WO2012160919A1 - Produit cosmétique - Google Patents

Produit cosmétique Download PDF

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Publication number
WO2012160919A1
WO2012160919A1 PCT/JP2012/060766 JP2012060766W WO2012160919A1 WO 2012160919 A1 WO2012160919 A1 WO 2012160919A1 JP 2012060766 W JP2012060766 W JP 2012060766W WO 2012160919 A1 WO2012160919 A1 WO 2012160919A1
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Prior art keywords
water
hydrophilic
hydrophilic thickener
soluble
mass
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PCT/JP2012/060766
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English (en)
Japanese (ja)
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昭男 中塚
洋 山内
増田　剛
綾美 和島
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住友精化株式会社
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • 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
    • 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
    • A61K8/8158—Homopolymers or copolymers of amides or imides, e.g. (meth) acrylamide; Compositions of derivatives of such polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/10—General cosmetic use
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • 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
    • A61K2800/48—Thickener, Thickening system

Definitions

  • the present invention relates to a cosmetic containing a hydrophilic thickener.
  • hydrophilic thickeners examples include natural product thickeners typified by xanthan gum and guar gum, semi-synthetic thickeners typified by hydroxyethylcellulose, carboxymethylcellulose, carboxyvinyl polymer, polyethylene oxide, etc. Representative synthetic thickeners are widely used.
  • a hydrophilic polymer having a carboxyl group such as a carboxyvinyl polymer and an alkyl-modified carboxyvinyl polymer, exhibits excellent thickening with a small amount of use, and a refreshing feeling of use can be obtained. It is suitably used as a thickener, dispersant or emulsion stabilizer useful in the field.
  • Patent Document 1 by blending an alkyl-modified carboxyvinyl polymer and tranexamic acid, it has an excellent skin improvement effect while maintaining a refreshing feeling of use, and has been conventionally used as an emulsifier. It has been shown that an emulsified composition having excellent stability over time can be provided without blending an agent.
  • Patent Document 2 discloses a transparent gel makeup that contains a specific urea stabilizer, has long-term stability, is less sticky, has a refreshing feeling, and has good skin familiarity. Fees have been proposed.
  • Patent Document 3 proposes a body cosmetic material that is imparted with transparency and a refreshing feeling by neutralizing a carboxyvinyl polymer and / or an alkyl-modified carboxyvinyl polymer with an alkali agent. ing.
  • Patent Document 4 uses a combination of a hydrophobic oil-absorbing powder, an alkyl-modified carboxyvinyl polymer and a basic substance, so that when applied to the skin, the gel-like makeup has a good feeling of stickiness and no shine due to sebum. It is said that a fee can be obtained.
  • Patent Document 5 when a specific polyhydric alcohol-modified silicone compound and an alkyl-modified carboxyvinyl polymer, cyclic silicone, powder and water are blended, the emulsion stability is excellent even in a low viscosity region, and the dispersibility of the powder is excellent.
  • An oil-in-water cosmetic that is good and maintains good fluidity over time without any change in viscosity, is stable against heat and light, and has no stickiness and a refreshing feel. It is supposed to be obtained.
  • Patent Document 6 (a) an alkyl-modified carboxyvinyl polymer, (b) xanthan gum, (c) pentylene glycol and / or 1,2-hexanenediol, (d) a polyhydric alcohol fatty acid ester, and an alkyl glucoside are selected.
  • the cosmetic composition containing one or two kinds and water does not contain a surfactant or paraben containing ethylene oxide or propylene oxide addition polymer, is excellent in use feeling, and has a reduced viscosity even after long-term storage. It is said that no alteration such as separation occurs.
  • Patent Document 7 relates to an oil-in-water cosmetic containing organic powder, an oil component, a carboxyvinyl polymer and / or an alkyl-added carboxyvinyl polymer, and anhydrous silicic acid having an average particle size of 0.001 to 0.1 ⁇ m. More specifically, Patent Document 7 is excellent in a makeup effect that produces a matte feeling by suppressing unwanted gloss on the face, and spreads evenly on the skin without causing the powder to squeeze, refreshing and refreshing. The oil-in-water cosmetics.
  • JP-A-9-263510 JP 2009-190986 A Japanese Patent Laid-Open No. 11-322539 JP-A-9-249543 Japanese Patent Laid-Open No. 2005-232088 JP 2009-196954 A JP 2002-3338 A
  • hydrophilic thickeners such as carboxyvinyl polymer and alkyl-modified carboxyvinyl polymer that have been conventionally used, it is difficult to sufficiently meet such needs.
  • an object of the present invention is to provide a cosmetic material that has a light touch feeling as well as a refreshing feeling when applied to the skin.
  • the present invention relates to a cosmetic containing a hydrophilic thickener.
  • the concentration (0.5% by mass) of the hydrophilic thickener in the aqueous liquid is a value based on the mass of the aqueous liquid.
