WO2014084174A1 - ウレタン型ポリマー及びその用途 - Google Patents
ウレタン型ポリマー及びその用途 Download PDFInfo
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- WO2014084174A1 WO2014084174A1 PCT/JP2013/081670 JP2013081670W WO2014084174A1 WO 2014084174 A1 WO2014084174 A1 WO 2014084174A1 JP 2013081670 W JP2013081670 W JP 2013081670W WO 2014084174 A1 WO2014084174 A1 WO 2014084174A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
- A61K8/06—Emulsions
- A61K8/062—Oil-in-water emulsions
-
- 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
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/87—Polyurethanes
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- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
- C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
- C08G18/0861—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers
- C08G18/0866—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers the dispersing or dispersed phase being an aqueous medium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
- C08G18/2835—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds having less than 5 ether groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
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- 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
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- 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
- powders such as silica and titanium are often contained in an oil-in-water emulsion composition, and water thickened with a natural viscosity modifier or a urethane type viscosity modifier.
- a natural viscosity modifier or a urethane type viscosity modifier When these powders are added to the oil emulsified composition, the powders are immediately separated by precipitation or the like. Therefore, in order to thicken the oil-in-water emulsion composition containing powder, an alkali thickening type viscosity modifier having good stability (product stability) after thickening is generally used.
- an oil-in-water emulsion composition is normally manufactured by emulsifying water and an oil-soluble component using an emulsifier.
- gel oil-in-water emulsion compositions produced using an alkali thickening viscosity modifier usually use a surfactant (for example, an anionic surfactant or a nonionic surfactant) as an emulsifier. Without it, it cannot be manufactured.
- a surfactant for example, an anionic surfactant or a nonionic surfactant
- cosmetics for example, lotions
- an aqueous phase and oil can be used without using a surfactant.
- Many cosmetics in a state where the phases are separated are also commercially available.
- the present invention has been made in order to solve the above-described problems, and has the same characteristics as an existing urethane type viscosity modifier (specifically, a coating film when a product after addition is used as a coating film). It is a novel type that can be used as a urethane-type viscosity modifier that is excellent in long-term storage stability, as well as an alkali thickening-type viscosity modifier, while having good water resistance and being hardly affected by pH, etc. An object is to provide a urethane type polymer.
- the present invention provides the following general formula (1):
- R 2 represents an aliphatic hydrocarbon group having 5 to 12 carbon atoms
- C monoglyceryl ether compound
- R 3 represents a hydrocarbon group having 4 to 13 carbon atoms, q represents a number of 2 or 3
- this invention is a urethane type viscosity regulator which consists of said urethane type polymer.
- the present invention also provides a urethane type viscosity adjusting agent aqueous solution characterized by containing the above urethane type viscosity adjusting agent and water.
- the present invention also provides the urethane type polymer (I) described above, A water-insoluble oil or wax-like substance (II) having a melting point of 100 ° C. or lower, It is an oil-in-water emulsion composition characterized by containing water (III). Furthermore, this invention is cosmetics characterized by containing said oil-in-water type emulsion composition.
- an aqueous agent solution can be provided. Furthermore, according to the present invention, the oil-in-water emulsion composition is excellent in product stability, can stably disperse the powder for a long time when the powder is added, and does not use a surfactant as an emulsifier. And a cosmetic containing the same.
- the urethane type polymer of the present invention is obtained by reacting a monohydroxy compound (A), a polyethylenelene glycol (B), a monoglyceryl ether compound (C), and an isocyanate compound (D).
- R 1 is an aliphatic hydrocarbon group having 24 to 36 carbon atoms.
- aliphatic hydrocarbon groups include tetracosyl, isotetracosyl, hexacosyl, isohexacosyl, octacosyl, isooctacosyl, triacontyl, isotricontyl, dotriacontyl, isodotriacontyl, tetracoacontyl Group, isotetratriacontyl group, 2-decyltetradecyl group, 2-dodecylhexadecyl group, alkyl group such as 2-tetradecyloctadecyl group, 2-hexadecyloctadecyl group; tetracocenyl group, isotetracocenyl group, Hexacosenyl group, isohexacocenyl group, o
- Polyethylenelenglycol (B) is represented by the following general formula (2).
- n means the average degree of polymerization and represents a number of 2 to 1000. Among them, the number of 20 to 800 is preferable, the number of 50 to 700 is more preferable, and the number of 100 to 500 is still more preferable because the function of the viscosity modifier is good. When the number of n is less than 2, water solubility is lowered and the function as a viscosity modifier is lowered. On the other hand, when the number of n exceeds 1000, the function as a viscosity modifier will fall.
- the monoglyceryl ether compound (C) is represented by the following general formula (3).
- the isocyanate compound (D) is represented by the following general formula (4).
- R 3 represents a hydrocarbon group having 4 to 13 carbon atoms
- q represents a number of 2 or 3.
- q represents a number of 2 or 3.
- isocyanate compounds include tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 2,2-dimethylpentane diisocyanate, 3-methoxyhexane diisocyanate, octamethylene diisocyanate, 2,2,4-trimethylpentane diisocyanate, Aliphatic diisocyanates such as nonamethylene diisocyanate, decamethylene diisocyanate, 3-butoxyhexane diisocyanate, dodecamethylene diisocyanate, 4,4-biscyclohexylmethane diisocyanate; metaphenylene diisocyanate, paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, dimethylbenzene diisocyanate , Aromatic diisocyanates such as ethylbenzene diisocyanate, isopropylbenzene
- the diisocyanate compound is preferable because the reaction control is easy, the viscosity of the resulting urethane type polymer is low, and the handling is easy, and the function as a viscosity modifier is good. More preferred.
