Organopolysiloxane, powder treatment agent, and treated powder and cosmetic product

Abstract

Provided is an organopolysiloxane suitable as a powder treatment agent having high long-term storage stability and high reactivity with a powder surface. An organopolysiloxane represented by the following average structural formula (1). [Chemical Formula 1] # imgabs0 # (In formula (1), R is an alkyl group or the like, R10 is a polyoxyalkylene group having a hydrolyzable silyl group at an end and is one or more groups present in one molecule, R11 is a group selected from R10 or R, A is an organopolysiloxane fragment having a specific structure, a and b are independently a number of 0-3, e is a number of 0-50, f is a number of 0-2000, g is a number of 0-10, and h is 0 or 1. The bonding sequence of siloxane units included by e, f, g and h can be blocks or random. ).

Description

Technical Field

[0001] The present invention relates to an organopolysiloxane having a hydrolyzable silyl group via a specific linking group, a powder treating agent, and treated powder and cosmetics treated with the powder treating agent. Background Art

[0002] As a powder treatment agent for powders to be added to cosmetics, a treatment agent having a hydrolyzable silyl group and a hydrosilyl group as a reaction site with the powder surface is studied. In the powder surface treatment of the treatment agent, an organopolysiloxane group as a hydrophobicity-imparting group and a polyoxyalkylene group as a hydrophilicity-imparting group are studied respectively.

[0003] For example, Patent Document 1 describes a hydrophilic treated powder treated with a polyether-modified silicone having a hydrolyzable silyl group. In Patent Document 1, although the dispersion of the treated powder in an aqueous material is discussed, there is no record of being able to form a Pickering emulsion. In addition, since the hydrolyzable silyl group of the polyether-modified silicone as the treating agent is directly bonded to the silicon atom of the siloxane bond of the main chain, the steric hindrance is large, resulting in low reactivity between the treating agent and the powder, and therefore, poor long-term storage stability. Furthermore, when the hydrophilic treated powder is combined with cosmetics, there are still problems with the stability over time (the ability to resist changes in its physical and chemical properties over time) and the deterioration of the feeling of use such as stickiness.

[0004] In addition, Patent Document 2 describes a processed powder using an organopolysiloxane having a hydrosilyl group and a polyoxyalkylene group or a polyglyceryl group, which has excellent dispersibility in water and can be emulsified into oil. However, the organopolysiloxane has a low stability over time, which leads to gelation through the cross-linking reaction between the hydrosilyl groups. In addition, due to the low reactivity of the hydrosilyl group on the powder surface, there is a tendency that the powder surface cannot be fully processed, thereby failing to obtain satisfactory dispersibility and emulsification stability. Moreover, sometimes unreacted hydrosilyl groups react with water to generate hydrogen, which has an adverse effect on the expansion and stability of the cosmetic container. Prior art literature Patent Literature

[0005] Patent Document 1: Japanese Patent Application Publication No. 2004-155978 Patent Document 2: Japanese Patent Application Publication No. 2010-30954 Summary of the invention Problem that the invention aims to solve

[0006] Therefore, the object of the present invention is to provide an organopolysiloxane which has high long-term storage stability and high reactivity with the powder surface and is suitable as a powder treatment agent. In addition, the object of the present invention is to provide a treated powder capable of stabilizing a water-in-oil type Pickering emulsion. Furthermore, the object of the present invention is to provide a cosmetic formulated with the Pickering emulsion.

[0007] Solutions for solving problems The present inventors have conducted intensive studies to solve the above problems and have found that an organopolysiloxane represented by the following average structural formula (1) can solve the above problems, thereby completing the present invention. That is, the present invention provides the following organopolysiloxane. [1] An organopolysiloxane represented by the following average structural formula (1). [Chemical formula 1] [In formula (1), R is independently a group selected from a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 30 carbon atoms, a fluoroalkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms, and R 10 Independently, a group represented by the following average structural formula (2) is [Chemical formula 2] (In formula (2), X is a divalent hydrocarbon group having 1 to 10 carbon atoms, s is a number from 1 to 100, and t is a number from 0 to 50. The bonding sequence of the oxyalkylene units enclosed by s and t may be block or random. v is a number from 1 to 10, and R 12 is independently a group selected from an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 12 carbon atoms, R 13 Each of them is independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and w is a number from 0 to 2. R 11 Selected from R 10 or a group in R, A is independently an organopolysiloxane segment represented by the following average structural formula (3) or formula (4), [Chemical formula 3] [Chemical formula 4] (In formula (3), R and R 10has the same meaning as above, c is a number from 0 to 3, i is a number from 0 to 10, j is a number from 0 to 100, Q is an oxygen atom or a divalent hydrocarbon group having 1 to 3 carbon atoms, and in formula (4), X has the same meaning as above. The bonding sequence of the siloxane units enclosed by i and j may be block or random. In the formula (1), a and b are independently a number of 0 to 3, e is a number of 0 to 50, f is a number of 0 to 2000, g is a number of 0 to 10, and h is 0 or 1. The bonding sequence of the siloxane units enclosed by e, f, g and h may be block or random. In the formula (1), there is one or more R 10 . 〕 [2] A powder treatment agent comprising the organopolysiloxane described in [1], wherein the water content is 2000 ppm or less. [3] A powder surface-treated with the powder treating agent described in [2]. [4] A method for treating powder, wherein the powder described in [3] is inorganic powder or organic powder. [5] A cosmetic comprising the treated powder described in [4]. [6] The cosmetic as described in [5], further comprising water and an oily agent. Effects of the Invention

[0009] The organopolysiloxane of the present invention having a group in which a polyoxyalkylene group and a hydrolyzable silyl group are bonded via a polyurethane bond has high long-term storage stability and high reactivity with the surface of the powder. In addition, the treated powder obtained by surface treatment using the organopolysiloxane of the present invention can be oriented at the interface with water and an oil agent to form a Pickering emulsion, and in particular, can stabilize a water-in-oil type Pickering emulsion that was previously difficult to stabilize. Therefore, the cosmetic containing the treated powder is free of the stickiness or irritation peculiar to surfactants, has a uniform cosmetic film, has good spreadability, ductility, and adhesion during application, has an excellent feel of use, and is also a cosmetic with excellent stability over time. DETAILED DESCRIPTION

[0010] Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.

[0011] [Organopolysiloxane] The organopolysiloxane of the present invention is an organopolysiloxane represented by the following average structural formula (1).

[0012] [Chemical formula 5]

[0013] In the formula (1), R is independently a group selected from a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 30 carbon atoms, a fluoroalkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms. It is preferably a group selected from an alkyl group having 1 to 16 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms, and a phenyl group, and most preferably a methyl group.

[0014] In the formula (1), R 10 is a group represented by the following average structural formula (2), characterized in that at least one, preferably 1 to 50, and more preferably 2 to 20 R 10 . R 10 As shown in the following average structural formula (2), it is a group having a hydrolyzable silyl group at the end, and the hydrolyzable silyl group and the polyoxyalkylene group are bonded by a urethane bond. It should be noted that, as shown in the average structural formula (1), the R 10 The siloxane moiety may be located at the end of the siloxane molecular chain or in the middle of the siloxane molecular chain (molecular chain side chain), or may be located at either or both of the above.

[0015] [Chemical formula 6]

[0016] In the formula (2), X is a divalent hydrocarbon group having 1 to 10 carbon atoms, preferably a divalent hydrocarbon group having 2 to 8 carbon atoms, and most preferably a trimethylene group or a 2-methyltrimethylene group.

[0017] In the formula (2), s is a number of 1 to 100, preferably 4 to 20. t is a number of 0 to 50, preferably 0 to 20. It should be noted that s+t is preferably 4 to 50, more preferably 8 to 20. If the value of s+t is within this range, sufficient hydrophilicity can be imparted when the powder is treated, which is preferred. In addition, the bonding order of the oxyalkylene units enclosed by s and t may be block or random.

[0018] In the above formula (2), v is a number of 1 to 10, preferably 1 to 6; more preferably v=1, v=2, v=3, v=6; and even more preferably v=3.

