WO2017170200A1 - ジェル組成物、化粧料、およびジェル組成物の製造方法 - Google Patents
ジェル組成物、化粧料、およびジェル組成物の製造方法 Download PDFInfo
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- WO2017170200A1 WO2017170200A1 PCT/JP2017/011953 JP2017011953W WO2017170200A1 WO 2017170200 A1 WO2017170200 A1 WO 2017170200A1 JP 2017011953 W JP2017011953 W JP 2017011953W WO 2017170200 A1 WO2017170200 A1 WO 2017170200A1
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- mass
- gel composition
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- 239000000203 mixture Substances 0.000 title claims abstract description 94
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- 238000004519 manufacturing process Methods 0.000 title claims description 27
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- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 claims abstract description 65
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 21
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- 125000000217 alkyl group Chemical group 0.000 claims abstract description 14
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- 239000007787 solid Substances 0.000 claims description 20
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 16
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- 150000004665 fatty acids Chemical class 0.000 claims description 15
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 14
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- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
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- RFIMISVNSAUMBU-UHFFFAOYSA-N 2-(hydroxymethyl)-2-(prop-2-enoxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC=C RFIMISVNSAUMBU-UHFFFAOYSA-N 0.000 claims description 5
- XSSOJMFOKGTAFU-UHFFFAOYSA-N 3-[2-(2-prop-2-enoxyethoxy)ethoxy]prop-1-ene Chemical compound C=CCOCCOCCOCC=C XSSOJMFOKGTAFU-UHFFFAOYSA-N 0.000 claims description 3
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 claims description 3
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- 229930006000 Sucrose Natural products 0.000 claims description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 3
- 235000013681 dietary sucrose Nutrition 0.000 claims description 3
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- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 25
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- 230000000052 comparative effect Effects 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
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- 238000000034 method Methods 0.000 description 4
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- FYRWKWGEFZTOQI-UHFFFAOYSA-N 3-prop-2-enoxy-2,2-bis(prop-2-enoxymethyl)propan-1-ol Chemical compound C=CCOCC(CO)(COCC=C)COCC=C FYRWKWGEFZTOQI-UHFFFAOYSA-N 0.000 description 3
- CMVNWVONJDMTSH-UHFFFAOYSA-N 7-bromo-2-methyl-1h-quinazolin-4-one Chemical compound C1=CC(Br)=CC2=NC(C)=NC(O)=C21 CMVNWVONJDMTSH-UHFFFAOYSA-N 0.000 description 3
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- 238000001035 drying Methods 0.000 description 2
- 238000009775 high-speed stirring Methods 0.000 description 2
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 2
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- GOHZKUSWWGUUNR-UHFFFAOYSA-N 2-(4,5-dihydroimidazol-1-yl)ethanol Chemical compound OCCN1CCN=C1 GOHZKUSWWGUUNR-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
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- A61K8/442—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof substituted by amido group(s)
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- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- A61K8/8147—Homopolymers or copolymers of acids; Metal or ammonium salts thereof, e.g. crotonic acid, (meth)acrylic acid; Compositions of derivatives of such polymers
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- A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/02—Preparations for cleaning the hair
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
Definitions
- the present invention is, for example, a gel composition that can be suitably used as a thickening agent for viscous liquids and gel cosmetics, used for hair care such as shampoo, skin care such as body shampoo, face wash, etc., a method for producing the same, And a cosmetic comprising the gel composition.
- a thickener for cosmetics for example, natural products such as xanthan gum, semi-synthetic materials such as hydroxyethyl cellulose, and synthetic materials such as carboxyvinyl polymers and alkyl-modified carboxyvinyl polymers are widely used.
- carboxyl group-containing polymers such as carboxyvinyl polymers and alkyl-modified carboxyvinyl polymers exhibit excellent thickening with a small amount of use and can control the feeling of use of cosmetics, and are therefore used in various cosmetics. Yes.
- carboxyl group-containing polymer examples include a carboxyvinyl polymer obtained by reacting acrylic acid and pentaerythritol allyl ether as a crosslinking agent in a specific mixed solvent (see Patent Document 1), and a specific amount of olefinic unsaturated.
- a copolymer obtained by reacting a carboxylic acid monomer with a specific amount of (meth) acrylic acid alkyl ester (alkyl group having 10 to 30 carbon atoms) (see Patent Document 2), a specific amount of olefinic unsaturated carboxylic acid
- a copolymer obtained by reacting an acid monomer with a specific amount of (meth) acrylic acid alkyl ester (alkyl group having 10 to 30 carbon atoms) and a crosslinking agent see Patent Document 3
- an olefinically unsaturated carboxylic acid Alkyls such as copolymers (see Patent Document 4) obtained by reacting monomers with alkyl esters of (meth) acrylic acid (alkyl group having 8 to 30 carbon atoms)
- Modified carboxyvinyl polymers are known. These carboxyl group-containing polymers are usually used in cosmetics by dissolving in water or the like and then neutralizing with an alkali component to obtain a neutralized viscous liquid of about
- the coconut oil fatty acid amidopropyl betaine has excellent detergency, safety and low irritation to the skin. Hypoallergenic and safe enough to be used for baby shampoos. It is used for cleaning cosmetics such as shampoo.