  • the hydrophilic thickener is a polymer containing a carboxylate or sulfonate as a monomer unit, such as acrylate, methacrylate or 2-acrylamido-2methylpropanesulfonate, the corresponding carboxyl Taking the mass of acid or sulfonic acid as the mass of each monomer unit, the concentration of the hydrophilic thickener in the aqueous liquid is calculated.
  • the concentration of the hydrophilic thickener is generally in the range of about 0.2% by mass to 1% by mass.
  • concentration of the thickener is 0.2% by mass or less, there is a high possibility that appropriate rheological properties cannot be obtained sufficiently.
  • concentration of the thickener exceeds 1% by mass, a sticky feeling and a skin residue tend to occur. Therefore, the concentration of the hydrophilic thickener is generally about 0.5% by mass. That is, it can be considered that the viscosity characteristic of the aqueous liquid having a concentration of 0.5% by mass substantially corresponds to the viscosity characteristic of the actual cosmetic.
  • the hydrophilic thickener may be a crosslinked polymer of a water-soluble ethylenically unsaturated monomer that has been crosslinked with a water-soluble crosslinking agent.
  • the water-soluble crosslinking agent is at least selected from the group consisting of N, N′-methylenebisacrylamide, ethylene glycol dimethacrylate, ethylene glycol diglycidyl ether, polyethylene glycol dimethacrylate, polyethylene glycol diglycidyl ether, and water-soluble sucrose allyl ether.
  • One kind of compound may be included.
  • a hydrophilic thickener having such a configuration can satisfy the above-mentioned characteristics (1), (2) and (3) particularly easily.
  • the cosmetic according to this embodiment contains at least water and a hydrophilic thickener.
  • the hydrophilic thickener is dissolved or dispersed in water.
  • Consists of water and a hydrophilic thickener and, if necessary, a neutralizing agent The hydrophilic thickener is dispersed or dissolved in water. The concentration of the hydrophilic thickener is 0.5% by mass.
  • the hydrophilic thickener is selected based on the viscosity characteristics at 25 ° C. of the aqueous liquid having a pH of 6.8 to 7.0. More specifically, in the hydrophilic thickener, the zero shear viscosity ⁇ 0 , the yield stress ⁇ y and the yield strain ⁇ y of the aqueous liquid satisfy the following characteristics (1), (2) and (3): Can be selected.
  • the zero shear viscosity ⁇ 0 , the yield stress ⁇ y and the yield strain ⁇ y are determined by steady flow viscosity measurement that measures the shear viscosity of an aqueous liquid.
  • the zero shear viscosity ⁇ 0 is a value obtained by extrapolating the viscosity to zero shear rate in a graph showing the relationship between the viscosity and the shear rate. According to the steady flow viscosity measurement described later, the viscosity in the low shear region in the range of the shear rate of 1 ⁇ 10 ⁇ 5 to 1 ⁇ 10 ⁇ 2 (1 / second) can be measured with high accuracy. In the case of the aqueous liquid containing the hydrophilic thickener according to the present embodiment, in such a low shear region, a region where the viscosity can be regarded as not substantially changing depending on the shear rate is often observed.
  • the viscosity in this region can be regarded as zero shear viscosity. More specifically, the viscosity at a shear rate of 1 ⁇ 10 ⁇ 5 (1 / second) can be regarded as zero shear viscosity.
  • the hydrophilic thickener in the case of the hydrophilic thickener according to the present embodiment, in the curve representing the relationship between the strain of the aqueous liquid and the shear stress, up to a certain shear stress, after the behavior as an apparent linear elastic body is shown, The strain begins to increase sharply with increasing shear stress.
  • the shear stress and strain at the yield point can be defined as yield stress ⁇ y and yield strain ⁇ y , respectively.
  • Yield distortion is related to tactile sensation such as freshness and stickiness of cosmetics. If the yield strain is small, the feel is refreshed, and if the yield strain is large, the stickiness is increased.
  • the magnitude of the yield stress is related to the tactile sensation such as lightness and weight in the tactile sensation when the cosmetic is taken out of the container and started to be applied to the skin. If the yield stress is small, the feel is light, and if the yield stress is large, the feel is heavy.
  • the value of zero shear viscosity corresponds to the minimum amount of shear stress required to make the cosmetic flow as a viscous material when it is applied to the cosmetic during application to the skin. Then you can understand.
  • the zero shear viscosity ⁇ 0 is in the range of 1 ⁇ 10 3 Pa ⁇ s to 1 ⁇ 10 6 Pa ⁇ s, so that it has an appropriate hardness without excessive flow. Meanwhile, it is possible to obtain a cosmetic having a smooth touch. If the zero shear viscosity is less than 1 ⁇ 10 3 Pa ⁇ s, the cosmetic tends to be sol and does not have a yield point with respect to shear stress. From the same viewpoint, the zero shear viscosity ⁇ 0 is more preferably 2 ⁇ 10 3 Pa ⁇ s to 8 ⁇ 10 5 Pa ⁇ s.
