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WO2023182149A1 - Method for thickening oily component and composition containing oily component - Google Patents

Method for thickening oily component and composition containing oily component Download PDF

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Publication number
WO2023182149A1
WO2023182149A1 PCT/JP2023/010344 JP2023010344W WO2023182149A1 WO 2023182149 A1 WO2023182149 A1 WO 2023182149A1 JP 2023010344 W JP2023010344 W JP 2023010344W WO 2023182149 A1 WO2023182149 A1 WO 2023182149A1
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WO
WIPO (PCT)
Prior art keywords
oil
oil component
fatty acid
ppg
smdi
Prior art date
Application number
PCT/JP2023/010344
Other languages
French (fr)
Japanese (ja)
Inventor
麻利華 前橋
友紀 竹石
聡人 安谷
圭英 近藤
Original Assignee
株式会社Adeka
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Publication of WO2023182149A1 publication Critical patent/WO2023182149A1/en

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/02—Inorganic compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/06—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/06—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite
    • A61K47/08—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite containing oxygen, e.g. ethers, acetals, ketones, quinones, aldehydes, peroxides
    • A61K47/14—Esters of carboxylic acids, e.g. fatty acid monoglycerides, medium-chain triglycerides, parabens or PEG fatty acid esters
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
    • A61K47/34—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyesters, polyamino acids, polysiloxanes, polyphosphazines, copolymers of polyalkylene glycol or poloxamers
    • 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
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/25—Silicon; Compounds thereof
    • 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
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/31—Hydrocarbons
    • 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
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/37—Esters of carboxylic acids
    • 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
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/39—Derivatives containing from 2 to 10 oxyalkylene groups
    • 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
    • A61K8/86—Polyethers
    • 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
    • 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
    • A61K8/89—Polysiloxanes
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/06—Ointments; Bases therefor; Other semi-solid forms, e.g. creams, sticks, gels
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere

Definitions

  • the present invention relates to a method for significantly thickening an oil component, and an oil component-containing composition obtained using the method.
  • Products such as paints, cleaning agents, adhesives, cosmetics, pharmaceuticals, pesticides, inks, dyes, etc. are in the form of water-based or oil-based compositions, and various additives are used to obtain compositions with suitable viscosity or fluidity for use.
  • a viscosity agent or viscosity modifier is used.
  • Patent Document 1 describes a method for easily producing polyurethane suitable as a water-based thickener.
  • Patent Document 2 describes a viscosity modifier made of a specific urethane compound as a viscosity modifier that has little temperature dependence and maintains a constant viscosity under any conditions.
  • thickeners or viscosity modifiers for modifying the viscosity or fluidity of oil-based compositions is also active. Thickeners for oils that can be thickened to a gel-like or elastic jelly-like state are described.
  • Patent Document 4 describes a viscosity modifier for water-based paints consisting of a smectite clay mineral and a condensed phosphate.
  • Patent Document 5 describes a thickening agent for liquids consisting of silanized pyrogenically produced silicic acid.
  • Patent Document 6 In the market, there is a need for a method for significantly increasing the viscosity of an oil component, and for a composition whose viscosity is adjusted to a value suitable for use by such a method.
  • an object of the present invention is to provide a thickening method that can significantly increase the oil component, an oil component-containing composition, and a thickener composition obtained using the method.
  • the present inventors conducted extensive research and found a thickening method that can further significantly increase the oil component, resulting in the present invention. That is, the present invention comprises (PPG-12/SMDI) copolymer (A), silica particles (B), polyglycerin whose polymerization degree of glycerin is 2 to 20, and fatty acid whose carbon number is 8 to 20.
  • An oil component comprising mixing a polyglycerol fatty acid ester (C), which is a monoester or diester of , with one or more oil components (D) selected from ester oil, hydrocarbon oil and silicone oil This is a method of thickening.
  • the present invention also provides a copolymer (PPG-12/SMDI) (A), a silica particle (B), a polyglycerin having a polymerization degree of 2 to 20, and a fatty acid having 8 to 20 carbon atoms.
  • An oil component-containing composition comprising a polyglycerin fatty acid ester (C) which is a monoester or diester of be.
  • the present invention provides silica particles (B) and polyglycerin fatty acid ester (C ), and a thickener composition containing a (PPG-12/SMDI) copolymer (A) for mixing with one or more oil components (D) selected from ester oils, hydrocarbon oils, and silicone oils. It is also a thing.
  • the method and thickener composition for thickening oil components of the present invention it is possible to significantly thicken one or more oil components selected from ester oils, hydrocarbon oils, and silicone oils.
  • oil components selected from ester oils, hydrocarbon oils, and silicone oils.
  • the viscosity can be easily adjusted to suit each product.
  • a cosmetic composition is prepared using the method of thickening an oil component of the present invention, a cosmetic composition having a viscosity suitable for use can be easily obtained.
  • the method for thickening an oil component according to the present invention is a method for thickening an oil component of the present invention, which consists of a (PPG-12/SMDI) copolymer (A), silica particles (B), and a polyester resin in which the degree of polymerization of glycerin is 2 to 20.
  • Polyglycerin fatty acid ester (C) which is a monoester or diester of glycerin and a fatty acid having 8 to 20 carbon atoms, is mixed with one or more oils selected from ester oils, hydrocarbon oils, and silicone oils. Including mixing with component (D).
  • the (PPG-12/SMDI) copolymer (A) used in the present invention consists of PPG-12 (polypropylene glycol-12; a polymer of propylene oxide with an average degree of polymerization of 12) and SMDI (dicyclohexylmethane 4,4'-diisocyanate).
  • the weight average molecular weight of the (PPG-12/SMDI) copolymer (A) used in the present invention is not particularly limited, but from the viewpoint of increasing the viscosity of the oil component, the weight average molecular weight of the (PPG-12/SMDI) copolymer (A) is as follows: It is preferably from 1,000 to 500,000, more preferably from 1,500 to 100,000, even more preferably from 1,500 to 50,000, and from 2,000 to 10,000. Most preferably. In the present invention, the weight average molecular weight of the (PPG-12/SMDI) copolymer (A) can be measured by gel permeation chromatography (GPC) and calculated in terms of styrene.
  • GPC gel permeation chromatography
  • the measurement conditions for GPC are as follows. [GPC measurement conditions] Equipment: LC-2000plus series (manufactured by JASCO Corporation) Column: KF-803 (manufactured by Showa Denko Co., Ltd.) Column temperature: 40°C Sample concentration: 0.1% by mass Developing solvent: Tetrahydrofuran Detection device: Intelligent differential refractometer RI-2031 (manufactured by JASCO Corporation) Reference material: TSKgel standard polystyrene (manufactured by Tosoh Corporation)
  • the (PPG-12/SMDI) copolymer (A) used in the present invention may be a commercially available product or may be produced by a known production method.
  • (PPG-12/SMDI) Copolymer (A) can be produced by, for example, reacting PPG-12 and SMDI until there are no reactive isocyanate groups, or reacting PPG-12 and SMDI to produce urethane.
  • An example is a method in which a prepolymer is produced and then reacted with a chain extender.
  • the type of chain extender is not particularly limited, but for example, one or more types selected from the group consisting of water, ethylenediamine, and propylene diamine can be used.
  • the amount of the urethane prepolymer produced by reacting PPG-12 and SMDI with the chain extender is not particularly limited, but the amount of the resulting (PPG-12/SMDI) copolymer (A)
  • the number of moles of the chain extender relative to the number of moles of isocyanate groups remaining in the urethane prepolymer (the number of moles of isocyanate groups of SMDI used minus the number of moles of hydroxyl groups of PPG-12) It is preferable that the number is 1.0 times or more (that is, the number of moles of the chain extender is greater than or equal to the number of moles of the isocyanate group remaining in the urethane prepolymer).
  • the molecular weight of the resulting (PPG-12/SMDI) copolymer (A) can be easily adjusted to a desired range by extending the molecular chain of the urethane prepolymer using a chain extender.
  • a chain extender since water can be used as a solvent or dispersion medium for the obtained (PPG-12/SMDI) copolymer (A), various concentrations can be obtained by adjusting the amount of water blended.
  • An aqueous solution or dispersion of (PPG-12/SMDI) copolymer (A) can be obtained.
  • the method for producing a urethane prepolymer by reacting PPG-12 and SMDI is not particularly limited, and can be produced by a known method, but for example, by reacting PPG-12 and SMDI, Depending on the situation, a prepolymer mixing method can be used in which the prepolymer is added and dispersed in a solvent containing an emulsifier.
  • a prepolymer mixing method can be used in which the prepolymer is added and dispersed in a solvent containing an emulsifier.
  • the emulsifier for example, known anionic surfactants, nonionic surfactants, cationic surfactants, and mixtures of these surfactants can be used.
  • the solvent for example, ethanol, propanol, butanol, hexane, toluene, ethyl acetate, butyl acetate, water, etc. can be used.
  • the ratio of PPG-12 and SMDI used in the production of the (PPG-12/SMDI) copolymer (A) is not particularly limited, but from the viewpoint of the various properties of the resulting (PPG-12/SMDI) copolymer (A), PPG -12 and SMDI are preferably used in a molar ratio of 1:0.05 to 1:5, more preferably 1:0.1 to 1:1, and 1:0.2 to 1. It is even more preferable to use the molar ratio of :0.5.
  • the viewpoint of particularly significantly thickening the oil component is due to the synergistic thickening effect of the (PPG-12/SMDI) copolymer (A), silica particles (B), and polyglycerin fatty acid ester (C).
  • the molar ratio of PPG-12 and SMDI in a raw material consisting of PPG-12 and SMDI is 1:0.2 to 1:0.5. It is particularly preferable to use a method in which these are reacted until there are no reactive isocyanate groups.
  • Each reaction in the method for producing the (PPG-12/SMDI) copolymer (A) is not particularly limited as long as the conditions are such that each raw material can react. Furthermore, the entire amount of each raw material may be added at once and reacted, or may be added in several portions and reacted. Specifically, for example, the raw materials for each component are added to the reaction system at once or in several batches and heated at a temperature of 30 to 160°C, preferably 40 to 160°C, under increased pressure, reduced pressure, or normal pressure. Examples include a method of mixing in an environment and maintaining the mixture for 30 minutes to 10 hours until the reaction is completed.
  • 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, and boron fluoride; water.
  • Organometallic compounds such as tetraisopropyl titanate, dibutyltin dichloride, dibutyltin oxide, dibutyltin bis(2-ethylhexylthioglycolate); Sodium acetate, potassium acetate, sodium propionate, potassium propionate, sodium octylate, octyl Examples include soaps such as potassium acid, sodium laurate, and potassium laurate.
  • the blending amount of these catalysts is not particularly limited, but is 0.01 to 1% by mass based on the total mass of each raw material.
  • the (PPG-12/SMDI) copolymer described above as the (PPG-12/SMDI) copolymer (A)
  • a synergistic effect with the silica particles (B) and the polyglycerol fatty acid ester (C) is achieved.
  • the thickening effect can significantly thicken oil components, making it suitable for use in products containing oil components such as paints, adhesives, fuels, lubricants, foods, and cosmetics. Each product can be provided with a different viscosity.
  • the silica particles (B) used in the present invention are not particularly limited as long as they are silica particles commonly used in the fields of paints, adhesives, fuels, lubricants, foods, cosmetics, etc., and include silica anhydride, silicon dioxide, etc.
  • Various types of silica particles can be used, including:
  • the shape and form of the silica particles used in the present invention are not particularly limited, and examples thereof include spherical silica particles, plate-shaped silica particles, porous silica particles, amorphous silica particles, atomized silica particles, amorphous silica particles, and crystalline silica particles.
  • Silica particles, colloidal silica, silica gel, silica airgel, silica sol, etc. can be used.
  • the particle size of the silica particles (B) used in the present invention is not particularly limited and can be adjusted as appropriate depending on the purpose.
  • the average particle size may be 1 nm to 100 ⁇ m.
  • the average particle diameter of the silica particles is preferably 1 nm to 1 ⁇ m, more preferably 1 nm to 500 nm.
  • the thickness is preferably 1 nm to 100 nm, even more preferably.
  • the average particle diameter of silica particles is measured by a dynamic light scattering method in accordance with JIS Z 8828 (2019).
  • the silica particles (B) used in the present invention may be hydrophilic silica particles or hydrophobic silica particles, but from the viewpoint of the effect of thickening the oil component of the present invention, hydrophobic silica particles Silica particles are preferred.
  • hydrophobic silica particles for example, hydrophobic silica particles obtained by hydrophobizing the surface of silica particles can be used, and as the hydrophobizing method, for example, alkoxysilanes, silazane, siloxanes, etc. , halogenated silanes, saturated fatty acids, amino acids, esters, waxes, etc. can be used.
  • hydrophobized silica particles subjected to dimethylsilylation treatment with alkoxysilanes or halogenated silanes are preferable.
  • silica particles may be produced by a known method, or commercially available products may be used.
  • Commercially available silica particles that can be used in the present invention include, for example, the AEROSIL (registered trademark) series manufactured by EVONIK, the Efficium (registered trademark) series, the Tixosil (registered trademark) series, and Zeosil (registered trademark) manufactured by SOLVEY. series, QSG series manufactured by Shin-Etsu Silicone Co., Ltd., Seahoster (registered trademark) series manufactured by Nippon Shokubai Co., Ltd., etc. can be used.
  • the synergistic thickening effect with the (PPG-12/SMDI) copolymer (A) and the polyglycerin fatty acid ester (C) improves the oil content.
  • Products that can significantly thicken ingredients and have a viscosity suitable for use in products containing oil components, such as paints, adhesives, fuels, lubricants, foods, and cosmetics. can be provided.
  • the polyglycerin fatty acid ester (C) used in the present invention is a monoester or diester of polyglycerin having a polymerization degree of 2 to 20 and a fatty acid having 8 to 20 carbon atoms.
  • fatty acids having 8 to 20 carbon atoms include saturated straight chain fatty acids having 8 to 20 carbon atoms, saturated branched fatty acids having 8 to 20 carbon atoms, and saturated branched fatty acids having 8 to 20 carbon atoms. Examples include certain unsaturated straight chain fatty acids, unsaturated branched fatty acids having 8 to 20 carbon atoms, etc.
  • fatty acids having 8 to 18 carbon atoms are preferred; More preferred are certain saturated straight chain fatty acids, saturated branched fatty acids having 8 to 18 carbon atoms, or unsaturated straight chain fatty acids having 8 to 18 carbon atoms.
  • the degree of polymerization of glycerin in polyglycerin is a value calculated based on the hydroxyl value (mgKOH/g) of polyglycerin based on the description in "Polyglycerin Ester" (edited by Sakamoto Pharmaceutical Co., Ltd., published in 1994). It is.
  • polyglycerin fatty acid esters examples include polyglyceryl-2 caprylate, polyglyceryl-4 caprylate, polyglyceryl-5 caprylate, polyglyceryl-6 caprylate, polyglyceryl-8 caprylate, polyglyceryl-10 caprylate, and lauric acid.
  • polyglycerol fatty acid ester (C) is preferred from the viewpoint of significantly thickening the oil component through a synergistic thickening effect with the (PPG-12/SMDI) copolymer (A) and silica particles (B).
  • the HLB of the polyglycerin fatty acid ester (C) used in the present invention is not particularly limited, the synergistic thickening effect with the (PPG-12/SMDI) copolymer (A) and silica particles (B) can significantly reduce the oil component.
  • the HLB of the polyglycerin fatty acid ester (C) is preferably 6.0 to 20.0, more preferably 7.0 to 19.0, and more preferably 9.5 to 18. It is even more preferably 0, and particularly preferably 10.0 to 17.5.
