters such as γ-oryzanol, skin astringents such as zinc oxide and tannic acid, and antiseborrheic agents such as sulfur and thianthol.

  Vitamins such as vitamin A oil, retinol, retinol acetate, retinol palmitate, vitamin B2 such as riboflavin, riboflavin butyrate, flavin adenine nucleotide, vitamin B6 such as pyridoxine hydrochloride, pyridoxine dioctanoate Vitamin C such as L-ascorbic acid, L-ascorbic acid dipalmitate, L-ascorbic acid-2-sodium sulfate, dl-α-tocopherol-L-ascorbic acid diester dipotassium, calcium pantothenate, D -Pantothenic alcohols, pantothenyl ethyl ether, pantothenic acids such as acetyl pantothenyl ethyl ether, vitamin Ds such as ergocalciferol, cholecalciferol, nicotinic acid, benzyl nicotinate, Nicotinic acids such as succinic acid amide, dl-α-tocopherol, dl-α-tocopherol acetate, dl-α-tocopherol nicotinate, vitamin E such as dl-α-tocopherol succinate, vitamin P, biotin, etc. .

  Amino acids include arginine, aspartic acid, cystine, cysteine, methionine, serine, leucine, isoleucine, tryptophan, alanine, glycine, proline and the like, nucleic acids such as deoxyribonucleic acid, and hormones such as estradiol and ethinylestradiol.

  When the silicone phosphate triester of the present invention alone or a silicone phosphate ester mixture containing it is used as a cosmetic, it is prepared by a conventional method using other components in combination as necessary. , Cream, solid, gel, paste and the like. The cosmetics of the present invention are not particularly limited in their dosage forms such as oil-based, water-in-oil emulsified system, oil-in-water emulsified system, specifically, emulsion, cream, cosmetic liquid, cosmetic oil, lip Skin care cosmetics such as cream, hand cream, face wash, foundation, makeup base, blusher, eye shadow, mascara, eyeliner, eyebrow, overcoat agent, lipstick, lip gloss makeup cosmetics, hair tonic, It can be carried out with various cosmetics such as hair cream, shampoo, rinse, conditioner, scalp such as hair conditioner or cosmetics for hair.

  Examples are shown below, but the present invention is not limited to these examples. In the following examples,% means mass%.

1 Production of silicone phosphate triesters
[Production Example 1]
265 g of carbinol-modified silicone (formula 2) and 136 g of tetrahydrofuran were mixed and cooled to -40 ° C. After adding 200 ml of lithium diisopropylamide (LDA) (1 mol / THF solution) dropwise and reacting for 90 minutes, 7.8 g of phosphorus oxychloride (formula 1) was added and allowed to react for 1 hour. After raising the temperature to 25 ° C. and further aging for 2 hours, 42 g of concentrated hydrochloric acid was added to terminate the reaction. The mixture containing silicone phosphate triester was obtained by washing with methanol and distilling off the solvent. According to ³¹ P-NMR measurement, the composition ratio of the obtained mixture was 92% for the formula (I) as a triester, 1% for the formula (II) as a diester, and other by-products containing polyphosphoric acid. 7%.

[Production Example 2]
302 g of carbinol-modified silicone (formula 3) and 150 g of tetrahydrofuran were mixed and cooled to −40 ° C. After 74 ml of n-butyllithium (1.6 mol / hexane solution) was added dropwise and reacted for 90 minutes, 5.4 g of phosphorus oxychloride (Formula 1) was added and reacted for 1 hour. After raising the temperature to 25 ° C. and aging for another 2 hours, 10 g of water was added to terminate the reaction. The mixture containing silicone phosphate triester was obtained by washing with methanol and distilling off the solvent. According to ³¹ P-NMR measurement, the composition ratio of the obtained mixture was 83% for the formula (I) as a triester and 17% for the formula (II) as a diester.

[Production Example 3]
291 g of carbinol-modified silicone (formula 2), 87 g of tetrahydrofuran and 19 g of triethylamine were mixed and cooled to −40 ° C. A mixed solution of 8.6 g of phosphorus oxychloride (Formula 1) and 18 g of tetrahydrofuran was added dropwise in about 30 minutes. After aging at −40 ° C. for 5 hours and at 25 ° C. for 12 hours, the mixture was washed with methanol and the solvent was distilled off to obtain a mixture containing silicone phosphate triester. According to ³¹ P-NMR measurement, the composition ratio of the obtained mixture was 64% for formula (I) as a triester, 18% for formula (II) as a diester, and other by-products containing polyphosphoric acid. 18%.

