WO2023106180A1 - オイルゲル化剤及び化粧料 - Google Patents
オイルゲル化剤及び化粧料 Download PDFInfo
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- WO2023106180A1 WO2023106180A1 PCT/JP2022/044196 JP2022044196W WO2023106180A1 WO 2023106180 A1 WO2023106180 A1 WO 2023106180A1 JP 2022044196 W JP2022044196 W JP 2022044196W WO 2023106180 A1 WO2023106180 A1 WO 2023106180A1
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- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/59—Mixtures
- A61K2800/594—Mixtures of polymers
Definitions
- the present invention relates to an oil gelling agent and a cosmetic containing the oil gelling agent.
- Oil gelling agents that can gel hydrophobic oils and silicone oils are widely used as materials that make up cosmetics, etc., due to their ability to solidify oils.
- Hydrocarbon polymers such as polyethylene wax, long-chain fatty acids, and long-chain alcohols are well known as such gelling agents.
- an oil gelling agent that has a characteristic structure and is often used in cosmetics as an oil gelling agent there is known one in which a part of the hydroxyl group is acylated based on a sugar skeleton (Patent Document 1).
- Patent Document 2 A gelling agent based on an acrylic polymer that can adjust hydrophobicity and hydrogen bonding properties by adjusting the ratio of constituent monomers is known (Patent Document 2). However, there is room for improvement with respect to the variety of oils that can be gelled.
- the present invention has been made in view of the above circumstances, and an object of the present invention is to provide an oil gelling agent capable of gelling various oil agents such as hydrocarbon oils and higher alcohols.
- an amphipathic (meth)acrylic monomer is used as a main structural unit, and a hydrophilic (meth)acrylic monomer is used to gel a polar oil agent.
- a gelling agent capable of gelling various oils such as hydrocarbon oils and higher alcohols can be obtained, and the present invention has been completed.
- the present invention provides the following oil gelling agents and cosmetics.
- an amphiphilic (meth)acrylic monomer represented by the following general formula (1) (In the formula, R 1 is a hydrogen atom or a methyl group, and R 2 is a linear or branched C 1-21 alkyl group.)
- a hydrophilic (meth)acrylic monomer represented by the following general formula (2) (In the formula, R 1 is a hydrogen atom or a methyl group, and R 3 is a linear or branched alkylene group having 2 to 10 carbon atoms.) as a structural unit, wherein the mass ratio (b) / (a) of (a) and (b) is 0 ⁇ [(b) / (a)] ⁇ 0 .2 oil gelling agent.
- oils such as hydrocarbon oils and higher alcohols can be gelled.
- the oil gelling agent of the present invention is obtained by copolymerizing a specific (a) amphiphilic (meth)acrylic monomer and (b) a specific hydrophilic (meth)acrylic monomer, and the monomer is used as a structural unit. It is a copolymer containing Hereinafter, those used in a plurality of formulas such as R 1 are independent.
- amphiphilic (meth)acrylic monomer (a) The amphipathic (meth)acrylic monomer is a (meth)acrylic monomer represented by the following general formula (1), and can be used singly or in combination of two or more.
- R 1 is a hydrogen atom or a methyl group
- R 2 is a linear or branched C 1-21 alkyl group.
- R 1 is a hydrogen atom or a methyl group
- R 2 is a linear or branched C 1-21 alkyl group. From the viewpoint of hydrophobic interaction, R 2 is preferably an alkyl group having 11 to 21 carbon atoms, more preferably an alkyl group having 15 to 21 carbon atoms.
- the amphipathic (meth)acrylic monomer can be obtained by reacting glycidyl methacrylate or glycidyl acrylate with a fatty acid. From the viewpoint of reaction rate, it is preferable to carry out the reaction using a catalyst. Catalysts used include quaternary alkylammonium salts such as tetrabutylammonium bromide. In addition, from the viewpoint of uniformly mixing the reaction substrate and the catalyst, it is preferable to carry out the reaction in a solvent. Examples include hydrocarbon solvents. Furthermore, from the viewpoint of increasing the purity of the product, it is preferable to wash with water after the reaction.
- amphiphilic (meth)acrylic monomer represented by the formula (1) is represented by the following formula (1') (In the formula, R 1 and R 2 are the same as above.) It may contain an amphiphilic (meth)acrylic monomer represented by.
- the content of (1′) is preferably 1 mol or less, more preferably 0.5 to 0 mol, with respect to 1 mol of the amphiphilic (meth)acrylic monomer of (1), and is substantially free. is more preferred. Note that "substantially free of” means that even if it is contained, it is below the detection limit.
- hydrophilic (meth)acrylic monomer is a hydrophilic (meth)acrylic monomer represented by the following general formula (2).
- R 1 is a hydrogen atom or a methyl group
- R 3 is a linear or branched alkylene group having 2 to 10 carbon atoms.
- R 1 is a hydrogen atom or a methyl group
- R 3 is a linear or branched alkylene group having 2 to 10 carbon atoms. From the viewpoint of hydrophilicity, R 3 preferably has 2 to 5 carbon atoms, more preferably 2 to 3 carbon atoms.
- the mass ratio (b)/(a) of (a) and (b) is 0 ⁇ [(b)/(a)] ⁇ 0.2, and 0.03 ⁇ [(b)/(a)] ⁇ 0.2 is preferred, 0.05 ⁇ [(b)/(a)] ⁇ 0.20 is more preferred, 0.07 ⁇ [(b)/(a)] ⁇ 0.20 is more preferred, and 0 .14 ⁇ [(b)/(a)] ⁇ 0.20 is particularly preferred.
- the ratio of hydrophobicity and hydrogen bonding is good, and various oils can be gelled.
- the copolymer of the present invention can have a monomer comprising a silicone macromer as a structural unit. By grafting silicone chains, the compatibility with silicone oil is improved, and gelation of silicone oil becomes more possible.
- Silicone macromers include (meth)acrylic-modified silicone macromers represented by the following general formula (3). (In the formula, R 1 is a hydrogen atom or a methyl group, R 4 is a divalent organic group, R 5 is independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and an aryl group having 6 to 22 carbon atoms. is a group selected from and n is 1 to 100.)
- R 1 is a hydrogen atom or a methyl group
- R 4 is a divalent organic group, preferably an alkylene group having 2 to 6 carbon atoms, more preferably an alkylene group having 2 to 4 carbon atoms
- R 5 is independently a group selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and an aryl group having 6 to 22 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group.
- n is 1 to 100, preferably 10 to 90, more preferably 15 to 80, and even more preferably 20 to 70.
- Examples of compounds represented by general formula (3) include, but are not limited to, the following. (In the formula, n-Bu represents a normal-butyl group.)
- the amount of the (c) monomer in the total monomer is 35 to 50% by mass, preferably 35 to 45% by mass. If it is the above-mentioned ratio, the function as a gelling agent can be maintained more, while the compatibility to the silicone oil of a copolymer is improved more.
- the copolymer of the present invention may be composed only of the above (a), (b) or (a) to (c), and the copolymer of the present invention may contain monomers other than the above. It can be included as long as it does not impair the effects of the invention.
- a monomer other than the above is included as a structural unit, the amount thereof is preferably 0.05 to 5% by mass based on all the monomers.
- the total amount of the (a) monomer, (b) monomer and (c) monomer is preferably 95 to 99.95% by mass of all monomers, more preferably 97 to 99.93% by mass.
- 98.5 to 99.9% by mass is more preferable, and the upper limit may be 100.0% by mass.
- "among the monomers” means “among all the monomers constituting the copolymer”.
- Polymerization of the copolymer of the present invention is preferably carried out in the presence of a radical polymerization initiator such as benzoyl peroxide, lauroyl peroxide and azobisisobutyronitrile.
- a radical polymerization initiator such as benzoyl peroxide, lauroyl peroxide and azobisisobutyronitrile.
- Any of solution polymerization, emulsion polymerization, suspension polymerization, and bulk polymerization can be applied as the polymerization method.
- the solution polymerization method is preferable because it is easy to adjust the molecular weight of the resulting polymer to a desired range.
- the polymerization reaction may be carried out in a solvent.
- Solvents used at this time include aliphatic hydrocarbon organic solvents such as pentane, hexane, decane, dodecane, hexadecane and octadecane, and aromatic solvents such as benzene, toluene and xylene. Hydrocarbon organic solvents, alcohol organic solvents such as methanol, ethanol, isopropyl alcohol, propanol, butanol, hexanol and decanol, halogenated hydrocarbon organic solvents such as chloroform and carbon tetrachloride, ketone organic solvents such as acetone and methyl ethyl ketone. Solvents may be mentioned. However, from the viewpoint of use in cosmetics, it is preferable to carry out the polymerization reaction without a solvent or to use ethanol or isopropanol.
- the copolymer may be random, block or graft copolymer.
- Polystyrene equivalent number average molecular weight (Mn) in GPC of the polymer thus produced is preferably 5,000 to 200,000, more preferably 7,500 to 10,000, 10,000 to 50, 000 is more preferred.
- Mn Polystyrene equivalent number average molecular weight
- the number average molecular weight is a value obtained by GPC (gel permeation chromatography) analysis using polystyrene as a standard substance under the following conditions.
- the present invention uses the above copolymer as an oil gelling agent.
- the oil to be gelled is not particularly limited, and includes those described in (B) the oil component described later, preferably a liquid oil component.
- hydrocarbon oils, higher alcohols, and silicone oils are preferred.
- hydrocarbon oils and higher alcohols can be gelled, and more preferably, hydrocarbon oils, higher alcohols and silicone oils can be gelled.
- the (A) oil gelling agent of the present invention can be used in various cosmetics, and is particularly suitable for lip cosmetics. Since it forms a gel with high temperature stability, it becomes a stable composition and improves the feeling of use.
- the amount of the oil gelling agent contained in the cosmetic of the present invention varies depending on the dosage form of the cosmetic, but it can be used in the range of 0.5 to 99.0% by mass with respect to the entire cosmetic, and 1.0 ⁇ 50% by mass is preferred.
- an appropriate amount of ingredients that can be usually blended in cosmetics can be blended.
- Such components include (B) oil component, (C) ultraviolet absorbing component, (D) water, (E) surfactant, (F) powder, and (G) having an alcoholic hydroxyl group in its molecular structure.
- (J) a crosslinked organopolysiloxane having a hydrophilic group are examples of the silicone oils.
- a composition comprising a polysiloxane polymer and a liquid oil agent, (K) a silicone resin, and/or (L) a silicone wax may be included.