  • the HLB of the polyglycerol fatty acid ester (C) is the value determined by the Griffin method (Yoshida, Shindo, Ogaki, Yamanaka co-eds., "New Edition Surfactant Handbook", Kogaku Tosho Co., Ltd., 1996). p.234).
  • the polyglycerol fatty acid ester described above as the polyglycerol fatty acid ester (C)
  • a synergistic thickening effect with the (PPG-12/SMDI) copolymer (A) and the silica particles (B) is achieved.
  • oil components such as paints, adhesives, fuels, lubricants, foods, cosmetics, etc.
  • the oil component (D) used in the present invention is one or more oil components selected from ester oil, hydrocarbon oil, and silicone oil.
  • ester oils that can be used in the present invention include isopropyl myristate, cetyl octoate, isononyl isononanoate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, and decyl oleate.
  • hexyldecyl dimethyloctoate cetyl lactate, myristyl lactate, lanolin acetate, isocetyl stearate, isocetyl isostearate, cholesteryl 12-hydroxystearate, glyceryl di-2-ethylhexanoate, dipentaerythritol fatty acid ester, glyceryl monoisostearate , neopentyl glycol dicaprate, diisostearyl malate, glyceryl di-2-heptylundecanoate, trimethylolpropane tri-2-ethylhexanoate, trimethylolpropane triisostearate, pentaerythritol tetra-2-ethylhexanoate, Glyceryl tri-2-ethylhexanoate, glyceryl trioctanoate, glyceryl triisopalmitate, trimethyl
  • the viscosity of the ester oil at 25° C. is preferably 1 to 20,000 mPa ⁇ s, more preferably 3 to 10,000 mPa ⁇ s, and even more preferably 5 to 8,000 mPa ⁇ s.
  • the viscosity at 25°C is measured in accordance with JIS K 7117.
  • hydrocarbon oil examples include liquid paraffin, ozokerite, squalane, pristane, paraffin, isododecane, ceresin, squalene, petrolatum, microcrystalline wax, etc., and one or more of these can be used.
  • the viscosity of the hydrocarbon oil at 25° C. is preferably 1 to 200 mPa ⁇ s, more preferably 5 to 100 mPa ⁇ s, and even more preferably 10 to 50 mPa ⁇ s.
  • Silicone oils that can be used in the present invention include, for example, linear polysiloxanes (e.g., dimethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane, etc.); cyclic polysiloxanes (e.g., octamethylcyclotetrasiloxane, decamethylpolysiloxane, etc.); cyclopentasiloxane, dodecamethylcyclohexasiloxane, etc.), silicone resins forming three-dimensional network structures, silicone rubber, various modified polysiloxanes (amino-modified polysiloxane, polyether-modified polysiloxane, alkyl-modified polysiloxane, fluorine-modified polysiloxane) polysiloxane, etc.), and one or more of these can be used.
  • the viscosity of the silicone oil at 25° C. is preferably
  • the oil component (D) used in the present invention may be only one selected from ester oil, hydrocarbon oil, and silicone oil, or may be a mixture of two or more. From the viewpoint of the effect of thickening the oil component of the present invention, it is preferable that ester oil is included as the oil component (D).
  • the oil component (D) consists of an ester oil, a mixture containing an ester oil and a hydrocarbon oil, a mixture containing an ester oil and a hydrocarbon oil, a mixture containing an ester oil and a silicone oil, or a mixture containing an ester oil and a silicone oil. Alternatively, it may be a mixture containing an ester oil, a hydrocarbon oil, and a silicone oil, or a mixture containing an ester oil, a hydrocarbon oil, and a silicone oil.
  • the amount of the (PPG-12/SMDI) copolymer (A) to be mixed into the oil component (D) is not particularly limited, but it thickens the oil component (D) more significantly. From this point of view, it is preferable that the mass of the (PPG-12/SMDI) copolymer (A) mixed with the oil component (D) is 0.1 to 25 parts by mass based on 100 parts by mass of the oil component (D). , more preferably 0.2 to 20 parts by weight, even more preferably 0.3 to 15 parts by weight, particularly preferably 0.5 to 10 parts by weight.
  • the amount of silica particles (B) to be mixed into the oil component (D) is not particularly limited, but from the viewpoint of thickening the oil component more significantly, the amount of silica particles (B) mixed into the oil component (D) is
  • the mass of the silica particles (B) to be mixed in is preferably 0.1 to 25 parts by mass, more preferably 0.2 to 20 parts by mass, per 100 parts by mass of the oil component (D). It is even more preferably from 0.3 to 15 parts by weight, and particularly preferably from 0.5 to 10 parts by weight.
  • the amount of polyglycerin fatty acid ester (C) to be mixed into the oil component (D) is not particularly limited, but from the viewpoint of thickening the oil component more significantly,
  • the mass of the polyglycerin fatty acid ester (C) mixed in D) is preferably 1 to 100 parts by mass, more preferably 2 to 80 parts by mass, and more preferably 5 to 60 parts by mass, based on 100 parts by mass of the oil component. It is even more preferably 10 to 50 parts by weight, particularly preferably 10 to 50 parts by weight.
  • the oil component is based on the total amount of (PPG-12/SMDI) copolymer (A), silica particles (B), polyglycerin fatty acid ester (C) and oil component (D) to be mixed.
  • the amount of (D) is not particularly limited, but from the viewpoint of thickening the oil component more significantly, the amount of (PPG-12/SMDI) copolymer (A) to be mixed, silica particles (B), polyglycerin fatty acid ester (C ) and the oil component (D), preferably from 5 to 99% by mass, more preferably from 10 to 99% by mass, and even more preferably from 20 to 98% by mass.
  • the ratio of the amounts of the (PPG-12/SMDI) copolymer (A) and silica particles (B) to be mixed into the oil component is not particularly limited, but it is possible to increase the viscosity of the oil component more significantly.
  • the ratio of the (PPG-12/SMDI) copolymer (A) and silica particles (B) to be mixed in the oil component (D) should be 1:0.005 to 1:200 in terms of mass ratio. is preferable, 1:0.05 to 1:20 is more preferable, 1:0.1 to 1:10 is even more preferable, and 1:0.2 to 1:5 is particularly preferable. preferable.
  • the ratio of the amounts of the (PPG-12/SMDI) copolymer (A) and polyglycerin fatty acid ester (C) to be mixed into the oil component (D) is not particularly limited, but is more pronounced. From the viewpoint of thickening the oil component, the ratio of the (PPG-12/SMDI) copolymer (A) and polyglycerin fatty acid ester (C) to be mixed into the oil component (D) is 1:0.05 by mass. The ratio is preferably 1:500 to 1:500, more preferably 1:0.5 to 1:100, even more preferably 1:2 to 1:50, and 1:5 to 1:20. It is particularly preferable.
  • the ratio of the amounts of silica particles (B) and polyglycerin fatty acid ester (C) to be mixed into the oil component (D) is not particularly limited, but it thickens the oil component more significantly. From the viewpoint of The ratio is more preferably 1 to 1:100, even more preferably 1:2 to 1:50, and particularly preferably 1:3 to 1:20.
  • the amount of polyglycerol fatty acid ester (C) is determined based on the total amount of (PPG-12/SMDI) copolymer (A) and silica particles (B) mixed into oil component (D).
  • the ratio is not particularly limited, from the viewpoint of thickening the oil component more significantly, the total amount of the (PPG-12/SMDI) copolymer (A) and silica particles (B) to be mixed into the oil component (D) and the poly
  • the ratio to the amount of glycerin fatty acid ester (C) is preferably 1:0.4 to 1:100 in mass ratio, more preferably 1:0.8 to 1:50, and 1:1.
  • the ratio is even more preferably 1:30 to 1:30, and particularly preferably 1:2 to 1:15.
  • the ratio is not particularly limited, from the viewpoint of thickening the oil component more significantly, the total amount of the (PPG-12/SMDI) copolymer (A) and polyglycerin fatty acid ester (C) to be mixed into the oil component (D).
  • the ratio of the amount of silica particles (B) to the amount of silica particles (B) is preferably 1:0.005 to 1:15, more preferably 1:0.01 to 1:5, and 1:0 by mass. The ratio is even more preferably from .02 to 1:1, and particularly preferably from 1:0.04 to 1:0.5.
  • the ratio is not particularly limited, from the viewpoint of thickening the oil component more significantly, the total amount of silica particles (B) and polyglycerin fatty acid ester (C) to be mixed into the oil component and the (PPG-12/SMDI) copolymer
  • the ratio to the amount of (A) is preferably 1:0.005 to 1:15, more preferably 1:0.01 to 1:5, and 1:0.02 to 1:15 by mass.
  • the ratio is even more preferably 1:1, and particularly preferably 1:0.04 to 1:0.5.
  • the method for thickening oil components of the present invention it is possible to significantly thicken one or more oil components selected from ester oils, hydrocarbon oils, and silicone oils.
  • this method is used for paints, cleaning agents, adhesives, cosmetics, pharmaceuticals, agricultural chemicals, inks, dyes, etc.
  • the viscosity can be easily adjusted to suit each product.
  • it is preferable to prepare a cosmetic composition using the method of thickening an oil component of the present invention since the cosmetic composition can easily have a viscosity suitable for use.
  • the thickener composition of the present invention is a monoester of silica particles (B), polyglycerin having a polymerization degree of glycerin of 2 to 20, and fatty acid having 8 to 20 carbon atoms, or (PPG-12/SMDI) copolymer for mixing with polyglycerin fatty acid ester (C), which is a diester, into one or more oil components (D) selected from ester oil, hydrocarbon oil, and silicone oil.
  • the concentration of the (PPG-12/SMDI) copolymer (A) in the thickener composition containing the (PPG-12/SMDI) copolymer (A) is not particularly limited, but from the viewpoint of thickening the oil component more significantly,
  • the content is preferably 10 to 100% by mass, more preferably 50 to 100% by mass, based on the total amount of the thickener composition.
  • the thickener composition may also contain components commonly included in thickener compositions, such as emulsifiers, chain extenders, solvents, etc. that can be used when reacting PPG-12 and SMDI. Alternatively, it may contain a catalyst or the like.
  • the silica particles (B) and the polyglycerol fatty acid ester (C) are mixed into one or more oil components selected from ester oil, hydrocarbon oil, and silicone oil. By doing so, the viscosity of the oil component (D) can be significantly increased.
  • the oil component-containing composition of the present invention is an oil component-containing composition obtained using the above-described method of thickening an oil component, and specifically includes (PPG-12/SMDI) copolymer (A), The silica particles (B) and the polyglycerin fatty acid ester (C), which is a monoester or diester of polyglycerin having a polymerization degree of 2 to 20 and a fatty acid having 8 to 20 carbon atoms, are added to an ester oil.
  • PPG-12/SMDI copolymer
  • the silica particles (B) and the polyglycerin fatty acid ester (C), which is a monoester or diester of polyglycerin having a polymerization degree of 2 to 20 and a fatty acid having 8 to 20 carbon atoms, are added to an ester oil.
  • an oil component-containing composition obtained by thickening an oil component by mixing it with one or more oil components (D) selected from hydrocarbon oils and silicone oils, (PPG-12/SMDI ) Contains at least a copolymer (A), a silica particle (B), a polyglycerin fatty acid ester (C), and an oil component (D).
  • Oil component-containing composition comprises a (PPG-12/SMDI) copolymer (A), silica particles (B), polyglycerin whose polymerization degree is 2 to 20, and carbon atoms.
  • a polyglycerin fatty acid ester (C) that is a monoester or diester with a fatty acid having a number of 8 to 20, and one or more oil components (D) selected from ester oils, hydrocarbon oils, and silicone oils. ,including.
  • the oil component-containing composition of the present invention is suitably used as a cosmetic composition.
  • Contents and content ratios of (PPG-12/SMDI) copolymer (A), silica particles (B), polyglycerin fatty acid ester (C), and oil component (D) in the cosmetic composition of the present invention can be the content and content ratio of each component used in the oil component thickening method described above.
  • the content of the (PPG-12/SMDI) copolymer (A) in the cosmetic composition of the present invention is not particularly limited, and can be adjusted depending on the purpose, but it is 0.00% based on the total amount of the cosmetic composition. It is preferably from 0.01 to 20% by weight, more preferably from 0.1 to 15% by weight, and even more preferably from 0.2 to 10% by weight.
  • the content of silica particles (B) in the cosmetic composition of the present invention is not particularly limited and can be adjusted depending on the purpose, but it is 0.01 to 20% by mass based on the total amount of the cosmetic composition. It is preferably from 0.1 to 15% by weight, even more preferably from 0.2 to 10% by weight.
  • the content of polyglycerol fatty acid ester (C) in the cosmetic composition of the present invention is not particularly limited and can be adjusted depending on the purpose, but it is 0.1 to 50% by mass based on the total amount of the cosmetic composition. %, more preferably 1.0 to 40% by weight, even more preferably 2.0 to 30% by weight.
  • the content of the oil component (D) in the cosmetic composition of the present invention is not particularly limited and can be adjusted depending on the purpose, but it should be 1 to 90% by mass based on the total amount of the cosmetic composition. It is preferably 2 to 90% by mass, more preferably 3 to 80% by mass.
  • the specific type of cosmetics of the cosmetic composition of the present invention is not particularly limited, and includes toiletry products such as shampoos and conditioners, such as lotions, lotions, milky lotions, creams, facial cleansing foams, and cleansing products. Milk, cleansing lotion, hair tonic, hair liquid, setting lotion, hair bleach, color rinse, permanent wave liquid, lipstick, face pack, foundation, cologne, shampoo, conditioner, treatment, sunscreen, deodorant, perfume, cleansing oil, and cosmetic oil etc.
  • toiletry products such as shampoos and conditioners, such as lotions, lotions, milky lotions, creams, facial cleansing foams, and cleansing products.
  • the cosmetic composition of the present invention can be prepared by mixing a (PPG-12/SMDI) copolymer (A), silica particles (B), and a polyglycerin fatty acid ester (C) into an oil component (D), or After mixing, various properties (solubility, dispersibility, stability, usability, applicability, permeability, moisture retention, safety, design, optical properties) are determined depending on the purpose during storage, during use, and after use.
  • the cosmetic composition may also be obtained by further mixing other additives commonly used in cosmetic compositions in order to enhance or improve the cosmetic composition, fragrance, whitening properties, etc.). Alternatively, the cosmetic composition may be obtained using an oil component mixed with other additives.
  • additives include, for example, wax, powder components (excluding silica particles (B)), higher fatty acids, anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants (polyglycerin fatty acids (excluding ester (C)), humectants, water-soluble polymers, chelating agents, lower alcohols, polyhydric alcohols, sugars, amino acids and their derivatives, organic amines, pH adjusters, vitamins, antioxidants, and other ingredients can be added. One or more of these components may be optionally blended.
  • wax examples include beeswax, candelilla wax, cotton wax, carnauba wax, bayberry wax, privet wax, spermaceti wax, montan wax, bran wax, lanolin, kapok wax, acetic acid lanolin, liquid lanolin, sugarcane wax, lanolin fatty acid isopropyl, reduced lanolin, jojoba wax, and hard wax.
  • examples include lanolin, shellac wax, POE lanolin alcohol ether, POE lanolin alcohol acetate, POE cholesterol ether, lanolin fatty acid polyethylene glycol, and POE hydrogenated lanolin alcohol ether.
  • powder components include inorganic powders (such as talc, kaolin, mica, sericite, muscovite, phlogopite, synthetic mica, rhodochite, biotite, permiculite, magnesium carbonate, calcium carbonate, and silicic acid).