- the number of carbon atoms is less than 4, it is difficult to obtain from the market, which is not preferable for production.
- the number of carbon atoms exceeds 13, water solubility is lowered, and the function as a viscosity modifier is lowered.
- the value of q is 1, the obtained compound does not become a polymer and does not function as a viscosity modifier.
- the compounding ratio of each component is not particularly limited.
- the monohydroxy compound is used with respect to 10 mol of polyethylene glycol (B).
- (A) is preferably 10 to 30 moles
- monoglyceryl ether compound (C) is preferably 5 to 20 moles
- isocyanate compound (D) is preferably 20 to 50 moles. More preferably, the hydroxy compound (A) is 15 to 25 mol
- the monoglyceryl ether compound (C) is 8 to 15 mol
- the isocyanate compound (D) is 25 to 40 mol. If the blending ratio of each component deviates from the above blending ratio, a part of the blended raw material may remain in the system as an unreacted substance, or a good function as a viscosity modifier may not be obtained.
- a catalyst can be used to accelerate the reaction.
- catalysts include strong acids such as sulfuric acid and toluenesulfonic acid; metal halides such as titanium tetrachloride, hafnium chloride, zirconium chloride, aluminum chloride, gallium chloride, indium chloride, iron chloride, tin chloride, boron fluoride; water Sodium oxide, potassium hydroxide, sodium methylate, alkali metal or alkaline earth metal hydroxide such as sodium carbonate, alcoholate, carbonate; metal oxide such as aluminum oxide, calcium oxide, barium oxide, sodium oxide Organic metal compounds such as tetraisopropyl titanate, dibutyltin dichloride, dibutyltin oxide, dibutyltin bis (2-ethylhexylthioglycolate); soaps such as sodium octylate, potassium octylate, sodium laurate, potassium laurate Be mentionedThe blending amount of these catalysts is
- the urethane type polymer of the present invention obtained as described above can adjust the viscosity of water or an aqueous solution by adding to water or an aqueous solution, and the aqueous solution or gelled aqueous solution having viscosity by adjusting the addition amount. Can be obtained.
- the effect of adjusting the viscosity of the urethane type polymer of the present invention is less affected by changes in the pH of the liquid.
- the urethane type polymer of this invention does not reduce the water resistance of the coating film formed from the said liquid, when mix
- the urethane type polymer of the present invention does not cause problems such as sedimentation and separation when blended in paints and cosmetics.
- the urethane type polymer of the present invention should be used as a urethane type viscosity modifier that has the same characteristics as the existing urethane type viscosity modifier and is excellent in long-term storage stability like the alkali thickening type viscosity modifier. Can do.
- the urethane type polymer of the present invention can be used as a urethane type viscosity adjusting agent, but may be used in the form of an aqueous solution of urethane type viscosity adjusting agent.
- the urethane type viscosity modifier made of the urethane type polymer of the present invention is usually in a solid form, it must be pulverized and used for products such as paints and cosmetics.
- it since it takes a long time to dissolve the pulverized product in products such as paints and cosmetics, it is necessary to use a urethane type viscosity modifier in the form of an aqueous solution of urethane type viscosity modifier diluted with a solvent such as water. preferable.
- the urethane type viscosity modifier aqueous solution of the present invention contains a urethane-type viscosity modifier made of a urethane-type polymer and water.
- the water used in the urethane type viscosity modifier aqueous solution of the present invention is not particularly limited, and pure water, RO water, deionized water, distilled water, or the like can be used.
- the method for preparing the urethane type viscosity modifier aqueous solution of the present invention is not particularly limited. For example, after obtaining a urethane type polymer by the above reaction, water or the like is directly added therein to obtain a uniform aqueous solution. The stirring may be performed at a temperature of about 80 ° C. for about 1 to 3 hours.
- the urethane type viscosity modifier aqueous solution of the present invention may contain a solvent other than water together with water for the purpose of promoting the dilution rate or increasing the dilution concentration.
- solvents include alcohols such as methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol, propylene glycol, 1,2-butanediol, 1,3-butanediol; carbonization of 1 to 10 carbon atoms
- examples thereof include polyether solvents obtained by adding 1 to 10 moles of ethylene oxide and / or propylene oxide to an alcohol having a hydrogen group.
- a polyether solvent is preferable because it volatilizes and does not cause bad odor or the like and has a high effect of lowering the viscosity, and 3 to 10 ethylene oxide is added to a monohydric alcohol having an alkyl group having 5 to 10 carbon atoms.
- Mole-added polyether solvents are more preferred.
- the content of these solvents in the urethane type viscosity modifier aqueous solution is preferably 3 to 20% by mass, and more preferably 5 to 15% by mass.
- the urethane type viscosity modifier aqueous solution of the present invention may further contain additives known in the technical field as long as the effects of the present invention are not impaired from the viewpoint of imparting various properties.
- the urethane-type viscosity modifier aqueous solution of the present invention has the same characteristics as the existing urethane-type viscosity modifier, and is excellent in long-term storage stability like the alkali thickening-type viscosity modifier. It is easy to use in various products because it is easily dissolved in various products such as cosmetics.
- the urethane type viscosity adjusting agent and the urethane type viscosity adjusting agent aqueous solution of the present invention can be used for any product as long as it is used for adjusting the viscosity of the aqueous solution.