- the main object of the present invention is to provide a gel composition containing a betaine emulsifier and suitably used as a thickener such as a cosmetic, a method for producing the same, and a cosmetic containing the gel composition. To do.
- the present invention provides an invention having the following configuration.
- Item 1 100 parts by weight of (meth) acrylic acid (a), 2.5 to 5 parts by weight of (meth) acrylic acid alkyl ester (b) having an alkyl group having 18 to 24 carbon atoms, and two ethylenically unsaturated groups
- a gel composition comprising a neutralized product of an alkyl-modified carboxyl group-containing polymer, which is a copolymer of monomers containing not more than 0.1 parts by mass of the compound (c) and a betaine emulsifier.
- Item 2. Item 2. The gel composition according to Item 1, wherein the viscosity at 25 ° C when having the following composition is 50,000 mPa ⁇ s or more.
- composition A composition comprising 96 parts by weight of a 1% by weight neutralized viscous liquid of an alkyl-modified carboxyl group-containing polymer and 4 parts by weight of an aqueous solution of a betaine emulsifier (solid content is about 30% by weight).
- the alkyl-modified carboxyl group-containing polymer has a viscosity at 25 ° C. of not more than 1500 mPa ⁇ s and a light transmittance of not less than 90% when a 1% by weight neutralized viscous liquid is obtained, The maximum viscosity at 25 ° C.
- the compound (c) having two or more ethylenically unsaturated groups is at least one selected from the group consisting of pentaerythritol allyl ether, diethylene glycol diallyl ether, polyethylene glycol diallyl ether, and polyallyl saccharose. 5.
- the gel composition according to any one of 4. Item 6.
- Item 7. Item 7.
- a cosmetic comprising the gel composition according to any one of Items 1 to 6.
- an alkyl-modified carboxyl group-containing polymer which is a copolymer of monomers containing 0.1 parts by mass or less of the compound (c), is mixed with an alkali component.
- a step of preparing a Japanese product Mixing the neutralized product of the alkyl-modified carboxyl group-containing polymer with a betaine emulsifier; A method for producing a gel composition.
- a gel composition that contains a betaine emulsifier and can be suitably used as a thickener such as cosmetics, and a method for producing the same.
- the gel composition of the present invention includes a neutralized product of an alkyl-modified carboxyl group-containing polymer and a betaine-based emulsifier, and the gel composition of the present invention comprises an alkyl-modified carboxyl group-containing polymer (meth).
- the “neutralized viscous liquid” means that the pH of the aqueous dispersion of the alkyl-modified carboxyl group-containing polymer is a predetermined value (usually, the pH is about 3.5 to 6.5).
- Viscosity obtained by mixing an alkali component for example, alkali metal hydroxide such as sodium hydroxide, amines such as triethanolamine, diisopropanolamine, etc.
- an alkali component for example, alkali metal hydroxide such as sodium hydroxide, amines such as triethanolamine, diisopropanolamine, etc.
- the “1% by mass neutralized viscous liquid” means a neutralized viscous liquid in which the proportion of the neutralized product of the alkyl-modified carboxyl group-containing polymer is 1% by mass.
- the neutralized product of the alkyl-modified carboxyl group-containing polymer is a compound obtained by partially or completely neutralizing the alkyl-modified carboxyl group-containing polymer with the alkali component as described above.
- the neutralized product of the alkyl-modified carboxyl group-containing polymer is usually a partially neutralized product of the alkyl-modified carboxyl group-containing polymer. It is.
- the pH before neutralizing the alkyl-modified carboxyl group-containing polymer is usually about 2.5 to 3.
- the alkyl-modified carboxyl group-containing polymer is composed of 100 parts by weight of (meth) acrylic acid (hereinafter sometimes referred to as component (a)), and a (meth) acrylic acid alkyl ester having 18 to 24 carbon atoms in the alkyl group (
- component (b) may be 2.5 to 5 parts by mass
- component (c) the compound having two or more ethylenically unsaturated groups
- It is a copolymer. That is, at least the components (a) and (b) are copolymerized in the alkyl-modified carboxyl group-containing polymer of the present invention, and the component (c) is also copolymerized as necessary.
- (meth) acrylic acid (component (a)) at least one of acrylic acid and methacrylic acid can be used.
- the (meth) acrylic acid alkyl ester (component (b)) having an alkyl group having 18 to 24 carbon atoms is an ester of (meth) acrylic acid and a higher alcohol having an alkyl group having 18 to 24 carbon atoms. is there.
- Specific examples of component (b) include esters of (meth) acrylic acid and stearyl alcohol (ie, stearyl (meth) acrylate), esters of (meth) acrylic acid and eicosanol (ie, (meth) acrylic acid).
- Eicosanyl esters of (meth) acrylic acid and behenyl alcohol (ie, behenyl (meth) acrylate), esters of (meth) acrylic acid and tetracosanol (ie, tetracosanyl (meth) acrylate), etc.
- esters of (meth) acrylic acid and behenyl alcohol ie, behenyl (meth) acrylate
- esters of (meth) acrylic acid and tetracosanol ie, tetracosanyl (meth) acrylate
- stearyl methacrylate, eicosanyl methacrylate, behenyl methacrylate, tetracosanyl methacrylate and the like are preferably used.