  • inorganic powders such as talc, kaolin, mica, sericite, muscovite, phlogopite, synthetic mica, rhodochite, biotite, permiculite, magnesium carbonate, calcium carbonate, and silicic acid.
  • organic powders e.g. polyamide resin powder (nylon powder), polyethylene powder, polymethyl methacrylate powder, polystyrene powder, styrene and acrylic Acid copolymer resin powder, benzoguanamine resin powder, polytetrafluoroethylene powder, cellulose powder, etc.
  • Inorganic white pigments e.g., titanium dioxide, zinc oxide, etc.
  • Inorganic red pigments e.g., iron oxide (red iron oxide)
  • iron titanate e.
  • Inorganic brown pigments e.g., ⁇ -iron oxide, etc.
  • Inorganic yellow pigments e.g., yellow iron oxide, ocher, etc.
  • Inorganic black pigments e.g., black iron oxide, lower oxidation titanium, etc.
  • inorganic purple pigments e.g., manganese violet, cobalt violet, etc.
  • inorganic green pigments e.g., inorganic green pigment
  • Metal powder pigments e.g. aluminum powder, copper powder etc.
  • organic pigments such as zirconium, barium or aluminum lake (e.g. Red No. 201, Red No. 202, Red No. 204, Red No. 205, Red No. 220, Red No. 226, Red No. 228, Red No. 405, Orange 203); organic pigments such as Orange No. 204, Yellow No. 205, Yellow No. 401, and Blue No. 404, Red No. 3, Red No. 104, Red No. 106, Red No. 227, Red No.
  • Metal powder pigments e.g. aluminum powder, copper powder
  • organic pigments such as zirconium, barium or aluminum lake (e.g. Red No. 201, Red No. 202, Red No. 204, Red No. 205, Red No.
  • Red No. 401 Red No. 505.
  • Orange No. 205 Yellow No. 4, Yellow No. 5, Yellow No. 202, Yellow No. 203, Green No. 3, Blue No. 1, etc.
  • natural pigments for example, chlorophyll, ⁇ -carotene, etc.
  • higher fatty acids examples include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, undecylenic acid, tall oil fatty acid, isostearic acid, linoleic acid, linoleic acid, eicosapentaenoic acid (EPA), and docosahexaenoic acid. (DHA) and the like.
  • higher alcohols examples include straight chain alcohols (for example, lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, cetostearyl alcohol, etc.); branched chain alcohols (for example, 2-decyltetradecinol, lanolin alcohol, cholesterol, phytosterol, hexyldodecanol, isostearyl alcohol, octyldodecanol, etc.).
  • straight chain alcohols for example, lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, cetostearyl alcohol, etc.
  • branched chain alcohols for example, 2-decyltetradecinol, lanolin alcohol, cholesterol, phytosterol, hexyldodecanol, isostearyl alcohol, octyldodecanol, etc.
  • anionic surfactants include fatty acid soaps (e.g., sodium laurate, sodium palmitate, etc.); higher alkyl sulfate salts (e.g., sodium lauryl sulfate, potassium lauryl sulfate, etc.); alkyl ether sulfate salts (e.g., POE-triethanolamine lauryl sulfate, POE-sodium lauryl sulfate, etc.); N-acyl sarcosinate (e.g. sodium lauroyl sarcosine, etc.); Higher fatty acid amide sulfonates (e.g.
  • N-acylglutamates e.g. monosodium N-lauroylglutamate, disodium N-stearoylglutamate, N-myristoyl-L-glutamic acid); monosodium, etc.
  • sulfated oil e.g., funnel oil, etc.
  • POE-alkyl ether carboxylic acid POE-alkyl allyl ether carboxylate; ⁇ -olefin sulfonate; higher fatty acid ester sulfonate; secondary alcohol sulfuric acid Examples include ester salts; higher fatty acid alkylolamide sulfate ester salts; sodium lauroyl monoethanolamide succinate; N-palmitoylaspartic acid ditriethanolamine; sodium caseinate and the like.
  • cationic surfactants include alkyltrimethylammonium salts (e.g., stearyltrimethylammonium chloride, lauryltrimethylammonium chloride, etc.); alkylpyridinium salts (e.g., cetylpyridinium chloride, etc.); dialkyldimethylammonium salts (distearyldimethylammonium chloride, etc.); etc.); Alkyl quaternary ammonium salt; Alkyldimethylbenzylammonium salt; Alkylisoquinolinium salt; Dialkylmorpholinium salt; POE-alkylamine; Alkylamine salt; Amyl alcohol fatty acid derivative; Benzalkonium chloride; Benzethonium chloride, etc. can be mentioned.
  • alkyltrimethylammonium salts e.g., stearyltrimethylammonium chloride, lauryltrimethylammonium chloride, etc.
  • alkylpyridinium salts
  • amphoteric surfactants examples include imidazoline-based amphoteric surfactants (for example, 2-undecyl-N,N,N-(hydroxyethylcarboxymethyl)-2-imidazoline sodium, 2-cocoyl-2-imidazolinium hydroxide), side-1-carboxyethyloxy disodium salt, etc.); betaine surfactants (for example, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine (sodium cocoamphoacetate), lauryldimethylaminoacetic acid betaine, Alkylbetaine, amidobetaine, sulfobetaine, etc.).
  • imidazoline-based amphoteric surfactants for example, 2-undecyl-N,N,N-(hydroxyethylcarboxymethyl)-2-imidazoline sodium, 2-cocoyl-2-imidazolinium hydroxide), side-1-carboxyethyloxy diso
  • nonionic surfactants include sorbitan fatty acid esters (e.g., sorbitan monooleate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquioleate, sorbitan trioleate).
  • sorbitan fatty acid esters e.g., sorbitan monooleate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquioleate, sorbitan trioleate.
  • sorbitan fatty acid esters e.g., sorbitan monooleate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquioleate, sorbitan trioleate.
  • ate digly
  • POE-sorbit beeswax, etc. alkanolamides (e.g. coconut oil fatty acid diethanolamide, (lauric acid monoethanolamide, fatty acid isopropanolamide, etc.); POE-propylene glycol fatty acid ester; POE-alkylamine; POE-fatty acid amide; sucrose fatty acid ester; alkyl ethoxydimethylamine oxide; trioleyl phosphoric acid.
  • alkanolamides e.g. coconut oil fatty acid diethanolamide, (lauric acid monoethanolamide, fatty acid isopropanolamide, etc.
  • POE-propylene glycol fatty acid ester POE-alkylamine
  • POE-fatty acid amide sucrose fatty acid ester
  • alkyl ethoxydimethylamine oxide trioleyl phosphoric acid.
  • moisturizing agents examples include polyethylene glycol, xylitol, sorbitol, maltitol, chondroitin sulfate, hyaluronic acid, mucoitin sulfate, caronic acid, atelocollagen, cholesteryl-12-hydroxystearate, sodium lactate, bile salts, dl-pyrrolidone carvone.
  • moisturizing agents include polyethylene glycol, xylitol, sorbitol, maltitol, chondroitin sulfate, hyaluronic acid, mucoitin sulfate, caronic acid, atelocollagen, cholesteryl-12-hydroxystearate, sodium lactate, bile salts, dl-pyrrolidone carvone.
  • Examples include acid salts, short-chain soluble collagen, diglycerin (EO) PO adducts, Izayoi rosea extract, Yarrow extract, Melilot extract
  • natural water-soluble polymers include plant-based polymers (e.g., gum arabic, gum tragacanth, galactan, guar gum, carob gum, gum karaya, carrageenan, pectin, agar, quince seed (quince), algae colloid (cassou extract), starch). (rice, corn, potato, wheat), glycyrrhizic acid); Microbial polymers (e.g., xanthan gum, dextran, succinoglucan, bull run, gellan gum, etc.); Animal-based polymers (e.g., collagen, casein, albumin, gelatin, etc.) ) etc.
  • plant-based polymers e.g., gum arabic, gum tragacanth, galactan, guar gum, carob gum, gum karaya, carrageenan, pectin, agar, quince seed (quince), algae colloid (cassou extract), starch).
  • Microbial polymers e.g.,
  • water-soluble polymers examples include starch-based polymers (e.g., carboxymethyl starch, methylhydroxypropyl starch, etc.); cellulose-based polymers (methyl cellulose, ethyl cellulose, methyl hydroxypropyl cellulose, hydroxyethyl cellulose, sodium cellulose sulfate, hydroxypropyl Cellulose, carboxymethylcellulose, sodium carboxymethylcellulose, crystalline cellulose, cellulose powder, etc.); Alginic acid polymers (e.g. sodium alginate, alginate propylene glycol ester, etc.); Vinyl polymers (e.g.
  • polyvinyl alcohol polyvinyl methyl ether, polyvinyl pyrrolidone) , carboxyvinyl polymer, etc.
  • polyoxyethylene polymers e.g., polyoxyethylene polyoxypropylene copolymers such as polyethylene glycol 20,000, polyethylene glycol 40,000, polyethylene glycol 60,000, etc.
  • acrylic polymers Molecules eg, sodium polyacrylate, polyethyl acrylate, polyacrylamide, etc.
  • polyethyleneimine cationic polymers, and the like.
  • Examples of the chelating agent include 1-hydroxyethane-1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid tetrasodium salt, edetate disodium, edetate trisodium, edetate tetrasodium, polyphosphoric acid.
  • Examples include sodium acid, sodium metaphosphate, phosphoric acid, ascorbic acid, succinic acid, edetate, and the like.
  • lower alcohols examples include ethanol, propanol, isopropanol, isobutyl alcohol, and t-butyl alcohol.
  • polyhydric alcohols examples include dihydric alcohols (for example, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2-pentanediol, 1,5-pentanediol, 2,4-pentanediol, etc.); trihydric alcohols (for example, glycerin, trimethylolpropane, etc.) ); Tetrahydric alcohols (e.g., pentaerythritol such as 1,2,5,6-hexanetetraol, etc.); Pentahydric alcohols (e.g., xylitol, etc.); Hexahydric alcohols (e.g., sorbitol, mannitol, etc.); Polyhydric alcohols Alcohol polymers
  • diethylene glycol triethylene glycol, dipropylene glycol, polypropylene glycol, tetraethylene glycol, diglycerin, polyethylene glycol, triglycerin, tetraglycerin, polyglycerin, etc.); (alkyl glyceryl ethers (e.g.
  • propyl glyceryl ether , butyl glyceryl ether, pentyl glyceryl ether, hexyl glyceryl ether, cyclohexyl glyceryl ether, heptyl glyceryl ether, octyl glyceryl ether, ethylhexyl glyceryl ether, nonyl glyceryl ether, decyl glyceryl ether, hexadecyl glyceryl ether, oleyl glyceryl ether, octadecyl glyceryl ether, isostearyl glyceryl ether, etc.); alcohol alkyl ethers (e.g., ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, ethylene glycol monohex
  • monosaccharides include tricarbons (e.g., D-glycerylaldehyde, dihydroxyacetone, etc.); tetracarbons (e.g., D-erythrose, D-erythrulose, D-threose, erythritol, etc.); pentose (e.g., , L-arabinose, D-xylose, L-lyxose, D-arabinose, D-ribose, D-ribulose, D-xylulose, L-xylulose, etc.); hexoses (e.g., D-glucose, D-talose, D - Bucicose, D-galactose, D-fructose, L-galactose, L-mannose, D-tagatose, etc.); Seven carbon sugars (e.g., aldoheptose, heprose, etc.); Octos
  • oligosaccharides include sucrose, umbelliferose, lactose, planteose, isoliqunose, ⁇ , ⁇ -trehalose, raffinose, lichnose, umbilicin, stachyose, verbascose, and the like.
  • polysaccharides include cellulose, quince seed, chondroitin sulfate, starch, galactan, dermatan sulfate, glycogen, gum arabic, heparan sulfate, hyaluronic acid, gum tragacanth, keratan sulfate, chondroitin, xanthan gum, mucoitin sulfate, guar gum, dextran, and keratosulfate. , locust Bingham, succinoglucan, caronic acid, and the like.
  • amino acids examples include neutral amino acids (eg, threonine, cysteine, etc.); basic amino acids (eg, hydroxylysine, etc.).
  • amino acid derivatives include sodium acylsarcosine (sodium lauroylsarcosine), acylglutamate, sodium acyl ⁇ -alanine, glutathione, and pyrrolidone carboxylic acid.
  • organic amines examples include monoethanolamine, diethanolamine, triethanolamine, morpholine, triisopropanolamine, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-methyl-1-propanol, etc. can be mentioned.
  • pH adjuster examples include lactic acid-sodium lactate, succinic acid-sodium succinate, citric acid-sodium citrate, and sodium hydrogen carbonate.
  • the pH of the cosmetic composition of the present invention may be adjusted as appropriate depending on the intended use, but from the viewpoint of applicability to the skin, it is preferably 2.0 to 12.0.
  • vitamins examples include vitamins A, B1, B2, B6, C, E and their derivatives, pantothenic acid and its derivatives, biotin, and the like.
  • antioxidant examples include tocopherols, dibutylhydroxytoluene, butylhydroxyanisole, gallic acid esters, and the like.
  • ingredients that can be blended include, for example, anti-inflammatory agents (e.g., glycyrrhizic acid derivatives, glycyrrhetinic acid derivatives, salicylic acid derivatives, hinokitiol, zinc oxide, allantoin, etc.); skin whitening agents (e.g., saxifrage extract, arbutin, etc.); various extracts.
  • anti-inflammatory agents e.g., glycyrrhizic acid derivatives, glycyrrhetinic acid derivatives, salicylic acid derivatives, hinokitiol, zinc oxide, allantoin, etc.
  • skin whitening agents e.g., saxifrage extract, arbutin, etc.
  • Things e.g., sagebrush, sage, loquat, carrot, aloe, mallow, iris, grape, sagebrush, loofah, lily, saffron, nematode, ginger, hypericum, hypericum, ononis, garlic, chili pepper) , Chimpi, Touki, seaweed, etc.
  • activators e.g., royal jelly, photosensors, cholesterol derivatives, etc.
  • blood circulation promoters e.g., benzyl nicotinic acid ester, ⁇ -butoxyethyl nicotinic acid ester, capsaicin, zingerone, cantharis tincture
  • ictamol tannic acid, ⁇ -borneol, tocopherol nicotinate, inositol hexanicotinate, cyclanderate, cinnarizine, tolazoline, acetylcholine, verapamil,
  • the viscosity of the cosmetic composition of the present invention is not particularly limited and can be adjusted depending on the specific type and purpose of the cosmetic composition.
  • the viscosity of the cosmetic composition at 25°C is preferably 100 to 100,000 mPa ⁇ s, more preferably 200 to 80,000 mPa ⁇ s, and preferably 300 to 50,000 mPa ⁇ s. Even more preferred.
  • the viscosity at 25°C is measured in accordance with JIS K 7117.
  • Example 1 to 7 [Examples 1 to 7 and Comparative Examples 1 to 10] As Examples 1 to 7, (PPG-12/SMDI) copolymer 1 (A), silica particles 1 (B), and polyglycerin fatty acid esters 1 to 7 (C) were mixed in the mass% shown in Table 1 below. Each was added to oil component 1 (D) and mixed by stirring using a disper at room temperature to prepare an oil component-containing composition.
  • PPG-12/SMDI silica particles 1
  • C polyglycerin fatty acid esters 1 to 7
  • Example 8 to 10 and Comparative Examples 11 to 13 As Examples 8 to 10, (PPG-12/SMDI) copolymer (A), silica particles (B), polyglycerin fatty acid ester, and 1 to 3 (C) were each added in the mass % shown in Table 3 below. In addition to the oil component (D), the mixture was mixed by stirring using a disper at room temperature to prepare an oil component-containing composition. In addition, as Comparative Examples 11 to 13, (PPG-12/SMDI) copolymer 1 (A), silica particles 1 (B), and polyglycerin fatty acid ester 8 (C') were mixed in the mass percentage shown in Table 3 below.