- a silicone resin e.g., a silicone resin
- a silicone wax e.g., a silicone wax
- INCI International Nomenclature of Cosmetic Ingredients
- the cosmetic of the present invention can contain one or more oil components.
- oil component any of solid, semi-solid and liquid oils used in ordinary cosmetics can be used.
- liquid oils examples include one or more of silicone oils, hydrocarbon oils, higher fatty acids, polar oils such as ester oils and natural animal and vegetable oils, semi-synthetic oils, and/or fluorine-based oils. Hydrocarbon oil and silicone oil are preferred. As described above, even if the oil agent component (B) is a silicone oil, the oil gelling agent contained in the cosmetic composition of the present invention is compatible with any of them, so that the feeling of use is good and the usability and stability are improved. It is possible to provide excellent cosmetics.
- Silicone oils include low to high viscosity straight oils such as dimethicone (INCI), caprylyl methicone (INCI), phenyl trimethicone (INCI), hexyl dimethicone (INCI), hydrogen dimethicone (INCI), and diphenyl dimethicone (INCI).
- cyclic organopolysiloxanes such as cyclotetrasiloxane (INCI), cyclopentasiloxane (INCI), cyclohexasiloxane (INCI), tetrahydrotetramethylcyclotetrasiloxane, and tetramethyltetraphenylcyclotetrasiloxane , trimethylsiloxymethylsilane, tetrakistrimethylsiloxymethylsilane, branched organopolysiloxane, amino-modified organopolysiloxane, highly polymerized gum-like dimethylpolysiloxane, gum-like amino-modified organopolysiloxane, gum-like dimethylsiloxane/methyl Silicone rubbers such as phenylsiloxane copolymers, cyclic siloxane solutions of silicone gums and rubbers, trimethylsiloxy
- hydrocarbon oils examples include linear, branched, and volatile hydrocarbon oils.
- hydrocarbon oils include linear, branched, and volatile hydrocarbon oils.
- Higher fatty acids include lauric acid (INCI: Lauric Acid), myristic acid (INCI: Myristic Acid), palmitic acid (INCI: Palmitic Acid), stearic acid (INCI: Stearic Acid), behenic acid (INCI: Behenic Acid), Undecylenic Acid (INCI: Undecylenic Acid), Oleic Acid (INCI: Oleic Acid), Linoleic Acid (INCI: Linoleic Acid), Linolenic Acid (INCI: Linolenic Acid), Arachidonic Acid (INCI: Arachidonic Acid), Eicosapentaenoic Acid (EPA ) (INCI: Eicosapentaenoic Acid), docosahexaenoic acid (DHA) (INCI: Docosahexaenoic Acid), isostearic acid (INCI: Isostearic Acid), hydroxystearic acid (INCI: Hydroxystearic Acid), and the like.
- lauric acid
- Higher alcohols include lauryl alcohol (INCI), myristyl alcohol (INCI), cetanol (INCI), stearyl alcohol (INCI), behenyl alcohol (INCI), oleyl alcohol (INCI), isostearyl alcohol (INCI), octyldodecanol ( INCI), cetearyl alcohol (INCI), decyltetradecanol (INCI), cholesterol (INCI), phytosterols (INCI), batyl alcohol (INCI), oleyl glyceryl (INCI: Oleyl Glyceryl Ether), and the like.
- Ester oils include diisobutyl adipate (INCI), diethylhexyl adipate (INCI), diheptylundecyl adipate (INCI), n-alkylene monoisostearate (20-30) Glycol, isocetyl isostearate (INCI), trimethylolpropane triisostearate (INCI), ethylene glycol di-2-ethylhexanoate, cetyl 2-ethylhexanoate (INCI), triethylhexane Acid trimethylolpropane (INCI: Trimethylolpropane Triethylhexanoate), tetraethylhexanoate (INCI: Pentaerythrityl Tetraethylhexanoate), cetyl octanoate (INCI: Cetyl Ethylhexanoate), octyldodecyl myristate ( INC
- Glyceride oils include glyceryl acetate (INCI), triethylhexanoin (INCI), glyceryl triisostearate (INCI), triisopalmitin (INCI), glyceryl stearate (INCI), diisostearate
- Examples include glyceryl acid (INCI: Glyceryl Diisosterate), trimyristin (INCI), and (isostearic/myristic) glyceryl (INCI: Isostearic/Myristic Glycerides).
- Natural animal and vegetable oils and semi-synthetic oils include avocado oil (INCI: Persea Gratissima (Avocado) Oil), linseed oil (INCI: Linum Usitatissimum (Linseed) Seed Oil), almond oil (INCI: Prunus Amygdalus Dulcis (Sweet Almond) Oil ), primrose, perilla oil, olive oil, ) pock wax, kaya oil, carnauba wax (INCI: Copernicia Cerifera (Carnauba) wax), shark liver oil (INCI: cod liver oil), candelilla wax (INCI: Euphorbia Cerifera (Candelilla) Wax), beef tallow, beef leg tallow, beef bone fat, hydrogenated beef tallow, mustard oil, whale wax, hydrogenated palm oil (INCI: Hydrogenated Palm Oil), wheat germ oil (INCI: Triticum Vulgare) (Wheat) Germ Oil), sesame oil (INCI: Sesamum Indi
- fluorine-based oils examples include perfluoropolyether, perfluorodecalin (INCI), and perfluorooctane.
- the amount of the oil component (B) contained in the cosmetic of the present invention varies depending on the formulation system of the cosmetic, but is preferably 1 to 98% by mass based on the entire cosmetic. , 1 to 50% by mass is more preferable.
- UV absorbing component may further contain one or more ultraviolet absorbing components.
- UV absorbing components include UV absorbers and UV scattering agents.
- ultraviolet absorbers include benzoic acid-based ultraviolet absorbers such as PABA (INCI), anthranilic acid-based ultraviolet absorbers such as methyl anthranilate (INCI), and salicylic acid-based ultraviolet absorbers such as methyl salicylate (INCI).
- Absorbers such as octyl methoxycinnamate (INCI: Ethylhexyl Methoxycinnamate), benzophenone-based UV absorbers such as oxybenzone-1 (INCI: Benzophenone-1), urocanic acid-based UV absorbers such as ethyl urocanate
- cinnamic acid-based UV absorbers such as octyl methoxycinnamate (INCI: Ethylhexyl Methoxycinnamate)
- benzophenone-based UV absorbers such as oxybenzone-1 (INCI: Benzophenone-1)
- urocanic acid-based UV absorbers such as ethyl urocanate
- dibenzoylmethane-based ultraviolet absorbers such as t-butyl methoxydibenzoylmethane (INCI: ButylMethoxydibenzoylmethane), and the like are exempl
- ultraviolet absorbing and scattering agents examples include powders that absorb and scatter ultraviolet rays, such as fine particle titanium oxide, fine particle iron-containing titanium oxide, fine particle zinc oxide, fine particle cerium oxide, and composites thereof.
- powders that absorb and scatter ultraviolet rays such as fine particle titanium oxide, fine particle iron-containing titanium oxide, fine particle zinc oxide, fine particle cerium oxide, and composites thereof.
- cinnamic acid-based UV absorbers, dibenzoylmethane-based UV absorbers, titanium oxide, and zinc oxide are preferred.
- the cosmetic of the present invention may contain water according to its purpose. As a result, the cosmetic of the present invention can be made more excellent in usability by blending water according to the purpose of use.
- its blending amount is preferably in the range of 95% by mass or less with respect to the entire cosmetic.
- the cosmetic of the present invention may further contain one or more surfactants.
- Surfactants include anionic, cationic, nonionic and amphoteric surfactants, but the surfactants contained in the cosmetic of the present invention are not particularly limited, and are commonly used in cosmetics. Any used can be used.
- anionic surfactants include fatty acid soaps such as sodium stearate (INCI: sodium stearate) and TEA palmitate (INCI: TEA-palmitate), alkyl ether carboxylic acids and their salts, condensate salts of amino acids and fatty acids, alkanes Sulfonates, alkene sulfonates, fatty acid ester sulfonates, fatty acid amide sulfonates, formalin condensation sulfonates, alkyl sulfates, secondary higher alcohol sulfates, alkyl and allyl ether sulfates salts, sulfate ester salts of fatty acid esters, sulfate ester salts of fatty acid alkylolamides, sulfate ester salts such as sulfated castor oil (INCI: Sulfated Castor Oil), alkyl phosphates, ether phosphates, alkyl allyl
- Nonionic surfactants 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, methylglucoside fatty acid esters, alkyl polyglucosides, polyoxyethylene alkyl Ether, polyoxypropylene alkyl ether, polyoxyethylene alkylphenyl 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 hydrogenated castor oil, polyoxyethylene phytostanol ether, polyoxyethylene phytosterol ether, polyoxyethylene cholestanol ether, polyoxyethylene cholesterol ether, linear or branched polyoxyalkylene-modified organopol
- Amphoteric surfactants include betaine, aminocarboxylates, imidazoline derivatives, amidoamine types, and the like.
- linear or branched organopolysiloxanes having a polyoxyethylene chain in the molecule linear or branched organopolysiloxanes having a polyglycerin chain in the molecule, or alkyl copolymers of each Surfactants that are modified organopolysiloxanes are preferred.
- the blending amount is preferably 0.1 to 20% by mass, more preferably 0.2 to 10% by mass, based on the total cosmetic composition.
- the cosmetic of the present invention may further contain one or more powders.
- the powder if it is used in ordinary cosmetics, its shape (spherical, needle-like, plate-like, etc.), particle size (fumed, fine particles, pigment grade, etc.), particle structure (porous, non-porous, etc.) Porosity, etc.) can be used, for example, inorganic powders, organic powders, surfactant metal salt powders, colored pigments, pearl pigments, tar pigments, metal powder pigments, and natural pigments. and coloring agents such as dyes.