- examples of such products include water-based paints, water-based adhesives, water-based cleaning agents, cosmetics, and the like.
- cosmetics such as creams, cosmetic liquids, skin lotions, milky lotions, and liquid foundations that are strongly required to have long-term storage stability.
- the addition amount of the urethane type viscosity modifier of the present invention and the urethane type viscosity modifier aqueous solution in various products is the total amount of the system (total amount of the various products and the urethane type viscosity modifier or urethane type viscosity modifier aqueous solution of the present invention).
- the urethane type viscosity modifier is preferably added in an amount of 0.01 to 10% by mass, more preferably 0.03 to 5% by mass, and still more preferably 0.05 to 3% by mass.
- the addition amount is such that the urethane type viscosity modifier is less than 0.1% by mass, the function as the viscosity modifier may not be sufficiently exhibited.
- the amount of the urethane type viscosity modifier exceeds 10% by mass, the urethane type viscosity modifier may not be completely dissolved in various products.
- the oil-in-water emulsion composition of the present invention contains the urethane polymer (I) described above, an oil or waxy substance (II), and water (III).
- the oil or wax-like substance (II) used in the oil-in-water emulsified composition of the present invention only needs to be capable of forming an emulsion when mixed with water (III), and has a melting point of 100 ° C. or less. There is no particular limitation as long as it is water-insoluble. When the melting point exceeds 100 ° C. and / or is water-soluble, an emulsion cannot be formed when mixed with water (III).
- these components can be used individually or in combination of 2 or more types. Moreover, even if these components have a melting point exceeding 100 ° C., they can be used if the melting point can be reduced to 100 ° C. or less by using two or more types in combination.
- Water (III) used in the oil-in-water emulsion composition of the present invention is not particularly limited, and pure water, RO water, deionized water, distilled water, or the like can be used.
- urethane type polymer (I) also has a function as a viscosity regulator, the viscosity and form (viscous liquid, a gel-like body, etc.) of an oil-in-water type emulsion composition can be changed with the compounding quantity. .
- urethane type polymer (I) exceeds 10 parts by mass, an insoluble matter may remain or an effect corresponding to the addition amount may not be obtained.
- water (III) is less than 40 mass parts, it may become difficult to form an oil-in-water emulsion composition.
- water (III) exceeds 80,000 mass parts oil or wax-like substance (II) may decrease and emulsification may be impossible.
- the oil-in-water emulsion composition of the present invention further contains an alcohol (IV) represented by the following general formula (5) in addition to the components (I) to (III) from the viewpoint of improving product stability. can do.
- an alcohol (IV) represented by the following general formula (5) in addition to the components (I) to (III) from the viewpoint of improving product stability. can do.
- the alcohol (IV) is added, the product stability of the oil-in-water emulsion composition of the present invention itself is improved, and when an insoluble matter such as a powder is added to the oil-in-water emulsion composition of the present invention. In addition, the effect of suppressing powder separation and sedimentation is improved.
- alcohol (IV) examples include monohydric alcohols such as ethanol, propanol and isopropanol; ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,3-butylene Glycol, 1,4-butylene glycol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,3-hexanediol Dihydric alcohols such as 1,6-hexanediol, 1,2-heptanediol, 1,7-heptanediol, 1,2-octanediol, 1,8-octanediol, dihydroxybenzene; glycerin, trimethylolpropane Trihydric alcohols such as diglycerin, pentae Suritoru, polyhydr
- the amount of alcohol (IV) to be added may be adjusted according to the use of the oil-in-water emulsion composition, and is not particularly limited. However, alcohol (IV) is added to 100 parts by mass of oil or wax-like substance (II). The amount is preferably 1 to 30 parts by mass, more preferably 1 to 10 parts by mass. Product stability cannot fully be improved as alcohol (IV) is less than 1 mass part. On the other hand, when alcohol (IV) exceeds 30 mass parts, the effect corresponding to addition amount may not be acquired.
- the method for adding alcohol (IV) is not particularly limited, but is a method of adding and mixing with urethane type polymer (I), oil or wax-like substance (II) and water (III), urethane type polymer (I), For example, a method in which oil or wax-like substance (II) and water (III) are mixed and then added and mixed can be used.
- the oil-in-water emulsion composition of the present invention can contain powder from the viewpoint of imparting various effects (for example, coloring and the like) to the oil-in-water emulsion composition. Even if powder is added, the oil-in-water emulsion composition of the present invention can suppress powder separation and sedimentation and can stably disperse the powder for a long period of time.
- the amount of the powder added is not particularly limited as long as it does not impair the effects of the present invention, but is preferably based on 100 parts by mass of the total amount of oil or waxy substance (II) and water (III).
- the amount is 0.1 to 100 parts by mass, more preferably 1 to 80 parts by mass.
- the oil-in-water emulsion composition of the present invention is excellent in product stability, can stably disperse the powder for a long time when the powder is added, and does not use a surfactant as an emulsifier. Can be used in various applications.
- the oil-in-water emulsion composition of the present invention does not use a surfactant and has low irritation to the skin, it is preferably used for cosmetics and quasi-drugs. More preferably.
- the cosmetic of the present invention includes the oil-in-water emulsion composition described above.
- cosmetics that can be used include creams, facial cleansing creams, facial cleansing foams, cleansing creams, cleansing milks, cleansing lotions, massage creams, moisture creams, sun creams, hair liquids, set lotions, hair bleaches, color rinses, permanents.