[0019] In the formula (2), R 12 It is a group selected from an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 12 carbon atoms, and is preferably a methyl group. In the formula (2), R 13It is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and is preferably a hydrogen atom, a methyl group, an ethyl group or a propyl group. In the above formula (2), w is a number from 0 to 2, preferably 0 or 1, and more preferably 0.

[0020] In the formula (1), R 11 Selected from R 10 or a group in R, A is an organopolysiloxane segment represented by the following average structural formula (3) or formula (4), among which the following formula (3) is preferred.

[0021] [Chemical formula 7]

[0022] In formula (3), R and R 10 The meaning is the same as above, Q is an oxygen atom or a divalent hydrocarbon group having 1 to 3 carbon atoms, preferably an oxygen atom or a vinyl group. In the formula (3), c is a number from 0 to 3. i is a number from 0 to 10, preferably from 0 to 5. j is a number from 0 to 100, preferably from 0 to 50. If the values ​​of i and j are within the above ranges, the reactivity with the powder is good, which is preferred.

[0023] [Chemical formula 8] In the above formula (4), X has the same meaning as defined above.

[0024] In the formula (1), a and b are independently a number of 0 to 3. e is a number of 0 to 50, preferably 1 to 30, and more preferably 2 to 20. f is a number of 0 to 2000, preferably 1 to 1000, and more preferably 5 to 100. If the values ​​of e and f are respectively within the above ranges, the reactivity with the powder is good, which is preferred. g is a number of 0 to 10, preferably 0 to 8, and more preferably 0 to 5. h is a number of 0 or 1.

[0025] As a method for producing the organopolysiloxane of the present invention, there may be mentioned a method of reacting a polyoxyalkylene-modified organopolysiloxane having a hydroxyl group at a terminal with an isocyanate having a hydrolyzable silyl group.

[0026] Examples of the polyoxyalkylene-modified organopolysiloxane having a hydroxyl group at the terminal include organopolysiloxanes represented by the following average structural formula (1′).

[0027] [Chemical formula 9] In formula (1'), R, R 11 , A, a, b, e, f, g and h are the same as those shown in formula (1), R 14is a group represented by the following average structural formula (5), and the bonding order of the siloxane units enclosed by e, f, g and h may be block or random. It should be noted that in the above formula (1'), there is one or more R 14 . [Chemical formula 10]—XO-(C2H4O) s -(C3H6O) t -H (5) In formula (5), X, s and t are the same as those in formula (2), and the bonding order of the oxyalkylene units enclosed by s and t may be block or random.

[0029] As the isocyanate having a hydrolyzable silyl group, an isocyanate represented by the following formula (6) may be mentioned. [Chemical formula 11] In formula (6), R 12 , R 13 , v and w have the same meanings as above.

[0030] In addition, a solvent may be used as needed during the reaction. If it is an aprotic organic solvent, it is not particularly limited. Examples of the solvent include aromatic hydrocarbons such as toluene and xylene; aliphatic or alicyclic hydrocarbons such as n-pentane, n-hexane, and cyclohexane; and halogenated hydrocarbons such as dichloromethane, chloroform, and carbon tetrachloride. The reaction conditions are not particularly limited, but are preferably 50 to 120° C., and the reaction is preferably performed for 1 to 10 hours. Alternatively, the reaction may be carried out in the presence of a polyurethane catalyst. Examples of the polyurethane catalyst include amines such as triethylamine, triethyldiamine, and N-methylmorpholine; and organometallic compounds such as dibutyltin dilaurate and stannous oleate, which are known catalysts for forming polyurethane bonds. In addition, after such a polyurethane reaction, unreacted products, catalysts, and water are preferably distilled under reduced pressure at 80 to 120°C. By controlling the water content in the organopolysiloxane to 2000 ppm or less, preferably 1800 ppm or less, long-term storage stability is improved, so it is preferred when used as a powder treatment agent. It should be noted that the water content in the organopolysiloxane is a value measured by a Karl Fischer moisture meter.

[0031] [Powder treatment agent / treated powder] The organopolysiloxane of the present invention can be suitably used as a powder treatment agent. When used as a powder treatment agent, the water content in the organopolysiloxane is preferably 2000 ppm or less, more preferably 1800 ppm or less. Examples of the powder to be treated with the powder treating agent include inorganic powder, organic powder, surfactant metal salt powder (metal soap), color pigment, pearlescent pigment, and metal powder pigment.

[0032] Examples of the inorganic powder include powders of 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, red mica, biotite, lithium mica, silicic acid, silicic anhydride, aluminum silicate, magnesium silicate, magnesium aluminum silicate, calcium silicate, barium silicate, strontium silicate, metal tungstates, hydroxyapatite, vermiculite, calcite, bentonite, montmorillonite, hectorite, zeolite, ceramic powder, calcium hydrogen phosphate, aluminum oxide, aluminum hydroxide, boron nitride, and silicon dioxide. Preferred are powders of titanium oxide, zinc oxide, talc, mica, kaolin, sericite, muscovite, synthetic mica, phlogopite, red mica, biotite, lepidolite, silicic acid, silicic anhydride, bentonite, montmorillonite, hectorite, zeolite, ceramic powder, alumina, aluminum hydroxide, boron nitride, silicon dioxide, and the like.

[0033] Examples of organic powders include polyamide powder, polyester powder, polyethylene powder, polypropylene powder, polystyrene powder, polyurethane powder, benzoguanidine powder, polymethylbenzoguanidine powder, tetrafluoroethylene powder, polymethyl methacrylate powder, cellulose powder, silk powder, nylon powder, 12-nylon powder, 6-nylon powder, silicone powder, silicone composite powder, styrene-acrylic copolymer powder, divinylbenzene-styrene copolymer powder, vinyl resin powder, urea resin powder, phenolic resin powder, fluororesin powder, silicone resin powder, acrylic resin powder, melamine resin powder, epoxy resin powder, polycarbonate resin powder, microcrystalline fiber powder, starch powder, lauroyl lysine powder, etc. Preferred are polyethylene powder, polypropylene powder, polyurethane powder, polymethyl methacrylate powder, cellulose powder, silk powder, nylon powder, silicone powder, silicone composite powder, acrylic resin powder, and starch powder.

[0034] Examples of surfactant metal salt powders (metal soaps) include powders of zinc stearate, aluminum stearate, calcium stearate, magnesium stearate, zinc myristate, magnesium myristate, zinc hexadecanoate, calcium hexadecanoate phosphate, and sodium hexadecyl zinc phosphate. Examples of color pigments include inorganic red pigments of 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; inorganic black pigments such as black iron oxide and carbon black; 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 dark blue and ultramarine; mixtures of tar-based pigments subjected to lake treatment; mixtures of natural pigments subjected to lake treatment; and composite powders of these powders.

[0035] As pearlescent pigments, titanium oxide-coated mica, bismuth oxychloride, titanium oxide-coated bismuth oxychloride, titanium oxide-coated talc, fish scale foil, titanium oxide-coated colored mica, etc. can be cited; as metal powder pigments, powders selected from aluminum powder, copper powder, stainless steel powder, etc. can be cited.

[0036] These powders may be used regardless of their shape, particle size, and particle structure as long as they are commonly used powders, but are preferably spherical and have a particle size in the range of 5 nm to 1 μm.

[0037] The method for producing treated powder of the present invention is a method of treating the above-mentioned powder with a powder treating agent containing the above-mentioned organopolysiloxane, and dry treatment, wet treatment, etc. can be selected. As an apparatus, a bead mill, a hammer mill, a Nauta mixer, etc. can be used. The surface treatment is preferably performed by heating so that the hydrolyzable alkoxysilyl group of the powder treatment agent reacts sufficiently with the powder surface. The temperature is preferably 30 to 150° C., particularly preferably 30 to 110° C. The treatment time is preferably 5 minutes to 10 hours. The amount of the powder treatment agent used is 0.1 to 30 parts by mass of the organopolysiloxane represented by the formula (1) in the powder treatment agent, preferably 0.5 to 10 parts by mass, relative to 100 parts by mass of the powder. When the surface treatment agent is used, an optional component such as an organic solvent may be added as needed. Furthermore, in order to obtain a desired treated powder, in addition to the above-mentioned treatment steps, treatment steps such as stirring, pulverizing, and drying may be added as necessary.