- inorganic powder examples include titanium oxide (INCI: Titanium Dioxide), zirconium oxide (INCI: Zirconium Dioxide), zinc oxide (INCI: Zinc Oxide), cerium oxide (INCI: Cerium Oxide), magnesium oxide, barium sulfate, Calcium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, talc (INCI), mica (INCI), kaolin (INCI), sericite, synthetic mica, phlogopite, red mica, biotite, lethia mica, silica (INCI), Al Silicate (INCI: Aluminum Silicate), Mg Silicate (INCI: Magnesium Silicate), Silicate (Al/Mg) (INCI: Magnesium Aluminum Silicate), Ca Silicate (INCI: Calcium Silicate), Barium Silicate, Silicon Strontium acid, metal tungstate, hydroxyapatite (INCI), vermiculite, hydilite, bentonite (INCI), montmorillonite
- Organic powders include polyamide powder, polyacrylic acid/acrylic acid ester powder, polyester powder, polyethylene powder, polypropylene powder, polystyrene powder, polyurethane, benzoguanamine powder, polymethylbenzoguanamine powder, tetrafluoroethylene powder, polymethyl methacrylate powder, Cellulose (INCI), silk powder, nylon powder, nylon-12 (INCI), nylon-6 (INCI), crosslinked spherical dimethylpolysiloxane fine powder having a structure of crosslinked dimethylpolysiloxane, crosslinked spherical polymethylsilsesquioxane Oxane fine powder, crosslinked spherical organopolysiloxane rubber surface coated with polymethylsilsesquioxane particles, hydrophobized silica, styrene-acrylic acid copolymer, divinylbenzene-styrene copolymer, vinyl Resins, urea resins, phenolic resins, fluor
- Surfactant metal salt powder includes, for example, zinc undecylenate (INCI: Zinc Undecylenate), aluminum isostearate (INCI: Aluminum Isostearate), zinc stearate (INCI: Zinc Stearate), Al stearate ( INCI: Aluminum Stearate), Ca Stearate (INCI: Calcium Stearate), Magnesium Stearate (INCI: Magnesium Stearate), Zinc Myristate (INCI: Zinc Myristate), Mg Myristate (INCI: Magnesium Myristate), Cetyl Phosphate (zinc /Na) (INCI: Sodium Zinc Cetyl Phosphate), calcium cetyl phosphate, zinc palmitate (INCI: Zinc Palmitate), aluminum palmitate, zinc laurate (INCI: Zinc Laurate), and the like.
- zinc undecylenate INCI: Zinc Undecylenate
- aluminum isostearate INCI: Aluminum Is
- colored pigments include inorganic red pigments such as iron oxide, iron hydroxide and iron titanate, inorganic brown pigments such as ⁇ -iron oxide, inorganic yellow pigments such as yellow iron oxide and ocher, black iron oxide, Inorganic black pigments such as carbon black (INCI), inorganic purple pigments such as manganese violet (INCI: Manganese violet), cobalt violet, etc., chromium hydroxide (INCI: Chromium Hydroxide Green), chromium oxide (INCI: Chromium Oxide Greens), oxidation Inorganic green pigments such as cobalt and cobalt titanate (INCI: Cobalt Titanium Oxide), inorganic blue pigments such as Prussian blue and ultramarine blue, lakes of tar pigments, lakes of natural pigments, and powders thereof Synthetic resin powder obtained by combining
- 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, and titanium oxide-coated colored mica;
- examples include aluminum powder, copper powder, stainless steel powder, and the like.
- Tar pigments include 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, Red 230, Red No. 401, Red No. 505, Yellow No. 4, Yellow No. 5, Yellow No. 202, Yellow No. 203, Yellow No. 204, Yellow No. 401, Blue No. 1, Blue No. 2, Blue No. 201, Blue No. 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, etc.; : Laccaic Acid), calsamin, brasilin, crocin and the like.
- crosslinked spherical dimethylpolysiloxane fine powder having a structure crosslinked with dimethylpolysiloxane, crosslinked spherical polymethylsilsesquioxane fine powder, crosslinked spherical polysiloxane rubber surface
- Powders and coloring agents having Commercially available products include KMP-590, KSP-100, KSP-101, KSP-102, KSP-105 and KSP-300 (all manufactured by Shin-Etsu Chemical Co., Ltd.).
- These powders can also be used by compounding powders or treating them with general oils, silicone oils, fluorine compounds, surfactants, etc., as long as they do not interfere with the effects of the present invention.
- plasma treatment, mechanochemical treatment, etc. may or may not be surface-treated in advance. 1 type, or 2 or more types can be used as needed.
- the blending amount is preferably 99% by mass or less based on the entire cosmetic. preferable.
- the cosmetic of the present invention may further contain one or more compounds having an alcoholic hydroxyl group in the molecular structure.
- the alcohol compound having 12 or more carbon atoms for constituting the monomer unit (II) of the above copolymer is excluded from the alcoholic hydroxyl group-containing compound.
- Examples of such compounds include lower alcohols such as ethanol (INCI: Alcohol) and isopropanol (INCI: Isopropyl Alcohol), sugar alcohols such as sorbitol (INCI) and maltose (INCI), cholesterol (INCI), sitosterol (INCI: Beta-Sitosterol), phytosterols (INCI), lanosterol (INCI) and other sterols, BG (INCI: Butylene Glycol), PG (INCI: Propylene Glycol), DPG (INCI: Dipropylene Glycol), pentylene glycol (INCI), etc.
- water-soluble monohydric alcohols and water-soluble polyhydric alcohols are commonly used.
- the compounding amount thereof is preferably 98% by mass or less relative to the total cosmetic composition.
- the cosmetic of the present invention may further contain one or more water-soluble or water-swellable polymer compounds.
- these water-soluble or water-swellable polymer compounds include gum arabic (INCI: Acacia Senegal Gum), tragacanth gum (INCI: Astragalus Gummifer Gum), galactan, and locust bean gum (INCI: Ceratonia Siliqua Gum).
- guar gum Cyamopsis Tetragonoloba (Guar) Gum
- karaya gum INCI: Sterculia Urens Gum
- carrageenan INCI: Chondrus Crispus (Carrageenan)
- pectin INCI
- agar INCI: Agar
- quince seed quince
- rice starch INCI: Oryza Sativa (Rice) Starch
- wheat starch INCI: Triticum Vulgare (Wheat) Starch
- potato starch INCI: Solanum Tuberosum (Potato) Starch
- tragacanth INCI : Astragalus Gummifer Gum
- xanthan gum INCI
- dextran INCI
- succinoglycan INCI
- pullulan INCI
- other microbial-based polymer compounds collagen (INCI), casein (INCI ), animal polymer
- water-soluble polymer compounds also include film-forming agents such as polyvinyl alcohol (INCI) and PVP (INCI).
- film-forming agents such as polyvinyl alcohol (INCI) and PVP (INCI).
- the blending amount of the water-soluble or water-swellable polymer compound is preferably 25% by mass or less with respect to the total cosmetic composition.
- a composition comprising a crosslinked organopolysiloxane polymer having no hydrophilic groups and a liquid oil agent
- the cosmetic of the present invention further comprises one or more crosslinked organopolysiloxane polymers having no hydrophilic groups.
- a composition (I) consisting of a substance and a liquid oil agent may also be included.
- the crosslinked organopolysiloxane polymer is obtained by reacting an alkylhydrogenpolysiloxane with a crosslinking agent having a hydrosilylation-reactive unsaturated group.
- alkylhydrogenpolysiloxane examples include methylhydrogenpolysiloxane having linear or partially branched units, methylhydrogenpolysiloxane grafted with an alkyl chain having 6 to 20 carbon atoms, and the like. Two or more hydrogen atoms bonded to a silicon atom are required on average in a molecule.
- the cross-linking agent include those having two or more hydrosilylation-reactive carbon-carbon double bonds in the molecule, such as methylvinylpolysiloxane and ⁇ , ⁇ -alkenyldiene.
- the resulting crosslinked organopolysiloxane polymer is treated with, for example, a low-viscosity silicone having a kinematic viscosity of 0.65 mm 2 /sec (25°C) to 100.0 mm 2 /sec (25°C) above its own weight, liquid paraffin, squalane, isododecane. and the like, glyceride oils such as trioctanoin, and liquid oils such as ester oils.
- the “kinematic viscosity” in the present invention is a value measured at 25° C. using a Canon-Fenske viscometer according to JIS Z8803:2011.
- compositions of these crosslinked organopolysiloxane polymers and liquid oils are commercially available.
- the blending amount is preferably 0.1 to 50% by mass, preferably 1 to 50% by mass, based on the total cosmetic composition. 30% by mass is more preferred.
- composition comprising a crosslinked organopolysiloxane polymer having a hydrophilic group and a liquid oil
- the cosmetic of the present invention further comprises a crosslinked organopolysiloxane polymer having one or more hydrophilic groups.
- a composition comprising a liquid oil may also be included.
- the hydrophilic group is preferably a polyether group or a polyglycerin group.
- the crosslinked organopolysiloxane polymer having polyether groups and/or polyglycerin groups is obtained by reacting alkylhydrogenpolysiloxane with a crosslinking agent having hydrosilylation-reactive unsaturated groups.
- alkylhydrogenpolysiloxane examples include methylhydrogenpolysiloxane grafted with a polyoxyethylene chain and methylhydrogenpolysiloxane grafted with a polyglycerin chain. two or more are required on average.
- Cross-linking agents include methylvinylpolysiloxane, ⁇ , ⁇ -alkenyl dienes, glycerol triallyl ether, polyoxyalkynylated glycerol triallyl ether, trimethylolpropane triallyl ether, polyoxyalkynylated trimethylolpropane triallyl ether, and the like. includes those having two or more hydrosilylatable carbon-carbon double bonds in the molecule.
- a crosslinked product obtained by reacting these has one or more hydrophilic groups.
- the resulting crosslinked organopolysiloxane polymer is treated with, for example, a low-viscosity silicone having a kinematic viscosity of 0.65 mm 2 /sec (25°C) to 100.0 mm 2 /sec (25°C) above its own weight, liquid paraffin, squalane, isododecane.
- Hydrocarbon oils such as trioctanoin, glyceride oils such as trioctanoin, and liquid oils such as ester oils are allowed to swell.
- crosslinked organopolysiloxanes are available as commercial products.
- KSG-210, KSG-240, KSG-710 pasted with silicone oil KSG-310, KSG-320, KSG-330, KSG-340, KSG- 820, KSG-830, KSG-840 (all manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.
- the blending amount is preferably 0.1 to 50% by mass, preferably 1 to 30%, based on the total cosmetic composition. % by mass is more preferred.
- the cosmetic of the present invention may further contain one or more silicone resins (K).
- the silicone resin is a group consisting of silicone network compounds containing SiO 4/2 units and/or R'SiO 3/2 (R' is an alkyl group), linear acrylic/silicone grafts, or block copolymers thereof. It is preferable to be more selected.
- the linear acrylic/silicone graft or block copolymer has one or more selected from pyrrolidone moieties, long-chain alkyl moieties, polyoxyalkylene moieties and fluoroalkyl moieties, and anionic moieties such as carboxylic acids. You can do it.