- Comparative product 6 Hydroxymethyl cellulose (trade name: HEC, manufactured by Sumitomo Seika Co., Ltd.)
- Comparative product 7 methylcellulose (trade name: Meserose MC, manufactured by Sakai Kogyo Co., Ltd.)
- Comparative product 8 Carboxyvinyl polymer (trade name: Carbopol 980, manufactured by Nippon Lubrizol Corporation)
- Example 1 Viscosity test
- the inventive products 1 to 9 and comparative products 1 to 8 are added to pure water so as to be 1.5% by mass and completely dissolved, and each corner is then measured using a rheometer (viscoelasticity measuring device).
- the storage elastic modulus (G ′) and loss elastic modulus (G ′′) at the frequency ( ⁇ ) were measured.
- the results are shown in Table 2.
- G ′ is the ability to hold the stress stored inside the measurement liquid.
- Elastic component and G "means a viscous component in which the energy given to the measurement liquid escapes as heat. If G ′ is higher than G ′′, the liquid has an elastic property (solid property), so that sedimentation and separation of components in the liquid are difficult to occur. If the difference is constant, the viscous body exhibits the same behavior regardless of the frequency.
- the used rheometer and measurement conditions are as follows.
- some of the products of the present invention have a smaller difference between G ′ and G ′′ in a region where the angular frequency is low, but in both cases, G ′ is better than G ′′.
- G ′ is better than G ′′.
- a large value is shown, and it is considered that sedimentation and separation of components in the liquid hardly occur.
- the comparative product has an angular frequency region where G ′ is smaller than G ′′ except for the comparative product 8, and it is considered that the sedimentation and separation of components in the liquid are likely to occur.
- sedimentation and separation of components in the liquid are difficult to occur, but since it is an alkali thickener (sodium polyacrylate), it is difficult to use it without being affected by pH.
- Example 2 Stability test
- Gels were prepared by dissolving 1% by mass of the viscosity modifiers of the inventive products 1 to 9, and the comparative products 1 to 2, 4 and 6 to 8 respectively in pure water. Thereafter, titanium oxide powder was added to each prepared gel so as to be 5% by mass, and the mixture was stirred with a stirrer for 1 hour until uniform. The gel in which titanium oxide was uniformly dispersed was allowed to stand in a thermostatic bath at 25 ° C., and the behavior of titanium oxide was confirmed visually. The results are shown in Table 3.
- the characteristics similar to those of the existing urethane type viscosity modifier (specifically, the water resistance of the coating film when the product after addition is made into a coating film is good.
- a novel urethane-type polymer that can be used as a urethane-type viscosity modifier that is excellent in long-term storage stability like an alkali thickening-type viscosity modifier. be able to.
- the urethane type viscosity modifier and the urethane type viscosity adjuster have the same characteristics as the existing urethane type viscosity adjuster and are excellent in long-term storage stability like the alkali thickening type viscosity adjuster.
- An aqueous agent solution can be provided.
- I-1 to I-6 Urethane type polymer synthesized above I′-1 to I′-5: Comparative urethane type polymer synthesized above I′-6: Hydroxymethyl cellulose (trade name: HEC, Sumitomo Seika) (Made by Co., Ltd.)
- I′-7 Methylcellulose (trade name: Meserose MC, manufactured by Sakai Kogyo Co., Ltd.)
- I′-8 Carboxyvinyl polymer (trade name: Carbopol 980, manufactured by Nippon Lubrizol Corporation) Note)
- I'-6 to I'-8 are commercially available viscosity modifiers.
- II-1 Liquid paraffin (0.85-0.89 g / ml (20 ° C.), manufactured by Wako Pure Chemical Industries, Ltd.)
- II-2 Olive oil III: Water IV-1: 1,2-propylene glycol IV-2: 1,3-butanediol IV-3: 1,2-hexanediol
- the oil-in-water emulsion composition was prepared by the same method as the preparation method of the oil-in-water emulsion composition of the product 10 of the present invention except that the raw materials and / or the blending ratio thereof were changed as shown in Table 6 below. (Invention products 11 to 20) were obtained.
- the oil-in-water emulsion composition was prepared by the same method as that for the oil-in-water emulsion composition of the product 10 of the present invention except that the raw materials and / or the blending ratio thereof were changed as shown in Table 7 below. (Comparative products 9 to 19) were obtained.
- Example 3 Evaluation of stability of oil-in-water emulsion composition
- the oil-in-water emulsion compositions of the present invention and the comparative product prepared above were sealed in a 100 mL screw tube and left in a thermostatic bath at 25 ° C. After standing, the state after 1 hour, 1 week, 1 month, 2 months, 3 months and 4 months was visually observed and evaluated according to the following criteria.
- ⁇ No change in the emulsified state
- ⁇ A transparent oil phase can be slightly confirmed at the top of the oil-in-water emulsion composition.
- - The water phase and the oil phase are completely separated. The results of this evaluation are shown in Table 8. Show. In addition, when the water phase and the oil phase are completely separated (evaluation), the subsequent evaluation is not performed.
- the oil-in-water emulsion composition of the present invention is less likely to cause separation of the water phase and the oil phase for a long time than the oil-in-water emulsion composition of the comparative product. Excellent stability.
- oil-in-water emulsion composition containing powder a powder in which equal amounts of silicone-treated talc, silicone-treated mica, silicone-treated sericite, and silicone-treated titanium oxide (both SA series manufactured by Miyoshi Kasei Co., Ltd.) are mixed is prepared. The stability was evaluated.