- one type of component (b) constituting the monomer may be used, or two or more types may be used.
- component (b) for example, trade name Blemmer VMA-70 manufactured by Nippon Oil & Fats Co., Ltd. (stearyl methacrylate is 10 to 20 parts by mass, eicosanyl methacrylate is 10 parts by mass)
- stearyl methacrylate is 10 to 20 parts by mass
- eicosanyl methacrylate is 10 parts by mass
- To 20 parts by mass 59 to 80 parts by mass of behenyl methacrylate, and 1 part by mass or less of tetracosanyl methacrylate) can be used.
- the proportion of component (b) in the alkyl-modified carboxyl group-containing polymer is 2.5 to 5 parts by mass with respect to 100 parts by mass of (meth) acrylic acid (component (a)).
- the proportion of the component (b) is preferably 3 to 4 parts by mass with respect to 100 parts by mass of the component (a). Part.
- the proportion of component (b) is less than 2.5 parts by mass relative to 100 parts by mass of component (a)
- the viscosity of the gel composition tends to be low in the presence of a betaine emulsifier.
- the amount exceeds 5 parts by mass the viscosity of the gel composition tends to be low.
- the compound having two or more ethylenically unsaturated groups is a compound having two or more ethylenically unsaturated groups having polymerizability.
- a component (c) comprises the monomer of the alkyl-modified carboxyl group containing polymer as needed.
- the component (c) include pentaerythritol polyallyl ethers such as pentaerythritol diallyl ether, pentaerythritol triallyl ether, pentaerythritol tetraallyl ether, etc.
- ether diethylene glycol diallyl ether, polyethylene glycol diallyl ether, polyallyl saccharose and the like.
- the component (c) constituting the monomer may be one type or two or more types as necessary.
- the proportion of component (c) in the alkyl-modified carboxyl group-containing polymer is 0.1 parts by mass or less, preferably 0.0001-0.100, per 100 parts by mass of (meth) acrylic acid (component (a)). 05 parts by mass, more preferably 0.001 to 0.044 parts by mass.
- the ratio of a component (c) exceeds 0.1 mass part, the viscosity of a gel composition will fall easily and there exists a possibility that the stability of the cosmetics using the said gel composition may deteriorate.
- the monomer other than the above-mentioned components (a) to (c) (other monomer capable of copolymerization with at least one of components (a) to (c)) Body) may be copolymerized.
- lauryl (meth) acrylate can be used in a proportion of more than 0 parts by weight and 1 part by weight or less with respect to 100 parts by weight of the total amount of components (a) to (c).
- the total ratio of components (a) to (c) in the monomer constituting the alkyl-modified carboxyl group-containing polymer is not particularly limited, but is preferably 50% by mass or more, more preferably About 80% by mass to 100% by mass, more preferably about 90% by mass to 100% by mass, and particularly preferably about 95% by mass to 100% by mass.
- the total ratio may be substantially 100% by mass.
- the production method of the alkyl-modified carboxyl group-containing polymer is not particularly limited, and a raw material containing at least the above-mentioned component (a) and component (b), and a solution obtained by adding a polymerization initiator to a solvent are treated with an inert gas atmosphere. There is a method of polymerizing by heating while stirring under.
- the inert gas for making the inert gas atmosphere is not particularly limited, and examples thereof include nitrogen gas and argon gas.
- the solvent is not particularly limited as long as at least the component (a) and the component (b) are dissolved but the produced alkyl-modified carboxyl group-containing polymer is not dissolved and does not inhibit the copolymerization reaction.
- Specific examples of the solvent include hydrocarbon solvents such as normal pentane, normal hexane, normal heptane, cyclopentane and cyclohexane; ester solvents such as methyl acetate, ethyl acetate, propyl acetate and butyl acetate.
- a solvent may be used by 1 type and may be used in combination of 2 or more type. Among these solvents, normal hexane, normal heptane, ethyl acetate and the like are preferably used.
- the amount of the solvent used is preferably 300 to 5,000 parts by mass with respect to 100 parts by mass of component (a), from the viewpoint of improving the stirring operability and economy.
- the polymerization initiator for example, a radical polymerization initiator is preferable.
- the polymerization initiator include ⁇ , ⁇ ′-azoisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (methylisobutyrate), and the like. is there.
- 2,2'-azobis (methyl isobutyrate) is preferable from the viewpoint of easily obtaining a high molecular weight alkyl-modified carboxyl group-containing polymer.
- a polymerization initiator may be used by 1 type and may be used in combination of 2 or more types.
- the amount of the polymerization initiator used is preferably about 0.00003 mol to 0.002 mol with respect to 1 mol of component (a) from the viewpoint of keeping the reaction rate moderate.
- the polymerization temperature is preferably about 50 ° C. to 90 ° C., more preferably about 55 ° C. to 75 ° C., from the viewpoint of keeping the reaction rate moderate.
- the polymerization time varies depending on the polymerization temperature, but is usually about 0.5 to 5 hours.