- the silicone network compound is preferably a silicone network compound represented by MQ, MDQ, MT, MDT, MDTQ.
- M, D, T, and Q represent R 3 SiO 1/2 units, R 2 SiO 2/2 units, RSiO 3/2 units, and SiO 4/2 units, respectively.
- the silicone network compound may contain one or more selected from pyrrolidone moieties, long-chain alkyl moieties, polyoxyalkylene moieties, fluoroalkyl moieties, and amino moieties in the molecule. Examples of commercially available products include, but are not limited to, KF-7312J, KF-7312K, and KF-7312T (all manufactured by Shin-Etsu Chemical Co., Ltd.).
- the silicone resin may be dissolved in a low-viscosity silicone oil, a volatile silicone oil, or another solvent.
- the blending amount is preferably 0.1 to 20% by mass, more preferably 1 to 10% by mass, based on the total amount of the cosmetic.
- the cosmetic of the present invention may also contain a silicone wax (L) depending on its purpose.
- silicone wax include polylactone-modified polysiloxane in which polylactone, which is a ring-opening polymer of a lactone compound having a five-membered ring or more, is bonded, pyrrolidone group, long-chain alkyl group, polyoxyalkylene group, fluoroalkyl group, carboxylic acid, and the like. and acrylic-modified polysiloxane containing in the molecule at least one functional group selected from the anionic groups of .
- examples of commercially available products include KP-561P and KP-562P (both manufactured by Shin-Etsu Chemical Co., Ltd.) as waxes having long-chain alkyl groups.
- silicone waxes examples include silicone-modified olefin waxes obtained by subjecting an olefin wax to an addition reaction with an organohydrogenpolysiloxane having one or more SiH bonds per molecule.
- the olefin wax is obtained by copolymerizing ethylene and one or more dienes, or copolymerizes ethylene with one or more olefins selected from ⁇ -olefins having 3 to 12 carbon atoms and one or more dienes. It is obtained by polymerization, and the diene is preferably vinylnorbornene.
- silicone wax When a silicone wax is used, its blending amount is preferably 0.1 to 20% by mass, more preferably 1 to 10% by mass, based on the total cosmetic composition.
- the cosmetics of the present invention may include ingredients that are commonly used in cosmetics, such as oil-soluble gelling agents, antiperspirants, moisturizers, antibacterial and antiseptic agents, as long as they do not interfere with the effects of the present invention. agents, salts, antioxidants, skin beautifying ingredients (whitening agents, cell activators, rough skin ameliorators, blood circulation promoters, skin astringents, antiseborrheic agents, etc.), vitamins, amino acids, polymer compounds for hair fixation etc. can be added.
- oils-soluble gelling agents such as oil-soluble gelling agents, antiperspirants, moisturizers, antibacterial and antiseptic agents, as long as they do not interfere with the effects of the present invention.
- agents, salts, antioxidants, skin beautifying ingredients whitening agents, cell activators, rough skin ameliorators, blood circulation promoters, skin astringents, antiseborrheic agents, etc.
- vitamins, amino acids, polymer compounds for hair fixation etc. can be added.
- oil-soluble gelling agents examples include metal soaps such as Al stearate (INCI: Aluminum stearate), Mg stearate (INCI: Magnesium stearate), zinc myristate (INCI: Zinc Myristate), lauroyl glutamic acid (INCI: Lauroyl Glutamic Acid) and other amino acid derivatives, dextrin palmitate (INCI: Dextrin Palmitate), dextrin isostearate (INCI: Dextrin Isostearate), (INCI: Dextrin Palmitate/Ethylhexanoate), etc.
- metal soaps such as Al stearate (INCI: Aluminum stearate), Mg stearate (INCI: Magnesium stearate), zinc myristate (INCI: Zinc Myristate), lauroyl glutamic acid (INCI: Lauroyl Glutamic Acid) and other amino acid derivatives, dextrin palmitate (INCI: Dextrin Palmitate), de
- sucrose palmitate INCI: Sucrose Palmitate
- sucrose fatty acid esters such as sucrose stearate
- caprylic acid fructooligosaccharide caprylate INCI: Fructooligosaccharide Caprylate
- hexyldecanoic acid fructooligosaccharides INCI: Fructooligos accharide Hexyldecanoate
- oils selected from benzylidene derivatives of sorbitol such as fructo-oligosaccharide fatty acid esters, monobenzylidene sorbitol and dibenzylidene sorbitol, organic modified clay minerals such as dimethylbenzyldodecylammonium montmorillonite clay and dimethyldioctadecylammonium montmorillonite clay. Soluble gelling agents are included.
- antiperspirant for example, 1 selected from chlorohydroxy Al (INCI: Aluminum Chlorohydrate), aluminum chloride (INCI: Aluminum Chloride), aluminum sesquichlorohydrate, zirconyl hydroxychloride, aluminum zirconium hydroxychloride, aluminum zirconium glycine complex, etc.
- One or more antiperspirants are included.
- moisturizing agents examples include glycerin (INCI), sorbitol (INCI), PG (INCI), DPG (INCI), BG (INCI), pentylene glycol (INCI), glucose (INCI), xylitol (INCI), maltitol. (INCI), polyethylene glycol, hyaluronic acid (INCI: Hyaluronic Acid), chondroitin sulfate, pyrrolidone carboxylate, polyoxyethylene methyl glucoside, polyoxypropylene methyl glucoside, etc. be done.
- antibacterial and antiseptic agents examples include alkyl paraoxybenzoic acid, benzoic acid (INCI), sodium benzoate (INCI), sorbic acid (INCI), potassium sorbate (INCI), and potassium sorbate (INCI). ), phenoxyethanol (INCI), antibacterial agents such as benzoic acid, salicylic acid, phenol (INCI), sorbic acid, paraoxybenzoic acid alkyl ester, p-chloro-m-cresol (INCI), hexachlorophene (INCI), benza
- One or more antimicrobial preservatives selected from ruconium chloride (INCI), chlorhexidine 2HCl (INCI: Chlorhexidine Dihydrochloride), triclocarban (INCI), photosensitizer, phenoxyethanol and the like.
- Examples of salts include inorganic salts, organic acid salts, amine salts and amino acid salts.
- inorganic salts include sodium salts, potassium salts, magnesium salts, calcium salts, aluminum salts, zirconium salts, and zinc salts of inorganic acids such as hydrochloric acid, sulfuric acid, carbonic acid, and nitric acid; organic acid salts include, for example, acetic acid ( INCI: Acetic Acid), dehydroacetic acid (INCI: Dehydroacetic Acid), citric acid (INCI: Citric Acid), malic acid (INCI: Malic Acid), succinic acid (INCI: Succinic Acid), ascorbic acid (INCI: Ascorbic Acid) , organic acid salts such as stearic acid (INCI); amine salts and amino acid salts such as amine salts such as TEA (INCI: triethanolamine), amino acids such as glutamic acid (INCI: glutamic acid), etc.
- acetic acid INCI: Acetic
- hyaluronic acid (INCI: Hyaluronic Acid)
- salts such as chondroitin sulfate, tetrachloro (Al/zirconium) hydrate (INCI: Aluminum Zirconium Tetrachlorohydrate), etc.
- chondroitin sulfate tetrachloro (Al/zirconium) hydrate
- ICI Aluminum Zirconium Tetrachlorohydrate
- antioxidants include tocopherol (INCI), BHA (INCI), BHT (INCI), and phytic acid (INCI), and examples of pH adjusters include lactic acid (INCI) and citric acid (INCI).
- Citric Acid Citric Acid
- Glycolic Acid Glycolic Acid
- Succinic Acid INCI: Citric Acid
- Tartaric Acid INCI: Tartaric Acid
- Malic Acid INCI: Malic Acid
- K Carbonate INCI: Potassium Carbonate
- Carbonic Acid Hydrogen Na INCI: Sodium Bicarbonate
- Ammonium Bicarbonate (INCI: Ammonium Bicarbonate), etc.
- Chelating agents include alanine (INCI), EDTA-2Na (INCI: Disodium EDTA), Na polyphosphate (INCI: Sodium Polyphosphate), Sodium Metaphosphate (INCI: Sodium Metaphosphate), Phosphoric Acid (INCI: Phosphoric Acid), etc.
- Cooling Agents Menthol (INCI), Camphor Camphor, etc.
- Anti-inflammatory Agents Allantoin (INCI), Glycyrrhizic Acid (INCI: Glycyrrhizic Acid) and salts thereof, glycyrrhetinic acid (INCI) and stearyl glycyrrhetinate (INCI), tranexamic acid, azulene (INCI), etc. .
- Skin-beautifying ingredients include whitening agents such as placenta extract (INCI), arbutin (INCI), glutathione (INCI), saxifrage extract (INCI: Saxifraga Sarmentosa Extract), royal jelly (INCI), photosensitizers, and cholesterol derivatives.
- whitening agents such as placenta extract (INCI), arbutin (INCI), glutathione (INCI), saxifrage extract (INCI: Saxifraga Sarmentosa Extract), royal jelly (INCI), photosensitizers, and cholesterol derivatives.
- cell activator such as calf blood extract, rough skin improver, nonanoic acid vanillylamide, benzyl nicotinate (INCI: Benzyl Nicotinate), nicotinic acid ⁇ -butoxyethyl ester, capsaicin (INCI), acetylzingerone (INCI), beans Tiger beetle extract, ictamol (INCI), caffeine (INCI), tannic acid, borneol (INCI), tocopheryl nicotinate (INCI: tocopheryl nicotinate), inositol hexanicotinate, cyclanderate, cinnarizine, tolazoline, acetylcholine, verapamil , cepharanthine, blood circulation promoters such as oryzanol (INCI), skin astringents such as zinc oxide (INCI: Zinc Oxide), tannic acid (INCI: Tannic Acid), etc., sulfur (INCI:
- vitamins examples include vitamin A oil, retinol (INCI), retinyl acetate (INCI), vitamin A such as retinyl palmitate (INCI), riboflavin (INCI), and riboflavin tetrabutyrate (INCI).
- vitamin B2 such as flavin adenine dinucleotide 2Na (INCI: Disodium Flavine Adenine Dinucleotide)
- vitamins such as pyridoxine HCl (INCI), pyridoxine dioctanoate, pyridoxine dipalmitate (INCI: Pyridoxine Dipalmitate)
- B6 B vitamins such as vitamin B12 and its derivatives, vitamin B15 and its derivatives, ascorbic acid (INCI), ascorbyl dipalmitate (INCI), disodium ascorbyl sulfate (INCI)
- Vitamin C such as L-ascorbic acid phosphate diester dipotassium
- Vitamin D such as ergocalciferol (INCI), cholecalciferol (INCI), tocopherol (INCI), tocopheryl acetate (INCI: Tocopheryl Acetate), nicotinic acid Tocopherol (INCI: Tocopheryl Nicotinate), vitamin E such
- amino acids examples include glycine (INCI), valine (INCI), leucine (INCI), isoleucine (INCI), serine (INCI), threonine (INCI), phenylalanine (INCI), arginine (INCI), and lysine (INCI).