- Example 4 Evaluation of stability of oil-in-water emulsion composition containing powder
- the oil-in-water emulsion compositions containing the powders of the present invention and the comparative product prepared above were put in a 100 mL screw tube, sealed, and left in a thermostatic bath at 25 ° C. After standing, the state after 1 hour, 1 week, 1 month, 2 months, 3 months and 4 months was visually observed and evaluated according to the following criteria.
- ⁇ The powder is uniformly dispersed.
- ⁇ A transparent oil phase can be slightly observed at the top of the oil-in-water emulsion composition.
- - The powder is precipitated and separated at the top of the oil-in-water emulsion composition. The result of this evaluation is shown in Table 11. In addition, when powder settles (evaluation *), subsequent evaluation is not performed.
- the oil-in-water emulsified composition of the present invention has a powder precipitation and separation of the water phase and the oil phase compared to the oil-in-water emulsified composition of the comparative product. Was difficult to occur for a long time and was excellent in stability.
- the product stability is excellent, the powder can be stably dispersed for a long time when the powder is added, and a surfactant is not used as an emulsifier.
- An oil-in-water emulsion composition and a cosmetic containing the same can be provided.
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Abstract
Description
しかしながら、肌への低刺激性及び安全性が要求される化粧料(例えば、化粧水)においては、界面活性剤の使用が望ましくないため、例えば、界面活性剤を使用せずに水相と油相とが分離した状態の化粧料も多く市販されている。
また、本発明は、既存のウレタン型粘性調整剤と同様の特性を有しつつ、アルカリ増粘型粘性調整剤と同様に長期保存安定性に優れるウレタン型粘性調整剤及びウレタン型粘性調整剤水溶液を提供することを目的とする。
さらに、本発明は、製品安定性に優れ、粉体を添加した場合に長期間安定的に粉体を分散させることができ、しかも乳化剤として界面活性剤を使用しない水中油型乳化組成物、及びそれを含有する化粧料を提供することを目的とする。
すなわち、本発明は、下記の一般式(1):
下記の一般式(2):
下記の一般式(3):
下記の一般式(4):
を反応させて得られるウレタン型ポリマーである。
また、本発明は、上記のウレタン型粘性調整剤と水とを含有することを特徴とするウレタン型粘性調整剤水溶液である。
融点が100℃以下で非水溶性のオイル又はワックス状物質(II)と、
水(III)と
を含有することを特徴とする水中油型乳化組成物である。
さらに、本発明は、上記の水中油型乳化組成物を含有することを特徴とする化粧料である。
また、本発明によれば、既存のウレタン型粘性調整剤と同様の特性を有しつつ、アルカリ増粘型粘性調整剤と同様に長期保存安定性に優れるウレタン型粘性調整剤及びウレタン型粘性調整剤水溶液を提供することができる。
さらに、本発明によれば、製品安定性に優れ、粉体を添加した場合に長期間安定的に粉体を分散させることができ、しかも乳化剤として界面活性剤を使用しない水中油型乳化組成物、及びそれを含有する化粧料を提供することができる。
本発明のウレタン型粘性調整剤水溶液は、ウレタン型ポリマーからなるウレタン型粘度調整剤と、水とを含有する。
本発明のウレタン型粘性調整剤水溶液に用いられる水は、特に限定されず、純水、RO水、脱イオン水、蒸留水等を用いることができる。
本発明のウレタン型粘性調整剤水溶液の調製方法としては、特に限定されないが、例えば、上記反応によってウレタン型ポリマーを得た後、その中に水等を直接添加し、均一な水溶液になるまで40~80℃程度の温度で1~3時間程度撹拌すればよい。
本発明のウレタン型粘性調整剤水溶液は、既存のウレタン型粘性調整剤と同様の特性を有しつつ、アルカリ増粘型粘性調整剤と同様に長期保存安定性に優れていることに加え、塗料や化粧品等の各種製品に容易に溶解するため、各種製品に使用し易い。
本発明の水中油型乳化組成物は、上記で説明したウレタン型ポリマー(I)と、オイル又はワックス状物質(II)と、水(III)とを含有する。