- the alkyl-modified carboxyl group-containing polymer is obtained. Obtainable. By setting the heating temperature at this time to 80 ° C. or higher, the drying time can be shortened. Moreover, the fall of the dispersibility to the water of the alkyl-modified carboxyl group containing polymer can be suppressed suitably by making heating temperature into 130 degrees C or less.
- the alkyl-modified carboxyl group-containing polymer (not in the presence of a betaine emulsifier) is 1% by weight neutralized viscosity.
- the viscosity at 25 ° C. in the case of a solid liquid is preferably 1500 mPa ⁇ s or less and the light transmittance is preferably 90% or more, and the viscosity is 100 to 1000 mPa ⁇ s and the light transmittance is 96% or more. More preferred.
- the light transmittance is preferably 90% or more, the maximum viscosity is 15000 to 26000 mPa ⁇ s, and the light transmittance is more preferably 96% or more.
- the viscosity and the light transmittance mean values measured by the methods described in the examples.
- the content of the neutralized product of the alkyl-modified carboxyl group-containing polymer is not particularly limited, but is preferably about 0.1% by mass to 2% by mass, more preferably 0.5% by mass. % To 1.5% by mass.
- the betaine emulsifier is preferably 2-lauryl-N-carboxylmethyl-N′- from the viewpoint of increasing the viscosity of the gel composition in the presence of the neutralized product of the alkyl-modified carboxyl group-containing polymer.
- Examples include hydroxyethyl imidazolinium betaine, lauric acid amidopropyl hydroxysulfobetaine, coconut oil fatty acid amidopropyl betaine, lauric acid amidopropyl betaine, myristyl amidopropyl betaine, and palm kernel oil fatty acid amidopropyl betaine.
- coconut oil fatty acid amidopropyl betaine from the viewpoint that foaming is good when the gel composition of the present invention is blended in cosmetics, and that the conditioning effect is obtained with low irritation.
- betaine emulsifiers may be used alone, or two or more thereof may be used in combination.
- the content of the betaine emulsifier is, for example, preferably about 0.67% by mass to 20% by mass as the betaine emulsifier aqueous solution having a solid content of about 30% by mass (the content of the betaine emulsifier About 0.2 to 6% by mass).
- the content of the aqueous solution of the betaine emulsifier is more preferably It is about 4 to 8% by mass (the content of the betaine emulsifier is about 1.2 to 2.4% by mass).
- the content of the aqueous solution of the betaine emulsifier is 0.67% by mass.
- the content of the betaine emulsifier is about 0.2% by mass to 0.8% by mass).
- the amount of the betaine emulsifier aqueous solution is about 0.67% by mass to 2.67% by mass (the content of the betaine emulsifier is about 0.2% by mass to 0.8% by mass).
- a gel composition having a high viscosity can be obtained even under a low pH range of 4.4 to 5.5, and it can be suitably used as a thickener for cosmetics and the like.
- the gel composition of the present invention has a particularly large difference in viscosity before and after adding the betaine emulsifier in such a low pH range.
- a gel composition having a high viscosity can be suitably obtained in a low pH range.
- the viscosity at 25 ° C. is preferably 50,000 mPa ⁇ s or more, and more preferably 100,000 mPa ⁇ s or more.
- the upper limit of the viscosity is not particularly limited because it varies depending on the application and purpose, but is preferably 200,000 mPa ⁇ s or less, more preferably 150,000 mPa ⁇ s or less.
- composition 96 parts by weight of a 1% by weight neutralized viscous liquid of an alkyl-modified carboxyl group-containing polymer and an aqueous solution of a betaine-based emulsifier (solid content is about 30% by weight; for example, 28 to 33% by weight, in particular 31.5% by weight )
- a composition comprising 4 parts by mass.
- the content of the betaine emulsifier is in the range of 0.2% by mass to 0.8% by mass
- the viscosity can be, for example, 20,000 mPa ⁇ s or more, and further 53,000 mPa ⁇ s or more. In this case, the upper limit of the viscosity is usually about 200,000 mPa ⁇ s.
- the details of the mechanism that the gel composition of the present invention has high viscosity and can be suitably used as a thickener for cosmetics and the like are not necessarily clear, but can be considered as follows, for example. That is, in the present invention, the neutralized product of the alkyl-modified carboxyl group-containing polymer contained in the gel composition is obtained by copolymerizing the above-mentioned components (a) to (c) in the predetermined amount.
- the neutralized product of the alkyl-modified carboxyl group-containing polymer and the betaine-based emulsifier preferably form an aggregate in water and thicken, so it is considered that the gel composition has a high viscosity. .
- the gel composition of the present invention usually contains water in addition to the components (a) to (c).
- the water content in the gel composition of the present invention is not particularly limited, but is preferably 91.4 to 99.3% by mass, more preferably 92.0 to 99.0% by mass.
- the gel composition of the present invention has other thickeners, alcohols, pH adjusters, humectants, oils, salts, anionic surfactants, nonionic surfactants, as long as the purpose is not impaired.
- Various additives such as a cationic surfactant, a chelating agent, an antiseptic, an antioxidant, an ultraviolet absorber, a dye, and a fragrance may be included.