  • oil component (D) an oil component-containing composition was prepared in the same manner as in the example.
  • the viscosity of each oil component-containing composition was measured using a B-type viscometer according to JIS K 7117 at 25° C. and 5 rpm, and the results are shown in Table 3.
  • Examples 8 to 10 how many times the viscosity after each mixing increased compared to the viscosity of the oil component-containing composition when the polyglycerin fatty acid ester was not mixed (Comparative Example 12)? were each calculated as the thickening ratio. The calculation results are also shown in Table 3.
  • the (PPG-12/SMDI) copolymer (A), the silica particles (B), and the specific polyglycerol fatty acid ester (C) are combined. It has been shown that by mixing with oil component (D), the viscosity of oil component (D) can be significantly increased. On the other hand, when only (PPG-12/SMDI) copolymer (A) and silica particles (B), or only silica particles (B) and specific polyglycerin fatty acid ester (C) are mixed in the oil component, the present invention In all cases, the thickening effect of the oil component (D) was inferior to those in Examples.

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Abstract

The present invention relates to: a method for thickening an oily component, said method comprising mixing a (PPG-12/SMDI) copolymer (A), silica particles (B) and a polyglycerol fatty acid ester (C), which is a monoester or diester of a polyglycerol having a degree of glycerol polymerization of 2-20 with a fatty acid having 8-20 carbon atoms, with one or more oily components (D) selected from among an ester oil, a hydrocarbon oil and silicone oil; a composition containing an oily component obtained by using this method; and a thickener composition.

Description

油成分を増粘する方法及び油成分含有組成物Method for thickening oil component and oil component-containing composition
　本発明は、油成分を顕著に増粘する方法、及び該方法を用いて得られる油成分含有組成物に関する。 The present invention relates to a method for significantly thickening an oil component, and an oil component-containing composition obtained using the method.
　塗料、洗浄剤、接着剤、化粧品、医薬品、農薬、インク、染料等の製品は水性あるいは油性組成物の形態であり、使用に適する粘度又は流動性を有する組成物を得るために、様々な増粘剤又は粘度調整剤が使用されている。例えば、特許文献１には、水系用増粘剤に適したポリウレタンを容易に製造する方法が記載されている。また、特許文献２には、温度依存性が少なくどの条件下においても一定幅の粘度を保つ粘性調整剤として、特定のウレタン化合物より成る粘性調整剤が記載されている。また、特に油性組成物の粘度又は流動性を改質させるための増粘剤又は粘度調整剤の開発も盛んであり、例えば特許文献３には、油脂、鉱物油、合成油等のオイルを、ゲル状あるいは弾力感のあるゼリー状に増粘させることができるオイル用の増粘剤が記載されている。 Products such as paints, cleaning agents, adhesives, cosmetics, pharmaceuticals, pesticides, inks, dyes, etc. are in the form of water-based or oil-based compositions, and various additives are used to obtain compositions with suitable viscosity or fluidity for use. A viscosity agent or viscosity modifier is used. For example, Patent Document 1 describes a method for easily producing polyurethane suitable as a water-based thickener. Further, Patent Document 2 describes a viscosity modifier made of a specific urethane compound as a viscosity modifier that has little temperature dependence and maintains a constant viscosity under any conditions. In addition, the development of thickeners or viscosity modifiers for modifying the viscosity or fluidity of oil-based compositions is also active. Thickeners for oils that can be thickened to a gel-like or elastic jelly-like state are described.
　また、上述したようなウレタンポリマー型以外の各種増粘剤又は粘度調整剤も開発されており、例えば、特許文献４には、スメクタイト系粘土鉱物及び縮合リン酸塩とからなる水性塗料用粘度調整剤が、特許文献５には、シラン化された熱分解的に製造されたケイ酸からなる液体用増粘剤が記載されている。 In addition, various thickeners or viscosity modifiers other than the urethane polymer type mentioned above have been developed. For example, Patent Document 4 describes a viscosity modifier for water-based paints consisting of a smectite clay mineral and a condensed phosphate. Patent Document 5 describes a thickening agent for liquids consisting of silanized pyrogenically produced silicic acid.
　しかし、上述した従来の粘度調整剤はいずれも、各種組成物を使用に適する粘度又は流動性とするために必要な添加量が多くなり、その結果、べたつきが生じる等感触が損なわれるといった問題が生じていた。よって、製品の粘度調整が容易で、製品にべたつき等の使用感の悪化を生じさせずに粘度を十分に向上させることのできる材料が求められていた。 However, all of the above-mentioned conventional viscosity modifiers require a large amount to be added in order to give various compositions a suitable viscosity or fluidity for use, resulting in problems such as stickiness and poor feel. was occurring. Therefore, there has been a need for a material that can easily adjust the viscosity of a product and that can sufficiently improve the viscosity without causing stickiness or other deterioration in the usability of the product.
　このような課題に関し、出願人は、特定のウレタンポリマーと、シリカ粒子と、油成分とを含むことで、良好な感触及び増粘効果を製品に付与する油性組成物が得られることを見出していた（特許文献６）。しかし、市場においては、更に油成分の粘度を顕著に増粘する方法、及びそのような方法により使用に適した粘度に調整された組成物が求められている。 Regarding these problems, the applicant has discovered that by containing a specific urethane polymer, silica particles, and an oil component, it is possible to obtain an oil-based composition that imparts a good feel and thickening effect to the product. (Patent Document 6). However, in the market, there is a need for a method for significantly increasing the viscosity of an oil component, and for a composition whose viscosity is adjusted to a value suitable for use by such a method.
特開平８－２５３５４８号公報Japanese Patent Application Publication No. 8-253548 特開平９－７１７６７号公報Japanese Patent Application Publication No. 9-71767 特開２０１１－１０２２５６号公報Japanese Patent Application Publication No. 2011-102256 特開平６－２９９１０４号公報Japanese Patent Application Publication No. 6-299104 特開平７－２３２９１２号公報Japanese Patent Application Publication No. 7-232912 国際公開第２０２１／１８２５００号International Publication No. 2021/182500
　従って、本発明は、油成分を顕著に増加できる増粘方法、該方法を用いて得られる油成分含有組成物及び増粘剤組成物を提供することを目的とする。 Therefore, an object of the present invention is to provide a thickening method that can significantly increase the oil component, an oil component-containing composition, and a thickener composition obtained using the method.
　そこで本発明者らは鋭意検討し、油成分を更に顕著に増加できる増粘方法を見出し、本発明に至った。即ち、本発明は、（ＰＰＧ－１２／ＳＭＤＩ）コポリマー（Ａ）と、シリカ粒子（Ｂ）と、グリセリンの重合度が２～２０であるポリグリセリンと炭素原子数が８～２０である脂肪酸とのモノエステル又はジエステルであるポリグリセリン脂肪酸エステル（Ｃ）とを、エステル油、炭化水素油及びシリコーン油から選ばれる１種又は２種以上の油成分（Ｄ）に混合することを含む、油成分を増粘する方法である。
　また、本発明は、（ＰＰＧ－１２／ＳＭＤＩ）コポリマー（Ａ）と、シリカ粒子（Ｂ）と、グリセリンの重合度が２～２０であるポリグリセリンと炭素原子数が８～２０である脂肪酸とのモノエステル又はジエステルであるポリグリセリン脂肪酸エステル（Ｃ）と、エステル油、炭化水素油及びシリコーン油から選ばれる１種又は２種以上の油成分（Ｄ）と、を含む油成分含有組成物でもある。
　更に、本発明は、シリカ粒子（Ｂ）と、グリセリンの重合度が２～２０であるポリグリセリンと炭素原子数が８～２０である脂肪酸とのモノエステル又はジエステルであるポリグリセリン脂肪酸エステル（Ｃ）と共に、エステル油、炭化水素油及びシリコーン油から選ばれる１種又は２種以上の油成分（Ｄ）に混合するための、（ＰＰＧ－１２／ＳＭＤＩ）コポリマー（Ａ）を含む増粘剤組成物でもある。 Therefore, the present inventors conducted extensive research and found a thickening method that can further significantly increase the oil component, resulting in the present invention. That is, the present invention comprises (PPG-12/SMDI) copolymer (A), silica particles (B), polyglycerin whose polymerization degree of glycerin is 2 to 20, and fatty acid whose carbon number is 8 to 20. An oil component comprising mixing a polyglycerol fatty acid ester (C), which is a monoester or diester of , with one or more oil components (D) selected from ester oil, hydrocarbon oil and silicone oil This is a method of thickening.
The present invention also provides a copolymer (PPG-12/SMDI) (A), a silica particle (B), a polyglycerin having a polymerization degree of 2 to 20, and a fatty acid having 8 to 20 carbon atoms. An oil component-containing composition comprising a polyglycerin fatty acid ester (C) which is a monoester or diester of be.
Furthermore, the present invention provides silica particles (B) and polyglycerin fatty acid ester (C ), and a thickener composition containing a (PPG-12/SMDI) copolymer (A) for mixing with one or more oil components (D) selected from ester oils, hydrocarbon oils, and silicone oils. It is also a thing.
　本発明の油成分を増粘する方法及び増粘剤組成物によれば、エステル油、炭化水素油及びシリコーン油から選ばれる１種又は２種以上の油成分を顕著に増粘することができ、このような油成分を含む塗料、洗浄剤、接着剤、化粧品、医薬品、農薬、インク、染料等に用いたときに、それぞれの製品に適した粘度に容易に調整することができる。特に、本発明の油成分の増粘方法を用いて化粧料組成物を調製すると、使用に適した粘度を有する化粧料組成物を容易に得ることができる。 According to the method and thickener composition for thickening oil components of the present invention, it is possible to significantly thicken one or more oil components selected from ester oils, hydrocarbon oils, and silicone oils. When used in paints, cleaning agents, adhesives, cosmetics, pharmaceuticals, agricultural chemicals, inks, dyes, etc. containing such oil components, the viscosity can be easily adjusted to suit each product. In particular, when a cosmetic composition is prepared using the method of thickening an oil component of the present invention, a cosmetic composition having a viscosity suitable for use can be easily obtained.
１．油成分を増粘する方法
　本発明の油成分を増粘する方法は、（ＰＰＧ－１２／ＳＭＤＩ）コポリマー（Ａ）と、シリカ粒子（Ｂ）と、グリセリンの重合度が２～２０であるポリグリセリンと炭素原子数が８～２０である脂肪酸とのモノエステル又はジエステルであるポリグリセリン脂肪酸エステル（Ｃ）とを、エステル油、炭化水素油及びシリコーン油から選ばれる１種又は２種以上の油成分（Ｄ）に混合することを含む。 1. Method for thickening an oil component The method for thickening an oil component according to the present invention is a method for thickening an oil component of the present invention, which consists of a (PPG-12/SMDI) copolymer (A), silica particles (B), and a polyester resin in which the degree of polymerization of glycerin is 2 to 20. Polyglycerin fatty acid ester (C), which is a monoester or diester of glycerin and a fatty acid having 8 to 20 carbon atoms, is mixed with one or more oils selected from ester oils, hydrocarbon oils, and silicone oils. Including mixing with component (D).
　本発明に用いる（ＰＰＧ－１２／ＳＭＤＩ）コポリマー（Ａ）は、ＰＰＧ－１２（ポリプロピレングリコール－１２；平均重合度が１２であるプロピレンオキシドの重合物）とＳＭＤＩ（ジシクロヘキシルメタン４，４’－ジイソシアネート）とのコポリマーである。本発明に用いる（ＰＰＧ－１２／ＳＭＤＩ）コポリマー（Ａ）の分子量は特に限定されないが、油成分をより増粘できる観点から、（ＰＰＧ－１２／ＳＭＤＩ）コポリマー（Ａ）の重量平均分子量は、１，０００～５００，０００であることが好ましく、１，５００～１００，０００であることがより好ましく、１，５００～５０，０００であることが更により好ましく、２，０００～１０，０００であることが最も好ましい。本発明において、（ＰＰＧ－１２／ＳＭＤＩ）コポリマー（Ａ）の重量平均分子量は、ゲル浸透クロマトグラフィー（ＧＰＣ）により測定し、スチレン換算で求めることができる。 The (PPG-12/SMDI) copolymer (A) used in the present invention consists of PPG-12 (polypropylene glycol-12; a polymer of propylene oxide with an average degree of polymerization of 12) and SMDI (dicyclohexylmethane 4,4'-diisocyanate). ) is a copolymer with The molecular weight of the (PPG-12/SMDI) copolymer (A) used in the present invention is not particularly limited, but from the viewpoint of increasing the viscosity of the oil component, the weight average molecular weight of the (PPG-12/SMDI) copolymer (A) is as follows: It is preferably from 1,000 to 500,000, more preferably from 1,500 to 100,000, even more preferably from 1,500 to 50,000, and from 2,000 to 10,000. Most preferably. In the present invention, the weight average molecular weight of the (PPG-12/SMDI) copolymer (A) can be measured by gel permeation chromatography (GPC) and calculated in terms of styrene.
　ＧＰＣの測定条件は次の通りである。
［ＧＰＣ測定条件］
装置：ＬＣ－２０００ｐｌｕｓ　ｓｅｒｉｅｓ（日本分光株式会社製）
カラム：ＫＦ－８０３（昭和電工株式会社製）
カラム温度：４０℃
試料濃度：０．１質量％
展開溶媒：テトラヒドロフラン
検出装置：インテリジェント示差屈折計ＲＩ－２０３１（日本分光株式会社製）
基準物質：ＴＳＫｇｅｌ標準ポリスチレン（東ソー株式会社製） The measurement conditions for GPC are as follows.
[GPC measurement conditions]
Equipment: LC-2000plus series (manufactured by JASCO Corporation)
Column: KF-803 (manufactured by Showa Denko Co., Ltd.)
Column temperature: 40℃
Sample concentration: 0.1% by mass
Developing solvent: Tetrahydrofuran Detection device: Intelligent differential refractometer RI-2031 (manufactured by JASCO Corporation)
Reference material: TSKgel standard polystyrene (manufactured by Tosoh Corporation)
　本発明に用いる（ＰＰＧ－１２／ＳＭＤＩ）コポリマー（Ａ）は、市販品を用いても、公知の製造方法により製造してもよい。（ＰＰＧ－１２／ＳＭＤＩ）コポリマー（Ａ）の製造方法としては、例えば、ＰＰＧ－１２とＳＭＤＩとを反応性のイソシアネート基がなくなるまで反応させる方法、及びＰＰＧ－１２とＳＭＤＩとを反応させてウレタンプレポリマーを製造した後に、鎖延長剤と反応させる方法が挙げられる。鎖延長剤を用いる場合の鎖延長剤の種類は特に限定されないが、例えば、水、エチレンジアミン、プロピレンジアミンからなる群から選ばれる１種又は２種以上を用いることができる。 The (PPG-12/SMDI) copolymer (A) used in the present invention may be a commercially available product or may be produced by a known production method. (PPG-12/SMDI) Copolymer (A) can be produced by, for example, reacting PPG-12 and SMDI until there are no reactive isocyanate groups, or reacting PPG-12 and SMDI to produce urethane. An example is a method in which a prepolymer is produced and then reacted with a chain extender. When using a chain extender, the type of chain extender is not particularly limited, but for example, one or more types selected from the group consisting of water, ethylenediamine, and propylene diamine can be used.