本発明の水中油型乳化組成物に用いられるオイル又はワックス状物質(II)は、水(III)と混合した際にエマルションを形成することができるものであればよく、融点が100℃以下且つ非水溶性であるものであれば特に限定されない。融点が100℃超過及び/又は水溶性である場合、水(III)と混合した際にエマルションを形成することができない。
ここで、本明細書において「非水溶性」とは、25℃の水への溶解度が、3g/100g以下(水100gに対する溶解度が3g以下)、好ましくは1g/100g以下であることを意味する。
混合の際、ウレタン型ポリマー(I)は、乳化剤と同様の機能を有するため、オイル又はワックス状物質(II)と水(III)とを乳化させることができる。また、ウレタン型ポリマー(I)は、粘性調整剤としての機能も有するため、その配合量によって水中油型乳化組成物の粘度及び形態(粘稠液体やゲル状体等)を変化させることができる。
使用可能な化粧料の例としては、クリーム、洗顔クリーム、洗顔フォーム、クレンジングクリーム、クレンジングミルク、クレンジングローション、マッサージクリーム、モイスチュアクリーム、日焼け止めクリーム、ヘアリキッド、セットローション、ヘアブリーチ、カラーリンス、パーマネントウェーブ液、ハンドクリーム、口紅、液状ファンデーション、化粧水、化粧液、乳液、オーデコロン、爪用化粧品、マスカラ、アイライナー、シャンプー、リンス、トリートメント、ボディーソープ等が挙げられる。
<ウレタン型ポリマーの合成>
(使用原料)
A-1:炭素数32のアルコール(2-テトラデシルオクタデカノール)の50EO付加物
A-2:炭素数32のアルコール(2-テトラデシルオクタデカノール)の250EO付加物
A-3:炭素数28のアルコール(2-ドデシルヘキサデカノール)の150EO付加物
A-4:炭素数24のアルコール(2-デシルテトラデシル)の150EO付加物
B-1:重量平均分子量11000のポリオキシエチレングリコール
B-2:重量平均分子量8000のポリオキシエチレングリコール
C-1:2-エチルヘキシルグリセリルエーテル
C-2:モノドデシルグリセリルエーテル
D-1:ヘキサメチレンジイソシアネート
D-2:メタフェニレンジイソシアネート
A'-1:炭素22のアルコール(2-デシルドデシル)150EO付加物
C'-1:ブチルグリセリルエーテル
*EO付加物:エチレンオキシド付加物
[本発明品1の合成]
温度計、窒素導入管及び攪拌機を備えた容量2000mLの4つ口フラスコに、267g(0.1モル)のA-1、550g(0.05モル)のB-1及び10.2g(0.05モル)のC-1を仕込み、系内を窒素置換後、80~90℃に昇温して溶融させ、均一になるまで混合した。各成分が均一に混合されたのを確認した後、25g(0.15モル)のD-1を系内に添加し、同温度で3時間反応させて本発明品1を得た。
原料及び/又はその配合割合を下記の表1に示すものに変えたこと以外は、本発明品1の合成と同様の条件下で合成を行い、本発明品2~9を得た。
[比較品1~5の合成]
原料及び/又はその配合割合を下記の表1に示すものに変えたこと以外は、本発明品1の合成と同様の条件下で合成を行い、比較品1~5を得た。
[比較品6~8]
比較品6~8として、市販の粘性調整剤を用いた。
比較品6:ヒドロキシメチルセルロース(商品名:HEC、住友精化株式会社製)
比較品7:メチルセルロース(商品名:メセロースMC、巴工業株式会社製)
比較品8:カルボキシビニルポリマー(商品名:カーボポール980、日本ルーブリゾール株式会社製)
本発明品1~9及び比較品1~8を純水に1.5質量%になるように添加して完全に溶解させた後、レオメーター(粘弾性測定装置)を使用して、各角周波数(ω)における貯蔵弾性率(G')及び損失弾性率(G")を測定した。その結果を表2に示す。ここで、G'は測定液体内部に蓄えられた応力を保持する能力(弾性成分)を示し、G"は測定液体に与えたエネルギーが熱となって逃げる粘性成分を意味する。G'がG"より高ければ、その液体は弾性的な性質(固体的な性質)を持つことになるため、液体内の成分の沈降や分離が起こり難くなる。また、G'とG"の差が一定であれば、粘性体がいずれの周波数であっても、同一の挙動を示すことになる。使用したレオメーター及び測定条件は以下の通りである。
装置名:MCR301(Anton Paar GmbH製)
<測定条件>
測定治具:PP50(パラレルプレート、φ50mm)
測定位置:0.5mm(ステージからパラレルプレートまでの距離)
歪み(振り角):5%
測定温度:25℃
これに対して比較品は、比較品8を除き、G'がG"より小さくなる角周波数の領域があり、液体内の成分の沈降や分離が起こり易いと考えられる。また、比較品8は、液体内の成分の沈降や分離が起こり難いが、アルカリ増粘剤(ポリアクリル酸ナトリウム)であるため、pHの影響を受けずに使用することが難しい。
本発明品1~9、並びに比較品1~2、4及び6~8の粘性調整剤をそれぞれ純水に1質量%溶解させてゲルを作製した。その後、作製した各ゲルに酸化チタンの粉末を5質量%になるように添加し、撹拌器で1時間、均一になるまで撹拌した。酸化チタンが均一に分散したゲルを、25℃の恒温槽内に静置し、目視にて酸化チタンの挙動を確認した。その結果を表3に示す。
(使用原料)
a-1:炭素数32のアルコール(2-テトラデシルオクタデカノール)の50EO付加物
a-2:炭素数24のアルコール(2-デシルテトラデシル)の150EO付加物
b-1:重量平均分子量11000のポリオキシエチレングリコール
c-1:モノオクチルグリセリルエーテル
c-2:モノドデシルグリセリルエーテル
d-1:ヘキサメチレンジイソシアネート
d-2:メタフェニレンジイソシアネート
a'-1:炭素22のアルコール(2-デシルドデシル)150EO付加物
c'-1:ブチルグリセリルエーテル
*EO付加物:エチレンオキシド付加物
温度計、窒素導入管及び攪拌機を備えた容量2000mLの4つ口フラスコに、267g(0.1モル)の原料(a-1)、550g(0.05モル)の原料(b-1)及び10.2g(0.05モル)の原料(c-1)を仕込み、系内を窒素置換後、80~90℃に昇温して溶融させ、均一になるまで混合した。各成分が均一に混合されたのを確認した後、25g(0.15モル)の原料(d-1)を系内に添加し、同温度で3時間反応させてウレタン型ポリマー(I-1)を得た。