  • the zero shear viscosity and the yield stress are correlated with the square of the yield stress ⁇ y within a certain coefficient a range as shown in Equation-1. Yes.
  • the coefficient a can be taken as a measure of the magnitude of the yield stress corresponding to the zero shear viscosity.
  • the coefficient a is in the range of 500 to 25000, the cosmetic tends to have a yield point for shear stress. When the coefficient a is less than 500, the touch of the cosmetic tends to be heavy. From the same viewpoint, the coefficient a is more preferably 1000 to 15000.
  • a thickener having a yield strain ⁇ y of less than 0.1% is hard and hardly deformed, and is difficult to exhibit the effect as a thickener.
  • the yield strain ⁇ y exceeds 3%, the stickiness of the cosmetic tends to become strong.
  • ⁇ 0 of an aqueous liquid containing water and a hydrophilic thickener is 1.0 ⁇ 10 3 to 1 ⁇ 10 6 Pa ⁇ s, but the coefficient a in Formula-1 is 100 to 400, (2) Does not satisfy the characteristics of Further, the yield strain ⁇ y is 1 to 10%, which is likely to be larger than the characteristic range of (3).
  • the hydrophilic thickener contained in the cosmetic according to the present embodiment is not particularly limited as long as it satisfies the characteristics of (1), (2) and (3). For example, as described below It has the structure which concerns on embodiment.
  • the hydrophilic thickener according to the present embodiment is, for example, a polymer of a water-soluble ethylenically unsaturated monomer that is cross-linked by a water-soluble cross-linking agent.
  • This hydrophilic thickener can be obtained, for example, by a method including a step of polymerizing a water-soluble ethylenically unsaturated monomer by suspension polymerization in the presence of a water-soluble crosslinking agent.
  • the reverse phase suspension polymerization method in which the polymerization reaction is carried out while dispersing water-phase droplets containing a water-soluble ethylenically unsaturated monomer, a water-soluble crosslinking agent and water in a hydrophobic solvent.
  • a water-soluble ethylenically unsaturated monomer a water-soluble crosslinking agent and water in a hydrophobic solvent.
  • the size of the polymer particles by adjusting the size of the polymer particles (particulate hydrophilic thickener) to be produced, the ratio of the water-soluble crosslinking agent to the water-soluble ethylenically unsaturated monomer, the amount of radical polymerization initiator, etc.
  • the hydrophilic thickener having the characteristics (1), (2) and (3) described above can be easily produced.
  • the water-soluble ethylenically unsaturated monomer is not particularly limited, but is preferably acrylic acid and its salt, methacrylic acid and its salt, 2-acrylamido-2-methylpropanesulfonic acid and its salt, acrylamide, It is at least one compound selected from the group consisting of methacrylamide and N, N-dimethylacrylamide.
  • a monomer having a carboxyl group that is, acrylic acid and a salt thereof, and methacrylic acid and a salt thereof are preferable from the viewpoint of obtaining sufficient viscosity.
  • the salt include sodium salt, potassium salt, ammonium salt, triethanolamine salt and diisopropanolamine salt.
  • the water-soluble crosslinking agent is preferably a compound having two or more polymerizable unsaturated groups and / or reactive functional groups.
  • the reactive functional group is a functional group that can react with a functional group such as a carboxyl group of the water-soluble ethylenically unsaturated monomer to form a crosslinked structure.
  • a specific example is a glycidyl group.
  • water-soluble crosslinking agents having two or more glycidyl groups include ethylene glycol diglycidyl ether and polyethylene glycol diglycidyl ether.
  • water-soluble crosslinking agents having two or more polymerizable unsaturated groups include N, N'-methylenebisacrylamide, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, and water-soluble sucrose allyl ether.
  • the degree of etherification of the water-soluble sucrose allyl ether is preferably 2.0 to 3.5, more preferably 2.2 to 3.2. If the degree of etherification of the water-soluble sucrose allyl ether is low, the allyl group, which is a functional group involved in the cross-linking reaction, is insufficient, and the cross-linking reaction tends not to proceed effectively. If the degree of etherification of the water-soluble sucrose allyl ether is high, the solubility in water decreases, so that the cross-linking reaction between the sucrose allyl ether and the water-soluble ethylenically unsaturated monomer is difficult to proceed in the aqueous phase. Tend.
  • This degree of etherification is the average value of the molar ratio of allyl ether groups to sucrose.
  • the degree of etherification can be calculated, for example, from the amount of acetic anhydride consumed at the time of reacting the hydroxyl group remaining in sucrose allyl ether with acetic anhydride in pyridine.
  • the water-soluble sucrose allyl ether can be obtained, for example, by adding sodium hydroxide as a catalyst to an aqueous sucrose solution to convert sucrose to alkaline sucrose and then adding allyl bromide dropwise to perform etherification. it can.