- aspartic acid Aspartic Acid
- glutamic acid INCI: Glutamic Acid
- cystine INCI
- cysteine INCI
- methionine arginine
- tryptophan etc.
- nucleic acids such as DNA (INCI), hormones
- examples include one or more amino acids selected from estradiol (INCI), ethinyl estradiol (INCI), and the like.
- hair fixative polymer compounds include amphoteric, anionic, cationic and nonionic polymer compounds, and polyvinylpyrrolidone such as PVP (INCI) and (VP/VA) copolymer (INCI).
- -based polymer compounds (methyl vinyl ether/maleic acid) copolymer (INCI: PVM/MA Copolymer) and other acidic vinyl ether-based polymer compounds, (VA/crotonic acid) copolymer (INCI: VA/Crotonates Copolymer) and other acidic polyacetic acid
- Acidic acrylic polymer compounds such as vinyl polymer compounds, (meth)acrylic acid/alkyl (meth)acrylate copolymers, (meth)acrylic acid/alkyl (meth)acrylate/alkylacrylamide copolymers, N-methacryloyl Amphoteric acrylics such as ethyl-N,N-dimethylammonium/ ⁇ -N-methylcarboxybetaine/alkyl (
- Naturally occurring polymer compounds such as cellulose or derivatives thereof, keratin and collagen or derivatives thereof can be suitably used.
- resins, fragrances, pH adjusters, chelating agents, cooling agents, anti-inflammatory agents, nucleic acids, hormones, clathrate compounds can also be blended as other components.
- Cosmetics in the present invention include emulsions, creams, cleansing agents, packs, massage agents, beauty essences, beauty oils, cleansers, deodorants, hand creams, lip balms, wrinkle concealers, etc., containing the above cosmetic ingredients.
- skin care cosmetics makeup base, concealer, white powder, liquid foundation, oily foundation, blusher, eye shadow, mascara, eyeliner, eyebrow, lipstick and other makeup cosmetics, shampoo, rinse, treatment, hair setting agents, etc.
- various shapes such as liquid, emulsion, cream, solid, paste, gel, powder, press, multilayer, mousse, spray, and stick can be selected. can be done.
- aqueous, oily, water-in-oil emulsions, oil-in-water emulsions, non-aqueous emulsions, and multi-emulsions such as W/O/W and O/W/O can be selected as the form of the cosmetic. can be done.
- the compounding amount is the compounding amount of the compounded product.
- Methyl cellulose (INCI) (2% aqueous solution) (Note 2) 7.0 7.
- Guanine (INCI) 1.0 9.
- Preservative appropriate amount 10.
- Perfume Appropriate amount 11.
- Purified water 63.0 Total 100.0 (Note 1) Shin-Etsu Chemical Co., Ltd.: KSG-18 (Note 2) Manufactured by Shin-Etsu Chemical Co., Ltd.: METOLOSE SM-4000 (Note 3) Made by SEPIC: Sepigel 305
- Hybrid silicone composite powder (Note 2) 3.0 (Display name: (vinyldimethicone/methicone silsesquioxane) crosspolymer (INCI: (INCI: Vinyldimethicone/Methicone Silsesquioxane Crosspolymer)) 7. Polyglycerin co-modified branched silicone (Note 3) 0.6 (Display name: Polyglyceryl-3 disiloxane dimethicone (INCI)) 8. Polyglycerin co-modified branched silicone (Note 4) 0.3 (Display name: Lauryl polyglyceryl-3 polydimethylsiloxyethyl dimethicone (INCI)) 9.
- Alkyl-silicone treated pigment (Note 5) 10.0 (Display name: triethoxysilylethyl polydimethylsiloxyethylhexyl dimethicone (INCI)) 10.
- BG (INCI: Butylene Glycol) 5.0 11. sodium chloride 0.5 12. Sodium citrate 0.2 13. Preservative appropriate amount 14. Perfume Appropriate amount 15.
- the cream foundation obtained as described above is non-sticky, spreads lightly, has good pigment dispersibility, has excellent adhesion, is easy to apply, and has a very beautiful finish film with a matte finish.
- a /O cream foundation was obtained.
- Hybrid silicone composite powder (Note 1) 3.0 (Display name: (vinyldimethicone/methicone silsesquioxane) crosspolymer (INCI: Vinyldimethicone/Methicone Silsesquioxane Crosspolymer)) 7. Alkyl-silicone treated pigment (Note 2) Appropriate amount (display name: iron oxide (INCI: Iron Oxides), triethoxysilylethyl polydimethylsiloxyethylhexyl dimethicone (INCI)) 8. Mica-treated titanium oxide remaining amount Total 100.0 (Note 1) Shin-Etsu Chemical Co., Ltd.: KSP-100 (Note 2) Shin-Etsu Chemical Co., Ltd.: KTP-09
- A Components 2-3 were mixed.
- B Components 6-8 were mixed.
- C Components 1, 4 to 5 are mixed, and the mixture obtained in A is added and heated.
- D Add the material obtained in C to the material obtained in B and pour into a container.
- the eye color obtained as described above is non-greasy and non-sticky, spreads lightly, has refreshing usability, has excellent adhesion, and is well-applied and has excellent long-lasting makeup. was in color.
- the cosmetic containing the oil gelling agent of the present invention spreads lightly, and has a light spreadability and a refreshing feeling after use, such as a dry and smooth feeling on the back skin. Therefore, by applying the cosmetic composition of the present invention, it is possible to impart softness, smoothness, and emollient effects without impairing the evaporation of moisture appropriately, and to impart a wide range of properties from natural gloss to matte feeling.
- the cosmetic of the present invention has excellent usability and good stability over time.
- the cosmetic of the present invention has excellent usability and good stability over time, and is extremely useful in practical use.
- the composition of the present invention is a raw material component of cosmetics in practical use, and therefore has great industrial utility.