[Production Example 4]
6.1 g of phosphorus oxychloride (formula 1) was dissolved in 93 g of tetrahydrofuran at 25 ° C. To this solution, a mixed solution of 300 g of carbinol-modified silicone (formula 4) and 8.1 g of triethylamine was dropped in about 2 hours. After aging for 15 hours, 0.7 g of water and 4.1 g of triethylamine were added to complete the reaction. After washing with methanol, the solvent was distilled off to obtain a mixture containing silicone phosphate triester. According to ³¹ P-NMR measurement, the composition ratio of the obtained mixture was 11% for the formula (I) as a triester, 66% for the formula (II) as a diester, and the formula (III) as a monoester. Was 3%, and other by-products containing polyphosphoric acid were 20%.

2 Formulation examples
The mixture containing the silicone phosphate triester produced in the above production example was used in the following formulation. Therefore, in the following examples, for example, “product of Production Example 1” means a mixture containing the silicone phosphate triester obtained in Production Example 1.

[Examples 1 to 4, Comparative Examples 1 to 5]
Hair oil Hair oils having the formulation shown in Table 1 were prepared by the following production methods, and the following methods were used to evaluate the moist feeling of the hair, the lack of stickiness, and the smoothness of the hair. The results are shown in Table 1.

（注１）ＫＦ−９６Ａ−６ＣＳ（信越化学工業社製）
（注２）ＫＦ−９６Ａ−１０ＣＳ（信越化学工業社製）
（注３）ＫＦ−９６Ａ−２０ＣＳ（信越化学工業社製）
（注４）ＫＦ−９６Ａ−５０ＣＳ（信越化学工業社製）
（注５）ＫＦ−９６Ａ−１００ＣＳ（信越化学工業社製）
（注６） ＫＦ−９９５（信越化学工業社製）

(Note 1) KF-96A-6CS (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Note 2) KF-96A-10CS (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Note 3) KF-96A-20CS (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Note 4) KF-96A-50CS (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Note 5) KF-96A-100CS (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Note 6) KF-995 (manufactured by Shin-Etsu Chemical Co., Ltd.)

(Production method)
A. Ingredients 1-10 are mixed uniformly.
B. Fill A into a container.

(Evaluation method) Sensory evaluation by hair bundles Hair bundles of Japanese women with damaged hair were impregnated in each hair oil, and the hair bundles after 24 hours of drying were evaluated. 20 panelists specializing in cosmetics evaluation have 7 levels of evaluation for each of the following items: “moist hair”, “no stickiness” and “smooth hair” according to the following criteria. Using the average score of the panel, it was determined according to the following criteria.
[Evaluation criteria]
(Evaluation result): (Grade)
Very good: 6 points Good: 5 points Somewhat good: 4 points Normal: 3 points Somewhat bad: 2 points Bad: 1 point Very bad: 0 points
[Criteria]
(Average score): (Judgment)
5.0 or more: ◎ Very good 3.5 or more to less than 5.0: ○ Good 1.5 or more to less than 3.5: △ Defect Less than 1.5: × Very poor

(result)
From the results of the sensory evaluation on the hair bundle, the hair oils of Examples 1 to 4 were hair oils with excellent moist feeling, no stickiness, and smooth hair. Since the hair oils of Comparative Examples 1 to 3 are blended with dimethylpolysiloxane having a short silicone chain length, the hair oils of Comparative Examples 4 and 5 are inferior in silicone chain length. Since dimethylpolysiloxane having a long length was blended, the hair had a moist feeling, but had a sticky feeling and was inferior in hair smoothness.

[Examples 5 to 8, Comparative Examples 6 to 9]
O / W hair conditioner

（注７）ゲナミンＫＤＭ−Ｐ（クラリアントジャパン社製）

(Note 7) Genamine KDM-P (manufactured by Clariant Japan)

(Production method)
A. Ingredients 1-12 are uniformly dissolved at 80 ° C.
B. Ingredients 13-15 are uniformly dissolved at 80 ° C.
C. Add A to B and emulsify at 80 ° C.
D. C is cooled and component 16 is added.
E. D is degassed and filled into a container.

(Evaluation methods)
The conditioners of Examples 5 to 8 and Comparative Examples 6 to 9 were subjected to a usage test on 20 panelists specializing in cosmetics evaluation. The results were “moisturizing hair”, “no stickiness”, and “smoothness of hair”. Each item was evaluated on a 7-point scale according to the above-mentioned evaluation criteria, and further judged according to the above-mentioned criteria using the average score of all panels.

(result)
The conditioners of Examples 5 to 8 were conditioners excellent in the moist feeling of the hair, no stickiness, and the smoothness of the hair. Since the conditioners of Comparative Examples 6 and 8 are blended with dimethylpolysiloxane having a short silicone chain length, Comparative Example 6 with a small blending amount is inferior to the moist feeling of the hair and the smoothness of the hair. Even the many conditioners of Comparative Example 8 had no moist feeling on the hair, had a sticky feeling, and were inferior to the smoothness of the hair. Moreover, since the conditioners of Comparative Examples 7 and 9 were blended with dimethylpolysiloxane having a long silicone chain length, they were excellent in moist hair but had a sticky feeling and were inferior in hair smoothness.