　ＰＰＧ－１２とＳＭＤＩとを反応させて製造したウレタンプレポリマーと、鎖延長剤とを反応させる際のそれぞれの配合量は特に限定されないが、得られる（ＰＰＧ－１２／ＳＭＤＩ）コポリマー（Ａ）の諸特性の観点から、ウレタンプレポリマーに残存しているイソシアネート基のモル数（用いたＳＭＤＩのイソシアネート基のモル数からＰＰＧ－１２の水酸基のモル数を引いた数）に対する、鎖延長剤のモル数が、１．０倍以上である（つまり、鎖延長剤のモル数がウレタンプレポリマーに残存しているイソシアネート基のモル数以上である）ことが好ましい。本発明においては、鎖延長剤によりウレタンプレポリマーの分子鎖を延長することで、得られる（ＰＰＧ－１２／ＳＭＤＩ）コポリマー（Ａ）の分子量を所望の範囲に容易に調整することができる。また、鎖延長剤として水を用いる場合、水は得られる（ＰＰＧ－１２／ＳＭＤＩ）コポリマー（Ａ）の溶媒又は分散媒として用いることができるため、水の配合量を調整することにより、各種濃度の（ＰＰＧ－１２／ＳＭＤＩ）コポリマー（Ａ）の水溶液又は分散液を得ることができる。 The amount of the urethane prepolymer produced by reacting PPG-12 and SMDI with the chain extender is not particularly limited, but the amount of the resulting (PPG-12/SMDI) copolymer (A) From the viewpoint of various properties, the number of moles of the chain extender relative to the number of moles of isocyanate groups remaining in the urethane prepolymer (the number of moles of isocyanate groups of SMDI used minus the number of moles of hydroxyl groups of PPG-12) It is preferable that the number is 1.0 times or more (that is, the number of moles of the chain extender is greater than or equal to the number of moles of the isocyanate group remaining in the urethane prepolymer). In the present invention, the molecular weight of the resulting (PPG-12/SMDI) copolymer (A) can be easily adjusted to a desired range by extending the molecular chain of the urethane prepolymer using a chain extender. In addition, when water is used as a chain extender, since water can be used as a solvent or dispersion medium for the obtained (PPG-12/SMDI) copolymer (A), various concentrations can be obtained by adjusting the amount of water blended. An aqueous solution or dispersion of (PPG-12/SMDI) copolymer (A) can be obtained.
　また、ＰＰＧ－１２とＳＭＤＩとを反応させてウレタンプレポリマーを製造する方法としては特に限定されず、公知の方法により製造することができるが、例えば、ＰＰＧ－１２とＳＭＤＩとを反応させ、必要に応じて乳化剤を含む溶媒中に加えて分散させるプレポリマーミキシング法を用いることができる。このとき、乳化剤としては、例えば、公知のアニオン界面活性剤、ノニオン界面活性剤、カチオン界面活性剤及びこれらの界面活性剤の混合物等を用いることができる。また、溶媒としては、例えば、エタノール、プロパノール、ブタノール、ヘキサン、トルエン、酢酸エチル、酢酸ブチル、水等を用いることができる。 Further, the method for producing a urethane prepolymer by reacting PPG-12 and SMDI is not particularly limited, and can be produced by a known method, but for example, by reacting PPG-12 and SMDI, Depending on the situation, a prepolymer mixing method can be used in which the prepolymer is added and dispersed in a solvent containing an emulsifier. At this time, as the emulsifier, for example, known anionic surfactants, nonionic surfactants, cationic surfactants, and mixtures of these surfactants can be used. Further, as the solvent, for example, ethanol, propanol, butanol, hexane, toluene, ethyl acetate, butyl acetate, water, etc. can be used.
　（ＰＰＧ－１２／ＳＭＤＩ）コポリマー（Ａ）の製造に用いるＰＰＧ－１２とＳＭＤＩの使用比率は特に限定されないが、得られる（ＰＰＧ－１２／ＳＭＤＩ）コポリマー（Ａ）の諸特性の観点から、ＰＰＧ－１２とＳＭＤＩとを１：０．０５～１：５のモル比で用いることが好ましく、１：０．１～１：１のモル比で用いることがより好ましく、１：０．２～１：０．５のモル比で用いることが更により好ましい。 The ratio of PPG-12 and SMDI used in the production of the (PPG-12/SMDI) copolymer (A) is not particularly limited, but from the viewpoint of the various properties of the resulting (PPG-12/SMDI) copolymer (A), PPG -12 and SMDI are preferably used in a molar ratio of 1:0.05 to 1:5, more preferably 1:0.1 to 1:1, and 1:0.2 to 1. It is even more preferable to use the molar ratio of :0.5.
　（ＰＰＧ－１２／ＳＭＤＩ）コポリマー（Ａ）の製造方法においては、本発明の効果を損なわない範囲でＰＰＧ－１２、ＳＭＤＩと反応し得るその他の原料を用いてもよいが、本発明の油成分を増粘するという効果の観点からは、ＰＰＧ－１２とＳＭＤＩからなる原料を用いて反応性のイソシアネート基がなくなるまで反応させる方法か、ＰＰＧ－１２とＳＭＤＩからなる原料を反応させて得られたウレタンプレポリマーに、鎖延長剤のみを反応させる方法のいずれかの製造方法とすることが好ましい。 In the method for producing (PPG-12/SMDI) copolymer (A), other raw materials that can react with PPG-12 and SMDI may be used as long as they do not impair the effects of the present invention, but the oil component of the present invention From the viewpoint of the effect of thickening PPG-12 and SMDI, the method of reacting until the reactive isocyanate group is exhausted, or It is preferable to use any of the production methods in which only a chain extender is reacted with a urethane prepolymer.
　本発明においては、（ＰＰＧ－１２／ＳＭＤＩ）コポリマー（Ａ）、シリカ粒子（Ｂ）、ポリグリセリン脂肪酸エステル（Ｃ）との相乗的な増粘効果により、油成分を特に顕著に増粘する観点からは、（ＰＰＧ－１２／ＳＭＤＩ）コポリマーの製造方法として、ＰＰＧ－１２とＳＭＤＩからなる原料における、ＰＰＧ－１２とＳＭＤＩのモル比が１：０．２～１：０．５となる量で、これらを反応性のイソシアネート基がなくなるまで反応させる方法を用いることが特に好ましい。 In the present invention, the viewpoint of particularly significantly thickening the oil component is due to the synergistic thickening effect of the (PPG-12/SMDI) copolymer (A), silica particles (B), and polyglycerin fatty acid ester (C). As a method for producing a (PPG-12/SMDI) copolymer, the molar ratio of PPG-12 and SMDI in a raw material consisting of PPG-12 and SMDI is 1:0.2 to 1:0.5. It is particularly preferable to use a method in which these are reacted until there are no reactive isocyanate groups.
　（ＰＰＧ－１２／ＳＭＤＩ）コポリマー（Ａ）の製造方法の各反応は、各原料が反応できる条件であれば特に限定されない。また、各原料の全量を一括で投入して反応させても数回に分割して投入して反応させてもよい。具体的には、例えば、各成分の原料をそれぞれ一度に又は数回に分割して反応系内に入れて３０～１６０℃、好ましくは４０～１６０℃の温度で、加圧、減圧又は常圧環境下で混合し、反応が完了するまで３０分～１０時間維持する方法が挙げられる。 Each reaction in the method for producing the (PPG-12/SMDI) copolymer (A) is not particularly limited as long as the conditions are such that each raw material can react. Furthermore, the entire amount of each raw material may be added at once and reacted, or may be added in several portions and reacted. Specifically, for example, the raw materials for each component are added to the reaction system at once or in several batches and heated at a temperature of 30 to 160°C, preferably 40 to 160°C, under increased pressure, reduced pressure, or normal pressure. Examples include a method of mixing in an environment and maintaining the mixture for 30 minutes to 10 hours until the reaction is completed.
　また、（ＰＰＧ－１２／ＳＭＤＩ）コポリマー（Ａ）の製造方法の各反応において、反応を促進させるために触媒を使用することも可能である。触媒の例としては、硫酸、トルエンスルフォン酸等の強酸；四塩化チタン、塩化ハフニウム、塩化ジルコニウム、塩化アルミニウム、塩化ガリウム、塩化インジウム、塩化鉄、塩化スズ、フッ化硼素等の金属ハロゲン化物；水酸化ナトリウム、水酸化カリウム、ソヂウムメチラート、炭酸ナトリウム等のアルカリ金属又はアルカリ土類金属の水酸化物、アルコラート物、炭酸塩；酸化アルミニウム、酸化カルシウム、酸化バリウム、酸化ナトリウム等の金属酸化物；テトライソプロピルチタネート、ジブチル錫ジクロライド、ジブチル錫オキサイド、ジブチル錫ビス（２－エチルヘキシルチオグリコレート）等の有機金属化合物；酢酸ナトリウム、酢酸カリウム、プロピオン酸ナトリウム、プロピオン酸カリウム、オクチル酸ナトリウム、オクチル酸カリウム、ラウリン酸ナトリウム、ラウリン酸カリウム等の石鹸が挙げられる。これらの触媒の配合量は、特に限定されないが、各原料の合計質量に対して０．０１～１質量％である。なお、触媒を使用しなくても反応は進むが、触媒を使用すると反応速度が上がるので、反応時間を短縮する効果が得られる。 Additionally, in each reaction of the method for producing (PPG-12/SMDI) copolymer (A), a catalyst can be used to accelerate the reaction. Examples of 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, and boron fluoride; water. Alkali metal or alkaline earth metal hydroxides, alcoholates, carbonates such as sodium oxide, potassium hydroxide, sodium methylate, sodium carbonate; metal oxides such as aluminum oxide, calcium oxide, barium oxide, sodium oxide, etc. Organometallic compounds such as tetraisopropyl titanate, dibutyltin dichloride, dibutyltin oxide, dibutyltin bis(2-ethylhexylthioglycolate); Sodium acetate, potassium acetate, sodium propionate, potassium propionate, sodium octylate, octyl Examples include soaps such as potassium acid, sodium laurate, and potassium laurate. The blending amount of these catalysts is not particularly limited, but is 0.01 to 1% by mass based on the total mass of each raw material. Although the reaction proceeds even without the use of a catalyst, the use of a catalyst increases the reaction rate, resulting in the effect of shortening the reaction time.
　本発明においては、（ＰＰＧ－１２／ＳＭＤＩ）コポリマー（Ａ）として上述した（ＰＰＧ－１２／ＳＭＤＩ）コポリマーを用いることで、シリカ粒子（Ｂ）、ポリグリセリン脂肪酸エステル（Ｃ）との相乗的な増粘効果により、油成分を顕著に増粘することができ、油成分を含有する塗料、粘接着剤、燃料、潤滑剤、食品、化粧料等の製品に用いた際に、使用に適した粘度を有する各製品を提供することができる。 In the present invention, by using the (PPG-12/SMDI) copolymer described above as the (PPG-12/SMDI) copolymer (A), a synergistic effect with the silica particles (B) and the polyglycerol fatty acid ester (C) is achieved. The thickening effect can significantly thicken oil components, making it suitable for use in products containing oil components such as paints, adhesives, fuels, lubricants, foods, and cosmetics. Each product can be provided with a different viscosity.
　本発明に用いるシリカ粒子（Ｂ）は、塗料、粘接着剤、燃料、潤滑剤、食品、化粧料等の分野で通常用いられるシリカ粒子であれば特に限定されず、無水ケイ酸、二酸化ケイ素を含む各種のシリカ粒子を用いることができる。本発明に用いるシリカ粒子の形状・形態も特に限定されず、例えば、球状シリカ粒子、板状シリカ粒子、多孔質シリカ粒子、不定形シリカ粒子、煙霧状シリカ粒子、非晶質シリカ粒子、結晶質シリカ粒子、コロイダルシリカ、シリカゲル、シリカエアロゲル、シリカゾル等を用いることができる。 The silica particles (B) used in the present invention are not particularly limited as long as they are silica particles commonly used in the fields of paints, adhesives, fuels, lubricants, foods, cosmetics, etc., and include silica anhydride, silicon dioxide, etc. Various types of silica particles can be used, including: The shape and form of the silica particles used in the present invention are not particularly limited, and examples thereof include spherical silica particles, plate-shaped silica particles, porous silica particles, amorphous silica particles, atomized silica particles, amorphous silica particles, and crystalline silica particles. Silica particles, colloidal silica, silica gel, silica airgel, silica sol, etc. can be used.
　本発明に用いるシリカ粒子（Ｂ）の粒子径は特に限定されず、目的に応じて適宜調節することができ、例えば、平均粒子径は１ｎｍ～１００μｍであってもよい。得られる油性組成物の増粘効果及び化粧料組成物の感触及び使用感を向上させる観点からは、シリカ粒子の平均粒子径は１ｎｍ～１μｍであることが好ましく、１ｎｍ～５００ｎｍであることがより好ましく、１ｎｍ～１００ｎｍであることが更により好ましい。本発明において、シリカ粒子の平均粒子径は、ＪＩＳ　Ｚ　８８２８（２０１９）に準拠して動的光散乱法により測定される。 The particle size of the silica particles (B) used in the present invention is not particularly limited and can be adjusted as appropriate depending on the purpose. For example, the average particle size may be 1 nm to 100 μm. From the viewpoint of improving the thickening effect of the obtained oily composition and the feel and feel of the cosmetic composition, the average particle diameter of the silica particles is preferably 1 nm to 1 μm, more preferably 1 nm to 500 nm. The thickness is preferably 1 nm to 100 nm, even more preferably. In the present invention, the average particle diameter of silica particles is measured by a dynamic light scattering method in accordance with JIS Z 8828 (2019).
　本発明に用いるシリカ粒子（Ｂ）は、親水性のシリカ粒子であっても、疎水性のシリカ粒子であってもよいが、本発明の油成分を増粘するという効果の観点から、疎水性シリカ粒子であることが好ましい。疎水性シリカ粒子としては、例えば、シリカ粒子の表面を疎水化処理することにより得られる疎水性シリカ粒子を用いることができ、疎水化処理方法としては、例えば、アルコキシシラン類、シラザン類、シロキサン類、ハロゲン化シラン類、飽和脂肪酸、アミノ酸、エステル、ワックス等による処理方法を用いることができる。これらの中でも、アルコキシシラン類、ハロゲン化シラン類によるジメチルシリル化処理がされた疎水化シリカ粒子であることが好ましい。 The silica particles (B) used in the present invention may be hydrophilic silica particles or hydrophobic silica particles, but from the viewpoint of the effect of thickening the oil component of the present invention, hydrophobic silica particles Silica particles are preferred. As the hydrophobic silica particles, for example, hydrophobic silica particles obtained by hydrophobizing the surface of silica particles can be used, and as the hydrophobizing method, for example, alkoxysilanes, silazane, siloxanes, etc. , halogenated silanes, saturated fatty acids, amino acids, esters, waxes, etc. can be used. Among these, hydrophobized silica particles subjected to dimethylsilylation treatment with alkoxysilanes or halogenated silanes are preferable.
　このようなシリカ粒子としては、公知の方法により製造してもよく、市販品を用いてもよい。本発明に用いることができる市販のシリカ粒子としては、例えば、ＥＶＯＮＩＫ社製のＡＥＲＯＳＩＬ（登録商標）シリーズ、ＳＯＬＶＥＹ社製のＥｆｆｉｃｉｕｍ（登録商標）シリーズ、Ｔｉｘｏｓｉｌ（登録商標）シリーズ、Ｚｅｏｓｉｌ（登録商標）シリーズ、信越シリコーン社製のＱＳＧシリーズ、日本触媒社製のシーホスター（登録商標）シリーズ等を用いることができる。 Such silica particles may be produced by a known method, or commercially available products may be used. Commercially available silica particles that can be used in the present invention include, for example, the AEROSIL (registered trademark) series manufactured by EVONIK, the Efficium (registered trademark) series, the Tixosil (registered trademark) series, and Zeosil (registered trademark) manufactured by SOLVEY. series, QSG series manufactured by Shin-Etsu Silicone Co., Ltd., Seahoster (registered trademark) series manufactured by Nippon Shokubai Co., Ltd., etc. can be used.