- the present invention is not limited to the above embodiments.
- the above-described embodiment is an example, and any device having substantially the same configuration as the technical idea described in the claims of the present invention and exhibiting the same effect is the present invention. included in the technical scope of
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Abstract
Description
1.(a)下記一般式(1)で示される両親媒性(メタ)アクリルモノマーと、
(b)下記一般式(2)で示される親水性(メタ)アクリルモノマーと
を構成単位として含む共重合体であるオイルゲル化剤であって、前記(a)と(b)の質量比(b)/(a)が、0<[(b)/(a)]≦0.2であるオイルゲル化剤。
2.さらに、(c)下記一般式(3)
で示されるシリコーンマクロマーからなるモノマーを、全モノマー中35~50質量%を構成単位として含む1記載のオイルゲル化剤。
3.1又は2に記載のオイルゲル化剤を含有する化粧料。
本発明のオイルゲル化剤は、特定の(a)両親媒性(メタ)アクリルモノマーと、(b)特定の親水性(メタ)アクリルモノマーを共重合することによって得られ、上記モノマーを構成単位として含む共重合体である。以下、R1等の複数の式に用いられているものは、それぞれ独立である。
(a)両親媒性(メタ)アクリルモノマーは、下記一般式(1)で示される(メタ)アクリルモノマーであり、1種単独で又は2種以上組み合わせて用いることができる。
上記両親媒性(メタ)アクリルモノマーは、グリシジルメタクリレート、又はグリシジルアクリレートを、脂肪酸と反応させることで得ることができる。反応速度の観点から、触媒を用いて反応させることが好ましい。用いられる触媒としては、テトラブチルアンモニウムブロマイド等の4級アルキルアンモニウム塩が挙げられる。また、反応基質と触媒を均一に混合するという観点から、溶媒中で反応させることが好ましく、用いられる溶媒としてはジメチルアセトアミド、ジメチルホルムアミド、アセトニトリル等の非プロトン性極性溶媒、トルエン等の芳香族系炭化水素系溶媒が挙げられる。さらに、生成物の純度を高める観点から、反応後に水洗を行うことが好ましい。
(b)親水性(メタ)アクリルモノマーは、下記一般式(2)で表される親水性(メタ)アクリルモノマーである。
本発明の共重合体はシリコーンマクロマーからなるモノマーを構成単位として有することができる。シリコーン鎖をグラフト化することで、シリコーン油への相溶性が向上し、シリコーン油のゲル化がより可能となる。シリコーンマクロマーとしては、下記一般式(3)で示される(メタ)アクリル変性シリコーンマクロマーが挙げられる。
本発明の共重合体の重合は、ベンゾイルパーオキサイド、ラウロイルパーオキサイド、アゾビスイソブチロニトリル等のラジカル重合開始剤の存在下に行なわれることが好ましい。重合方法は、溶液重合法、乳化重合法、懸濁重合法、バルク重合法のいずれの方法の適用も可能である。これらの中でも、溶液重合法は、得られる重合体の分子量を所望の範囲に調整することが容易であるため好ましい。重合反応は、溶媒中で行ってもよく、この際用いられる溶媒としては、ペンタン、ヘキサン、デカン、ドデカン、ヘキサデカン、オクタデカン等の脂肪族炭化水素系有機溶剤、ベンゼン、トルエン、キシレン等の芳香族炭化水素系有機溶剤、メタノール、エタノール、イソプロピルアルコール、プロパノール、ブタノール、ヘキサノール、デカノール等のアルコール系有機溶剤、クロロホルム、四塩化炭素等のハロゲン化炭化水素系有機溶剤、アセトン、メチルエチルケトン等のケトン系有機溶剤が挙げられる。しかし、化粧品用途として用いる観点からは、無溶媒で重合反応を行うか、エタノール又はイソプロパノールを使用することが好ましい。共重合体はランダム、ブロック、グラフト共重合体のいずれでもよい。
[測定条件]
展開溶媒:テトラヒドロフラン(THF)
流量:0.6mL/min
検出器:示差屈折率検出器(RI)
カラム:TSK Guardcolumn SuperH-H
TSKgel SuperHM-N(6.0mmI.D.×15cm×1)
TSKgel SuperH2500(6.0mmI.D.×15cm×1)
装置:HLC 8320 GPC
(いずれも東ソー社製)
カラム温度:40℃
試料注入量:50μL(濃度0.3質量%のTHF溶液)
本発明は、上記共重合体をオイルゲル化剤として用いるものである。ゲル化されるオイルとしては特に限定されず、後述する(B)油剤成分に記載のものが挙げられ、液状の油性成分が好ましい。中でも、炭化水素油、高級アルコール、シリコーン油が好ましい。炭化水素油及び高級アルコールがゲル化できることが好ましく、炭化水素油、高級アルコール及びシリコーン油がゲル化できることがより好ましい。
本発明の(A)オイルゲル化剤は、各種の化粧品に使用することができるが、特に口唇化粧料に好適である。温度安定性が高いゲルを形成するため、安定な組成物となり、使用感が向上する。本発明の化粧料に含まれるオイルゲル化剤の配合量は化粧料の剤形によって異なるが、化粧料全体に対して0.5~99.0質量%の範囲で使用可能であり、1.0~50質量%が好ましい。
上述のように本発明の化粧料は、1種又は2種以上の油剤成分を含むことができる。油剤成分としては、通常の化粧料に使用される、固体、半固体、液状のいずれの油剤も使用することができる。
本発明の化粧料は、さらに1種又は2種以上の紫外線吸収成分を含むことができる。これにより、本発明の化粧料は使用感良好で使用性及び持続性に優れる上、紫外線を吸収することのできる化粧料となる。紫外線吸収成分としては、紫外線吸収剤及び紫外線散乱剤が包含される。紫外線吸収剤としては、PABA(INCI)等の安息香酸系紫外線吸収剤、アントラニル酸メチル(INCI:Methyl Anthranilate)等のアントラニル酸系紫外線吸収剤、サリチル酸メチル(INCI:Methyl Salicylate)等のサリチル酸系紫外線吸収剤、メトキシケイヒ酸オクチル(INCI:Ethylhexyl Methoxycinnamate)等のケイ皮酸系紫外線吸収剤、オキシベンゾン-1(INCI:Benzophenone-1)等のベンゾフェノン系紫外線吸収剤、ウロカニン酸エチル等のウロカニン酸系紫外線吸収剤、t-ブチルメトキシジベンゾイルメタン(INCI:Butyl Methoxydibenzoylmethane)等のジベンゾイルメタン系紫外線吸収剤等が例示される。また、先に述べた紫外線吸収性の官能基を備えるシリコーン誘導体を用いてもよい。紫外線吸収散乱剤としては、微粒子酸化チタン、微粒子鉄含有酸化チタン、微粒子酸化亜鉛、微粒子酸化セリウム及びそれらの複合体等、紫外線を吸収散乱する粉体が挙げられる。これらのうち、ケイ皮酸系紫外線吸収剤、ジベンゾイルメタン系紫外線吸収剤、酸化チタン、酸化亜鉛が好ましい。
本発明の化粧料には、その目的に応じて水を配合することができる。これにより、本発明の化粧料は使用目的に応じて水を配合することで、より使用性にすぐれた化粧料となる。(D)水を配合する場合、その配合量は化粧料全体に対して95質量%以下の範囲が好ましい。
本発明の化粧料は、さらに1種又は2種以上の界面活性剤を含むことができる。これにより、本発明の化粧料は使用目的に応じて界面活性剤を配合することで、より使用性にすぐれた化粧料となる。界面活性剤としては、アニオン性、カチオン性、非イオン性及び両性の界面活性剤があるが、本発明の化粧料に含まれる界面活性剤は特に制限されるものではなく、通常の化粧料に使用されるものであれば、いずれのものも使用することができる。
本発明の化粧料はさらに1種又は2種以上の粉体を含んでもよい。粉体としては、通常の化粧料に使用されるものであれば、その形状(球状、針状、板状等や粒子径(煙霧状、微粒子、顔料級等)、粒子構造(多孔質、無孔質等)を問わず、いずれのものも使用することができる。例えば無機粉体、有機粉体、界面活性剤金属塩粉体、有色顔料、パール顔料、タール色素、金属粉末顔料、天然色素、染料等の着色剤が挙げられる。
本発明の化粧料は、さらに1種又は2種以上の分子構造中にアルコール性水酸基を有する化合物を含んでもよい。ただし上記共重合体のモノマー単位(II)を構成するための炭素数12以上のアルコール化合物は、該アルコール性水酸基を有する化合物から除かれる。かかる化合物としては、エタノール(INCI:Alcohol)、イソプロパノール(INCI:Isopropyl Alcohol)等の低級アルコール、ソルビトール(INCI)、マルトース(INCI)等の糖アルコール等があり、コレステロール(INCI)、シトステロール(INCI:Beta-Sitosterol)、フィトステロールズ(INCI)、ラノステロール(INCI)等のステロール、BG(INCI:Butylene Glycol)、PG(INCI:Propylene Glycol)、DPG(INCI:Dipropylene Glycol)、ペンチレングリコール(INCI)等の多価アルコール等があるが、通常は水溶性一価のアルコール、水溶性多価アルコールが多く用いられる。(G)分子構造中にアルコール性水酸基を有する化合物を配合する場合、その配合量は化粧料全体に対して98質量%以下が好ましい。
本発明の化粧料は、さらに1種又は2種以上の水溶性又は水膨潤性高分子化合物を含んでもよい。これら水溶性又は水膨潤性高分子化合物としては、例えば、アラビアゴム(INCI:Acacia Senegal Gum)、トラガカントゴムノキガム(INCI:Astragalus Gummifer Gum)、ガラクタン、ローカストビーンガム(INCI:Ceratonia Siliqua Gum)、グアーガム(INCI:Cyamopsis Tetragonoloba (Guar) Gum)、カラヤガム(INCI:Sterculia Urens Gum)、カラギーナン(INCI:Chondrus Crispus (Carrageenan))、ペクチン(INCI)、カンテン(INCI:Agar)、クインスシード(マルメロ)(INCI:Pyrus Cydonia Seed)、コメデンプン(INCI:Oryza Sativa (Rice) Starch)、コムギデンプン(INCI:Triticum Vulgare (Wheat) Starch)、バレイショデンプン(INCI:Solanum Tuberosum (Potato) Starch)、トラガント(INCI:Astragalus Gummifer Gum)等の植物系高分子化合物、キサンタンガム(INCI)、デキストラン(INCI)、サクシノグリカン(INCI)、プルラン(INCI)等の微生物系高分子化合物、コラーゲン(INCI)、カゼイン(INCI)、アルブミン、ゼラチン(INCI)等の動物系高分子化合物、カルボキシメチルデンプンNa(INCI:Sodium Carboxymethyl Starch)、ヒドロキシプロピルデンプン(INCI:Hydroxypropyl Starch)等のデンプン系高分子化合物、メチルセルロース(INCI)、エチルセルロース(INCI)、ヒドロキシプロピルメチルセルロース(INCI)、カルボキシメチルセルロース、ヒドロキシメチルセルロース、ヒドロキシプロピルセルロース(INCI)、ニトロセルロース(INCI)、セルロース硫酸Na(INCI:Sodium Cellulose Sulfate)、カルボキシメチルセルロースナトリウム、結晶セルロース(INCI:Microcrystalline Cellulose)、セルロース末のセルロース高分子化合物、アルギン酸Na(INCI:Algin)、アルギン酸PG(INCI:Propylene Glycol Alginate)等のアルギン酸系高分子化合物、ポリビニルメチルエーテル、カルボキシビニルポリマー等のビニル系高分子化合物、ポリオキシエチレン系高分子化合物、ポリオキシエチレンポリオキシプロピレン共重合体系高分子化合物、ポリアクリル酸Na(INCI:Sodium Polyacrylate)、ポリアクリル酸エチル(INCI:Polyethylacrylate)、ポリアクリルアミド(INCI)、(アクリルアミド/アクリロイルジメチルタウリンNa)コポリマー(INCI:Acrylamide/Sodium Acryloyldimethyltaurate Copolymer)のアクリル系高分子、ポリエチレンイミン、カチオンポリマー等他の合成水溶性高分子化合物、ベントナイト(INCI)、ケイ酸(Al/Mg)(INCI:Magnesium Aluminum Silicate)、モンモリロナイト(INCI)、バイデライト、ノントロナイト、サポナイト、ヘクトライト(INCI)、シリカ(INCI)等の無機系水溶性高分子化合物等がある。また、これらの水溶性高分子化合物には、ポリビニルアルコール(INCI)やPVP(INCI)等の皮膜形成剤も含まれる。水溶性又は水膨潤性高分子化合物の配合量は、化粧料全体に対して25質量%以下が好ましい。