[Example 9]
Emulsified lotion (component) (%)
1. Cetyl alcohol 0.2
2. Product of Production Example 1 0.5
3. Phospholipid / phytosterol mixture (8: 1) (Note 8) 0.5
4). Polyoxyethylene (40 mol) hydrogenated castor oil 0.1
5. Tocopherol acetate 0.5
6). Stearic acid triethanolamine 0.5
7). Purified water remaining amount 8. Ethanol 10.0
9. Perfume appropriate amount (Note 8) Phytocompo-PP (manufactured by Nippon Seika Co., Ltd.)

(Production method)
(1) Components 1 to 6 are heated to 75 ° C. and uniformly mixed and dissolved.
(2) Heat components 7 and 8 to 75 ° C. and mix and dissolve uniformly (3) Add (2) to (1) and emulsify.
(4) (3) was cooled, component 9 was added, and an emulsified lotion was obtained.

(result)
The emulsified lotion of Example 9 was an emulsified lotion excellent in “moist feeling”, “no stickiness”, and “smoothness”.

[Example 10]
Emulsion (component) (%)
1. Stearic acid 0.5
2. Polyoxyethylene monostearate (20 mol) sorbitan 1.0
3. Tetraoleic acid polyoxypropylene (40 mol) sorbitol 1.0
4). Behenyl alcohol 1.5
5. Liquid paraffin 2.0
6). Glyceryl tri-2-ethylhexanoate 5.0
7). Product of Production Example 1 5.0
8). Acrylic acid / methacrylic acid alkyl ester copolymer 0.1
9. Xanthan gum 0.1
10. Sodium hydroxide 0.05
11.1,3-butylene glycol 8.0
12 Preservative appropriate amount13. Perfume appropriate amount14. Purified water remaining

(Production method)
(1) Components 1 to 7 are mixed uniformly at 80 ° C.
(2) Components 8 to 14 are uniformly mixed at 80 ° C.
(3) Add (2) to (1) and emulsify.
(4) (3) was cooled with stirring to obtain an emulsion.

(result)
The emulsion of Example 10 was an emulsion excellent in “moist feeling”, “no stickiness”, and “smoothness”.

[Example 11]
O / W cream (ingredient) (%)
1. Decaglyceryl pentaoleate 2.5
2. Behenyl alcohol 1.5
3. Vaseline 3.0
4). Heavy liquid isoparaffin 1.0
5. Glyceryl tri-2-ethylhexanoate 1.0
6). Product of Production Example 2 5.0
7). Purified water remaining amount 8. Glycerin 7.0
9. Acrylic acid / methacrylic acid alkyl ester copolymer 0.2
10. Sodium hydroxide 0.09
11. Preservative appropriate amount 12. Perfume

(Production method)
(1) Components 1 to 6 are mixed uniformly at 80 ° C.
(2) Components 7-12 are mixed uniformly at 80 ° C.
(3) Add (2) to (1) and emulsify.
(4) (3) was cooled with stirring to obtain a cream.

(result)
The O / W type cream of Example 11 was an O / W type cream excellent in “moist feeling”, “no stickiness”, and “smoothness”.

[Example 12]
W / O cream (ingredient) (%)
1. Microcrystalline wax 1.5
2. Beeswax 1.5
3. Cetyl alcohol 3.0
4). Product of Production Example 2 5.0
5. Hydrogenated soybean phospholipid 1.0
6). Squalane 35.0
7). Sorbitan sesquioleate 3.0
8). Propylene glycol 10.0
9. Preservative appropriate amount10. Perfume proper amount11. Purified water remaining

(Production method)
(1) Components 1 to 7 are heated to 75 ° C. and mixed and dissolved uniformly.
(2) Components 8 and 11 are heated to 75 ° C. and mixed and dissolved uniformly.
(3) Add (2) to (1) and emulsify.
(4) (3) was cooled, components 9 and 10 were added, and a W / O type cream was obtained.

(result)
The W / O type cream of Example 12 was a W / O type cream excellent in “moist feeling”, “no stickiness”, and “smoothness”.

[Example 13]
Oil cleansing (ingredient) (%)
1. Polyoxyethylene tetraoleate (30 mol) sorbit 8.0
2. Polyglyceryl diisostearate 0.5
3. 3. Liquid paraffin remaining Glyceryl tri-2-ethylhexanoate 25.0
5. Product of Production Example 3 5.0
6). Preservative appropriate amount 7. Perfume

(Production method)
(1) Components 1 to 7 were uniformly mixed at room temperature to obtain oil cleansing.

(result)
The oil cleansing of Example 13 was an oil cleansing excellent in “moist feeling”, “no stickiness”, and “smoothness”.