- the gel composition of the present invention can be suitably used as a thickening agent for viscous liquid or gel cosmetics used in hair care such as shampoo, skin care such as body shampoo and face wash.
- the cosmetic of the present invention includes the gel composition of the present invention, and may further include various cosmetic ingredients blended in the cosmetic.
- the pH of the gel composition can be adjusted to a desired value by adding an alkali component before and after mixing the betaine emulsifier.
- various additives may be further mixed.
- Various additives can be mixed before and after mixing the neutralized product of the alkyl-modified carboxyl group-containing polymer and the betaine emulsifier.
- Production Example 2 A white fine powdery alkyl-modified carboxyl group-containing polymer (polymer) in the same manner as in Production Example 1 except that the amount of Blemmer VMA70 (Nippon Yushi Co., Ltd.) used in Production Example 1 was changed to 1.125 g. 2) 45 g was obtained.
- Production Example 5 In Production Example 1, the amount of use of Blemmer VMA70 (manufactured by NOF Corporation) was changed to 1.125 g, and the amount of pentaerythritol allyl ether (mixture of pentaerythritol triallyl ether and pentaerythritol tetraallyl ether) was changed to 0.1. 45 g of a white fine powdery alkyl-modified carboxyl group-containing polymer (polymer 5) was obtained in the same manner as in Production Example 1 except that the amount was changed from 02 g to 0.135 g.
- Example 1 Ultra-high speed stirring system with disper blades ( ⁇ 40mm) K. Using ROBOMIX (manufactured by PRIMIX Co., Ltd.), 10 g of the polymer 1 was gradually added and dispersed in a 2 L beaker containing 977.7 g of distilled water at a stirring speed of 5000 rpm. After stirring at 5000 rpm for 10 minutes, the stirring speed was lowered to 3000 rpm and stirring was continued for 20 minutes. Thereafter, 12.3 g of an 18% by mass aqueous sodium hydroxide solution was added at a stirring speed of 1400 revolutions per minute to prepare a colorless and transparent neutralized viscous liquid. The neutralized viscous liquid had a pH of 6.4.
- This neutralized viscous liquid was subjected to spindle rotor No. 5 at 25 ° C. using a BH type rotational viscometer.
- the viscosity after 1 minute was measured at a rotation speed of 5 at 20 revolutions per minute, and found to be 330 mPa.s. s (an aqueous solution of a betaine emulsifier (solid content is about 30% by mass), but 0% by mass).
- this neutralized viscous liquid is subdivided into 200 L beakers, and 6 g of coconut oil fatty acid amide propyl betaine liquid as a betaine emulsifier under a stirring speed of 500 revolutions per minute using four paddle blades ( ⁇ 50 mm) Rikabion B-200, solid content 31.5% by mass) was slowly added, the stirring speed was increased to 1000 rpm, and mixed for 1 hour to prepare a gel composition (an aqueous solution of a betaine emulsifier (solid The content is about 30% by mass) and 4% by mass). About the gel composition at this time, spindle rotor No. was measured at 25 ° C. using a BH type rotational viscometer.
- Table 7 shows the viscosities of gel compositions prepared in the same manner so that an aqueous solution of a betaine emulsifier (solid content: about 30% by mass) is 6% by mass and 8% by mass.
- Example 2 A gel composition was prepared in the same manner as in Example 1 except that the polymer 1 was changed to the polymer 2 in Example 1, and the viscosity was measured. The results are shown in Tables 6 and 7.
- Example 3 In Example 1, a gel composition was prepared and the viscosity was measured in the same manner as in Example 1 except that the polymer 1 was changed to the polymer 3. The results are shown in Tables 6 and 7.
- Example 1 In Example 1, a gel composition was prepared and the viscosity was measured in the same manner as in Example 1 except that the polymer 1 was changed to the polymer 4. The results are shown in Tables 6 and 7.
- Example 2 In Example 1, a gel composition was prepared and the viscosity was measured in the same manner as in Example 1 except that the polymer 1 was changed to the polymer 5. The results are shown in Tables 6 and 7.
- Example 4 As in Example 1, an ultra-high speed stirring system T.D. with a disper blade ( ⁇ 40 mm) set. K. Using ROBOMIX (manufactured by Primix Co., Ltd.), 10 g of the polymer 1 was gradually added and dispersed in a 2 L beaker containing 987.7 g of distilled water at a stirring speed of 5000 rpm. After stirring at 5000 rpm for 10 minutes, the stirring speed was lowered to 3000 rpm and stirring was continued for 20 minutes.
- ROBOMIX manufactured by Primix Co., Ltd.
- 144 g of the neutralized viscous liquid in which the polymer 1 is adjusted to about pH 3.8 is subdivided into 200 L beakers, using a 4-paddle blade ( ⁇ 50 mm) at a stirring speed of 500 revolutions per minute. 8 (each coconut oil fatty acid amidopropyl betaine content (solid content) 0.25 mass%, 0.50 mass%, 0.75 mass%)
- Each gel composition was prepared by slowly adding (Rikabion B-200, manufactured by Shin Nippon Rika Co., Ltd., solid content: 31.5% by mass), increasing the stirring speed to 1000 rpm and mixing for 1 hour.