  • a water-soluble sucrose allyl ether can be efficiently obtained by adjusting the amount of allyl bromide to a range of 2 to 6 times mol, preferably 2 to 5 times mol of sucrose. it can.
  • the etherification reaction temperature is, for example, about 80 ° C. Usually, the reaction is completed in about 3 hours after the addition of allyl bromide.
  • Water-soluble sucrose allyl ether can be recovered by adding alcohol to the aqueous phase separated from the reaction solution, filtering out precipitated salts, and distilling off excess alcohol and water.
  • the degree of crosslinking of the hydrophilic thickener can be adjusted by the ratio of the water-soluble crosslinking agent to the water-soluble ethylenically unsaturated monomer. As the degree of crosslinking of the hydrophilic thickener increases, the zero shear viscosity tends to increase.
  • the molar ratio of the water-soluble crosslinking agent to the water-soluble ethylenically unsaturated monomer is preferably 1 ⁇ 10 ⁇ . 4 to 5 ⁇ 10 ⁇ 3 , more preferably 2 ⁇ 10 ⁇ 4 to 3 ⁇ 10 ⁇ 3 .
  • hydrophobic solvent used in the reverse phase suspension polymerization for example, a petroleum hydrocarbon solvent selected from aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons is used.
  • aliphatic hydrocarbon examples include n-pentane, n-hexane and n-heptane.
  • alicyclic hydrocarbon examples include cyclopentane, methylcyclopentane, cyclohexane, and methylcyclohexane.
  • Aromatic hydrocarbons include benzene, toluene and xylene.
  • At least one hydrophobic solvent selected from n-hexane, n-heptane, cyclohexane and toluene is preferably used as an industrial general-purpose solvent.
  • the ratio of the hydrophobic solvent is, for example, 100 to 200 parts by mass with respect to 100 parts by mass of the aqueous phase containing the water-soluble ethylenically unsaturated monomer.
  • the aqueous phase containing a water-soluble ethylenically unsaturated monomer or the like, or the hydrophobic solvent may contain other components such as a surfactant and a radical initiator.
  • Surfactant is mainly used to stabilize the suspended state during polymerization.
  • the surfactant is not particularly limited as long as it is usually used in reverse phase suspension polymerization.
  • sorbitan fatty acid ester polyglycerin fatty acid ester, sucrose fatty acid ester, sorbitol fatty acid ester, modified polyethylene wax, modified polypropylene wax, polyvinyl alcohol, polyethylene oxide, cellulose ether (hydroxyethyl cellulose, ethyl cellulose, etc.), sodium alkylbenzene sulfonate,
  • one or more surfactants selected from polyoxyethylene alkylphenyl ether sulfates.
  • the amount of the surfactant is preferably 0.1 to 10.0% by mass, more preferably 0.5 to 5.0% by mass with respect to the water-soluble ethylenically unsaturated monomer. If the amount of the surfactant is small, there may be a problem in the stability of the suspension state during polymerization, and if the amount of the surfactant is large, it tends to be economically disadvantageous.
  • the radical initiator is not particularly limited as long as it is used for normal radical polymerization, but potassium persulfate, ammonium persulfate, sodium persulfate, azo initiators and the like are preferably used.
  • potassium persulfate, ammonium persulfate, sodium persulfate, azo initiators and the like are preferably used.
  • 2,2'-azobis (2-methylpropionamidine) dihydrochloride can be used as a radical initiator.
  • the amount of the radical initiator is preferably 0.01 to 0.5% by mass, more preferably 0.02 to 0.2% by mass, based on the water-soluble ethylenically unsaturated monomer. If the amount of the radical initiator is small, the polymerization reaction tends not to proceed or a long time is required for the reaction. When the amount of the radical initiator is increased, the chain length of the polymer to be produced is shortened, and the zero shear viscosity ⁇ 0 of the aqueous liquid of the hydrophilic thickener tends to decrease.
  • the size of the droplets containing a water-soluble ethylenically unsaturated monomer and the like is closely related to the size of the polymer particles obtained.
  • the above-described characteristics (1) can be obtained by carrying out reverse phase suspension polymerization at a stirring speed of 600 to 1000 rpm. ), (2) and (3) are likely to be able to obtain polymer particles of a suitable size.
  • the molecular weight and the degree of crosslinking of the crosslinked polymer can be adjusted by the amount of the water-soluble crosslinking agent to be added.
  • the properties as a hydrophilic thickener can be used for each application. It can be easily adapted accordingly.
  • the polymer particles thus obtained are usually spherical, and this shape is maintained even in a 0.5% by mass aqueous liquid. It is presumed that the shape may affect various properties, tactile sensations and feelings of use in cosmetics using the same.
  • the polymerization reaction temperature is, for example, 50 to 80 ° C.
  • the reaction time is, for example, 30 minutes to 3 hours.