[Example 14]
Cleansing cream (ingredient) (%)
1. Stearic acid 3.0
2. Cetanol 2.0
3. Tetraoleic acid polyoxypropylene (40 mol) sorbitol 1.0
4). Polyoxyethylene monostearate (20 mol) sorbitan 1.0
5. Glyceryl tri-2-ethylhexanoate 20.0
6). Liquid paraffin 20.0
7). Product of Production Example 4 5.0
8). Acrylic acid / methacrylic acid alkyl ester copolymer 0.1
9.1,3-butylene glycol 7.0
10. Sodium hydroxide 0.05
11. Purified water remaining amount 12. Preservative appropriate amount13. Perfume

(Production method)
(1) Components 1 to 7 are mixed uniformly at 80 ° C.
(2) Components 8 to 13 are mixed uniformly at 80 ° C.
(3) Add (1) to (2) and emulsify.
(4) Cooling with stirring (3) gave a cleansing cream.

(result)
The cleansing cream of Example 14 was a cleansing cream excellent in “moist feeling”, “no stickiness”, and “smoothness”.

[Example 15]
Styling water (ingredient) (%)
1. Ethanol 15.0
2. Stearyltrimethylammonium chloride 0.2
3. Polyoxyethylene isostearate (50 mol) hydrogenated castor oil 0.2
4). Product of Production Example 1 0.2
5. Purified water remaining amount 6. Hydroxypropylcellulose 0.01
7). Highly polymerized methylpolysiloxane emulsion (Note 9) 2.0
8). Preservative appropriate amount 9. Perfume appropriate amount (Note 9) BY11-007 (manufactured by Toray Dow Corning)

(Production method)
(1) Components 1 to 9 were mixed uniformly at room temperature to obtain styling water.

(result)
The styling water of Example 15 was a styling water excellent in “moist feeling”, “no stickiness”, and “smoothness”.

[Example 16]
Hair wax (ingredient) (%)
1. 1. Purified water remaining amount Propylene glycol 10.0
3. Polyethylene glycol monostearate 3.0
4). Vaseline 10.0
5. Paraffin wax 3.0
6). Cetostearyl alcohol 3.0
7). Behenyl alcohol 3.0
8). Product of Production Example 2 3.0
9. Ethanol 5.0
10. Purified water 15.0
11. Vinylpyrrolidone 1.0
12 Acrylic acid / methacrylic acid alkyl ester copolymer 0.15
13. Sodium hydroxide 0.05
14 Preservative appropriate amount15. Perfume

(Production method)
(1) Components 1 to 3 are uniformly mixed at 80 ° C.
(2) Components 4 to 8 are mixed uniformly at 80 ° C.
(3) Add (2) to (1) and emulsify.
(4) After adding components 9 to 15 to (3), the mixture was cooled with stirring to obtain a hair wax.

(result)
The hair wax of Example 16 was a hair wax excellent in “moist feeling”, “no stickiness”, and “smoothness”.

[Example 17]
O / W type mascara (component) (%)
1. Stearic acid 2.0
2. Beeswax 10.0
3. Cetostearyl alcohol 1.0
4). Polyoxyethylene (20 mol) sorbitan monooleate 1.5
5. Sorbitan sesquioleate 0.5
6). Product of Production Example 2 5.0
7). Black iron oxide 5.0
8). Silicic anhydride 3.0
9. Purified water remaining amount 10.1,3-butylene glycol 10.0
11. Triethanolamine 1.5
12 Alkyl acrylate copolymer emulsion (Note 10) 30.0
13. Preservative appropriate amount14. Perfume appropriate amount (Note 10) iodosol 32A707 (45% solids) (made by NSC Japan)

(Production method)
(1) Components 1 to 3 are uniformly mixed at 80 ° C.
(2) Components 4 to 8 are processed with a roller.
(3) Components 9 to 14 are mixed uniformly at 80 ° C.
(4) After mixing (1) and (2), (3) is added and emulsified.
(5) (4) was cooled to obtain an O / W type mascara.

(result)
The O / W type mascara of Example 17 was an O / W type mascara excellent in “moist feeling”, “no stickiness”, and “smoothness”.

[Example 18]
Paste lip gloss (component) (%)
1. Product of Production Example 4 3.0
2. Diisostearyl malate 10.0
3. Stearyl lactate 10.0
4). Hydrogenated polyisobutene 30.0
5. 5. Triethylhexanoin remaining amount Liquid paraffin 5.0
7). Microcrystalline wax 2.0
8.12-Hydroxystearic acid 0.1
9. α-olefin-vinylpyrrolidone copolymer (Note 11) 0.5
10. Silicic anhydride (Note 12) 3.5
11. Bengala 0.1
12 Red 201 No. 0.3
13. Black iron oxide 0.05
14 Titanium oxide 0.2
15. Soy phospholipid 0.01
16. p-Methoxycinnamic acid-2-ethylhexyl 3.0
17. Preservative appropriate amount 18. Perfume appropriate amount (Note 11) ANTARON V-220 (manufactured by ISP)
(Note 12) AEROSIL 200 (Nippon Aerosil Co., Ltd.)