- the pH is 4. It can be seen that the gel composition has a high viscosity even under a low pH of about 4 to 5.5.
- various components should be uniformly mixed in a low viscosity state before adding betaine emulsifier, and then betaine emulsifier should be added.
- a gel composition having a high viscosity can be suitably prepared in a low pH range.
- the viscosity of the composition is very low. Can be easily uniformly dispersed and dissolved, and then a predetermined amount of a betaine emulsifier is added (for example, coconut oil fatty acid amidopropyl betaine content (solid content) of 0.25% by mass,. 50 mass%, 0.75 mass%), it turns out that a highly viscous gel composition is obtained.
- a betaine emulsifier for example, coconut oil fatty acid amidopropyl betaine content (solid content) of 0.25% by mass,. 50 mass%, 0.75 mass
- Example 3 A neutralized viscous liquid having a pH of about 3.8 was prepared in the same manner as in Example 4 except that the polymer 5 was used instead of the polymer 1. Next, by adding a predetermined amount of 18 mass% sodium hydroxide aqueous solution and stirring uniformly, the pH was changed as shown in Table 9, and the viscosity at each pH of the neutralized viscous liquid was measured (Table 9 coconut oil fatty acid amidopropyl betaine content (solid content) 0 mass% (standard)). The results are shown in Table 9.
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Abstract
Description
項1. (メタ)アクリル酸(a)100質量部、アルキル基の炭素数が18~24である(メタ)アクリル酸アルキルエステル(b)2.5~5質量部、およびエチレン性不飽和基を2個以上有する化合物(c)0.1質量部以下を含む単量体の共重合体であるアルキル変性カルボキシル基含有重合体の中和物と、ベタイン系乳化剤とを含む、ジェル組成物。
項2. 以下の組成を有する場合の25℃における粘度が、50,000mPa・s以上となる、項1に記載のジェル組成物。
(組成)
アルキル変性カルボキシル基含有重合体の1質量%中和粘稠液96質量部と、ベタイン系乳化剤の水溶液(固形分が約30質量%)4質量部とからなる組成。
項3. 前記アルキル変性カルボキシル基含有重合体は、1質量%中和粘稠液とした場合の25℃下における粘度が1500mPa・s以下、光透過率が90%以上であり、
当該1質量%中和粘稠液100質量部に対して、0.25~3質量部の塩化ナトリウムを添加したときの25℃下における最高粘度が、15,000~40,000mPa・sであり、光透過率が90%以上である、項1または2に記載のジェル組成物。
項4. 前記ベタイン系乳化剤の含有量が、0.2質量%~0.8質量%の範囲内にあり、
pHが4.4~5.5の範囲にある、項1または3に記載のジェル組成物。
項5. 前記エチレン性不飽和基を2個以上有する化合物(c)が、ペンタエリスリトールアリルエーテル、ジエチレングリコールジアリルエーテル、ポリエチレングリコールジアリルエーテルおよびポリアリルサッカロースからなる群より選ばれた少なくとも1種である、項1~4のいずれかに記載のジェル組成物。
項6. 前記ベタイン系乳化剤が、ヤシ油脂肪酸アミドプロピルベタインである、項1~5のいずれかに記載のジェル組成物。
項7. 項1~6のいずれかに記載のジェル組成物を含む、化粧料。
項8. (メタ)アクリル酸(a)100質量部、アルキル基の炭素数が18~24である(メタ)アクリル酸アルキルエステル(b)2.5~5質量部、およびエチレン性不飽和基を2個以上有する化合物(c)0.1質量部以下を含む単量体の共重合体であるアルキル変性カルボキシル基含有重合体と、アルカリ成分とを混合して、前記アルキル変性カルボキシル基含有重合体の中和物を調製する工程と、