[0038] [Cosmetics] The present invention also provides a cosmetic containing powder surface-treated with the powder treating agent (treated powder) (hereinafter referred to as "the cosmetic of the present invention"). The cosmetic may contain a medium permitted in cosmetics in addition to the treated powder. The content of the treated powder of the present invention is preferably 0.1 to 90% by mass, more preferably 0.2 to 50% by mass, and even more preferably 0.5 to 20% by mass of the entire cosmetic.

[0039] In addition, the cosmetic of the present invention preferably further comprises water and an oily agent in addition to the above-mentioned treated powder. Therefore, the cosmetic of the present invention is a cosmetic having good emulsification stability and good feeling during use. The content of water is preferably 1 to 98% by mass of the total cosmetic, more preferably 2 to 90% by mass, and further preferably 3 to 80% by mass. If the content of water is within the above range, a cosmetic having good stability and usability can be obtained. The content of oil is preferably 1 to 98% by mass of the total cosmetic, more preferably 2 to 50% by mass, and further preferably 3 to 40% by mass. If the content of oil is within the above range, a cosmetic having good stability and usability can be obtained.

[0040] In addition, the cosmetic of the present invention may further include a hydrophilic substance selected from propylene glycol, trimethylene glycol, dipropylene glycol, 1,3-butylene glycol, methyl propanediol, pentanediol, glycerol, diglycerol, ethylhexylglycerol, triglycerol, polyglycerol and ethanol. These hydrophilic substances are preferably 1 to 80% by mass of the total cosmetic, more preferably 1 to 40% by mass, and further preferably 3 to 30% by mass. If the content of the hydrophilic substance is within the above range, a cosmetic having good stability and usability can be obtained.

[0041] Examples of the oil contained in the cosmetic of the present invention include volatile oils such as volatile silicone oils and volatile organic oils, and oils other than volatile oils permitted in cosmetics. Examples of the volatile silicone oil include dimethylpolysiloxane (dimer, trimer, tetramer, pentamer), caprylyl methylsiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, tetramethyltetrahydrocyclotetrasiloxane, tritrimethylsiloxymethylsilane and tetratrimethylsiloxysilane. Examples of the volatile organic oil include hydrocarbon oils and ester oils, and specific examples include α-olefin oligomers, light isoparaffins, isododecane, light liquid isoparaffins, and butyl acetate. As the volatile oil agent, dimethylpolysiloxane (tetramer, pentamer), caprylylmethylsiloxane, tritrimethylsiloxymethylsilane, tetratrimethylsiloxysilane, light isoparaffin, isododecane, light liquid isoparaffin, butyl acetate and the like are preferred. The amount of these volatile oil agents blended is preferably 1 to 98% by mass, more preferably 2 to 50% by mass, and even more preferably 3 to 30% by mass, based on the entire cosmetic.

[0042] Examples of oils other than volatile oils include one or more nonvolatile silicone oils, hydrocarbon oils, higher fatty acids, higher alcohols, ester oils, glyceride oils, polar oils such as natural animal and plant oils, semi-synthetic oils, and fluorinated oils.

[0043] Examples of the nonvolatile silicone oil include nonvolatile dimethylpolysiloxane, phenyl trimethicone, methylphenylpolysiloxane, dimethylsiloxyphenyl trimethicone, diphenylsiloxyphenyl trimethicone (for example, KF-56A manufactured by Shin-Etsu Chemical Co., Ltd.), methylhexylpolysiloxane, methylhydrogenpolysiloxane, dimethylsiloxane-methylphenylsiloxane copolymers, and other linear or branched organopolysiloxanes having low to high viscosities; tetramethyltetraphenylcyclotetrasiloxane, amino-modified organopolysiloxane, and high viscosity organopolysiloxanes. Silicone rubbers such as colloidal dimethylpolysiloxane with a low degree of polymerization, colloidal amino-modified organopolysiloxane, colloidal dimethylsiloxane-methylphenylsiloxane copolymer; and cyclic siloxane solutions of silicone rubber or rubber; trimethylsiloxysilicic acid, cyclic organopolysiloxane solutions of trimethylsiloxysilicic acid; higher alkoxy-modified organopolysiloxanes such as stearyl silicone; higher fatty acid-modified organopolysiloxanes; alkyl-modified organopolysiloxanes; long-chain alkyl-modified organopolysiloxanes; fluorine-modified organopolysiloxanes, silicone resins and dissolved silicone resins, etc.

[0044] Examples of the non-volatile hydrocarbon oil include non-volatile ozokerite, squalane, synthetic squalane, vegetable squalane, squalene, ceresin, paraffin, paraffin wax, polyethylene wax, polyethylene-polypropylene wax, (ethylene / propylene / styrene) copolymer, (butylene / propylene / styrene) copolymer, liquid paraffin, liquid isoparaffin, pristane, polyisobutene, hydrogenated polyisobutene, microcrystalline wax, and vaseline.

[0045] Examples of the nonvolatile higher fatty acid include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, undecylenic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA), isostearic acid, and 12-hydroxystearic acid.

[0046] Examples of the nonvolatile higher alcohols include lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, behenyl alcohol, cetyl alcohol, oleyl alcohol, isostearyl alcohol, hexyldodecanol, octyldodecanol, cetearyl alcohol, 2-decyltetradecyl alcohol, cholesterol, phytosterol, POE cholesterol ether, monostearyl glyceryl ether (baty alcohol), monooleyl glyceryl ether (baty alcohol), and the like.

[0047] Examples of the nonvolatile ester oil include diisobutyl adipate, 2-hexyldecyl adipate, di-2-heptylundecanyl adipate, N-alkylethylene glycol monoisostearate, isostearyl isostearate, trimethylolpropyl triisostearate, ethylene glycol di-2-ethylhexanoate, hexadecyl 2-ethylhexanoate, trimethylolpropyl tri-2-ethylhexanoate, pentaerythritol tetra-2-ethylhexanoate, hexadecyl octanoate, octyldodecyl oleate, oleyl oleate, octyldodecyl oleate, decyl oleate, neopentyl glycol dioctanoate, neopentyl glycol dicaprate, coconut oil monooctanoate / caprate, triethyl citrate, 2-ethylhexyl succinate, isostearyl stearate , butyl stearate, diisopropyl sebacate, di-2-ethylhexyl sebacate, hexadecyl lactate, tetradecyl lactate, isononyl isononanoate, isotridecyl isononanoate, isopropyl palmitate, 2-ethylhexyl palmitate, 2-hexyldecyl palmitate, 2-heptylundecanyl palmitate, 12-hydroxystearate cholesterol ester, dipentaerythritol fatty acid ester, isopropyl myristate, octyldodecyl myristate, 2-hexyldecyl myristate, tetradecyl myristate, hexyldecyl dimethyloctanoate, ethyl laurate, hexyl laurate, 2-octyldodecyl N-lauroyl-L-glutamate, isopropyl lauroyl sarcosinate, diisostearyl malate, etc.

[0048] Examples of the nonvolatile glyceride oil include acetylglyceride, triisooctanoin, triisoglyceryl stearate, triisopalmitin, monoglyceryl stearate, di-2-heptylundecanoic acid glyceryl, trimyristin, myristic acid isostearic acid diglyceryl, and ethylhexanoic acid triglyceride.