(Production method)
(1) Components 1 to 9 are dissolved and mixed at 100 ° C.
(2) Add components 10 to 18 to (1) and mix and disperse uniformly.
(3) (2) was poured into a tube and cooled to obtain a pasty lip gloss.

(result)
The pasty lip gloss of Example 18 was a pasty lip gloss excellent in “moist feeling”, “no stickiness”, and “smoothness”.

[Example 19]
Stick-shaped lipstick (ingredient) (%)
1. Polyethylene wax 10.0
2. Carnauba wax 5.0
3. Paraffin wax 2.0
4. Cetyl 2-ethylhexanoate 5 Product of Production Example 4 5.0
6). Liquid paraffin 10.0
7). Isotridecyl isononanoate 10.0
8). Red 202 0.5
9. Yellow 4 2.0
10. Titanium oxide 0.5
11. Black iron oxide 0.1
12 α-Tocopherol 0.5
13. Perfume

(Production method)
(1) Components 1 to 7 are uniformly dissolved and mixed at 100 ° C.
(2) Add components 8 to 13 to (1) and mix uniformly.
(3) (2) was poured into a container and cooled to obtain a stick-shaped lipstick.

(result)
The stick-shaped lipstick of Example 19 was a stick-shaped lipstick excellent in “moist feeling”, “no stickiness”, and “smoothness”.

[Example 20]
Oily eye shadow (component) (%)
1. Dextrin fatty acid ester (Note 13) 2.0
2. Product of Production Example 4 2.0
3. Diisostearyl malate 2.5
4.2 Cetyl 2-ethylhexanoate 13.0
5. Dextrin laurate 2.0
6). Dextrin myristate 5.0
7). Dextrin behenate 5.0
8). 8. Liquid paraffin remaining Hydrogenated polyisobutene 1.5
10. Silica anhydride 6.0
11. Nylon powder 5.0
12 Silicone-treated talc (Note 14) 5.5
13. Red No. 202 0.05
14 Yellow No. 4 aluminum lake 0.05
15. Blue No. 1 aluminum rake 0.05
16. Mica titanium 1.5
17. Preservative appropriate amount 18. Perfume appropriate amount (Note 13) Leo Pearl TT (Chiba Flour Mills)
(Note 14) 5% dimethylpolysiloxane treatment

(Production method)
(1) Components 1 to 9 are dissolved and mixed at 100 ° C.
(2) Add components 10 to 18 to (1) and mix and disperse uniformly.
(3) (2) was poured into a container and solidified by cooling to obtain an oily eye color.

(result)
The oily eye shadow of Example 20 was an oily eye shadow excellent in “moist feeling”, “no stickiness”, and “smoothness”.

[Example 21]
Solid powder foundation (component) (%)
1. Dimethylpolysiloxane-treated talc 30.0
2. Mica treated with dimethylpolysiloxane 15.0
3. Dimethylpolysiloxane-treated mica titanium oxide 15.0
4). 4. Sericite treated with dimethylpolysiloxane Synthetic phlogopite 5.0
6). Yellow iron oxide 2.0
7). Bengala 0.5
8). Black iron oxide 0.2
9. Preservative appropriate amount10. Product of Production Example 3 3.0
11. Liquid paraffin 3.0
12 Dimethylpolysiloxane 1.0
13. Glyceryl 2-ethylhexanoate 2.0
14 Perfume

(Production method)
(1) Components 1 to 9 are uniformly dispersed at 75 ° C. in a Henschel mixer (Mitsui Miike).
(2) Components 10 to 13 are mixed and dissolved uniformly.
(3) While stirring (1) with a Henschel mixer, add (2) and 14 and uniformly disperse.
(4) Grind (3) with a pulverizer.
(5) (4) was filled into a metal pan and compression molded to obtain a solid powdery foundation.

(result)
The solid powder foundation of Example 21 was a solid powder foundation excellent in “moist feeling”, “no stickiness”, and “smoothness”.

[Example 22]
Solid powder eye shadow (component) (%)
1. Synthetic gold mica treated with dimethylpolysiloxane 10.0
2. 2. Dimethylpolysiloxane-treated talc Titanium oxide coated mica 30.0
4). Boron nitride 5.0
5. Polyethylene terephthalate / aluminum / epoxy laminated powder 5.0
6). Ultramarine 2.0
7). Red 202 0.5
8). Polyalkyl acrylate 1.0
9. Preservative appropriate amount10. Product of Preparation Example 2 4.0
11. Liquid paraffin 3.0
12 Dimethylpolysiloxane 2.0
13. Glyceryl 2-ethylhexanoate 2.0
14 Perfume

(Production method)
(1) Components 1 to 9 are uniformly dispersed at 75 ° C. in a Henschel mixer (Mitsui Miike).
(2) Components 10 to 13 are mixed and dissolved uniformly.
(3) While stirring (1) with a Henschel mixer, add (2) and 14 and uniformly disperse.
(4) Grind (3) with a pulverizer.
(5) A metal pan was filled with (4) and compression molded to obtain a solid powder eye shadow.