(使用原料)
I-1~I-6:上記で合成したウレタン型ポリマー
I'-1~I'-5:上記で合成した比較用ウレタン型ポリマー
I'-6:ヒドロキシメチルセルロース(商品名:HEC、住友精化株式会社製)
I'-7:メチルセルロース(商品名:メセロースMC、巴工業株式会社製)
I'-8:カルボキシビニルポリマー(商品名:カーボポール980、日本ルーブリゾール株式会社製)
注)I'-6~I'-8は、市販の粘性調整剤である。
II-1:流動パラフィン(0.85~0.89g/ml(20℃)、和光純薬工業社製)
II-2:オリーブ油
III:水
IV-1:1,2-プロピレングリコール
IV-2:1,3-ブタンジオール
IV-3:1,2-ヘキサンジオール
1000mLのビーカーに原料(III)及び原料(I-1)を入れ、50℃に加熱して原料(I-1)を完全に溶解させた後、同温度で撹拌しながら原料(II-1)を添加した。添加終了後、撹拌を10分間続けることで水中油型乳化組成物(本発明品10)を得た。なお、水中油型乳化組成物は、全体で500gとなるようにし、各原料の配合割合(質量%)は下記の表6の通りにした。
上記で調製した本発明品及び比較品の水中油型乳化組成物を、100mLのスクリュー管に入れて密封し、25℃の恒温槽に放置した。放置後、1時間、1週間、1ヶ月、2ヶ月、3ヶ月及び4ヶ月経過後の状態を目視で観察し、下記の基準で評価した。
○:乳化状態に変化なし
△:水中油型乳化組成物の上部に透明な油相がわずかに確認できる
・:水相と油相とが完全に分離している
この評価の結果を表8に示す。なお、水相と油相とが完全に分離した場合(評価・)、その後の評価は行っていない。
次に、シリコーン処理タルク、シリコーン処理マイカ、シリコーン処理セリサイト及びシリコーン処理酸化チタン(いずれも三好化成社製のSAシリーズ)をそれぞれ等量混合した粉体を含有する水中油型乳化組成物を調製し、その安定性を評価した。
1000mLのビーカーに原料(III)及び原料(I-1)を入れ、50℃に加熱して原料(I-1)を完全に溶解させた後、同温度で撹拌しながら原料(II-1)を添加した。添加終了後に撹拌を10分間続けた後、粉体を添加し、更に10分間撹拌を続けて粉体を均一に分散さることで水中油型乳化組成物(本発明品21)を得た。なお、水中油型乳化組成物は、全体で500gとなるようにし、各原料の配合割合(質量%)は下記の表9の通りにした。
上記で調製した本発明品及び比較品の、粉体を含有する水中油型乳化組成物を、100mLのスクリュー管に入れて密封し、25℃の恒温槽に放置した。放置後、1時間、1週間、1ヶ月、2ヶ月、3ヶ月及び4ヶ月経過後の状態を目視で観察し、下記の基準で評価した。
○:粉体が均一に分散している
△:水中油型乳化組成物の上部に透明な油相がわずかに確認できる
・:粉体が沈殿し、且つ水中油型乳化組成物の上部に分離した油相がはっきり確認できる
この評価の結果を表11に示す。なお、粉体が沈殿した場合(評価・)、その後の評価は行っていない。
Claims (12)
- 各成分の反応比は、ポリエチレングリコール(B)10モルに対して、モノヒドロキシ化合物(A)が10~30モル、モノグリセリルエーテル化合物(C)が5~20モル及びイソシアネート化合物(D)が20~50モルであることを特徴とする請求項1に記載のウレタン型ポリマー。
- モノヒドロキシ化合物(A)、ポリエチレングリコール(B)及びモノグリセリルエーテル化合物(C)の混合物に、イソシアネート化合物(D)を添加して反応させることを特徴とする請求項1又は2に記載のウレタン型ポリマー。
- 請求項1~3のいずれか一項に記載のウレタン型ポリマーからなるウレタン型粘性調整剤。
- 請求項4に記載のウレタン型粘性調整剤と水とを含有することを特徴とするウレタン型粘性調整剤水溶液。
- 請求項1~3のいずれか一項に記載のウレタン型ポリマー(I)と、
融点が100℃以下で非水溶性のオイル又はワックス状物質(II)と、
水(III)と
を含有することを特徴とする水中油型乳化組成物。 - 前記オイル又はワックス状物質(II)の25℃の水への溶解度が、3g/100g以下であることを特徴とする請求項6に記載の水中油型乳化組成物。
- 前記オイル又はワックス状物質(II)100質量部に対して、前記ウレタン型ポリマー(I)が0.1~10質量部、前記水(III)が40~80,000質量部であることを特徴とする請求項6又は7に記載の水中油型乳化組成物。
- 前記オイル又はワックス状物質(II)100質量部に対して、前記アルコール(IV)が1~30質量部であることを特徴とする請求項9に記載の水中油型乳化組成物。
- 粉体を更に含有することを特徴とする請求項6~10のいずれか1項に記載の水中油型乳化組成物。
- 請求項6~11のいずれか1項に記載の水中油型乳化組成物を含有することを特徴とする化粧料。
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EP13857879.4A EP2927256B1 (en) | 2012-11-29 | 2013-11-25 | Urethane-type polymer and use thereof |
CN201380062376.9A CN104822726B (zh) | 2012-11-29 | 2013-11-25 | 氨基甲酸酯型聚合物及其用途 |
JP2014550182A JP6159738B2 (ja) | 2012-11-29 | 2013-11-25 | ウレタン型ポリマー及びその用途 |
US14/440,432 US9745407B2 (en) | 2012-11-29 | 2013-11-25 | Urethane-type polymers and use thereof |
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Cited By (6)