本発明の化粧料は、さらに1種又は2種以上の親水性基を有しない架橋型オルガノポリシロキサン重合物と液状油剤からなる組成物(I)を含んでも良い。該架橋型オルガノポリシロキサン重合物は、アルキルハイドロジェンポリシロキサンとヒドロシリル化反応性不飽和基を有する架橋剤とを反応することによって得られる。
アルキルハイドロジェンポリシロキサンとしては直鎖ないし一部分岐単位を有するメチルハイドロジェンポリシロキサン、炭素数が6~20のアルキル鎖がグラフトされたメチルハイドロジェンポリシロキサン等を挙げることができる。ケイ素原子に結合した水素原子は、分子中に平均で二つ以上必要である。
架橋剤は、メチルビニルポリシロキサンやα,ω-アルケニルジエン等のように、分子中に二つ以上のヒドロシリル化反応可能な炭素-炭素二重結合を持つものが挙げられる。
得られた架橋型オルガノポリシロキサン重合物を、例えば自重以上の動粘度0.65mm2/秒(25℃)~100.0mm2/秒(25℃)の低粘度シリコーン、流動パラフィン、スクワラン、イソドデカン等の炭化水素油、トリオクタノイン等のグリセライド油、及びエステル油等の液状油剤で膨潤させる。
なお、本発明の「動粘度」は、JIS Z8803:2011記載のキャノン-フェンスケ粘度計を用いて25℃で測定した値である。
本発明の化粧料は、さらに1種又は2種以上の親水性基を有する架橋型オルガノポリシロキサン重合物と液状油剤からなる組成物を含んでもよい。該親水性基としては、ポリエーテル基、ポリグリセリン基が好ましい。該ポリエーテル基及び/又はポリグリセリン基を有する架橋型オルガノポリシロキサン重合物は、アルキルハイドロジェンポリシロキサンとヒドロシリル化反応性不飽和基を有する架橋剤とを反応することによって得られる。アルキルハイドロジェンポリシロキサンとしてポリオキシエチレン鎖がグラフトされたメチルハイドロジェンポリシロキサン、ポリグリセリン鎖がグラフトされたメチルハイドロジェンポリシロキサン等を挙げることができ、ケイ素原子に結合した水素原子は、分子中に平均で二つ以上必要である。
本発明の化粧料は、さらに1種又は2種以上のシリコーン樹脂(K)を含んでもよい。シリコーン樹脂は、SiO4/2単位及び/又はR’SiO3/2(R’はアルキル基)を含むシリコーン網状化合物、直鎖状のアクリル/シリコーングラフト、又はこれらのブロック共重合体からなる群より選ばれるものであることが好ましい。直鎖状のアクリル/シリコーングラフト又は前記ブロック共重合体は、ピロリドン部分、長鎖アルキル部分、ポリオキシアルキレン部分及びフルオロアルキル部分、カルボン酸等のアニオン部分の中から選択される1種以上を有していてよい。市販品としては、特に限定されるものではないが、シリコーン油や炭化水素油、アルコールに溶解したKP-541、KP-543、KP-545、KP-549、KP-550、KP-571、KP-575、KP-581(いずれも信越化学工業(株)製)等が例示される。
本発明の化粧料は、その目的に応じてシリコーンワックス(L)を含むこともできる。このシリコーンワックスとしては、5員環以上のラクトン化合物の開環重合物であるポリラクトンを結合させたポリラクトン変性ポリシロキサン、ピロリドン基、長鎖アルキル基、ポリオキシアルキレン基、フルオロアルキル基、カルボン酸等のアニオン基の中から選択された1種以上の官能基を分子中に含有するアクリル変性ポリシロキサン等が挙げられる。市販品としては、長鎖アルキル基を有するワックスとして、KP-561P、KP-562P(いずれも信越化学工業(株)製)等が例示される。
さらに本発明の化粧料には、本発明の効果を妨げない範囲で、通常の化粧料に使用される成分、例えば、油溶性ゲル化剤、制汗剤、保湿剤、防菌防腐剤、塩類、酸化防止剤、美肌用成分(美白剤、細胞賦活剤、肌荒れ改善剤、血行促進剤、皮膚収斂剤、抗脂漏剤等)、ビタミン類、アミノ酸類、毛髪固定用高分子化合物等を添加することができる。
パルミチン酸(53.2g)、テトラブチルアンモニウムブロマイド(6.71g)、トルエン(60mL)を300mLセパラブルフラスコに入れ、90℃で撹拌した。そこへ、滴下漏斗を用いて、メタクリル酸グリシジル(29.6g)を滴下した。その後、90℃で4時間撹拌した。反応後、飽和NaCl水溶液で3回洗浄し、有機相を回収して硫酸ナトリウムで脱水した。硫酸ナトリウムをろ過後、溶媒を留去して、下記一般式(4)で示される両親媒性メタクリルモノマー(AM1)を得た。
ステアリン酸(100.1g)、テトラブチルアンモニウムブロマイド(11.4g)、トルエン(100mL)を300mLセパラブルフラスコに入れ、90℃で撹拌した。そこへ、滴下漏斗を用いて、メタクリル酸グリシジル(50.0g)を滴下した。その後、90℃で4時間撹拌した。反応後、飽和NaCl水溶液で3回洗浄し、有機相を回収して硫酸ナトリウムで脱水した。硫酸ナトリウムをろ過後、溶媒を留去して、下記一般式(5)で示される両親媒性メタクリルモノマー(AM2)を得た。
セパラブルフラスコにイソプロピルアルコール(23.3g)を入れ、100℃で加熱した。AM1(31.6g)、2-ヒドロキシエチルメタクリレート(1.7g)、イソプロピルアルコール(16.6g)、パーブチルO(日本油脂株式会社製)(2.0g)を混合し、滴下ロートを用いて、セパラブルフラスコへ1時間かけて滴下した。滴下後、2時間撹拌して、追加でパーブチルO(0.3g)を加えた。さらに3時間撹拌し、反応を終了した。その後、溶媒を減圧留去して(110℃、1kPa以下)、目的の共重合体を得た。また、数平均分子量はMn=29,595であった。
セパラブルフラスコにイソプロピルアルコール(23.3g)を入れ、100℃で加熱した。AM2(31.6g)、2-ヒドロキシエチルメタクリレート(1.7g)、イソプロピルアルコール(16.6g)、パーブチルO(日本油脂株式会社製)(2.0g)を混合し、滴下ロートを用いて、セパラブルフラスコへ1時間かけて滴下した。滴下後、2時間撹拌して、追加でパーブチルO(0.3g)を加えた。さらに3時間撹拌し、反応を終了した。その後、溶媒を減圧留去して(110℃、1kPa以下)、目的の共重合体を得た。また、数平均分子量はMn=29,578であった。
セパラブルフラスコにイソプロピルアルコール(23.3g)を入れ、100℃で加熱した。AM2(30.0g)、2-ヒドロキシエチルメタクリレート(3.3g)、イソプロピルアルコール(16.6g)、パーブチルO(日本油脂株式会社製)(2.0g)を混合し、滴下ロートを用いて、セパラブルフラスコへ1時間かけて滴下した。滴下後、2時間撹拌して、追加でパーブチルO(0.3g)を加えた。さらに3時間撹拌し、反応を終了した。その後、溶媒を減圧留去して(110℃、1kPa以下)、目的の共重合体を得た。また、数平均分子量はMn=34,493であった。
セパラブルフラスコにイソプロピルアルコール(23.3g)を入れ、100℃で加熱した。AM2(28.3g)、2-ヒドロキシエチルメタクリレート(5.0g)、イソプロピルアルコール(16.6g)、パーブチルO(日本油脂株式会社製)(2.0g)を混合し、滴下ロートを用いて、セパラブルフラスコへ1時間かけて滴下した。滴下後、2時間撹拌して、追加でパーブチルO(0.3g)を加えた。さらに3時間撹拌し、反応を終了した。その後、溶媒を減圧留去して(110℃、1kPa以下)、目的の共重合体を得た。また、数平均分子量はMn=37,010であった。
セパラブルフラスコにイソプロピルアルコール(23.3g)を入れ、100℃で加熱した。AM1(19.0g)、2-ヒドロキシエチルメタクリレート(1.0g)、下記一般式(6)で示されるシリコーンマクロマー(13.3g)、イソプロピルアルコール(16.6g)、パーブチルO(日本油脂株式会社製)(2.0g)を混合し、滴下ロートを用いて、セパラブルフラスコへ1時間かけて滴下した。滴下後、2時間撹拌して、追加でパーブチルO(0.3g)を加えた。さらに3時間撹拌し、反応を終了した。その後、溶媒を減圧留去して(110℃、1kPa以下)、目的の共重合体を得た。また、数平均分子量はMn=35,450であった。
セパラブルフラスコにイソプロピルアルコール(23.3g)を入れ、100℃で加熱した。AM1(26.6g)、2-ヒドロキシエチルメタクリレート(6.7g)、イソプロピルアルコール(16.6g)、パーブチルO(日本油脂株式会社製)(2.0g)を混合し、滴下ロートを用いて、セパラブルフラスコへ1時間かけて滴下した。滴下後、2時間撹拌して、追加でパーブチルO(0.3g)を加えた。さらに3時間撹拌し、反応を終了した。その後、溶媒を減圧留去して(110℃、1kPa以下)、目的の共重合体を得た。また、数平均分子量はMn=30,128であった。
セパラブルフラスコにイソプロピルアルコール(23.3g)を入れ、100℃で加熱した。AM2(26.6g)、2-ヒドロキシエチルメタクリレート(6.7g)、イソプロピルアルコール(16.6g)、パーブチルO(日本油脂株式会社製)(2.0g)を混合し、滴下ロートを用いて、セパラブルフラスコへ1時間かけて滴下した。滴下後、2時間撹拌して、追加でパーブチルO(0.3g)を加えた。さらに3時間撹拌し、反応を終了した。その後、溶媒を減圧留去して(110℃、1kPa以下)、目的の共重合体を得た。また、数平均分子量はMn=35,280であった。
セパラブルフラスコにイソプロピルアルコール(23.3g)を入れ、100℃で加熱した。ステアリルメタクリレート(30.0g)、2-ヒドロキシエチルメタクリレート(3.3g)、イソプロピルアルコール(16.6g)、パーブチルO(日本油脂株式会社製)(2.0g)を混合し、滴下ロートを用いて、セパラブルフラスコへ1時間かけて滴下した。滴下後、2時間撹拌して、追加でパーブチルO(0.3g)を加えた。さらに3時間撹拌し、反応を終了した。その後、溶媒を減圧留去して(110℃、1kPa以下)、目的の共重合体を得た。また、数平均分子量はMn=21,630であった。
セパラブルフラスコにイソプロピルアルコール(23.3g)を入れ、100℃で加熱した。ステアリルメタクリレート(15.8g)、2-ヒドロキシエチルメタクリレート(17.5g)、イソプロピルアルコール(16.6g)、パーブチルO(日本油脂株式会社製)(2.0g)を混合し、滴下ロートを用いて、セパラブルフラスコへ1時間かけて滴下した。滴下後、2時間撹拌して、追加でパーブチルO(0.3g)を加えた。さらに3時間撹拌し、反応を終了した。その後、溶媒を減圧留去して(110℃、1kPa以下)、目的の共重合体を得た。また、数平均分子量はMn=15,617であった。
セパラブルフラスコにイソプロピルアルコール(23.3g)を入れ、100℃で加熱した。ステアリルメタクリレート(8.3g)、2-ヒドロキシエチルメタクリレート(25.0g)、イソプロピルアルコール(16.6g)、パーブチルO(日本油脂株式会社製)(2.0g)を混合し、滴下ロートを用いて、セパラブルフラスコへ1時間かけて滴下した。滴下後、2時間撹拌して、追加でパーブチルO(0.3g)を加えた。さらに3時間撹拌し、反応を終了した。その後、溶媒を減圧留去して(110℃、1kPa以下)、目的の共重合体を得た。また、数平均分子量はMn=18,937であった。