　本発明においては、シリカ粒子（Ｂ）として上述したシリカ粒子を用いることで、（ＰＰＧ－１２／ＳＭＤＩ）コポリマー（Ａ）、ポリグリセリン脂肪酸エステル（Ｃ）との相乗的な増粘効果により、油成分を顕著に増粘することができ、油成分を含有する塗料、粘接着剤、燃料、潤滑剤、食品、化粧料等の製品に用いた際に、使用に適した粘度を有する各製品を提供することができる。 In the present invention, by using the above-mentioned silica particles as the silica particles (B), the synergistic thickening effect with the (PPG-12/SMDI) copolymer (A) and the polyglycerin fatty acid ester (C) improves the oil content. Products that can significantly thicken ingredients and have a viscosity suitable for use in products containing oil components, such as paints, adhesives, fuels, lubricants, foods, and cosmetics. can be provided.
　本発明に用いるポリグリセリン脂肪酸エステル（Ｃ）は、グリセリンの重合度が２～２０であるポリグリセリンと炭素原子数が８～２０である脂肪酸とのモノエステル又はジエステルである。炭素原子数が８～２０である脂肪酸としては、例えば、炭素原子数が８～２０である飽和直鎖脂肪酸、炭素原子数が８～２０である飽和分岐脂肪酸、炭素原子数が８～２０である不飽和直鎖脂肪酸、炭素原子数が８～２０である不飽和分岐脂肪酸等が挙げられ、これらの中でも、炭素原子数が８～１８である脂肪酸が好ましく、炭素原子数が８～１８である飽和直鎖脂肪酸、炭素原子数が８～１８である飽和分岐脂肪酸、又は炭素原子数が８～１８である不飽和直鎖脂肪酸がより好ましい。本発明において、ポリグリセリンのグリセリンの重合度は、「ポリグリセリンエステル」（阪本薬品工業株式会社編　１９９４年出版）の記載に基づき、ポリグリセリンの水酸基価（ｍｇＫＯＨ／ｇ）に基づき算出される値である。 The polyglycerin fatty acid ester (C) used in the present invention is a monoester or diester of polyglycerin having a polymerization degree of 2 to 20 and a fatty acid having 8 to 20 carbon atoms. Examples of fatty acids having 8 to 20 carbon atoms include saturated straight chain fatty acids having 8 to 20 carbon atoms, saturated branched fatty acids having 8 to 20 carbon atoms, and saturated branched fatty acids having 8 to 20 carbon atoms. Examples include certain unsaturated straight chain fatty acids, unsaturated branched fatty acids having 8 to 20 carbon atoms, etc. Among these, fatty acids having 8 to 18 carbon atoms are preferred; More preferred are certain saturated straight chain fatty acids, saturated branched fatty acids having 8 to 18 carbon atoms, or unsaturated straight chain fatty acids having 8 to 18 carbon atoms. In the present invention, the degree of polymerization of glycerin in polyglycerin is a value calculated based on the hydroxyl value (mgKOH/g) of polyglycerin based on the description in "Polyglycerin Ester" (edited by Sakamoto Pharmaceutical Co., Ltd., published in 1994). It is.
　このようなポリグリセリン脂肪酸エステルとしては、例えば、カプリン酸ポリグリセリル－２、カプリル酸ポリグリセリル－４、カプリル酸ポリグリセリル－５、カプリル酸ポリグリセリル－６、カプリル酸ポリグリセリル－８、カプリル酸ポリグリセリル－１０、ラウリン酸ポリグリセリル－２、ラウリン酸ポリグリセリル－４、ラウリン酸ポリグリセリル－５、ラウリン酸ポリグリセリル－６、ラウリン酸ポリグリセリル－８、ラウリン酸ポリグリセリル－１０、ミリスチン酸ポリグリセリル－２、ミリスチン酸ポリグリセリル－４、ミリスチン酸ポリグリセリル－５、ミリスチン酸ポリグリセリル－６、ミリスチン酸ポリグリセリル－８、ミリスチン酸ポリグリセリル－１０、パルミチン酸ポリグリセリル－２、パルミチン酸ポリグリセリル－４、パルミチン酸ポリグリセリル－５、パルミチン酸ポリグリセリル－６、パルミチン酸ポリグリセリル－８、パルミチン酸ポリグリセリル－１０、ステアリン酸ポリグリセリル－２、ステアリン酸ポリグリセリル－４、ステアリン酸ポリグリセリル－５、ステアリン酸ポリグリセリル－６、ステアリン酸ポリグリセリル－８、ステアリン酸ポリグリセリル－１０、イソステアリン酸ポリグリセリル－２、イソステアリン酸ポリグリセリル－４、イソステアリン酸ポリグリセリル－５、イソステアリン酸ポリグリセリル－６、イソステアリン酸ポリグリセリル－８、イソステアリン酸ポリグリセリル－１０、ミリストレイン酸ポリグリセリル－２、ミリストレイン酸ポリグリセリル－４、ミリストレイン酸ポリグリセリル－５、ミリストレイン酸ポリグリセリル－６、ミリストレイン酸ポリグリセリル－８、ミリストレイン酸ポリグリセリル－１０、パルミトレイン酸ポリグリセリル－２、パルミトレイン酸ポリグリセリル－４、パルミトレイン酸ポリグリセリル－５、パルミトレイン酸ポリグリセリル－６、パルミトレイン酸ポリグリセリル－８、パルミトレイン酸ポリグリセリル－１０、オレイン酸ポリグリセリル－２、オレイン酸ポリグリセリル－４、オレイン酸ポリグリセリル－５、オレイン酸ポリグリセリル－６、オレイン酸ポリグリセリル－８、オレイン酸ポリグリセリル－１０、エライジン酸ポリグリセリル－２、エライジン酸ポリグリセリル－４、エライジン酸ポリグリセリル－５、エライジン酸ポリグリセリル－６、エライジン酸ポリグリセリル－８、エライジン酸ポリグリセリル－１０、エイコセン酸ポリグリセリル－２、エイコセン酸ポリグリセリル－４、エイコセン酸ポリグリセリル－５、エイコセン酸ポリグリセリル－６、エイコセン酸ポリグリセリル－８、エイコセン酸ポリグリセリル－１０、及びこれらのジエステル等が挙げられる。
　これらの中でも、（ＰＰＧ－１２／ＳＭＤＩ）コポリマー（Ａ）、シリカ粒子（Ｂ）との相乗的な増粘効果により油成分を顕著に増粘する観点からは、ポリグリセリン脂肪酸エステル（Ｃ）は、カプリル酸ポリグリセリル－６、カプリン酸ポリグリセリル－２、ジカプリン酸ポリグリセリル－６、ラウリン酸ポリグリセリル－５、ラウリン酸ポリグリセリル－１０、ジイソステアリン酸ポリグリセリル－１０、及びジオレイン酸ポリグリセリル－１０からなる群から選ばれる１種又は２種以上を含むことが好ましく、カプリル酸ポリグリセリル－６、ジカプリン酸ポリグリセリル－６、ラウリン酸ポリグリセリル－５、ラウリン酸ポリグリセリル－１０、ジイソステアリン酸ポリグリセリル－１０、及びジオレイン酸ポリグリセリル－１０からなる群から選ばれる１種又は２種以上を含むことがより好ましい。 Examples of such polyglycerin fatty acid esters include polyglyceryl-2 caprylate, polyglyceryl-4 caprylate, polyglyceryl-5 caprylate, polyglyceryl-6 caprylate, polyglyceryl-8 caprylate, polyglyceryl-10 caprylate, and lauric acid. Polyglyceryl-2, polyglyceryl-4 laurate, polyglyceryl-5 laurate, polyglyceryl-6 laurate, polyglyceryl-8 laurate, polyglyceryl-10 laurate, polyglyceryl-2 myristate, polyglyceryl-4 myristate, polyglyceryl myristate- 5, polyglyceryl myristate-6, polyglyceryl myristate-8, polyglyceryl myristate-10, polyglyceryl palmitate-2, polyglyceryl palmitate-4, polyglyceryl palmitate-5, polyglyceryl palmitate-6, polyglyceryl palmitate-8, Polyglyceryl palmitate-10, polyglyceryl stearate-2, polyglyceryl stearate-4, polyglyceryl stearate-5, polyglyceryl stearate-6, polyglyceryl stearate-8, polyglyceryl stearate-10, polyglyceryl isostearate-2, isostearic acid Polyglyceryl-4, Polyglyceryl-5 Isostearate, Polyglyceryl-6 Isostearate, Polyglyceryl-8 Isostearate, Polyglyceryl-10 Isostearate, Polyglyceryl-2 Myristoleate, Polyglyceryl-4 Myristoleate, Polyglyceryl-5 Myristoleate Polyglyceryl streate-6, polyglyceryl myristoleate-8, polyglyceryl myristoleate-10, polyglyceryl palmitoleate-2, polyglyceryl palmitoleate-4, polyglyceryl palmitoleate-5, polyglyceryl palmitoleate-6, polyglyceryl palmitoleate-8, Polyglyceryl palmitoleate-10, polyglyceryl oleate-2, polyglyceryl oleate-4, polyglyceryl oleate-5, polyglyceryl oleate-6, polyglyceryl oleate-8, polyglyceryl oleate-10, polyglyceryl elaidate-2, elaidic acid Polyglyceryl-4, polyglyceryl elaidate-5, polyglyceryl elaidate-6, polyglyceryl elaidate-8, polyglyceryl elaidate-10, polyglyceryl eicosenoate-2, polyglyceryl eicosenoate-4, polyglyceryl eicosenoate-5, polyglyceryl eicosenoate- 6, polyglyceryl-8 eicosenoate, polyglyceryl-10 eicosenoate, and diesters thereof.
Among these, polyglycerol fatty acid ester (C) is preferred from the viewpoint of significantly thickening the oil component through a synergistic thickening effect with the (PPG-12/SMDI) copolymer (A) and silica particles (B). , polyglyceryl-6 caprylate, polyglyceryl-2 caprate, polyglyceryl-6 dicaprate, polyglyceryl-5 laurate, polyglyceryl-10 laurate, polyglyceryl-10 diisostearate, and polyglyceryl-10 dioleate. A group consisting of polyglyceryl-6 caprylate, polyglyceryl-6 dicaprate, polyglyceryl-5 laurate, polyglyceryl-10 laurate, polyglyceryl-10 diisostearate, and polyglyceryl-10 dioleate. It is more preferable to include one or more selected from.
　本発明に用いるポリグリセリン脂肪酸エステル（Ｃ）のＨＬＢは特に限定されないが、（ＰＰＧ－１２／ＳＭＤＩ）コポリマー（Ａ）、シリカ粒子（Ｂ）との相乗的な増粘効果により油成分を顕著に増粘する観点からは、ポリグリセリン脂肪酸エステル（Ｃ）のＨＬＢは６．０～２０．０であることが好ましく、７．０～１９．０であることがより好ましく、９．５～１８．０であることが更により好ましく、１０．０～１７．５であることが特に好ましい。本発明において、ポリグリセリン脂肪酸エステル（Ｃ）のＨＬＢは、Ｇｒｉｆｆｉｎの方法により求められた値（吉田、進藤、大垣、山中共編、「新版界面活性剤ハンドブック」，工学図書株式会社，１９９６年，ｐ．２３４）である。 Although the HLB of the polyglycerin fatty acid ester (C) used in the present invention is not particularly limited, the synergistic thickening effect with the (PPG-12/SMDI) copolymer (A) and silica particles (B) can significantly reduce the oil component. From the viewpoint of thickening, the HLB of the polyglycerin fatty acid ester (C) is preferably 6.0 to 20.0, more preferably 7.0 to 19.0, and more preferably 9.5 to 18. It is even more preferably 0, and particularly preferably 10.0 to 17.5. In the present invention, the HLB of the polyglycerol fatty acid ester (C) is the value determined by the Griffin method (Yoshida, Shindo, Ogaki, Yamanaka co-eds., "New Edition Surfactant Handbook", Kogaku Tosho Co., Ltd., 1996). p.234).
　本発明においては、ポリグリセリン脂肪酸エステル（Ｃ）として上述したポリグリセリン脂肪酸エステルを用いることで、（ＰＰＧ－１２／ＳＭＤＩ）コポリマー（Ａ）、シリカ粒子（Ｂ）との相乗的な増粘効果により、油成分を顕著に増粘することができ、油成分を含有する塗料、粘接着剤、燃料、潤滑剤、食品、化粧料等の製品に用いた際に、使用に適した粘度を有する各製品を提供することができる。 In the present invention, by using the polyglycerol fatty acid ester described above as the polyglycerol fatty acid ester (C), a synergistic thickening effect with the (PPG-12/SMDI) copolymer (A) and the silica particles (B) is achieved. , can significantly thicken oil components, and have a viscosity suitable for use in products containing oil components such as paints, adhesives, fuels, lubricants, foods, cosmetics, etc. Each product can be provided.