  • the polymerization temperature can be started by adjusting the bath temperature to 60 ° C. In this case, the start of the polymerization reaction can be confirmed from the fact that the temperature in the reaction vessel rises to 70 ° C. by the polymerization heat. Thereafter, the polymerization reaction is usually completed by carrying out an aging reaction for about 30 minutes to 3 hours.
  • the reaction may not be completed sufficiently, and the remaining water-soluble ethylenically unsaturated monomer may increase.
  • the product can be obtained by raising the bath temperature and distilling off the water and the petroleum hydrocarbon solvent in the reaction vessel.
  • the type of cosmetic according to the present embodiment is not particularly limited. Shampoo, moisturizing gel, hair setting gel, sunscreen, styling gel, eyeliner, mascara, lipstick and foundation.
  • the cosmetic according to this embodiment is used as a cream cosmetic such as cream, cream pack, massage cream and cleansing cream, or as a gel cosmetic such as cleansing gel, moisturizing gel, hair setting gel and styling gel, a refreshing feeling is obtained. And the merit regarding lightness is particularly great.
  • emulsions and creams that are oil-in-water emulsified cosmetics are aqueous containing oily components, water, hydrophilic thickeners, moisturizers, surfactants, chelating agents (such as sodium edetate), and the like. It is composed of other ingredients such as preservatives, fragrances and drugs.
  • an oil-in-water emulsified cosmetic is produced by a step of heating and dissolving a water phase and an oil phase at around 70 ° C., emulsifying with a homomixer, and then cooling with stirring.
  • Hydrophilic thickeners function as rheology control agents and emulsion stabilizers for these products.
  • the amount of the hydrophilic thickener is about 0.1 to 0.6% by mass with respect to all ingredients in the emulsion and about 0.2 to 2% by mass in the cream.
  • the oil component is not particularly limited, but may be natural oil, silicone oil, ester oil or the like in consideration of the texture to the skin, familiarity, appearance, slipperiness, and the like.
  • natural oils include paraffinic hydrocarbons such as liquid paraffin, olive oil, macadamia nut oil, castor oil, jojoba oil, orange luffy oil, beeswax, lanolin, mineral oil, and squalane.
  • paraffinic hydrocarbons such as liquid paraffin, olive oil, macadamia nut oil, castor oil, jojoba oil, orange luffy oil, beeswax, lanolin, mineral oil, and squalane.
  • silicone oil examples include modified silicone oils such as methylpolysiloxane, methylphenylpolysiloxane, cyclic methylsiloxane, and silicone polyether copolymer.
  • ester oils include various fatty acid esters.
  • octyldodecyl esters of various fatty acids such as oleic acid, erucic acid, myristic acid and ricinoleic acid are suitable.
  • oil components may be used alone or in combination of two or more.
  • the humectant is suitably selected from glycerin, propylene glycol, sorbit, polyethylene glycol, dipropylene glycol, 1,3-butylene glycol, diglycerin, mannitol, polyoxyethylene methyl glycoside, and the like.
  • nonionic glycerin monostearate polyoxyethylene sorbitan fatty acid ester, sorbitan fatty acid ester and the like are often used.
  • anionic, cationic or amphoteric surfactants can also be used.
  • Gel cosmetics such as a moisturizing gel and a hair setting gel contain water, a moisturizing agent, and optionally a drug such as a hair setting agent, and a hydrophilic thickener.
  • the amount of the hydrophilic thickener is preferably 0.3 to 1% by mass based on the mass of the gel cosmetic.
  • the hydrophilic thickener according to the present embodiment is used also in the fields of toiletries other than cosmetics, various detergents, industrial thickeners, and the like in which carboxyvinyl polymer has been mainly used. Accordingly, it is possible to provide a product to which effects such as a feeling of use and a feeling of application similar to a refreshing feeling and a light feeling of use are imparted.
  • sucrose. was allyl etherified.
  • 440 g of water was added, and excess oil was separated with a separatory funnel to obtain a crude sucrose allyl ether aqueous solution.
  • Hydrochloric acid was added to this crude sucrose allyl ether aqueous solution to adjust the pH to 6-8, and then water was removed using a rotary evaporator until the mass of the aqueous solution reached 480 g.
  • 200 g of ethanol was added to precipitate a by-product salt such as sodium bromide, and the precipitate was removed from the aqueous solution by filtration. Further, excess water was removed from the aqueous solution by using an evaporator to obtain 166 g of purified water-soluble sucrose allyl ether having a degree of etherification of 2.4.
  • n-heptane 330 g was placed in a 2 L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a nitrogen gas introduction tube, and a sucrose stearate ester (Mitsubishi Chemical Foods) as a surfactant.