前記アルキル変性カルボキシル基含有重合体の中和物と、ベタイン系乳化剤とを混合する工程と、
を備える、ジェル組成物の製造方法。
アルキル変性カルボキシル基含有重合体の1質量%中和粘稠液96質量部と、ベタイン系乳化剤の水溶液(固形分が約30質量%;例えば28~33質量%、特に詳しくは31.5質量%)4質量部とからなる組成。
(メタ)アクリル酸(a)100質量部、アルキル基の炭素数が18~24である(メタ)アクリル酸アルキルエステル(b)2.5~5質量部、およびエチレン性不飽和基を2個以上有する化合物(c)0.1質量部以下を含む単量体の共重合体である、前述のアルキル変性カルボキシル基含有重合体と、前述のアルカリ成分とを混合して、前記アルキル変性カルボキシル基含有重合体の中和物を調製する工程
前記アルキル変性カルボキシル基含有重合体の中和物と、前記ベタイン系乳化剤とを混合する工程
攪拌機、温度計、窒素吹き込み管および冷却管を備えた500mL容の四つ口フラスコに、アクリル酸45g(0.625モル)、ブレンマーVMA70(日本油脂株式会社製:メタクリル酸ステアリルが10~20質量部、メタクリル酸エイコサニルが10~20質量部、メタクリル酸ベヘニルが59~80質量部およびメタクリル酸テトラコサニルの含有量が1質量部以下の混合物)1.4g、ペンタエリスリトールアリルエーテル(ペンタエリスリトールトリアリルエーテルとペンタエリスリトールテトラアリルエーテルの混合物)0.02g、ノルマルヘキサン150gおよび2,2’-アゾビスメチルイソブチレート0.081g(0.00035モル)を仕込んだ。その後、フラスコの内容物を均一に攪拌しながら、フラスコ内の酸素を除去するために、溶液中に窒素ガスを吹き込んだ。その後、攪拌と窒素ガスの吹き込みを続けた状態で、内容物を加熱するため、オイルバスの設定を60~65℃に設定し、4時間保持した。その後、オイルバスの設定温度を90℃に設定して、ノルマルヘキサンを除去した。その後、フラスコの内容物を減圧乾燥機(Yamatho社製、バキュームドライオーブンDP33)に移し、オーブンの設定温度を110℃に設定し、設定圧力を10mmHgに設定して8時間乾燥し、白色微粉末状のアルキル変性カルボキシル基含有重合体(重合体1)45gを得た。
製造例1において、ブレンマーVMA70(日本油脂株式会社製)の使用量を1.125gに変更したこと以外は製造例1と同様にして、白色微粉末状のアルキル変性カルボキシル基含有重合体(重合体2)45gを得た。
製造例1において、ブレンマーVMA70(日本油脂株式会社製)の使用量を2.25gに変更したこと以外は製造例1と同様にして、白色微粉末状のアルキル変性カルボキシル基含有重合体(重合体3)46gを得た。
製造例1において、ブレンマーVMA70(日本油脂株式会社製)の使用量を0.68gに変更したこと以外は製造例1と同様にして、白色微粉末状のアルキル変性カルボキシル基含有重合体(重合体4)43gを得た。
製造例1において、ブレンマーVMA70(日本油脂株式会社製)の使用量を1.125gに変更し、ペンタエリスリトールアリルエーテル(ペンタエリスリトールトリアリルエーテルとペンタエリスリトールテトラアリルエーテルの混合物)の使用量を0.02gから0.135gに変更したこと以外は製造例1と同様にして、白色微粉末状のアルキル変性カルボキシル基含有重合体(重合体5)45gを得た。
製造例1から5で得られた重合体1から5の増粘剤としての特性を評価するため、それぞれの1質量%中和粘稠液、およびそれらに塩化ナトリウムを添加し攪拌して調製した電解質添加溶液について、粘度および光透過率を測定した。
評価試料としての重合体について3g毎の所定個数を量りとり、それぞれ脱イオン水285.9gに攪拌下、徐々に投入して分散させた。その後、さらに攪拌しながら6質量%水酸化ナトリウム水溶液11.1gを加えて、溶液が均一となるまで攪拌し、重合体の1質量%中和粘稠液とした。これら中和粘稠液のpHは6.0~6.5であった。また、前記中和粘稠液の各300gに、塩化ナトリウム0.75~9gを添加し、攪拌、溶解して、塩化ナトリウム濃度として0.25質量%、0.5質量%、0.75質量%、1質量%、2質量%、3質量%の電解質添加溶液を調製した。なお、下記評価では、前記1質量%中和粘稠液および各塩化ナトリウム濃度の電解質添加溶液を作成後に1時間静置したものを評価試料として用いた。
各評価試料について、BH型回転粘度計を用いて、25℃でスピンドルローターNo.6の回転速度を毎分20回転として1分後の粘度を測定した。測定結果を、重合体1は表1、重合体2は表2、重合体3は表3、重合体4は表4、重合体5は表5にそれぞれ示す。
各評価試料について、遠心分離器にて毎分2000回転で5分間の操作により脱泡した後、光路長1cmのセルを用いて、測定波長を425nmとして光透過率を測定した。通常、光透過率が90%以上であれば目視において透明であるといえる。測定結果を、表1~5に示す。