[0049] In addition, examples of non-volatile natural plant and animal oils and semi-synthetic oils include avocado oil, linseed oil, almond oil, insect wax, perilla oil, olive oil, cocoa butter, kapok wax, ginkgo oil, carnauba wax, liver oil, candelilla wax, refined candelilla wax, beef tallow, beef shank fat, beef bone fat, hardened beef tallow, apricot kernel oil, spermaceti, hardened oil, wheat germ oil, sesame oil, rice germ oil, rice bran oil, sugarcane wax, camellia oil, safflower oil, shea butter, Chinese tung oil, cinnamon oil, jojoba wax, squalane, squalene, shellac wax, tortoise oil, soybean oil, tea seed oil, camellia oil, evening primrose oil, corn oil, lard, Rapeseed oil, Japanese tung oil, rice bran oil, germ oil, horse fat, peach kernel oil, palm oil, palm kernel oil, castor oil, hardened castor oil, castor oil fatty acid methyl ester, sunflower oil, grape oil, bayberry wax, jojoba oil, hydrogenated jojoba oil, macadamia nut oil, beeswax, mink oil, white meadowfoam seed oil, cottonseed oil, cotton wax, cotton wax, wood wax, wood wax kernel oil, montan wax, coconut oil, hardened coconut oil, tri-coconut oil fatty acid glyceride, lanolin, peanut oil, lanolin, liquid lanolin, reduced lanolin, lanolin alcohol, hard lanolin, lanolin acetate, lanolin alcohol acetate, lanolin fatty acid isopropyl ester, egg yolk oil, etc.

[0050] Examples of the nonvolatile fluorine-based oil include perfluoropolyether, perfluorodecalin and perfluorooctane.

[0051] The amount of oils other than volatile oils allowed in the cosmetic of the present invention varies depending on the dosage form of the cosmetic, but is preferably in the range of 1 to 98% by mass, preferably 2 to 50% by mass, and more preferably 3 to 30% by mass of the total cosmetic.

[0052] The cosmetic of the present invention may further comprise one or more ultraviolet absorbers and / or ultraviolet scatterers. Therefore, the cosmetic of the present invention is not only good in feel, excellent in usability and durability, but also can shield ultraviolet rays. Examples of the ultraviolet absorber include benzoic acid ultraviolet absorbers such as p-aminobenzoic acid, anthranilic acid ultraviolet absorbers such as methyl anthranilate, salicylic acid ultraviolet absorbers such as methyl salicylate, cinnamic acid ultraviolet absorbers such as 2-ethylhexyl p-methoxycinnamate, benzophenone ultraviolet absorbers such as 2,4-dihydroxybenzophenone, urocanic acid ultraviolet absorbers such as ethyl urocanate, triazine ultraviolet absorbers such as bis-ethylhexyloxyphenol methoxyphenyl triazine, dibenzoylmethane ultraviolet absorbers such as 4-tert-butyl methoxydibenzoylmethane, etc. In addition, silicone derivatives having the above-mentioned ultraviolet absorbing functional groups can also be used. As the ultraviolet scattering agent, powders that absorb and scatter ultraviolet rays, such as micro-particle titanium oxide, titanium oxide containing micro-particle iron, micro-particle zinc oxide, micro-particle cerium oxide, and composites thereof, can be cited. Among them, cinnamic acid-based ultraviolet absorbers, dibenzoylmethane-based ultraviolet absorbers, micro-particle titanium oxide (for example, SPD-T5 manufactured by Shin-Etsu Chemical Co., Ltd.) and micro-particle zinc oxide (for example, SPD-Z5 manufactured by Shin-Etsu Chemical Co., Ltd.) are preferred.

[0053] The cosmetic of the present invention may include one or more surfactants. Therefore, the cosmetic of the present invention can be a cosmetic with more excellent emulsification stability and usability according to the purpose of use. As the surfactant, there are anionic surfactants, cationic surfactants, nonionic surfactants and amphoteric surfactants. The surfactant contained in the cosmetic is not particularly limited, as long as it is a surfactant used in a common cosmetic, it can be used.

[0054] If specific examples are given, examples of the anionic surfactant include fatty acid soaps such as sodium stearate and triethanolamine palmitate, alkyl ether carboxylic acids and salts thereof, condensate salts of amino acids and fatty acids, alkane sulfonates, olefin sulfonates, sulfonates of fatty acid esters, sulfonates of fatty acid amides, formalin condensation sulfonates, alkyl sulfate ester salts, secondary higher alcohol sulfate ester salts, alkyl and allyl ether sulfate ester salts, sulfate ester salts of fatty acid esters, sulfate ester salts of fatty acid alkanolamides, sulfate ester salts such as Turkey red oil, alkyl phosphates, ether phosphates, alkyl allyl ether phosphates, amide phosphates, N-acyl lactylates, N-acyl sarcosinates, N-acylamino acid-based surfactants, carboxyvinyl polymers, and polyacrylamide-based anionic surfactants. Examples of the cationic surfactant include alkylamine salts, amine salts such as polyamines and amino alcohol fatty acid derivatives, alkyl quaternary ammonium salts (eg, behenyltrimethylammonium chloride), aromatic quaternary ammonium salts, pyridinium salts, and imidazolium salts.

[0055] Examples of the nonionic surfactant include sorbitan fatty acid esters, glycerin fatty acid esters, polyglycerin fatty acid esters, propylene glycol fatty acid esters, polyethylene glycol fatty acid esters, sucrose fatty acid esters, methyl glucoside fatty acid esters, alkyl polyglucosides, polyoxyethylene alkyl ethers, polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyoxyethylene propylene glycol fatty acid esters, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene stanol ethers, polyoxyethylene phytosterol ethers, polyoxyethylene cholesteryl ethers, and polyoxyethylene cholesterol ethers; linear or branched polyoxyethylene The invention also includes but is not limited to: a linear or branched polyoxyethylene-alkyl co-modified organopolysiloxane (for example, KF-6017, KF-6017P, KF-6028 manufactured by Shin-Etsu Chemical Co., Ltd.), a linear or branched polyoxyethylene-alkyl co-modified organopolysiloxane (for example, KF-6038, KF-6048 manufactured by Shin-Etsu Chemical Co., Ltd.), a linear or branched polyglycerol-modified organopolysiloxane (for example, KF-6100, KF-6104, KF-6106 manufactured by Shin-Etsu Chemical Co., Ltd.), a linear or branched polyglycerol-alkyl co-modified organopolysiloxane (for example, KF-6105 manufactured by Shin-Etsu Chemical Co., Ltd.), an alkanolamide, a sugar ether, a sugar amide, and the like.

[0056] Examples of the amphoteric surfactant include betaine, aminocarboxylate, imidazoline derivatives, and amidoamine type amphoteric surfactants.

[0057] The cosmetic of the present invention may also include a composition consisting of one or more cross-linked organopolysiloxane polymers having no hydrophilic group and a liquid oil agent. The cross-linked organopolysiloxane polymer is obtained by reacting an alkyl hydrogen polysiloxane and / or an allyl hydrogen polysiloxane with a cross-linking agent having a reactive unsaturated group (reactive vinyl group) at the end of the molecular chain. Examples of the alkyl hydrogen polysiloxane include methyl hydrogen polysiloxane having a linear or partially branched unit, and methyl hydrogen polysiloxane grafted with an alkyl chain having 6 to 20 carbon atoms. The number of hydrogen atoms bonded to silicon atoms in the methyl hydrogen polysiloxane needs to be two or more on average in one molecule. Examples of the crosslinking agent include crosslinking agents having two or more reactive vinyl groups in one molecule, such as methyl vinyl polysiloxane and α,ω-alkenyl diene. As examples of these, compositions described in Japanese Patent No. 1925781, Japanese Patent No. 1932769, International Publication No. WO 03-24413, and Japanese Patent Application Laid-Open No. 2009-185296 can be cited. 2 / s(25℃)~100.0mm2 / s (25°C) low viscosity silicone, liquid paraffin, squalane, hydrocarbon oils such as isododecane, glyceryl ester oils such as triethylhexanoin, ester oils, etc., are used to make the cross-linked organopolysiloxane polymer plump. In addition, commercially available products of the composition composed of the cross-linked organopolysiloxane polymer without these hydrophilic groups and the liquid oil agent are not particularly limited, and examples thereof include KSG-15, KSG-16, KSG-18, KSG-18A, KSG-1610, USG-103 made into a paste with silicone oil, and USG-106, KSG-41, KSG-42, KSG-43, KSG-44, KSG-810 (all manufactured by Shin-Etsu Chemical Co., Ltd.) made into a paste with hydrocarbon oil or glyceryl ester oil. The amount of the composition comprising the crosslinked organopolysiloxane having no hydrophilic group and the liquid oil agent is preferably 0.1 to 50% by mass, more preferably 1 to 30% by mass, based on the total amount of the cosmetic.