　本発明に用いる油成分（Ｄ）は、エステル油、炭化水素油及びシリコーン油から選ばれる１種又は２種以上の油成分である。本発明に用いることができるエステル油としては、例えば、ミリスチン酸イソプロピル、オクタン酸セチル、イソノナン酸イソノニル、ミリスチン酸オクチルドデシル、パルミチン酸イソプロピル、ステアリン酸ブチル、ラウリン酸ヘキシル、ミリスチン酸ミリスチル、オレイン酸デシル、ジメチルオクタン酸ヘキシルデシル、乳酸セチル、乳酸ミリスチル、酢酸ラノリン、ステアリン酸イソセチル、イソステアリン酸イソセチル、１２－ヒドロキシステアリン酸コレステリル、ジ－２－エチルヘキサン酸グリセリル、ジペンタエリスリトール脂肪酸エステル、モノイソステアリン酸グリセリル、ジカプリン酸ネオペンチルグリコール、リンゴ酸ジイソステアリル、ジ－２－ヘプチルウンデカン酸グリセリル、トリ－２－エチルヘキサン酸トリメチロールプロパン、トリイソステアリン酸トリメチロールプロパン、テトラ－２－エチルヘキサン酸ペンタエリスリトール、トリ－２－エチルヘキサン酸グリセリル、トリオクタン酸グリセリル、トリイソパルミチン酸グリセリル、トリイソステアリン酸トリメチロールプロパン、セチル２－エチルヘキサノエート、２－エチルヘキシルパルミテート、トリミリスチン酸グリセリル、トリ－２－ヘプチルウンデカン酸グリセリル、ヒマシ油脂肪酸メチルエステル、オレイン酸オレイル、アセトグリセライド、パルミチン酸２－ヘプチルウンデシル、アジピン酸ジイソブチル、Ｎ－ラウロイル－Ｌ－グルタミン酸－２－オクチルドデシルエステル、アジピン酸ジ－２－ヘプチルウンデシル、エチルラウレート、セバシン酸ジ－２－エチルヘキシル、ミリスチン酸２－ヘキシルデシル、パルミチン酸２－ヘキシルデシル、アジピン酸２－ヘキシルデシル、セバシン酸ジイソプロピル、コハク酸２－エチルヘキシル、トリエチルヘキサノイン、パルミチン酸エチルヘキシル、トリ（カプリル酸／カプリン酸）グリセリル等が挙げられ、これらの１種又は２種以上を用いることができる。また、エステル油を含むアボカド油、ツバキ油、タートル油、マカデミアナッツ油、トウモロコシ油、ミンク油、オリーブ油、ナタネ油、卵黄油、ゴマ油、パーシック油、小麦胚芽油、サザンカ油、ヒマシ油、アマニ油、サフラワー油、綿実油、エノ油、大豆油、落花生油、茶実油、カヤ油、コメヌカ油、シナギリ油、日本キリ油、ホホバ油、胚芽油、トリグリセリド、カカオ脂、ヤシ油、硬化ヤシ油、パーム油、パーム核油、モクロウ核油、硬化油、モクロウ、硬化ヒマシ油等の油脂も用いることができる。エステル油の２５℃での粘度は、１～２００００ｍＰａ・ｓであることが好ましく、３～１００００ｍＰａ・ｓであることがより好ましく、５～８０００ｍＰａ・ｓであることが更により好ましい。本発明において、２５℃での粘度は、ＪＩＳ　Ｋ　７１１７に準拠して測定される。 The oil component (D) used in the present invention is one or more oil components selected from ester oil, hydrocarbon oil, and silicone oil. Examples of ester oils that can be used in the present invention include isopropyl myristate, cetyl octoate, isononyl isononanoate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, and decyl oleate. , hexyldecyl dimethyloctoate, cetyl lactate, myristyl lactate, lanolin acetate, isocetyl stearate, isocetyl isostearate, cholesteryl 12-hydroxystearate, glyceryl di-2-ethylhexanoate, dipentaerythritol fatty acid ester, glyceryl monoisostearate , neopentyl glycol dicaprate, diisostearyl malate, glyceryl di-2-heptylundecanoate, trimethylolpropane tri-2-ethylhexanoate, trimethylolpropane triisostearate, pentaerythritol tetra-2-ethylhexanoate, Glyceryl tri-2-ethylhexanoate, glyceryl trioctanoate, glyceryl triisopalmitate, trimethylolpropane triisostearate, cetyl 2-ethylhexanoate, 2-ethylhexyl palmitate, glyceryl trimyristate, tri-2-heptyl Glyceryl undecanoate, castor oil fatty acid methyl ester, oleyl oleate, acetoglyceride, 2-heptylundecyl palmitate, diisobutyl adipate, N-lauroyl-L-glutamic acid-2-octyldodecyl ester, di-2-heptyl adipate Undecyl, ethyl laurate, di-2-ethylhexyl sebacate, 2-hexyldecyl myristate, 2-hexyldecyl palmitate, 2-hexyldecyl adipate, diisopropyl sebacate, 2-ethylhexyl succinate, triethylhexanoin, Examples include ethylhexyl palmitate, glyceryl tri(caprylic acid/capric acid), and one or more of these can be used. In addition, avocado oil, camellia oil, turtle oil, macadamia nut oil, corn oil, mink oil, olive oil, rapeseed oil, egg yolk oil, sesame oil, persic oil, wheat germ oil, sasanquat oil, castor oil, linseed oil, including ester oil, Safflower oil, cottonseed oil, eno oil, soybean oil, peanut oil, tea seed oil, kaya oil, rice bran oil, linden oil, Japanese tung oil, jojoba oil, germ oil, triglycerides, cacao butter, coconut oil, hydrogenated coconut oil, Oils and fats such as palm oil, palm kernel oil, Japanese oak kernel oil, hydrogenated oil, Japanese oak oil, and hydrogenated castor oil can also be used. The viscosity of the ester oil at 25° C. is preferably 1 to 20,000 mPa·s, more preferably 3 to 10,000 mPa·s, and even more preferably 5 to 8,000 mPa·s. In the present invention, the viscosity at 25°C is measured in accordance with JIS K 7117.
　本発明に用いることができる炭化水素油としては、例えば、流動パラフィン、オゾケライト、スクワラン、プリスタン、パラフィン、イソドデカン、セレシン、スクワレン、ワセリン、マイクロクリスタリンワックス等が挙げられ、これらの１種又は２種以上を用いることができる。炭化水素油の２５℃での粘度は、１～２００ｍＰａ・ｓであることが好ましく、５～１００ｍＰａ・ｓであることがより好ましく、１０～５０ｍＰａ・ｓであることが更により好ましい。 Examples of the hydrocarbon oil that can be used in the present invention include liquid paraffin, ozokerite, squalane, pristane, paraffin, isododecane, ceresin, squalene, petrolatum, microcrystalline wax, etc., and one or more of these can be used. The viscosity of the hydrocarbon oil at 25° C. is preferably 1 to 200 mPa·s, more preferably 5 to 100 mPa·s, and even more preferably 10 to 50 mPa·s.
　本発明に用いることができるシリコーン油としては、例えば、鎖状ポリシロキサン（例えば、ジメチルポリシロキサン、メチルフェニルポリシロキサン、ジフェニルポリシロキサン等）；環状ポリシロキサン（例えば、オクタメチルシクロテトラシロキサン、デカメチルシクロペンタシロキサン、ドデカメチルシクロヘキサシロキサン等）、３次元網目構造を形成しているシリコーン樹脂、シリコーンゴム、各種変性ポリシロキサン（アミノ変性ポリシロキサン、ポリエーテル変性ポリシロキサン、アルキル変性ポリシロキサン、フッ素変性ポリシロキサン等）等が挙げられ、これらの１種又は２種以上を用いることができる。シリコーン油の２５℃での粘度は、１～２００ｍＰａ・ｓであることが好ましく、５～１００ｍＰａ・ｓであることがより好ましく、１０～５０ｍＰａ・ｓであることが更により好ましい。 Silicone oils that can be used in the present invention include, for example, linear polysiloxanes (e.g., dimethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane, etc.); cyclic polysiloxanes (e.g., octamethylcyclotetrasiloxane, decamethylpolysiloxane, etc.); cyclopentasiloxane, dodecamethylcyclohexasiloxane, etc.), silicone resins forming three-dimensional network structures, silicone rubber, various modified polysiloxanes (amino-modified polysiloxane, polyether-modified polysiloxane, alkyl-modified polysiloxane, fluorine-modified polysiloxane) polysiloxane, etc.), and one or more of these can be used. The viscosity of the silicone oil at 25° C. is preferably 1 to 200 mPa·s, more preferably 5 to 100 mPa·s, and even more preferably 10 to 50 mPa·s.
　本発明に用いる油成分（Ｄ）としては、エステル油、炭化水素油及びシリコーン油から選ばれる１種のみであってもよく、２種以上の混合物であってもよい。本発明の油成分を増粘するという効果の観点からは、油成分（Ｄ）として、エステル油を含むことが好ましい。このとき、油成分（Ｄ）がエステル油からなるか、エステル油と炭化水素油を含む混合物もしくはエステル油と炭化水素油からなる混合物、エステル油とシリコーン油を含む混合物もしくはエステル油とシリコーン油からなる混合物、又は、エステル油と炭化水素油とシリコーン油を含む混合物もしくはエステル油と炭化水素油とシリコーン油からなる混合物であってもよい。 The oil component (D) used in the present invention may be only one selected from ester oil, hydrocarbon oil, and silicone oil, or may be a mixture of two or more. From the viewpoint of the effect of thickening the oil component of the present invention, it is preferable that ester oil is included as the oil component (D). At this time, the oil component (D) consists of an ester oil, a mixture containing an ester oil and a hydrocarbon oil, a mixture containing an ester oil and a hydrocarbon oil, a mixture containing an ester oil and a silicone oil, or a mixture containing an ester oil and a silicone oil. Alternatively, it may be a mixture containing an ester oil, a hydrocarbon oil, and a silicone oil, or a mixture containing an ester oil, a hydrocarbon oil, and a silicone oil.
　本発明の油成分の増粘方法において、油成分（Ｄ）に混合する（ＰＰＧ－１２／ＳＭＤＩ）コポリマー（Ａ）の量は特に限定されないが、より顕著に油成分（Ｄ）を増粘する観点からは、油成分（Ｄ）に混合する（ＰＰＧ－１２／ＳＭＤＩ）コポリマー（Ａ）の質量が、油成分（Ｄ）１００質量部に対して０．１～２５質量部であることが好ましく、０．２～２０質量部であることがより好ましく、０．３～１５質量部であることが更により好ましく、０．５～１０質量部であることが特に好ましい。 In the method for thickening an oil component of the present invention, the amount of the (PPG-12/SMDI) copolymer (A) to be mixed into the oil component (D) is not particularly limited, but it thickens the oil component (D) more significantly. From this point of view, it is preferable that the mass of the (PPG-12/SMDI) copolymer (A) mixed with the oil component (D) is 0.1 to 25 parts by mass based on 100 parts by mass of the oil component (D). , more preferably 0.2 to 20 parts by weight, even more preferably 0.3 to 15 parts by weight, particularly preferably 0.5 to 10 parts by weight.
　本発明の油成分の増粘方法において、油成分（Ｄ）に混合するシリカ粒子（Ｂ）の量は特に限定されないが、より顕著に油成分を増粘する観点からは、油成分（Ｄ）に混合するシリカ粒子（Ｂ）の質量が、油成分（Ｄ）１００質量部に対して０．１～２５質量部であることが好ましく、０．２～２０質量部であることがより好ましく、０．３～１５質量部であることが更により好ましく、０．５～１０質量部であることが特に好ましい。 In the method for thickening an oil component of the present invention, the amount of silica particles (B) to be mixed into the oil component (D) is not particularly limited, but from the viewpoint of thickening the oil component more significantly, the amount of silica particles (B) mixed into the oil component (D) is The mass of the silica particles (B) to be mixed in is preferably 0.1 to 25 parts by mass, more preferably 0.2 to 20 parts by mass, per 100 parts by mass of the oil component (D). It is even more preferably from 0.3 to 15 parts by weight, and particularly preferably from 0.5 to 10 parts by weight.
　本発明の油成分の増粘方法において、油成分（Ｄ）に混合するポリグリセリン脂肪酸エステル（Ｃ）の量は特に限定されないが、より顕著に油成分を増粘する観点からは、油成分（Ｄ）に混合するポリグリセリン脂肪酸エステル（Ｃ）の質量が、油成分１００質量部に対して１～１００質量部であることが好ましく、２～８０質量部であることがより好ましく、５～６０質量部であることが更により好ましく、１０～５０質量部であることが特に好ましい In the method for thickening an oil component of the present invention, the amount of polyglycerin fatty acid ester (C) to be mixed into the oil component (D) is not particularly limited, but from the viewpoint of thickening the oil component more significantly, The mass of the polyglycerin fatty acid ester (C) mixed in D) is preferably 1 to 100 parts by mass, more preferably 2 to 80 parts by mass, and more preferably 5 to 60 parts by mass, based on 100 parts by mass of the oil component. It is even more preferably 10 to 50 parts by weight, particularly preferably 10 to 50 parts by weight.
　本発明の油成分の増粘方法において、混合する（ＰＰＧ－１２／ＳＭＤＩ）コポリマー（Ａ）、シリカ粒子（Ｂ）、ポリグリセリン脂肪酸エステル（Ｃ）と油成分（Ｄ）の合計量に対する油成分（Ｄ）の量は特に限定されないが、より顕著に油成分を増粘する観点からは、混合する（ＰＰＧ－１２／ＳＭＤＩ）コポリマー（Ａ）、シリカ粒子（Ｂ）、ポリグリセリン脂肪酸エステル（Ｃ）と油成分（Ｄ）の合計量に対して、５～９９質量％であることが好ましく、１０～９９質量％であることがより好ましく、２０～９８質量％であることが更により好ましい。 In the oil component thickening method of the present invention, the oil component is based on the total amount of (PPG-12/SMDI) copolymer (A), silica particles (B), polyglycerin fatty acid ester (C) and oil component (D) to be mixed. The amount of (D) is not particularly limited, but from the viewpoint of thickening the oil component more significantly, the amount of (PPG-12/SMDI) copolymer (A) to be mixed, silica particles (B), polyglycerin fatty acid ester (C ) and the oil component (D), preferably from 5 to 99% by mass, more preferably from 10 to 99% by mass, and even more preferably from 20 to 98% by mass.
　本発明の油成分の増粘方法において、油成分に混合する（ＰＰＧ－１２／ＳＭＤＩ）コポリマー（Ａ）とシリカ粒子（Ｂ）の量の比率は特に限定されないが、より顕著に油成分を増粘する観点からは、油成分（Ｄ）に混合する（ＰＰＧ－１２／ＳＭＤＩ）コポリマー（Ａ）とシリカ粒子（Ｂ）の比率は、質量比で１：０．００５～１：２００であることが好ましく、１：０．０５～１：２０であることがより好ましく、１：０．１～１：１０であることが更により好ましく、１：０．２～１：５であることが特に好ましい。 In the method for thickening an oil component of the present invention, the ratio of the amounts of the (PPG-12/SMDI) copolymer (A) and silica particles (B) to be mixed into the oil component is not particularly limited, but it is possible to increase the viscosity of the oil component more significantly. From the viewpoint of viscosity, the ratio of the (PPG-12/SMDI) copolymer (A) and silica particles (B) to be mixed in the oil component (D) should be 1:0.005 to 1:200 in terms of mass ratio. is preferable, 1:0.05 to 1:20 is more preferable, 1:0.1 to 1:10 is even more preferable, and 1:0.2 to 1:5 is particularly preferable. preferable.
　本発明の油成分の増粘方法において、油成分（Ｄ）に混合する（ＰＰＧ－１２／ＳＭＤＩ）コポリマー（Ａ）とポリグリセリン脂肪酸エステル（Ｃ）の量の比率は特に限定されないが、より顕著に油成分を増粘する観点からは、油成分（Ｄ）に混合する（ＰＰＧ－１２／ＳＭＤＩ）コポリマー（Ａ）とポリグリセリン脂肪酸エステル（Ｃ）の比率は、質量比で１：０．０５～１：５００であることが好ましく、１：０．５～１：１００であることがより好ましく、１：２～１：５０であることが更により好ましく、１：５～１：２０であることが特に好ましい。 In the method for thickening an oil component of the present invention, the ratio of the amounts of the (PPG-12/SMDI) copolymer (A) and polyglycerin fatty acid ester (C) to be mixed into the oil component (D) is not particularly limited, but is more pronounced. From the viewpoint of thickening the oil component, the ratio of the (PPG-12/SMDI) copolymer (A) and polyglycerin fatty acid ester (C) to be mixed into the oil component (D) is 1:0.05 by mass. The ratio is preferably 1:500 to 1:500, more preferably 1:0.5 to 1:100, even more preferably 1:2 to 1:50, and 1:5 to 1:20. It is particularly preferable.
　本発明の油成分の増粘方法において、油成分（Ｄ）に混合するシリカ粒子（Ｂ）とポリグリセリン脂肪酸エステル（Ｃ）の量の比率は特に限定されないが、より顕著に油成分を増粘する観点からは、油成分（Ｄ）に混合するシリカ粒子（Ｂ）とポリグリセリン脂肪酸エステル（Ｃ）の比率は、質量比で１：０．５～１：２００であることが好ましく、１：１～１：１００であることがより好ましく、１：２～１：５０であることが更により好ましく、１：３～１：２０であることが特に好ましい。 In the method for thickening an oil component of the present invention, the ratio of the amounts of silica particles (B) and polyglycerin fatty acid ester (C) to be mixed into the oil component (D) is not particularly limited, but it thickens the oil component more significantly. From the viewpoint of The ratio is more preferably 1 to 1:100, even more preferably 1:2 to 1:50, and particularly preferably 1:3 to 1:20.