(result)
The solid powder eye shadow of Example 22 was a solid powder eye shadow excellent in “moist feeling”, “no stickiness”, and “smoothness”.

[Example 23]
Solid powder face color (component) (%)
1. Mica 20.0
2. 2. Talc remaining amount Titanium oxide coated mica 10.0
4). Ultramarine 0.5
5. Red 226 0.2
6). Polyalkyl acrylate 1.0
7). Preservative appropriate amount 8. Product of Production Example 1 3.0
9. Liquid paraffin 2.0
10. Dimethylpolysiloxane 1.0
11.2-glyceryl ethylhexanoate 1.0
12 Perfume

(Production method)
(1) Components 1 to 7 are uniformly dispersed at 75 ° C. in a Henschel mixer (Mitsui Miike).
(2) Heat components 8 to 11 to 65 ° C. and uniformly mix and dissolve.
(3) While stirring (1) with a Henschel mixer, add (2) and 12 and uniformly disperse.
(4) Grind (3) with a pulverizer.
(5) A metal pan was filled with (4) and compression molded to obtain a solid powder face color.

(result)
The solid powder face color of Example 23 was a solid powder face color excellent in “moist feeling”, “no stickiness”, and “smoothness”.

[Example 24]
Stick concealer (ingredient) (%)
1. Paraffin wax 5.0
2. Polyethylene wax 5.0
3. Candelilla Row 2.0
4). Product of Production Example 4 15.0
5. Glyceryl tri-2-ethylhexanoate 15.0
6). Methylphenylpolysiloxane 5.0
7). Acetic acid liquid lanolin 10.0
8). 2-Ethylhexyl paramethoxycinnamate 5.0
9. Titanium oxide 20.0
10. Yellow iron oxide 2.0
11. Bengala 0.5
12 Black iron oxide 0.2
13. Mica 7.0
14 Preservative appropriate amount

(Production method)
(1) Components 1 to 8 are mixed and dissolved at 100 ° C.
(2) Ingredients 9 to 14 are uniformly mixed in (1) at 90 ° C.
(3) Process (2) with three rollers.
(4) (3) was defoamed, dissolved and filled in a capsule at 85 ° C., and then cooled at 4 ° C. to obtain a stick concealer.

(result)
The stick concealer of Example 24 was a stick concealer excellent in “moist feeling”, “no stickiness”, and “smoothness”.

[Example 25]
W / O type sunscreen (component) (%)
1. Zinc oxide 2.0
2. Silicone coated fine particle titanium oxide (Note 14) 5.0
3. Tri (capryl / capric acid) glyceryl 5.0
4). Glyceryl tri-2-ethylhexanoate 3.0
5. Octyl palmitate 3.0
6). 2-Ethylhexyl paramethoxycinnamate 10.0
7). Decamethylcyclopentasiloxane 10.0
8). Methyl polysiloxane, cetyl methyl polysiloxane, poly (oxyethylene, oxypropylene)
Methylpolysiloxane copolymer (Note 15) 1.8
9. Product of Production Example 3 3.0
10. Preservative appropriate amount11. Sodium chloride 0.3
12 Purified water remaining amount 13. Dipropylene glycol 5.0
14 Ethanol 5.0
15. Perfume proper amount (Note 15) ABIL EM-90 (Evonic Goldschmidt GMBH)

(Production method)
(1) After components 3 and 4 are heated and dissolved, components 1 and 2 are added and uniformly dispersed with a roller.
(2) After components 5 to 10 are dissolved at 70 ° C., (1) is added at 60 ° C. and mixed and dissolved uniformly.
(3) Components 11 to 13 are mixed and dissolved, and then added to (2) at 60 ° C. to emulsify.
(4) Components 14 and 15 were added to (3) and mixed uniformly to obtain a W / O type sunscreen.

(result)
The W / O-type sunscreen of Example 25 was a W / O-type sunscreen excellent in “moist feeling”, “no stickiness”, and “smoothness”.

[Example 26]
W / O type foundation (component) (%)
1. Polyoxyethylene methylsiloxane / polyoxypropylene oleyl methylsiloxane / dimethylsiloxane copolymer (Note 16) 2.0
2. PEG-3 Dimethicone (Note 17) 1.0
3. Dimethylpolysiloxane 20.0
4). Silicone-treated red iron oxide (Note 14) 1.0
5. Silicone-treated yellow iron oxide (Note 14) 1.5
6). Silicone-treated black iron oxide (Note 14) 0.5
7). Silicone-treated titanium oxide (Note 14) 10.0
8). Silicone-treated talc (Note 14) 5.0
9. Glyceryl tri-2-ethylhexanoate 5.0
10. Product of Production Example 2 5.0
11. Sorbitan sesquioleate 0.5
12 Purified water remaining amount 13.1,3-butylene glycol 15.0
14 Sodium chloride 0.5
15. Preservative appropriate amount 16. Perfume appropriate amount (Note 16) KF-6026 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Note 17) KF-6015 (manufactured by Shin-Etsu Chemical Co., Ltd.)