  • a sucrose stearate ester Mitsubishi Chemical Foods
  • Production Example 3 Except that the crosslinking agent was changed from N, N′-methylenebisacrylamide to 0.35 g of water-soluble sucrose allyl ether (0.4% by mass with respect to the aqueous acrylic acid solution), the same operation as in Production Example 2 was carried out. 102 g of a powder of hydrophilic thickener B, which was a polymer of acrylic acid and its sodium salt and was crosslinked with water-soluble sucrose allyl ether, was obtained.
  • N, N'-methylenebisacrylamide as a cross-linking agent was changed from 0.0184 g (0.02 mass% with respect to the acrylic acid aqueous solution) to 0.046 g (0.05 mass% with respect to the acrylic acid aqueous solution).
  • a powder of hydrophilic thickener C which is a polymer of acrylic acid and its sodium salt and is a polymer crosslinked with N, N′-methylenebisacrylamide, in the same manner as in Production Example 2 except that 102 g were obtained.
  • Production Example 5 Acrylic acid and its sodium were obtained in the same manner as in Production Example 3 except that the surfactant was changed from sucrose stearate to 3.0 g of sorbitan monostearate (manufactured by NOF Corporation, Nonion SP-60R). 103 g of powder of hydrophilic thickener D, which is a salt polymer and a polymer crosslinked with water-soluble sucrose allyl ether, was obtained.
  • Production Example 6 Production Example except that the amount of 2,2′-azobis (2-methylpropionamidine) dihydrochloride (V-50, manufactured by Wako Pure Chemical Industries, Ltd.) as an initiator was changed from 0.064 g to 0.037 g. In the same manner as in No. 5, 102 g of hydrophilic thickener E powder, which is a polymer of acrylic acid and its sodium salt and is a polymer crosslinked with water-soluble sucrose allyl ether, was obtained.
  • V-50 2,2′-azobis (2-methylpropionamidine) dihydrochloride
  • Production Example 7 The amount of water-soluble sucrose allyl ether as a crosslinking agent was changed from 0.35 g (0.4% by mass with respect to the aqueous acrylic acid solution) to 0.7 g (0.8% by mass with respect to the aqueous acrylic acid solution). Except that, 103 g of a hydrophilic thickener F powder, which is a polymer of acrylic acid and its sodium salt and is a polymer crosslinked with water-soluble sucrose allyl ether, was obtained in the same manner as in Production Example 6. It was.
  • the resulting slurry was heated to 90 ° C. to distill off n-hexane, and further dried under reduced pressure at 110 ° C. and 10 mmHg for 8 hours to obtain a powder of carboxyvinyl polymer A in the form of white fine powder. 42 g were obtained.
  • Production Example 9 42 g of white fine powdery carboxyvinyl polymer B powder was obtained by the same operation as in Production Example 8 except that the amount of pentaerythritol allyl ether was changed from 0.66 g to 1.32 g.
  • Production Example 10 BLEMMER VMA70 (Nippon Yushi Co., Ltd .: 10-20 parts by mass of stearyl methacrylate, 10-20 parts by mass of eicosanyl methacrylate, and 59-80 parts by mass of behenyl methacrylate, with a content of tetracosanyl methacrylate of 1
  • a white fine powdery alkyl-modified carboxyvinyl polymer (carboxyvinyl polymer C) powder 43 g was obtained in the same manner as in Production Example 8 except that 0.45 g of a mixture of less than or equal to part by mass was added to the reaction solution.
  • Example 1 Components 1 to 4 shown below were added in respective proportions and mixed uniformly. While stirring the mixture, Component 5 was added and mixed uniformly to obtain a moisturizing gel. “%” Means mass% based on the total mass of each component. The same applies to other examples and comparative examples described below. 1. Glycerin 7% 2. Propylene glycol 5% 3. Preservative 0.5% 4). Water 86.9% 5. Hydrophilic thickener B 0.6%
  • Example 2 A moisturizing gel was prepared in the same manner as in Example 1 except that the hydrophilic thickener B was changed to the hydrophilic thickener E.
  • Example 3 A moisturizing gel was prepared in the same manner as in Example 1 except that the hydrophilic thickener B was changed to the hydrophilic thickener D.
  • Example 4 Components 1 and 2 shown below were dissolved in water 3 and then component 4 was added with stirring and mixed uniformly to obtain a hair gel. 1. Glycerin 4% 2. Polyvinylpyrrolidone (PVP K-90 made by ISP Corp) 1% 3. 94.4% water 4). Hydrophilic thickener E 0.6%
  • Example 5 The following oil components 1 to 3 were mixed, and components 4 and 5 dissolved by heating in water were added thereto, and emulsified with a homomixer (13000 rpm). Thereafter, component 7 was added with stirring and mixed uniformly to obtain a cream. 1. Liquid paraffin 10% 2. Isopropyl palmitate 10% 3. Tri (capryl / capric acid) glyceryl 10% 4). Polysorbate 60 3% 5. Phenoxyethanol 0.5% 6). 65.9% water 7. Hydrophilic thickener E 0.6%
  • Example 6 A cream was prepared in the same manner as in Example 5 except that the hydrophilic thickener E was changed to the hydrophilic thickener D.