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WO2019049723A1 (ja) * | 2017-09-07 | 2019-03-14 | 株式会社Adeka | 水系ゲル化剤を含む皮膚用又は毛髪用洗浄剤組成物、並びに該水系ゲル化剤及び該洗浄剤組成物の製造方法 |
WO2019049725A1 (ja) * | 2017-09-07 | 2019-03-14 | 株式会社Adeka | 水系ゲル化剤を含む化粧料組成物、並びに該水系ゲル化剤及び該化粧料組成物の製造方法 |
WO2019049722A1 (ja) * | 2017-09-07 | 2019-03-14 | 株式会社Adeka | 水系ゲル化剤を含む毛髪化粧料組成物、並びに該水系ゲル化剤及び該毛髪化粧料組成物の製造方法 |
KR20190042650A (ko) | 2016-08-31 | 2019-04-24 | 가부시키가이샤 아데카 | 수계 겔화제 조성물 및 그것을 사용한 화장료 |
WO2020137679A1 (ja) | 2018-12-25 | 2020-07-02 | 株式会社Adeka | ウレタンポリマー及びこれを含む油類組成物 |
WO2020162248A1 (ja) * | 2019-02-07 | 2020-08-13 | 株式会社Adeka | ウレタン変性シリコーン及びそれを含有する油類組成物並びに化粧料組成物 |
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CN108586687B (zh) * | 2018-03-26 | 2020-11-03 | 四川大学 | 一种两嵌段非离子型聚氨酯含氟短链表面活性剂的制备方法 |
JP6408184B1 (ja) * | 2018-04-16 | 2018-10-17 | 株式会社 資生堂 | とろみ状の水性化粧料 |
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JP2000239649A (ja) | 1999-02-25 | 2000-09-05 | Asahi Denka Kogyo Kk | 粘性調整剤 |
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KR20190042650A (ko) | 2016-08-31 | 2019-04-24 | 가부시키가이샤 아데카 | 수계 겔화제 조성물 및 그것을 사용한 화장료 |
JPWO2019049722A1 (ja) * | 2017-09-07 | 2020-08-20 | 株式会社Adeka | 水系ゲル化剤を含む毛髪化粧料組成物、並びに該水系ゲル化剤及び該毛髪化粧料組成物の製造方法 |
WO2019049722A1 (ja) * | 2017-09-07 | 2019-03-14 | 株式会社Adeka | 水系ゲル化剤を含む毛髪化粧料組成物、並びに該水系ゲル化剤及び該毛髪化粧料組成物の製造方法 |
WO2019049725A1 (ja) * | 2017-09-07 | 2019-03-14 | 株式会社Adeka | 水系ゲル化剤を含む化粧料組成物、並びに該水系ゲル化剤及び該化粧料組成物の製造方法 |
WO2019049723A1 (ja) * | 2017-09-07 | 2019-03-14 | 株式会社Adeka | 水系ゲル化剤を含む皮膚用又は毛髪用洗浄剤組成物、並びに該水系ゲル化剤及び該洗浄剤組成物の製造方法 |
JPWO2019049723A1 (ja) * | 2017-09-07 | 2020-08-20 | 株式会社Adeka | 水系ゲル化剤を含む皮膚用又は毛髪用洗浄剤組成物、並びに該水系ゲル化剤及び該洗浄剤組成物の製造方法 |
JPWO2019049725A1 (ja) * | 2017-09-07 | 2020-08-20 | 株式会社Adeka | 水系ゲル化剤を含む化粧料組成物、並びに該水系ゲル化剤及び該化粧料組成物の製造方法 |
JP7179005B2 (ja) | 2017-09-07 | 2022-11-28 | 株式会社Adeka | 水系ゲル化剤を含む皮膚用又は毛髪用洗浄剤組成物、並びに該水系ゲル化剤及び該洗浄剤組成物の製造方法 |
JP7179006B2 (ja) | 2017-09-07 | 2022-11-28 | 株式会社Adeka | 水系ゲル化剤を含む化粧料組成物、並びに該水系ゲル化剤及び該化粧料組成物の製造方法 |
JP7179004B2 (ja) | 2017-09-07 | 2022-11-28 | 株式会社Adeka | 水系ゲル化剤を含む毛髪化粧料組成物、並びに該水系ゲル化剤及び該毛髪化粧料組成物の製造方法 |
WO2020137679A1 (ja) | 2018-12-25 | 2020-07-02 | 株式会社Adeka | ウレタンポリマー及びこれを含む油類組成物 |
KR20210107717A (ko) | 2018-12-25 | 2021-09-01 | 가부시키가이샤 아데카 | 우레탄 폴리머 및 이것을 포함하는 유류 조성물 |
WO2020162248A1 (ja) * | 2019-02-07 | 2020-08-13 | 株式会社Adeka | ウレタン変性シリコーン及びそれを含有する油類組成物並びに化粧料組成物 |
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EP2927256A4 (en) | 2016-06-01 |
CN104822726B (zh) | 2017-11-24 |
EP2927256B1 (en) | 2017-08-23 |
US20150299375A1 (en) | 2015-10-22 |
CN104822726A (zh) | 2015-08-05 |
EP2927256A1 (en) | 2015-10-07 |
JP6159738B2 (ja) | 2017-07-05 |
US9745407B2 (en) | 2017-08-29 |
JPWO2014084174A1 (ja) | 2017-01-05 |
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