[0058] The cosmetic of the present invention may also include a composition consisting of one or more cross-linked organopolysiloxane polymers with hydrophilic groups and a liquid oil. As the hydrophilic group, preferably a polyether group or a polyglycerol group. It can be obtained by reacting with a cross-linking agent having a cross-linked organic unsaturated group (reactive vinyl) containing the polyether group and / or the polyglycerol group. As alkyl hydrogen polysiloxane, methyl hydrogen polysiloxane grafted with polyoxyalkylene, methyl hydrogen polysiloxane grafted with a polyglycerol chain, etc., can be cited. Regarding the hydrogen atoms bonded to the silicon atom, an average of more than two are required in one molecule. The cross-linking agent can be cited as a cross-linking agent having more than two ethylene reaction sites in the molecule, such as methyl vinyl polysiloxane, α, ω-alkenyl diene, glycerol triallyl ether, polyoxyalkynylated glycerol triallyl ether, trimethylolpropane triallyl ether, polyoxyalkynylated trimethylolpropane triallyl ether, etc. The crosslinked product (crosslinked organopolysiloxane polymer) obtained by reacting the alkyl hydrogen polysiloxane with a crosslinking agent is a crosslinked product having at least one hydrophilic group in one molecule. 0.65mm above the deadweight 2 / s(25℃)~100.0mm 2 / s (25°C) low-viscosity silicone, liquid paraffin, squalane, hydrocarbon oils such as isododecane, glycerol ester oils such as triethylhexanoin, ester oils, etc., are used to swell the crosslinked organopolysiloxane polymer. As the composition, the composition described in Japanese Patent No. 2631772, Japanese Patent Laid-Open No. 9-136813, Japanese Patent Laid-Open No. 2001-342255, International Publication No. WO 03-20828 Pamphlet, Japanese Patent Laid-Open No. 2009-185296 is preferred. In addition, commercially available products of the composition composed of the cross-linked organopolysiloxane polymer having these hydrophilic groups and the liquid oil agent are not particularly limited, and examples thereof include KSG-210, KSG-240, and KSG-710 made into a paste with silicone oil; KSG-310, KSG-320, KSG-330, KSG-340, KSG-820, KSG-830, KSG-840, and KSG-850Z (all manufactured by Shin-Etsu Chemical Co., Ltd.) made into a paste with hydrocarbon oil or glyceride oil. The amount of the composition comprising the crosslinked organopolysiloxane having a hydrophilic group and the liquid oil agent is preferably 0.1 to 50% by mass, more preferably 1 to 30% by mass, based on the total amount of the cosmetic.

[0059] The cosmetic of the present invention may also contain silicone wax according to its purpose. The silicone wax is preferably a polylactone-modified polysiloxane of a ring-opening polymer of a lactone compound having more than five rings bonded thereto, i.e., polylactone. Alternatively, the silicone wax is preferably an acrylic acid-modified polysiloxane containing at least one functional group selected from anionic groups such as pyrrolidone, long-chain alkyl, polyoxyalkylene, fluoroalkyl, and carboxyl in the molecule. As commercially available products, KP-561P and KP-562P (both manufactured by Shin-Etsu Chemical Co., Ltd.) as waxes having long-chain alkyl groups can be exemplified.

[0060] In addition, the cosmetic of the present invention may further include ingredients commonly used in cosmetics, oil-soluble gelling agents (organic modified clay mineral mixtures), various powders, antiperspirants, moisturizers, antibacterial preservatives, fragrances, salts, antioxidants, pH adjusters, chelating agents, cooling agents, anti-inflammatory drugs, skin beautifying ingredients (whitening agents, cell activators, rough skin improving agents, blood circulation promoters, skin astringents, anti-seborrhea drugs, etc.), vitamins, amino acids, nucleic acids, hormones, inclusion compounds, etc.

[0061] Examples of the oil-soluble gelling agent include metal soaps such as aluminum stearate, magnesium stearate, and zinc myristate; amino acid derivatives such as N-lauroyl-L-glutamic acid and α,γ-di-n-butylamine; dextrin fatty acid esters such as dextrin palmitate, dextrin stearate, and dextrin 2-ethylhexanoate palmitate; sucrose fatty acid esters such as sucrose palmitate and sucrose stearate; low sugar fatty acid esters such as low sugar stearate and low sugar 2-ethylhexanoate; benzyl derivatives of sorbitol such as monobenzylidene sorbitol and bisbenzylidene sorbitol; and organic modified clay mineral mixtures such as dimethylbenzyldodecylamine montmorillonite and dimethylbisoctadecylamine hectorite.

[0062] The various powders described below are powders that have not been surface-treated with the organopolysiloxane represented by the average structural formula (1) of the present invention, and specifically include inorganic powders, color pigments, pearlescent pigments, and metal powder pigments. Examples of the inorganic powder include powders of 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, red mica, biotite, lithium mica, silicic acid, silicic anhydride, aluminum silicate, magnesium silicate, magnesium aluminum silicate, calcium silicate, barium silicate, strontium silicate, metal tungstates, hydroxyapatite, vermiculite, calcite, bentonite, montmorillonite, hectorite, zeolite, ceramic powder, calcium hydrogen phosphate, aluminum oxide, aluminum hydroxide, boron nitride, and silicon dioxide.

[0063] As the colored pigment, there can be mentioned 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 iron oxide yellow and loess; inorganic black pigments such as iron oxide black and carbon black; 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 dark blue and ultramarine; a mixture of tar-based pigments subjected to a color lake treatment; a mixture of natural pigments subjected to a color lake treatment; and a composite powder obtained by compounding these powders.

[0064] Examples of the pearlescent pigment include titanium oxide-coated muscovite, titanium oxide-coated mica, bismuth oxychloride, titanium oxide-coated bismuth oxychloride, titanium oxide-coated talc, fish scale foil, and titanium oxide-coated colored mica.

[0065] Examples of the metal powder pigment include aluminum powder, copper powder, and stainless steel powder.

[0066] The powder that can be added to the cosmetic of the present invention preferably has hydrophobicity on the surface. So-called hydrophobicity means that it does not disperse in water. Powders that have hydrophobicity on the surface of the powder from the beginning can be used directly, and powders that have been subjected to the following hydrophobic treatment can also be used as needed. By using a hydrophobic powder, the uniformity of the cosmetic film, the stability during application, and the adhesion are improved. In addition, the average particle size of the powder is preferably less than 200 μm. The shape and particle structure of the particles constituting the powder are not particularly limited. In addition, the average particle size is preferably less than 200 μm, more preferably less than 100 μm, and more preferably less than 50 μm. Among them, the average particle size is a volume average particle size, which can be measured by a laser scattering method, etc.

[0067] The above-mentioned powder is preferably a powder whose surface is hydrophobized by a treatment agent selected from at least one of silicone, fluorine compounds, silane coupling agents, titanium coupling agents, N-acylated amino acids and metal soaps. In particular, inorganic powders, colored pigments and pearlescent pigments are preferably used because they have hydrophilic surfaces.

[0068] Examples of the antiperspirant include aluminum hydrochloride, aluminum chloride, aluminum sesquichlorohydrate, zirconium chlorohydrate, aluminum zirconium chlorohydrate and aluminum zirconium glycinate complex.

[0069] Examples of the moisturizing agent include sorbitol, xylitol, maltitol, polyethylene glycol, polysaccharides, hydroxyethyl cellulose, xanthan gum, hyaluronic acid, chondroitin sulfate, pyrrolidone carboxylate, polyoxyethylene methyl glucoside, polyoxypropylene methyl glucoside, egg yolk lecithin, soybean lecithin, phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidylglycerol, phosphatidylinositol, and sphingomyelin.