  • Example 7 A moisturizing gel was prepared in the same manner as in Example 1 except that the hydrophilic thickener B was changed to the hydrophilic thickener A.
  • Example 8 A moisturizing gel was prepared in the same manner as in Example 1 except that the hydrophilic thickener B was changed to the hydrophilic thickener C.
  • Example 9 A moisturizing gel was prepared in the same manner as in Example 1 except that the hydrophilic thickener B was changed to the hydrophilic thickener F.
  • Comparative Example 1 The following component 4 was dissolved in water, components 1 to 3 were added, and then component 6 was mixed uniformly to obtain a moisturizing gel. 1. Glycerin 7% 2. Propylene glycol 5% 3. Phenoxyethanol 0.5% 4). Carboxy vinyl polymer A 0.5% 5. Water 83.8% 6.6% NaOH 3.2%
  • Comparative Example 2 A moisturizing gel was prepared in the same manner as in Comparative Example 1 except that carboxyvinyl polymer A was changed to carboxyvinyl polymer B.
  • Comparative Example 3 A moisturizing gel was prepared in the same manner as in Comparative Example 1 except that carboxyvinyl polymer A was changed to carboxyvinyl polymer C.
  • Comparative Example 4 The following components 1, 2, and 4 were dissolved in component 3 water, and component 5 was uniformly mixed therein to obtain a hair gel. 1. Glycerin 4% 2. Polyvinylpyrrolidone (PVP K-90 made by ISP Corp) 1% 3. Water 91.3% 4). Carboxy vinyl polymer A 0.5% 5.6% NaOH 3.2%
  • Comparative Example 5 The following oil components 1 to 3 were mixed. The component 7 was melt
  • Comparative Example 6 A cream was prepared in the same manner as in Comparative Example 6 except that carboxyvinyl polymer B was changed to carboxyvinyl polymer C.
  • the pH is adjusted to 6.8 to 7.0 using a predetermined amount of 6% by mass aqueous sodium hydroxide solution as a neutralizing agent, and the concentration of the polymer is adjusted to 0.5. It was set as mass%.
  • FIG. 1 is a graph showing the results of steady flow viscosity measurement of hydrophilic thickeners B and E and carboxyvinyl polymers A and B. Measurement temperature 25 °C Geometry: 60mm parallel prate Gap: 500 ⁇ m Shear rate: 1 ⁇ 10 ⁇ 5 to 1 ⁇ 10 ⁇ 3 (1 / s), 7 points / digit data loading conditions: Sampling time 5 seconds, 2 times within 2% tolerance, maximum measurement time 4 minutes / point (soft Version: Product version V5.7.0)
  • the zero shear viscosity ⁇ 0 was defined as the viscosity in a region where the viscosity is considered to be substantially unchanged depending on the shear rate in the low shear rate region of the curve representing the relationship between the viscosity ⁇ and the shear rate.
  • FIG. 2 is a graph showing the relationship between strain and shear stress for hydrophilic thickeners B and E and carboxyvinyl polymers A and B.
  • Viscosity characteristics of cosmetics The B-type viscosity of each cosmetic was measured using a BH-type rotational viscometer. The rotation speed of the spindle rotor was set to 20 rotations per minute, and the viscosity value one minute after starting the rotation of the rotor at 25 ° C. was read. Furthermore, the steady flow viscosity measurement of each cosmetic was performed under the same conditions as described above, and the zero shear viscosity, yield stress, and yield strain of the cosmetic were determined.
  • Table 1 shows the evaluation results of the properties of the hydrophilic thickeners A to F and the carboxyvinyl polymers A to C.
  • the viscosity characteristics of the aqueous liquids of the hydrophilic thickeners A to F are (1) 1 ⁇ 10 3 Pa ⁇ s ⁇ ⁇ 0 ⁇ 1 ⁇ 10 6 Pa ⁇ s, (2) 500 It was confirmed that all the conditions of ⁇ a ⁇ 25000 and (3) 0.1% ⁇ ⁇ y ⁇ 3% were satisfied.
  • FIG. 3 is a graph showing the relationship between the zero shear viscosity ⁇ 0 and the yield stress ⁇ y .
  • the hydrophilic thickeners A to F are all within this range.
  • the viscosity characteristics of the carboxyvinyl polymers A to C are located in the region inside the set of auxiliary lines 20 corresponding to the range of 100 ⁇ a ⁇ 400.
  • FIG. 4 is a graph showing the relationship between the yield strain ⁇ y and the yield stress ⁇ y . It can be seen that the hydrophilic thickeners A to F exhibit a lower yield strain even when the yield stress is higher than the carboxyl vinyl polymer.
  • Table 2 shows the evaluation results of cosmetics.
  • the hydrophilic thickeners B, E, and D have zero shear viscosities substantially equivalent to those of the carboxyl vinyl polymers A, B, and C, respectively.