セパラブルフラスコにイソプロピルアルコール(23.3g)を入れ、100℃で加熱した。ステアリルメタクリレート(11.6g)、2-ヒドロキシエチルメタクリレート(8.4g)、上記一般式(6)で示されるシリコーンマクロマー(13.3g)、イソプロピルアルコール(16.6g)、パーブチルO(日本油脂株式会社製)(2.0g)を混合し、滴下ロートを用いて、セパラブルフラスコへ1時間かけて滴下した。滴下後、2時間撹拌して、追加でパーブチルO(0.3g)を加えた。さらに3時間撹拌し、反応を終了した。その後、溶媒を減圧留去して(110℃、1kPa以下)、目的の共重合体を得た。また、数平均分子量はMn=20,670であった。
セパラブルフラスコにイソプロピルアルコール(23.3g)を入れ、100℃で加熱した。ステアリルメタクリレート(19.0g)、2-ヒドロキシエチルメタクリレート(1.0g)、上記一般式(6)で示されるシリコーンマクロマー(13.3g)、イソプロピルアルコール(16.6g)、パーブチルO(日本油脂株式会社製)(2.0g)を混合し、滴下ロートを用いて、セパラブルフラスコへ1時間かけて滴下した。滴下後、2時間撹拌して、追加でパーブチルO(0.3g)を加えた。さらに3時間撹拌し、反応を終了した。その後、溶媒を減圧留去して(110℃、1kPa以下)、目的の共重合体を得た。また、数平均分子量はMn=22,240であった。
実施例及び比較例の共重合体2gを、各油剤(イソドデカン(INCI)、イソステアリルアルコール(INCI)、デカメチルシクロペンタシロキサン(D5)(INCI:Cyclopentasiloxane)8gに溶解した。室温(25℃)に戻して、ゲルを形成させ、ゲル化能を評価した。評価結果は、耐熱性の高いゲル(50℃でもゲル状態を保持)を形成したものを「◎」ゲル化したものを「○」、増粘したものを「△」、溶解してしまったものを「×」、油剤へ溶解しなかったものを「不溶」とした。「〇」以上を合格とする。実施例と比較例を比較すると、実施例のゲル化剤は、疎水性の油剤と高級アルコールの両方をゲル化することができた。また、実施例5はシリコーン系の油剤をゲル化することができ、その他の油剤に関しても増粘効果があった。
(成分) 質量(%)
1.ポリエチレン(INCI) 14.0
2.マイクロクリスタリンワックス(INCI) 4.0
3.ポリブテン(INCI) 10.0
4.実施例4に記載のオイルゲル化剤 15.0
5.オクタン酸セチル 20.0
(INCI:Cetyl Ethylhexanoate)
6.トリイソステアリン (INCI) 37.0
7.顔料 適量
8.防腐剤 適量
9.香料 適量
合計 100.0
A:成分5~6を均一に混合した
B:成分1~4を加熱(90℃)して溶解し、Aで得られたものに加えて均一にした。
C:80℃で成分7~9をBで得られたものに加えて均一にした。
以上のようにして得られた口紅は、のびが軽くて油っぽさや粉っぽさがない上、さっぱりとした使用感を与えるものであった。また、耐水性や撥水性が良好で持ちも良く、安定性にも優れているものであった。
(成分) 質量(%)
1.実施例1に記載のオイルゲル化剤 8.0
2.架橋型メチルフェニルポリシロキサン(注1) 2.0
(表示名称:(ジメチコン/フェニルビニルジメチコン)クロスポリマー(INCI:Dimethicone/Phenyl Vinyl dimethicone crosspolymer)、ジフェニルシロキシフェニルトリメチコン)(INCI)
3.イソノナン酸イソトリデシル 5.0
(INCI:Isotridecyl Isononanoate)
4.DPG (INCI) 7.0
5.グリセリン(INCI) 5.0
6.メチルセルロース(INCI)(2%水溶液)(注2) 7.0
7.ポリアクリルアミド系乳化剤(注3) 2.0
(表示名称:ポリアクリルアミド(INCI)、(C13,14)イソパラフィン(INCI)、ラウレス-7(INCI)、水)
8.グアニン(INCI) 1.0
9.防腐剤 適量
10.香料 適量
11.精製水 63.0
合計 100.0
(注1)信越化学工業(株)製:KSG-18
(注2)信越化学工業(株)製:メトローズSM-4000
(注3)SEPIC製:セピゲル305
A:成分4~11を混合した。
B:成分1~3を混合し、Aで得られたものを加えて攪拌乳化した。
以上のようにして得られたクリームは、キメが細かく、のび広がりが軽くてべたつきや油っぽさがない上しっとりとしてみずみずしく、さっぱりとした使用感を与えるものであった。また、化粧持ちが非常に良く、温度変化や経時による変化もなく安定性に優れているO/W型クリームであることが確認された。
(成分) 質量(%)
1.実施例4に記載のオイルゲル化剤 4.0
2.ポリエーテル・アルキル共変性分岐型シリコーン(注1) 1.0
(表示名称:ラウリルPEG-9ポリジメチルシロキシエチルジメチコン(INCI)
3.トリエチルヘキサノイン(INCI) 2.0
4.オクタン酸セチル 5.0
(INCI:Cetyl Ethylhexanoate)
5.イソノナン酸イソトリデシル 9.0
(INCI:Isotridecyl Isononanoate)
6.ハイブリッドシリコーン複合紛体(注2) 3.0
(表示名称:(ビニルジメチコン/メチコンシルセスキオキサン)クロスポリマー(INCI:(INCI:Vinyldimethicone/Methicone Silsesquioxane Crosspolymer))
7.ポリグリセリン共変性分岐型シリコーン(注3) 0.6
(表示名称:ポリグリセリル-3ジシロキサンジメチコン(INCI))
8.ポリグリセリン共変性分岐型シリコーン(注4) 0.3
(表示名称:ラウリルポリグリセリル-3ポリジメチルシロキシエチルジメチコン(INCI))
9.アルキル・シリコーン処理顔料(注5) 10.0
(表示名称:トリエトキシシリルエチルポリジメチルシロキシエチルヘキシルジメチコン(INCI))
10.BG(INCI:Butylene Glycol) 5.0
11.塩化ナトリウム 0.5
12.クエン酸ナトリウム 0.2
13.防腐剤 適量
14.香料 適量
15.精製水 59.4
合計 100.0
(注1)信越化学工業(株)製:KF-6038
(注2)信越化学工業(株)製:KSP-100
(注3)信越化学工業(株)製:KF-6100
(注4)信越化学工業(株)製:KF-6105
(注5)信越化学工業(株)製:KF-9909
A:成分1~6を均一に混合した。
B:成分7~10を均一に混合した。
C:成分11~13、及び15の一部を混合溶解した。
D:Bで得られたものを成分15の残部に加え均一にした。
E:Cで得られたものをAで得られたものに加えて乳化した。
F:さらにDで得られたものをEで得られたものに加えて乳化し、最後に成分14を加えて均一にした。
以上のようにして得られたクリームファンデーションは、べたつきがなく、のび広がりも軽く、しかも、顔料の分散性が良く、密着感に優れ、おさまりも良く、マット感のある仕上がり膜の非常にきれいなW/Oクリームファンデーションが得られた。
(成分) 質量(%)
1.ジステアリン酸グリコール 12.0
(INCI:Glycol Distearate)
2.実施例4に記載のオイルゲル化剤 5.0
3.イソノナン酸イソトリデシル 35.0
(INCI:Isotridecyl Isononanoate)
4.キャンデリラロウ 2.0
(INCI:Euphorbia Cerifera(Candelilla)Wax)
5.レシチン(INCI) 0.2
6.ハイブリッドシリコーン複合紛体(注1) 3.0
(表示名称:(ビニルジメチコン/メチコンシルセスキオキサン)クロスポリマー(INCI:Vinyldimethicone/Methicone Silsesquioxane Crosspolymer))
7.アルキル・シリコーン処理顔料(注2) 適量
(表示名称:酸化鉄(INCI:Iron Oxides)、トリエトキシシリルエチルポリジメチルシロキシエチルヘキシルジメチコン(INCI))
8.マイカ処理酸化チタン 残量
合計 100.0
(注1)信越化学工業(株)製:KSP-100
(注2)信越化学工業(株)製:KTP-09
B:成分6~8を混合した。
C:成分1、4~5を混合し、Aで得られたものを加えて加温する。
D:Cで得られたものをBで得られたものに加えて、容器に流し込む。
以上のようにして得られたアイカラーは、油っぽさ、べたつきがなく、のび広がりも軽く、さっぱりとした使用性を持ち、しかも、密着感に優れ、おさまりも良く化粧もちに優れたアイカラーであった。
本発明の化粧料は、使用感に優れ、良好な経時安定性を有するので、実用上極めて有用である。また、本発明の組成物は、実用される化粧料の原料成分であるので、産業上の有用性は大きい。
Claims (3)
- 請求項1又は2に記載のオイルゲル化剤を含有する化粧料。
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005145851A (ja) | 2003-11-13 | 2005-06-09 | Chiba Flour Milling Co Ltd | オイルゲル化剤、その製造方法並びにそれを含有するオイルゲル及び化粧料 |
JP2012072081A (ja) * | 2010-09-28 | 2012-04-12 | Shin-Etsu Chemical Co Ltd | 化粧料 |
JP2016503792A (ja) * | 2012-12-20 | 2016-02-08 | ルブリゾル アドバンスド マテリアルズ, インコーポレイテッド | コポリマー増粘薬/安定剤を含有するカルボキシエチルアクリレートおよびケラチン性基材上のシリコーン沈着の喪失を緩和する方法 |
WO2016098456A1 (ja) | 2014-12-19 | 2016-06-23 | 株式会社 資生堂 | 共重合体および油性ゲル化剤 |
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- 2022-11-30 EP EP22904111.6A patent/EP4445960A1/en active Pending
- 2022-11-30 CN CN202280080439.2A patent/CN118354757A/zh active Pending
- 2022-11-30 KR KR1020247022224A patent/KR20240119099A/ko unknown
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005145851A (ja) | 2003-11-13 | 2005-06-09 | Chiba Flour Milling Co Ltd | オイルゲル化剤、その製造方法並びにそれを含有するオイルゲル及び化粧料 |
JP2012072081A (ja) * | 2010-09-28 | 2012-04-12 | Shin-Etsu Chemical Co Ltd | 化粧料 |
JP2016503792A (ja) * | 2012-12-20 | 2016-02-08 | ルブリゾル アドバンスド マテリアルズ, インコーポレイテッド | コポリマー増粘薬/安定剤を含有するカルボキシエチルアクリレートおよびケラチン性基材上のシリコーン沈着の喪失を緩和する方法 |
WO2016098456A1 (ja) | 2014-12-19 | 2016-06-23 | 株式会社 資生堂 | 共重合体および油性ゲル化剤 |
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KR20240119099A (ko) | 2024-08-06 |
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