[0070] As antimicrobial preservatives, there are alkyl parabens, benzoic acid, sodium benzoate, sorbic acid, potassium sorbate, phenoxyethanol, etc. As antimicrobial agents, there are benzoic acid, salicylic acid, carbolic acid, sorbic acid, alkyl parahydroxybenzoates, parachlorometacresol, hexachlorophene, hydroxychloroaniline, chlorhexidine chloride, trichlorocarbendazim, photosensitizers, phenoxyethanol, etc.

[0071] As the fragrances, they are natural fragrances and synthetic fragrances. As natural fragrances, they are plant fragrances separated from flowers, leaves, wood, peels, etc.; animal fragrances such as musk (bisabolol) and civet. As synthetic fragrances, they include hydrocarbons such as monoterpenes; alcohols such as aliphatic alcohols and aromatic alcohols; aldehydes such as terpene aldehydes and aromatic aldehydes; ketones such as alicyclic ketones; esters such as terpene esters; lactones; phenols; oxides; nitrogen-containing compounds; acetals, etc.

[0072] As the salts, inorganic salts, organic acid salts, amine salts and amino acids can be cited. As inorganic salts, sodium salts, potassium salts, magnesium salts, calcium salts, aluminum salts, zirconium salts, barium salts, zinc salts, etc. of inorganic acids such as hydrochloric acid, sulfuric acid, carbonic acid, nitric acid, etc. can be cited; as organic acid salts, salts of organic acids such as acetic acid, dehydroacetic acid, citric acid, malic acid, succinic acid, ascorbic acid, stearic acid, etc. can be cited; as amine salts and amino acid salts, salts of amines such as triethanolamine, salts of amino acids such as glutamic acid, etc. can be cited. In addition, other salts of hyaluronic acid, chondroitin sulfate, aluminum zirconium glycine complex, etc. can also be used, and neutralized salts of acids / bases used in cosmetic prescriptions can also be used.

[0073] Examples of the antioxidant include vitamin E, p-tert-butylphenol, butylhydroxyanisole, butylated hydroxytoluene (BHT), and phytic acid. Examples of the pH adjuster include lactic acid, citric acid, glycolic acid, succinic acid, tartaric acid, dl-malic acid, potassium carbonate, sodium bicarbonate, and ammonium bicarbonate.

[0075] Examples of the chelating agent include alanine, edetic acid sodium salt, sodium polyphosphate, sodium metaphosphate, phosphoric acid, and the like.

[0076] Examples of the cooling agent include L-menthol and camphor.

[0077] Examples of the anti-inflammatory drugs include allantoin, glycyrrhizic acid and its salts, glycyrrhetinic acid and glycyrrhetinic acid stearate, tranexamic acid, azulene, and the like.

[0078] As the skin beautifying ingredients (whitening agents, cell activators, rough skin improving agents, blood circulation promoting agents, skin astringents, anti-seborrhea drugs, etc.), there can be cited whitening agents such as placenta extract, arbutin, glutathione, and saxifrage extract; cell activators such as royal jelly, photosensitizers, cholesterol derivatives, and calf blood extracts; rough skin improving agents; blood circulation promoting agents such as nonanoic acid vanillamide, benzyl nicotinate, β-butoxyethyl nicotinate, capsaicin, turmeric, blister beetle tincture, ichthyol, caffeine, tannic acid, α-borneol, nicotinate tocopherol, inositol nicotinate, cycloamycin, cinnarizine, tolazoline, acetylcholine, isoprenoid, cepharanthin, and γ-oryzanol; skin astringents such as zinc oxide and tannic acid; anti-seborrhea drugs such as sulfur and dimethylthiothrene, etc.

[0079] Examples of the vitamins include vitamin A oil, vitamin A, vitamin A acetate, vitamin A palmitate, and the like; vitamin B2 such as riboflavin, riboflavin butyrate, riboflavin adenosine, and the like; vitamin B6 such as pyridoxine hydrochloride, pyridoxine diphenoxyacetate allyl ester, pyridoxine tripalmitate, and the like; vitamin B6 such as vitamin B12; vitamin B13 such as vitamin B14; vitamin B15 such as vitamin B16; vitamin B17 such as vitamin B18; vitamin B19 such as vitamin B20; vitamin B21 such as vitamin B22; vitamin B23 such as vitamin B24; vitamin B25 such as vitamin B26; vitamin B27 such as vitamin B28; vitamin B29 such as vitamin B29; vitamin B21 12 Its derivatives, vitamin B 15 and their derivatives; vitamin B types such as L-ascorbic acid, L-ascorbyl disalmitate, sodium L-ascorbic acid-2-sulfate, dipotassium L-ascorbyl phosphate, etc.; vitamin C types such as ergocalciferol and vitamin D3; vitamin E types such as α-tocopherol, β-tocopherol, γ-tocopherol, dl-α-tocopherol acetate, dl-α-tocopherol nicotinic acid, dl-α-tocopherol succinate, etc.; niacin types such as niacin, benzylnicotinic acid, vitamin PP, etc.; pantothenic acids such as vitamin H, vitamin P, calcium pantothenate, D-panthenol, panthenyl ether, acetyl panthenyl ether, etc., biotin, etc.

[0080] Examples of the amino acids include glycine, valine, leucine, isoleucine, serine, threonine, phenylalanine, arginine, lysine, asparagine, glutamic acid, cystine, cystine, methionine, and tryptophan.

[0081] Examples of the nucleic acid include deoxyribonucleic acid and the like.

[0082] Examples of the hormone include estradiol and vinyl estradiol.

[0083] Examples of the inclusion complex include cyclodextrin and the like.

[0084] In addition, the cosmetics of the present invention can be formulated with the above-mentioned cosmetic ingredients, and as cosmetics, examples include skin care cosmetics, emulsions, skin creams, makeup bases, concealers, powders, liquid foundations, oily foundations, blushers, eye shadows, mascara, eyeliners, eyebrow pencils, lipsticks and other makeup cosmetics; shampoo, conditioner, conditioning agent, fixative and other hair cosmetics; antiperspirants, sunscreen oils, sunscreen lotions, sunscreen creams and other ultraviolet protection cosmetics, etc.

[0085] As the form of these cosmetics, various forms can be selected, such as liquid, emulsion, cream, solid, paste, gel, powder, pressurized, multi-layered, mousse, spray, and stick.

[0086] The cosmetics may be in various forms such as aqueous, oily, water-in-oil emulsions, oil-in-water emulsions, nonaqueous emulsions, or complex emulsions such as W / O / W or O / W / O. [Example]

[0087] Hereinafter, the present invention will be specifically described by showing manufacturing examples, examples of the cosmetics of the present invention, and comparative examples, but the present invention is not limited to the following examples. It should be noted that, unless otherwise specified, the "%" described below means "mass %", and the mass % of each component is expressed by taking the total mass of each example as 100%. The viscosity is a value at 25°C.

[0088] The polyoxyalkylene-modified organopolysiloxane used in the production examples can be synthesized by a known method, such as the method described in International Publication No. 2002 / 055588 or Japanese Patent Application Laid-Open No. 2001-55307.