  • Examples 1 to 6 With Comparative Examples 1 to 6 in Table 2, the yield stress and yield strain of the aqueous liquid of the thickener when the equivalent thickener with zero shear viscosity was used The effect on the properties of moisturizing gels, hair gels or creams can be evaluated.
  • the cosmetics of Examples 1 to 6 had lower yield strain and yield stress, and particularly significantly lower yield strain than the cosmetics of Comparative Examples 1 to 6 having the same formulation except for the thickener. This is considered to have contributed to a good refreshing feeling and light usability.
  • the cosmetics of Examples 7 to 9 are moisturizing gels containing a hydrophilic thickener A, C or F.
  • Example 7 is a moisturizing gel containing a hydrophilic thickener A having the lowest zero shear viscosity among the hydrophilic thickeners A to F.
  • a moisturizing gel having such a low zero shear viscosity and having a yield point in the relationship between strain and shear stress cannot be obtained by a method of blending a normal carboxyvinyl polymer.
  • the cosmetic of Example 9 is a moisturizing gel containing the hydrophilic thickener F having the highest zero shear viscosity among the hydrophilic thickeners A to F. According to the conventional method of blending carboxyvinyl polymer, it is impossible to obtain a cosmetic material having such a low yield stress while having a high zero shear viscosity.

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Abstract

L'invention concerne un produit cosmétique contenant un agent épaississant hydrophile, la viscosité à cisaillement est nul (η0), la limite d'élasticité (σy) et la déformation élastique (γy) d'une solution aqueuse comprenant de l'eau et l'agent épaississant hydrophile à une concentration de 0,5 % en masse et ayant une valeur de pH de 6,8-7,0 satisfaisant les exigences suivantes (1), (2) et (3) à 25 °C : (1) 1 × 103 Pa·s ≤ η0 ≤ 1 × 106 Pa·s ; (2) 500 ≤ a ≤ 25 000, la relation entre η0 et σy étant représentée par la formule -1:η0 = a×σy 2 ; et (3) 0,1 % ≤ γy ≤ 3 %.
PCT/JP2012/060766 2011-05-23 2012-04-20 Produit cosmétique WO2012160919A1 (fr)

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JP2015151336A (ja) * 2014-02-10 2015-08-24 住友精化株式会社 弱酸性化粧料用増粘剤、及び当該増粘剤を配合してなる弱酸性化粧料
JP2016147813A (ja) * 2015-02-10 2016-08-18 住友精化株式会社 紫外線吸収剤を含有する組成物
CN107847419A (zh) * 2015-08-04 2018-03-27 住友精化株式会社 凝胶状组合物
JP7060916B2 (ja) 2016-04-28 2022-04-27 住友精化株式会社 水中油乳化型メイクアップ化粧料

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JP6921493B2 (ja) * 2015-10-30 2021-08-18 小林製薬株式会社 水中油型乳化組成物
JP6674242B2 (ja) * 2015-12-08 2020-04-01 花王株式会社 化粧料の肌への浸透感の評価方法
WO2023171609A1 (fr) * 2022-03-07 2023-09-14 住友精化株式会社 Copolymère réticulé acide (méth)acrylique/ester alkylique de l'acide (méth)acrylique et son utilisation

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JP2006225650A (ja) * 2005-01-31 2006-08-31 Rohm & Haas Co 水性系のレオロジー調整剤
JP2007238575A (ja) * 2006-03-13 2007-09-20 Shiseido Co Ltd 水溶性増粘剤及びこれを配合した化粧料
JP2008516950A (ja) * 2004-10-14 2008-05-22 アイエスピー インヴェストメンツ インコーポレイテッド レオロジー調整剤／ヘアスタイリング樹脂

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JP2008516950A (ja) * 2004-10-14 2008-05-22 アイエスピー インヴェストメンツ インコーポレイテッド レオロジー調整剤／ヘアスタイリング樹脂
JP2006225650A (ja) * 2005-01-31 2006-08-31 Rohm & Haas Co 水性系のレオロジー調整剤
JP2007238575A (ja) * 2006-03-13 2007-09-20 Shiseido Co Ltd 水溶性増粘剤及びこれを配合した化粧料

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015151336A (ja) * 2014-02-10 2015-08-24 住友精化株式会社 弱酸性化粧料用増粘剤、及び当該増粘剤を配合してなる弱酸性化粧料
JP2016147813A (ja) * 2015-02-10 2016-08-18 住友精化株式会社 紫外線吸収剤を含有する組成物
CN107847419A (zh) * 2015-08-04 2018-03-27 住友精化株式会社 凝胶状组合物
CN107847419B (zh) * 2015-08-04 2021-03-16 住友精化株式会社 凝胶状组合物
JP7060916B2 (ja) 2016-04-28 2022-04-27 住友精化株式会社 水中油乳化型メイクアップ化粧料

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