(Production method)
(1) Components 1 to 3 are mixed uniformly.
(2) Components 4 to 11 are uniformly dispersed with a roller.
(3) Add (2) to (1) and mix uniformly.
(4) Components 12 to 16 were added to (3) and emulsified to obtain a W / O type foundation.

(result)
The W / O type foundation of Example 26 was a W / O type foundation excellent in “moist feeling”, “no stickiness”, and “smoothness”.

[Example 27]
O / W type foundation (component) (%)
1. Monooleic acid polyoxyethylene (20 mol) sorbitan 0.5
2. Sorbitan sesquioleate 0.5
3. 1,3-butylene glycol 10.0
4). Silicone-treated titanium oxide (Note 14) 10.0
5. Silicone-treated Bengala (Note 14) 0.4
6). Silicone-treated yellow iron oxide (Note 14) 2.0
7). Silicone-treated black iron oxide (Note 14) 0.1
8). Silicone-treated talc (Note 14) 5.0
9. Carboxyvinyl polymer 0.3
10. Triethanolamine 1.0
11. Purified water remaining amount 12. Ethanol 2.0
13. Stearic acid 1.0
14 Behenyl alcohol 0.5
15. Liquid paraffin 1.0
16. Product of Production Example 2 2.0
17. Glyceryl tri-2-ethylhexanoate 1.0
18. 2-Ethylhexyl paramethoxycinnamate 2.0
19. Vaseline 0.5
20. Antiseptic suitable amount 21. Perfume

(Production method)
(1) Components 1 to 8 are uniformly dispersed with a roller.
(2) Mix components 9-12 uniformly.
(3) Add (1) to (2) and mix uniformly.
(4) Components 13 to 20 are mixed and dissolved at 80 ° C.
(5) Add (4) to (3) at 80 ° C. and emulsify.
(6) (5) was cooled, component 21 was added, and an O / W type foundation was obtained.

(result)
The O / W type foundation of Example 27 was an O / W type foundation excellent in “moist feeling”, “no stickiness”, and “smoothness”.

[Example 28]
Oily solid foundation (component) (%)
1. Talc 15.0
2. Mica 10.0
3. Silicone-treated titanium oxide (Note 14) 15.0
4). Silicone-treated Bengala (Note 14) 1.0
5. Silicone-treated yellow iron oxide (Note 14) 3.0
6). Silicone-treated black iron oxide (Note 14) 0.2
7). Polyethylene wax 7.0
8). Microcrystalline wax 6.0
9. 10. Glyceryl tri-2-ethylhexanoate remaining 10 Product of Production Example 1 5.0
11. Dimethylpolysiloxane 5.0
12 Liquid paraffin 20.0
13. Polyoxyethylene methylsiloxane / polyoxypropylene oleyl methylsiloxane / dimethylsiloxane copolymer (Note 16) 2.0
14 Preservative appropriate amount15. Perfume

(Production method)
(1) Components 7 to 14 are dissolved by heating at 90 ° C.
(2) Add components 1 to 6 to (1) and uniformly disperse with a roller.
(3) Component 15 was added to (2), dissolved at 80 ° C., and then filled into a metal pan to obtain an oily solid foundation.

(result)
The oily solid foundation of Example 28 was an oily solid foundation excellent in “moist feeling”, “no stickiness”, and “smoothness”.

[Example 29]
Makeup base (ingredient) (%)
1. Cetostearyl alcohol 2.0
2. 2-Ethylhexyl paramethoxycinnamate 5.0
3. Product of Preparation Example 4 8.0
4). Glyceryl tri-2-ethylhexanoate 3.0
5. Purified water remaining amount 6. N-stearoyl-N-methyltaurine sodium 0.5
7). Carboxyvinyl polymer 0.1
8). Acrylic acid / methacrylic acid alkyl ester copolymer 0.1
9. Sodium hydroxide 0.05
10. Ethanol 10.0
11.1,3-butylene glycol 10.0
12 Preservative appropriate amount13. Perfume

(Production method)
(1) Components 1 to 4 are uniformly dissolved at 80 ° C.
(2) Components 5 to 13 are uniformly dissolved at 80 ° C.
(3) Add (1) to (2) and emulsify.
(4) Component 14 was added to (3) and cooled to obtain a makeup base.

(result)
The makeup base of Example 29 was a makeup base excellent in “moist feeling”, “no stickiness”, and “smoothness”.