[0089] (Manufacturing Example 1) 100 g of polyoxyalkylene-modified organopolysiloxane having a hydroxyl group at the terminal of the following structural formula (1'-1), 50 g of toluene and 5 g of triethylamine were placed in a reactor and heated to 80°C while stirring. Here, 14 g of isocyanate having a hydrolyzable silyl group of the following structural formula (6-1) was dripped in while being kept below 90°C, and the mixture was aged at 100°C for 5 hours. The solvent was removed by vacuum stripping the reaction solution at 110°C. 1 The H-NMR spectrum confirmed that the chemical shift of the N-(CH2)3-Si portion of the isocyanate having a hydrolyzable silyl group changed to 0.64→0.62, 1.70→1.58, and 3.26→3.14 respectively through this reaction, thereby obtaining a colorless, transparent liquid organopolysiloxane of the following structural formula (1-1). The moisture content of the organopolysiloxane was measured by a Karl Fischer moisture meter, and the moisture content was 800 ppm. In addition, the organopolysiloxane did not gel even after being stored at 25°C for 30 days, and had high stability. [Chemical formula 12]

[0090] (Manufacturing Example 2) 200 g of polyoxyalkylene-modified organopolysiloxane having a hydroxyl group at the end of the following structural formula (1'-2), 50 g of toluene and 5 g of triethylamine were placed in a reactor and stirred to 80°C. Here, 21 g of isocyanate having a hydrolyzable silyl group of the following structural formula (6-1) was dripped in while being kept below 90°C, and the mixture was aged at 100°C for 5 hours. The reaction solution was subjected to reduced pressure stripping at 110°C to remove the solvent, etc., thereby obtaining a colorless, transparent liquid organopolysiloxane of the following structural formula (1-2). The moisture content of the organopolysiloxane was measured by a Karl Fischer moisture meter, and the moisture content was 1200 ppm. In addition, the organopolysiloxane did not gel after being stored at 25°C for 30 days, and had high stability. [Chemical formula 13]

[0091] (Manufacturing Example 3) 300 g of polyoxyalkylene-modified organopolysiloxane having a hydroxyl group at the end of the following structural formula (1'-3), 100 g of toluene and 10 g of triethylamine were placed in a reactor and stirred to 80°C. Here, 85 g of isocyanate having a hydrolyzable silyl group of the following structural formula (6-1) was dripped in while being kept below 90°C, and it was aged at 100°C for 5 hours. The reaction solution was subjected to reduced pressure stripping at 110°C to remove the solvent, etc., thereby obtaining a colorless, transparent liquid organopolysiloxane of the following structural formula (1-3). The moisture content of the organopolysiloxane was measured by a Karl Fischer moisture meter, and the moisture content was 400 ppm. In addition, the organopolysiloxane did not gel after being stored at 25°C for 30 days, and had high stability. [Chemical formula 14]

[0092] (Manufacturing Example 4) 100 g of a polyoxyalkylene-modified organopolysiloxane having a hydroxyl group at the end of the following structural formula (1'-4) and 50 g of toluene were placed in a reactor and stirred to reach 80°C. Here, 24 g of an isocyanate having a hydrolyzable silyl group of the following structural formula (6-4) was dripped in while being kept below 90°C, and the mixture was aged at 100°C for 5 hours. The reaction solution was subjected to reduced pressure stripping at 110°C to remove the solvent, etc., thereby obtaining a colorless, transparent liquid organopolysiloxane of the following structural formula (1-4). The moisture content of the organopolysiloxane was measured by a Karl Fischer moisture meter, and the moisture content was 1800 ppm. In addition, the organopolysiloxane did not gel after being stored at 25°C for 30 days, and had high stability. [Chemical formula 15]

[0093] (Manufacturing Example 5) 100 g of a polyoxyalkylene-modified organopolysiloxane having a hydroxyl group at the end of the following structural formula (1'-5) and 50 g of toluene were placed in a reactor and stirred to reach 80°C. Here, 6 g of an isocyanate having a hydrolyzable silyl group of the following structural formula (6-4) was dripped in while being kept below 90°C, and the mixture was aged at 100°C for 5 hours. The reaction solution was subjected to reduced pressure stripping at 110°C to remove the solvent, etc., thereby obtaining a colorless, transparent liquid organopolysiloxane of the following structural formula (1-5). The moisture content of the organopolysiloxane was measured by a Karl Fischer moisture meter, and the moisture content was 1000 ppm. In addition, the organopolysiloxane did not gel after being stored at 25°C for 30 days, and had high stability. [Chemical formula 16]

[0094] (Manufacturing Example 6) 100g of polyoxyalkylene-modified organopolysiloxane having a hydroxyl group at the end of the following structural formula (1'-6) and 50g of toluene were charged into a reactor and stirred to reach 80°C. Here, 5g of isocyanate having a hydrolyzable silyl group of the following structural formula (6-4) was dripped in while being kept below 90°C, and it was aged at 100°C for 5 hours. The reaction solution was subjected to reduced pressure stripping at 110°C to remove the solvent, etc., thereby obtaining a colorless, transparent liquid organopolysiloxane of the following structural formula (1-6). The moisture content of the organopolysiloxane was measured by a Karl Fischer moisture meter, and the moisture content was 1000ppm. In addition, the organopolysiloxane did not gel after being stored at 25°C for 30 days, and had high stability. [Chemical formula 17]

[0095] (Comparative Manufacturing Example 1) 100 g of methyl hydrogen organopolysiloxane of the following structural formula (1"-1), 50 g of 2-propanol, 0.03 g of 3.0% ethanol solution of chloroplatinic acid, 37 g of allyl polyether of the following structural formula (1"-2) and 13 g of vinyltriethoxysilane were charged into a reactor and aged at 85°C for 5 hours while stirring. The reaction liquid was subjected to reduced pressure stripping at 110°C to remove the solvent, etc., thereby obtaining a light yellow liquid organopolysiloxane of the following structural formula (1"-3). The moisture content of the organopolysiloxane was measured by a Karl Fischer titrator, and the moisture content was 1500 ppm. In addition, the organopolysiloxane was confirmed to increase in viscosity after being stored at 25°C for 30 days. [Chemical formula 18]

[0096] (Comparative Manufacturing Example 2) 100 g of methyl hydrogen organopolysiloxane of the following structural formula (1"-4), 50 g of 2-propanol, 0.03 g of 3.0% ethanol solution of chloroplatinic acid and 355 g of allyl polyether of the following structural formula (1"-5) were charged into a reactor and aged at 85°C for 5 hours while stirring. The reaction solution was subjected to reduced pressure stripping at 110°C to remove the solvent, thereby obtaining an organopolysiloxane of the following structural formula (1"-6). The moisture content of the organopolysiloxane was measured by a Karl Fischer moisture meter, and the moisture content was 400 ppm. In addition, the organopolysiloxane was confirmed to gel after being stored at 25°C for 1 day, and had poor stability. [Chemical formula 19]

[0097] (Manufacturing Examples 1 to 7), (Comparative Manufacturing Examples to 2) Production Example 1 100 g of titanium oxide CR-50 (manufactured by Ishihara Sangyo Co., Ltd., Japan) was added to a stirrer, and 5 g of the organic polysiloxane obtained in Production Example 1 dissolved in 10 g of hexane was slowly added to the stirrer while stirring, and stirred at 25°C for 1 hour. Thereafter, the mixture was dried by heating at 100°C for 3 hours to obtain a white powder. 1 H-NMR confirmed that there was no unreacted ethoxy group.

[0098] Production Example 2 200 g of zinc oxide MZ-500 (manufactured by Tayca Co., Ltd., Japan) was added to a stirrer, and 6 g of the organic polysiloxane obtained in Production Example 2 dissolved in 10 g of hexane was slowly added to the stirrer while stirring, and stirred at 25°C for 1 hour. Thereafter, the mixture was dried by heating at 110°C for 3 hours to obtain a white powder. 1 H-NMR confirmed that there was no unreacted ethoxy group.

[0099] Production Example 3 500 g of black iron oxide BL-100P (manufactured by Titan Kogyo, Ltd.) was added to a stirrer, and a solution of 15 g of the organopolysiloxane obtained in Production Example 3 dissolved in 15 g of ethanol was slowly added to the stirrer while stirring, and stirred at 25° C. for 3 hours. Thereafter, the mixture was dried by heating at 90° C. for 3 hours, thereby obtaining a black powder. 1 H-NMR confirmed that there was no unreacted ethoxy group.

[0100] Production Example 4 50 g of cellulose nanofibers were added to a stirrer, and a solution of 6 g of the organopolysiloxane obtained in Manufacturing Example 4 dissolved in 10 g of methanol was slowly added to the stirrer while stirring, and stirred at 25°C for 3 hours. Thereafter, the mixture was dried by heating at 100°C for 5 hours, thereby obtaining a white powder. 1 H-NMR confirmed that there was no unreacted methoxy group.

[0101] Production Example 5 100 g of spherical silica was added to a stirrer, and a solution of 4 g of the organopolysiloxane obtained in Production Example 1 dissolved in 10 g of hexane was slowly added to the stirrer while stirring, and stirred at 25° C. for 3 hours. Thereafter, the mixture was dried by heating at 100° C. for 5 hours, thereby obtaining a white powder. 1 H-NMR confirmed that there was no unreacted ethoxy group.