ディスパー羽根(Φ40mm)をセットした超高速攪拌システムT.K.ロボミックス(プライミクス株式会社製)を使用して、蒸留水977.7gの入った2Lビーカーに、10gの重合体1を毎分5000回転の攪拌速度下、徐々に投入して分散させた。10分間5000回転で攪拌した後、攪拌速度を毎分3000回転に下げ、20分間攪拌継続した。その後、毎分1400回転の攪拌速度で18質量%水酸化ナトリウム水溶液12.3gを入れ、無色透明な中和粘稠液を調製した。この中和粘稠液のpHは、6.4であった。この中和粘稠液を、BH型回転粘度計を用いて、25℃でスピンドルローターNo.5の回転速度を毎分20回転として1分後の粘度を測定したところ、330mPa.sであった(ベタイン系乳化剤の水溶液(固形分が約30質量%)が、0質量%)。この中和粘稠液144gを200Lビーカーに小分けし、4枚パドル翼(Φ50mm)を用いて毎分500回転の攪拌速度下で、ベタイン系乳化剤としてヤシ油脂肪酸アミドプロピルベタイン液6g(新日本理化株式会社製リカビオンB-200、固形分31.5質量%)をゆっくり添加し、攪拌速度を毎分1000回転に上げて1時間混合し、ジェル組成物を調製した(ベタイン系乳化剤の水溶液(固形分が約30質量%)が、4質量%)。このときのジェル組成物について、BH型回転粘度計を用いて、25℃でスピンドルローターNo.7の回転速度を毎分20回転として1分後の粘度を測定したところ、104,400mPa.sであった。これらの結果を表6に示す。また、ベタイン系乳化剤の水溶液(固形分が約30質量%)が6質量%、8質量%となるようにして、同様に調製したジェル組成物の当該粘度を表7に示す。
実施例1において、重合体1を重合体2に変更したこと以外は実施例1と同様にして、ジェル組成物を調製し、粘度を測定した。結果を表6及び表7に示す。
実施例1において、重合体1を重合体3に変更したこと以外は実施例1と同様にして、ジェル組成物を調製し、粘度を測定した。結果を表6及び表7に示す。
実施例1において、重合体1を重合体4に変更したこと以外は実施例1と同様にして、ジェル組成物を調製し、粘度を測定した。結果を表6及び表7に示す。
実施例1において、重合体1を重合体5に変更したこと以外は実施例1と同様にして、ジェル組成物を調製し、粘度を測定した。結果を表6及び表7に示す。
(実施例4)
実施例1と同様、ディスパー羽根(Φ40mm)をセットした超高速攪拌システムT.K.ロボミックス(プライミクス株式会社製)を使用して、蒸留水987.7gの入った2Lビーカーに、10gの重合体1を毎分5000回転の攪拌速度下、徐々に投入して分散させた。10分間5000回転で攪拌した後、攪拌速度を毎分3000回転に下げ、20分間攪拌継続した。その後、毎分1400回転の攪拌速度で18質量%水酸化ナトリウム水溶液2.3gを入れ、pH3.8程度の中和粘稠液を調製した。次に、18質量%水酸化ナトリウム水溶液を所定量加えて均一に攪拌することによって、表8に示されるように、pHを変化させて、中和粘稠液の各pHにおける粘度を測定した(表8のヤシ油脂肪酸アミドプロピルベタイン含量(固形分)0質量%(基準))。結果を表8に示す。なお、粘度の測定方法は、実施例1と同じである。
重合体1の代わり重合体5を用いたこと以外は、実施例4と同様にして、pH3.8程度の中和粘稠液を調製した。次に、18質量%水酸化ナトリウム水溶液を所定量加えて均一に攪拌することによって、表9に示されるようにpHを変化させて、中和粘稠液の各pHにおける粘度を測定した(表9のヤシ油脂肪酸アミドプロピルベタイン含量(固形分)0質量%(基準))。結果を表9に示す。
Claims (8)
- (メタ)アクリル酸(a)100質量部、アルキル基の炭素数が18~24である(メタ)アクリル酸アルキルエステル(b)2.5~5質量部、およびエチレン性不飽和基を2個以上有する化合物(c)0.1質量部以下を含む単量体の共重合体であるアルキル変性カルボキシル基含有重合体の中和物と、ベタイン系乳化剤とを含む、ジェル組成物。
- 以下の組成を有する場合の25℃における粘度が、50,000mPa・s以上となる、請求項1に記載のジェル組成物。
(組成)
アルキル変性カルボキシル基含有重合体の1質量%中和粘稠液96質量部と、ベタイン系乳化剤の水溶液(固形分が約30質量%)4質量部とからなる組成。 - 前記アルキル変性カルボキシル基含有重合体は、1質量%中和粘稠液とした場合の25℃下における粘度が1500mPa・s以下、光透過率が90%以上であり、
当該1質量%中和粘稠液100質量部に対して、0.25~3質量部の塩化ナトリウムを添加したときの25℃下における最高粘度が、15,000~40,000mPa・sであり、光透過率が90%以上である、請求項1または2に記載のジェル組成物。 - 前記ベタイン系乳化剤の含有量が、0.2質量%~0.8質量%の範囲内にあり、
pHが4.4~5.5の範囲にある、請求項1または3に記載のジェル組成物。 - 前記エチレン性不飽和基を2個以上有する化合物(c)が、ペンタエリスリトールアリルエーテル、ジエチレングリコールジアリルエーテル、ポリエチレングリコールジアリルエーテルおよびポリアリルサッカロースからなる群より選ばれた少なくとも1種である、請求項1~4のいずれかに記載のジェル組成物。
- 前記ベタイン系乳化剤が、ヤシ油脂肪酸アミドプロピルベタインである、請求項1~5のいずれかに記載のジェル組成物。
- 請求項1~6のいずれかに記載のジェル組成物を含む、化粧料。
- (メタ)アクリル酸(a)100質量部、アルキル基の炭素数が18~24である(メタ)アクリル酸アルキルエステル(b)2.5~5質量部、およびエチレン性不飽和基を2個以上有する化合物(c)0.1質量部以下を含む単量体の共重合体であるアルキル変性カルボキシル基含有重合体と、アルカリ成分とを混合して、前記アルキル変性カルボキシル基含有重合体の中和物を調製する工程と、
前記アルキル変性カルボキシル基含有重合体の中和物と、ベタイン系乳化剤とを混合する工程と、
を備える、ジェル組成物の製造方法。
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