[Example 30]
Body milk (ingredient) (%)
1. Stearic acid 1.0
2. Monooleic acid polyoxyethylene (20 mol) sorbitan 0.5
3. Sorbitan sesquioleate 0.5
4). Behenyl alcohol 0.5
5. Glyceryl 2-ethylhexanoate 2.0
6). Liquid paraffin 2.0
7). Product of Production Example 1 5.0
8). Ethanol 10.0
9. Dipropylene glycol 10.0
10. Triethanolamine 1.0
11. Purified water remaining amount 12. Glycerin 5.0
13.1,3-Butylene glycol 5.0
14 Acrylic acid / methacrylic acid alkyl ester copolymer 0.2
15. Preservative appropriate amount 16. Perfume

(Production method)
(1) Components 1 to 7 are uniformly dissolved at 80 ° C.
(2) Components 8 to 16 are uniformly dissolved at 80 ° C.
(3) Add (1) to (2) and emulsify.
(4) (3) was stirred and cooled to obtain body milk.

(result)
The body milk of Example 30 was a body milk excellent in “moist feeling”, “no stickiness”, and “smoothness”.

[Example 31]
Remover (ingredient) (%)
1.1,3-Butylene glycol 15.0
2. Alkyl acrylate copolymer emulsion (Note 10) 2.5
3. L-Arginine 0.5
4). 4. Purified water remaining amount Light liquid isoparaffin (Note 18) 3.0
6). Product of Production Example 1 2.0
7). Preservative appropriate amount 8. Perfume appropriate amount (Note 18) IP Solvent 1620 (made by Idemitsu Kosan Co., Ltd.)

(Production method)
(1) Components 1 to 4 are mixed uniformly.
(2) Components 5 to 8 are added to (1) at 60 ° C. and emulsified.
(3) (2) was cooled with stirring to obtain a remover.

(result)
The remover of Example 31 was a remover excellent in “moist feeling”, “no stickiness”, and “smoothness”.

[Example 32]
Non-aqueous mascara (component) (%)
1. Rosin acid pentaerythritol 10.0
2. Candelilla resin 3.0
3. Beeswax 2.0
4). Ceresin wax 2.0
5. Dextrin palmitate 2.0
6). Trimethylsiloxysilicic acid 3.0
7). Dimethyl distearyl ammonium hectorite 5.0
8). Propion carbonate 1.0
9. Light liquid isoparaffin (Note 18) Product of Production Example 2 3.0
11. Black iron oxide 5.0
12 Silica 3.0
13. Talc 5.0

(Production method)
(1) Ingredients 1-5 are heated to 110 ° C.
(2) Add components 6 to 10 to (1) and mix.
(3) Components 11 to 13 are added to and mixed with (2).
(4) (3) was processed with a roller to obtain a non-aqueous mascara.

(result)
The non-aqueous mascara of Example 32 was a non-aqueous mascara excellent in “moist feeling”, “no stickiness”, and “smoothness”.

[Example 33]
Oily eyeliner (component) (%)
1. Ceresin wax 11.0
2. Polyisobutylene 16.0
3. Polyethylene wax 8.0
4). Light liquid isoparaffin 5 Product of Production Example 1 3.0
6). Silicone-treated black iron oxide (Note 14) 15.0
7). Silicone-treated talc (Note 14) 5.0
8). Preservative appropriate amount 9. Perfume

(Production method)
(1) Ingredients 1-5 are heated to 100 ° C. and mixed uniformly.
(2) Ingredients 6-9 are heated to 80 ° C. and mixed uniformly.
(3) Add (2) to (1) and mix uniformly.
(4) (3) was processed with a roller to obtain an oily eyeliner.

(result)
The oily eyeliner of Example 33 was an oily eyeliner excellent in “moist feeling”, “no stickiness”, and “smoothness”.

Claims (3)

Formula (I)

(In the formula, each R ₁ independently represents an alkyl group having 1 to 4 carbon atoms, and R may have at least one selected from —O— and —CO—.) Cosmetics containing 1 type, or 2 or more types of the silicone phosphoric acid triester represented by the divalent hydrocarbon group of -7, and n represents the integer in any one of 5-40. Formula (I)

(In the formula, each R ₁ independently represents an alkyl group having 1 to 4 carbon atoms, and R may have at least one selected from —O— and —CO—.) 1 to 2 or more of 60 to 100% by mass of a silicone phosphoric acid triester represented by a divalent hydrocarbon group of ˜7, and n represents an integer of 5 to 40),
Formula (II)

(Wherein R ₁ , R and n are the same as defined in the above formula (I)), one or more silicone phosphate diesters represented by 0 to 35% by mass, and
Formula (III)

(Wherein R ₁ , R and n are the same as defined in the above formula (I)), a silicone phosphate ester mixture composed of 0 to 5% by mass of one or more of the silicone phosphate monoesters represented by the formula (I) The cosmetic according to claim 1, which is contained. The cosmetic according to claim 1 or 2, further comprising an oil agent.