[0102] Production Example 6 100 g of spherical silica was added to a stirrer, and a solution of 2 g of the organopolysiloxane obtained in Production Example 5 dissolved in 10 g of hexane was slowly added to the stirrer while stirring, and stirred at 25°C for 3 hours. Thereafter, the mixture was dried by heating at 100°C for 5 hours, thereby obtaining a white powder. 1 H-NMR confirmed that there was no unreacted methoxy group.

[0103] Production Example 7 100 g of talc was added to a stirrer, and a solution of 2 g of the organopolysiloxane obtained in Production Example 6 dissolved in 10 g of hexane was slowly added to the stirrer while stirring, and stirred at 25° C. for 3 hours. Thereafter, the mixture was dried by heating at 100° C. for 5 hours, thereby obtaining a white powder. 1 H-NMR confirmed that there was no unreacted methoxy group.

[0104] Comparative Manufacturing Example 1 100 g of titanium oxide CR-50 (manufactured by Ishihara Sangyo Co., Ltd., Japan) was added to a stirrer, and 5 g of the organic polysiloxane obtained in Comparative Manufacturing Example 1 dissolved in 10 g of hexane was slowly added to the stirrer while stirring, and stirred at 25°C for 1 hour. Thereafter, the mixture was dried by heating at 100°C for 3 hours, thereby obtaining a white powder. 1 H-NMR confirmed that unreacted ethoxy groups remained.

[0105] Comparative Manufacturing Example 2 50 g of cellulose nanofibers were added to a stirrer, and 6 g of the organic polysiloxane obtained in Comparative Manufacturing Example 2 dissolved in 10 g of methanol was slowly added to the stirrer while stirring, and stirred at 25° C. for 3 hours. Thereafter, the mixture was dried by heating at 100° C. for 5 hours, thereby obtaining a white powder. 1 H-NMR confirmed that unreacted hydrosilyl groups remained.

[0106] (Examples 1 to 4 and Comparative Examples 1 to 5) Emulsified creams having the formulations shown in the following table were prepared by a conventional method, and their stability over time and usability were evaluated. [Evaluation method of stability over time] Regarding the temporal stability, the emulsified cream obtained with the formulation shown in the following table was left to stand for 1 month at 25° C., and the presence or absence of emulsion separation was visually confirmed. The presence of emulsion separation was evaluated as ×, and the absence of emulsion separation was evaluated as ◎. [Sensory evaluation method] As an evaluation of usability, about 5 g of the emulsified cream obtained by the combination shown in Table 1 below was applied to the skin of 5 expert panelists, and the spreadability and non-stickiness during application were evaluated by sensory evaluation. It should be noted that the so-called spreadability during application refers to the length or area that is physically extended. In addition, regarding the stickiness, the presence or absence of adhesion was evaluated. According to the number of expert panelists who answered "effective", the following evaluation criteria were used.

[0107] [Evaluation criteria] ◎: 4-5 people answered that it is effective ○: 3 people answered that it is effective △: 2 people answered that it is effective ×: 1 or 0 people answered that it is effective

[0108] [Table 1] The blending of the components in Table 1 was adjusted so that the total was 100. KF-6017: Made by Shin-Etsu Chemical Co., Ltd., polyoxyethylene-methyl polysiloxane copolymer CR-50: Made by Ishihara Industries, Japan, titanium oxide Dimethylpolysiloxane: Kinematic viscosity at 25°C is 6 mm 2 / s

[0109] As shown in Table 1, it was confirmed that the emulsified creams of Examples 1 to 4 of the present invention were emulsified creams in which the treated powder obtained in the manufacturing example acted as an emulsifier to form a stable water-in-oil type Pickering emulsion, and they had excellent stability over time, good spreadability when applied, and were not sticky.

[0110] On the other hand, Comparative Examples 1 to 5 had poor stability over time and poor feeling during application. From the above, it can be seen that the cosmetic using the treated powder of the present invention has excellent stability over time and excellent feeling during use.

[0111] [Example 5] O / W Sunscreen <Preparation of cosmetics> A: Components (9) to (16) were uniformly mixed at 85°C. B: Components (1) to (6) were uniformly mixed at 85°C. C: The mixture obtained in the above step B, component (7) and component (8) were added to the mixture obtained in the above step A at 80°C and emulsified, and then slowly cooled to obtain an O / W sunscreen. (Note 1) Made by Shin-Etsu Chemical Co., Ltd.; SPD-Z5 (Note 2) Made by Shin-Etsu Chemical Co., Ltd.; SPD-T5 It was confirmed that the obtained O / W sunscreen had high stability over time, was non-sticky, and had an excellent feeling during use.

[0112] [Example 6] Powder foundation <Preparation of cosmetics> A: Components 1 to 3 were uniformly mixed. B: Components 4 to 12 were uniformly mixed. C: The mixture obtained in the above step A was added to the mixture obtained in the above step B and uniformly mixed using a Henschel mixer. The obtained powder was passed through a 100-mesh sieve and then pressed into a metal tray using a die to obtain a powder foundation. (Note 1) Made by Shin-Etsu Chemical Co., Ltd.; KF-56A (Note 2) Made by Shin-Etsu Chemical Co., Ltd.; KSG-15 (Note 3) Made by Shin-Etsu Chemical Co., Ltd.; KF-9909 treated (Note 4) Made by Shin-Etsu Chemical Co., Ltd.; KTP-09-Series The obtained powder foundation had good spreadability and excellent feeling during use.

[0113] [Example 7] Lotion <Preparation of cosmetics> Components (1) to (9) were uniformly mixed. The obtained emulsion has high stability over time, is smooth to spread and extend, and has an excellent feel when used.

[0114] [Example 8] Mascara <Preparation of cosmetics> A: Ingredients 1 to 7 were mixed under heating. B: Components 8 to 11 were processed using a three-roll mill. C: Components 12 to 14 were added to the mixture obtained in the above step B and heated. D: The mixture obtained in the above step C was added to the mixture obtained in the above step A and emulsified, and then cooled to obtain a mascara. The obtained mascara has high temporal stability, good spreadability, and excellent smearability.

Claims

1. An organopolysiloxane represented by the following average structural formula (1), [Chemical formula 1] In formula (1), R is independently selected from a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 30 carbon atoms, a fluoroalkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms. 10 Independently, a group represented by the following average structural formula (2) is [Chemical formula 2] In formula (2), X is a divalent hydrocarbon group having 1 to 10 carbon atoms, s is a number from 1 to 100, t is a number from 0 to 50, the bonding sequence of the oxyalkylene units enclosed by s and t is block or random, v is a number from 1 to 10, and R 12 is independently a group selected from an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 12 carbon atoms, R 13 are independently hydrogen atoms or monovalent hydrocarbon groups having 1 to 6 carbon atoms, w is a number from 0 to 2, R 11 Selected from R 10 or a group in R, A is independently an organopolysiloxane segment represented by the following average structural formula (3) or formula (4), [Chemical formula 3] [Chemical formula 4] In formula (3), R and R 10 is the same as the above, c is a number from 0 to 3, i is a number from 0 to 10, j is a number from 0 to 100, Q is an oxygen atom or a divalent hydrocarbon group having 1 to 3 carbon atoms, in formula (4), X is the same as the above, the bonding sequence of the siloxane units enclosed by i and j is block or random, In the formula (1), a and b are independently a number of 0 to 3, e is a number of 0 to 50, f is a number of 0 to 2000, g is a number of 0 to 10, h is 0 or 1, the bonding sequence of the siloxane units enclosed by e, f, g and h is block or random, and there is one or more R in the formula (1) 10 .

2. A powder treatment agent comprising the organopolysiloxane according to claim 1, wherein: The moisture content is below 2000ppm.

3. A powder surface-treated with the powder treating agent according to claim 2.

4. A method for treating a powder, wherein: The powder described in claim 3 is an inorganic powder or an organic powder.

5. A cosmetic comprising the treated powder according to claim 4.

6. The cosmetic according to claim 5, wherein It further comprises water and an oil.

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