　本発明の油成分の増粘方法において、油成分（Ｄ）に混合する（ＰＰＧ－１２／ＳＭＤＩ）コポリマー（Ａ）とシリカ粒子（Ｂ）の合計量に対するポリグリセリン脂肪酸エステル（Ｃ）の量の比率は特に限定されないが、より顕著に油成分を増粘する観点からは、油成分（Ｄ）に混合する（ＰＰＧ－１２／ＳＭＤＩ）コポリマー（Ａ）とシリカ粒子（Ｂ）の合計量とポリグリセリン脂肪酸エステル（Ｃ）の量との比率は、質量比で１：０．４～１：１００であることが好ましく、１：０．８～１：５０であることがより好ましく、１：１～１：３０であることが更により好ましく、１：２～１：１５であることが特に好ましい。 In the method for thickening an oil component of the present invention, the amount of polyglycerol fatty acid ester (C) is determined based on the total amount of (PPG-12/SMDI) copolymer (A) and silica particles (B) mixed into oil component (D). Although the ratio is not particularly limited, from the viewpoint of thickening the oil component more significantly, the total amount of the (PPG-12/SMDI) copolymer (A) and silica particles (B) to be mixed into the oil component (D) and the poly The ratio to the amount of glycerin fatty acid ester (C) is preferably 1:0.4 to 1:100 in mass ratio, more preferably 1:0.8 to 1:50, and 1:1. The ratio is even more preferably 1:30 to 1:30, and particularly preferably 1:2 to 1:15.
　本発明の油成分の増粘方法において、油成分（Ｄ）に混合する（ＰＰＧ－１２／ＳＭＤＩ）コポリマー（Ａ）とポリグリセリン脂肪酸エステル（Ｃ）の合計量に対するシリカ粒子（Ｂ）の量の比率は特に限定されないが、より顕著に油成分を増粘する観点からは、油成分（Ｄ）に混合する（ＰＰＧ－１２／ＳＭＤＩ）コポリマー（Ａ）とポリグリセリン脂肪酸エステル（Ｃ）の合計量とシリカ粒子（Ｂ）の量との比率は、質量比で１：０．００５～１：１５であることが好ましく、１：０．０１～１：５であることがより好ましく、１：０．０２～１：１であることが更により好ましく、１：０．０４～１：０．５であることが特に好ましい。 In the method for thickening an oil component of the present invention, the amount of silica particles (B) relative to the total amount of (PPG-12/SMDI) copolymer (A) and polyglycerol fatty acid ester (C) to be mixed into the oil component (D). Although the ratio is not particularly limited, from the viewpoint of thickening the oil component more significantly, the total amount of the (PPG-12/SMDI) copolymer (A) and polyglycerin fatty acid ester (C) to be mixed into the oil component (D). The ratio of the amount of silica particles (B) to the amount of silica particles (B) is preferably 1:0.005 to 1:15, more preferably 1:0.01 to 1:5, and 1:0 by mass. The ratio is even more preferably from .02 to 1:1, and particularly preferably from 1:0.04 to 1:0.5.
　本発明の油成分の増粘方法において、油成分（Ｄ）に混合するシリカ粒子（Ｂ）とポリグリセリン脂肪酸エステル（Ｃ）の合計量に対する（ＰＰＧ－１２／ＳＭＤＩ）コポリマー（Ａ）の量の比率は特に限定されないが、より顕著に油成分を増粘する観点からは、油成分に混合するシリカ粒子（Ｂ）とポリグリセリン脂肪酸エステル（Ｃ）の合計量と（ＰＰＧ－１２／ＳＭＤＩ）コポリマー（Ａ）の量との比率は、質量比で１：０．００５～１：１５であることが好ましく、１：０．０１～１：５であることがより好ましく、１：０．０２～１：１であることが更により好ましく、１：０．０４～１：０．５であることが特に好ましい。 In the method for thickening an oil component of the present invention, the amount of (PPG-12/SMDI) copolymer (A) relative to the total amount of silica particles (B) and polyglycerin fatty acid ester (C) to be mixed in the oil component (D). Although the ratio is not particularly limited, from the viewpoint of thickening the oil component more significantly, the total amount of silica particles (B) and polyglycerin fatty acid ester (C) to be mixed into the oil component and the (PPG-12/SMDI) copolymer The ratio to the amount of (A) is preferably 1:0.005 to 1:15, more preferably 1:0.01 to 1:5, and 1:0.02 to 1:15 by mass. The ratio is even more preferably 1:1, and particularly preferably 1:0.04 to 1:0.5.
　上記油成分に（ＰＰＧ－１２／ＳＭＤＩ）コポリマー（Ａ）、シリカ粒子（Ｂ）、ポリグリセリン脂肪酸エステル（Ｃ）を油成分（Ｄ）に混合する場合は、（Ａ）、（Ｂ）、（Ｃ）成分をそれぞれ別々に添加してもよく、これらの成分のうちの２種以上を予め混合した後、混合液を油成分（Ｄ）に添加してもよい。また、後述するように、（ＰＰＧ－１２／ＳＭＤＩ）コポリマー（Ａ）を含む増粘剤組成物を調製し、増粘剤組成物をシリカ粒子（Ｂ）とポリグリセリン脂肪酸エステル（Ｃ）共に、油成分（Ｄ）に混合してもよい。 When (PPG-12/SMDI) copolymer (A), silica particles (B), and polyglycerin fatty acid ester (C) are mixed into the oil component (D), (A), (B), ( The components C) may be added separately, or two or more of these components may be mixed in advance, and then the mixed liquid may be added to the oil component (D). Further, as described below, a thickener composition containing the (PPG-12/SMDI) copolymer (A) was prepared, and the thickener composition was added to both the silica particles (B) and the polyglycerol fatty acid ester (C). It may be mixed with the oil component (D).
　本発明の油成分の増粘方法によれば、エステル油、炭化水素油及びシリコーン油から選ばれる１種又は２種以上の油成分を顕著に増粘することができ、このような油成分を含む塗料、洗浄剤、接着剤、化粧品、医薬品、農薬、インク、染料等に本方法を用いたときに、それぞれの製品に適した粘度に容易に調整することができる。特に、本発明の油成分の増粘方法を用いて化粧料組成物を調製すると、使用に適した粘度を有する化粧料組成物とすることが容易にできるため好ましい。 According to the method for thickening oil components of the present invention, it is possible to significantly thicken one or more oil components selected from ester oils, hydrocarbon oils, and silicone oils. When this method is used for paints, cleaning agents, adhesives, cosmetics, pharmaceuticals, agricultural chemicals, inks, dyes, etc., the viscosity can be easily adjusted to suit each product. In particular, it is preferable to prepare a cosmetic composition using the method of thickening an oil component of the present invention, since the cosmetic composition can easily have a viscosity suitable for use.
２．増粘剤組成物
　本発明の増粘剤組成物は、シリカ粒子（Ｂ）と、グリセリンの重合度が２～２０であるポリグリセリンと炭素原子数が８～２０である脂肪酸とのモノエステル又はジエステルであるポリグリセリン脂肪酸エステル（Ｃ）と共に、エステル油、炭化水素油及びシリコーン油から選ばれる１種又は２種以上の油成分（Ｄ）に混合するための、（ＰＰＧ－１２／ＳＭＤＩ）コポリマー（Ａ）を含む増粘剤組成物である。 2. Thickener Composition The thickener composition of the present invention is a monoester of silica particles (B), polyglycerin having a polymerization degree of glycerin of 2 to 20, and fatty acid having 8 to 20 carbon atoms, or (PPG-12/SMDI) copolymer for mixing with polyglycerin fatty acid ester (C), which is a diester, into one or more oil components (D) selected from ester oil, hydrocarbon oil, and silicone oil. A thickener composition containing (A).
　（ＰＰＧ－１２／ＳＭＤＩ）コポリマー（Ａ）を含む増粘剤組成物における（ＰＰＧ－１２／ＳＭＤＩ）コポリマー（Ａ）の濃度は特に限定されないが、より顕著に油成分を増粘する観点からは、増粘剤組成物全量に対して１０～１００質量％であることが好ましく、５０～１００質量％であることがより好ましい。
　また、増粘剤組成物は、増粘剤組成物に一般的に含まれる成分を含んでもよく、また、ＰＰＧ－１２とＳＭＤＩを反応させる際に用いることができる乳化剤、鎖延長剤、溶媒、又は触媒等を含んでもよい。 The concentration of the (PPG-12/SMDI) copolymer (A) in the thickener composition containing the (PPG-12/SMDI) copolymer (A) is not particularly limited, but from the viewpoint of thickening the oil component more significantly, The content is preferably 10 to 100% by mass, more preferably 50 to 100% by mass, based on the total amount of the thickener composition.
The thickener composition may also contain components commonly included in thickener compositions, such as emulsifiers, chain extenders, solvents, etc. that can be used when reacting PPG-12 and SMDI. Alternatively, it may contain a catalyst or the like.
　本発明の増粘剤組成物によれば、シリカ粒子（Ｂ）とポリグリセリン脂肪酸エステル（Ｃ）と共にエステル油、炭化水素油及びシリコーン油から選ばれる１種又は２種以上の油成分に混合することで、油成分（Ｄ）を顕著に増粘することができる。 According to the thickener composition of the present invention, the silica particles (B) and the polyglycerol fatty acid ester (C) are mixed into one or more oil components selected from ester oil, hydrocarbon oil, and silicone oil. By doing so, the viscosity of the oil component (D) can be significantly increased.
　本発明の油成分含有組成物は、前述した油成分を増粘する方法を用いて得られる油成分含有組成物であり、具体的には、（ＰＰＧ－１２／ＳＭＤＩ）コポリマー（Ａ）と、シリカ粒子（Ｂ）と、グリセリンの重合度が２～２０であるポリグリセリンと炭素原子数が８～２０である脂肪酸とのモノエステル又はジエステルであるポリグリセリン脂肪酸エステル（Ｃ）とを、エステル油、炭化水素油及びシリコーン油から選ばれる１種又は２種以上の油成分（Ｄ）に混合することにより油成分を増粘して得られる油成分含有組成物であり、（ＰＰＧ－１２／ＳＭＤＩ）コポリマー（Ａ）、シリカ粒子（Ｂ）、ポリグリセリン脂肪酸エステル（Ｃ）、及び油成分（Ｄ）を少なくとも含有する。 The oil component-containing composition of the present invention is an oil component-containing composition obtained using the above-described method of thickening an oil component, and specifically includes (PPG-12/SMDI) copolymer (A), The silica particles (B) and the polyglycerin fatty acid ester (C), which is a monoester or diester of polyglycerin having a polymerization degree of 2 to 20 and a fatty acid having 8 to 20 carbon atoms, are added to an ester oil. , an oil component-containing composition obtained by thickening an oil component by mixing it with one or more oil components (D) selected from hydrocarbon oils and silicone oils, (PPG-12/SMDI ) Contains at least a copolymer (A), a silica particle (B), a polyglycerin fatty acid ester (C), and an oil component (D).
３．油成分含有組成物
　本発明の油成分含有組成物は、（ＰＰＧ－１２／ＳＭＤＩ）コポリマー（Ａ）と、シリカ粒子（Ｂ）と、グリセリンの重合度が２～２０であるポリグリセリンと炭素原子数が８～２０である脂肪酸とのモノエステル又はジエステルであるポリグリセリン脂肪酸エステル（Ｃ）と、エステル油、炭化水素油及びシリコーン油から選ばれる１種又は２種以上の油成分（Ｄ）と、を含む。 3. Oil component-containing composition The oil component-containing composition of the present invention comprises a (PPG-12/SMDI) copolymer (A), silica particles (B), polyglycerin whose polymerization degree is 2 to 20, and carbon atoms. A polyglycerin fatty acid ester (C) that is a monoester or diester with a fatty acid having a number of 8 to 20, and one or more oil components (D) selected from ester oils, hydrocarbon oils, and silicone oils. ,including.
　本発明の油成分含有組成物は、化粧料組成物として好適に用いられる。本発明の化粧料組成物中の、（ＰＰＧ－１２／ＳＭＤＩ）コポリマー（Ａ）、シリカ粒子（Ｂ）、ポリグリセリン脂肪酸エステル（Ｃ）、及び油成分（Ｄ）のそれぞれの含有量及び含有比率は、前述した油成分の増粘方法において用いる各成分の含有量及び含有比率とすることができる。 The oil component-containing composition of the present invention is suitably used as a cosmetic composition. Contents and content ratios of (PPG-12/SMDI) copolymer (A), silica particles (B), polyglycerin fatty acid ester (C), and oil component (D) in the cosmetic composition of the present invention can be the content and content ratio of each component used in the oil component thickening method described above.
　本発明の化粧料組成物中の（ＰＰＧ－１２／ＳＭＤＩ）コポリマー（Ａ）の含有量は特に限定されず、目的に応じて調整することができるが、化粧料組成物全量に対して０．０１～２０質量％であることが好ましく、０．１～１５質量％であることがより好ましく、０．２～１０質量％であることが更により好ましい。 The content of the (PPG-12/SMDI) copolymer (A) in the cosmetic composition of the present invention is not particularly limited, and can be adjusted depending on the purpose, but it is 0.00% based on the total amount of the cosmetic composition. It is preferably from 0.01 to 20% by weight, more preferably from 0.1 to 15% by weight, and even more preferably from 0.2 to 10% by weight.
　本発明の化粧料組成物中のシリカ粒子（Ｂ）の含有量は特に限定されず、目的に応じて調整することができるが、化粧料組成物全量に対して０．０１～２０質量％であることが好ましく、０．１～１５質量％であることがより好ましく、０．２～１０質量％であることが更により好ましい。 The content of silica particles (B) in the cosmetic composition of the present invention is not particularly limited and can be adjusted depending on the purpose, but it is 0.01 to 20% by mass based on the total amount of the cosmetic composition. It is preferably from 0.1 to 15% by weight, even more preferably from 0.2 to 10% by weight.
　本発明の化粧料組成物中のポリグリセリン脂肪酸エステル（Ｃ）の含有量は特に限定されず、目的に応じて調整することができるが、化粧料組成物全量に対して０．１～５０質量％であることが好ましく、１．０～４０質量％であることがより好ましく、２．０～３０質量％であることが更により好ましい。 The content of polyglycerol fatty acid ester (C) in the cosmetic composition of the present invention is not particularly limited and can be adjusted depending on the purpose, but it is 0.1 to 50% by mass based on the total amount of the cosmetic composition. %, more preferably 1.0 to 40% by weight, even more preferably 2.0 to 30% by weight.
　本発明の化粧料組成物中の油成分（Ｄ）の含有量は特に限定されず、目的に応じて調整することができるが、化粧料組成物全量に対して１～９０質量％であることが好ましく、２～９０質量％であることがより好ましく、３～８０質量％であることが更により好ましい。 The content of the oil component (D) in the cosmetic composition of the present invention is not particularly limited and can be adjusted depending on the purpose, but it should be 1 to 90% by mass based on the total amount of the cosmetic composition. It is preferably 2 to 90% by mass, more preferably 3 to 80% by mass.
　本発明の化粧料組成物の具体的な化粧料の種類は特に限定されず、例えば、シャンプーやリンス等のトイレタリー製品も含まれ、例えば、化粧水、化粧液、乳液、クリーム、洗顔フォーム、クレンジングミルク、クレンジングローション、養毛剤、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、口紅、パック、ファンデーション、オーデコロン、シャンプー、リンス、トリートメント、サンスクリーン、防臭剤、香水、クレンジングオイル及び化粧オイル等が挙げられる。 The specific type of cosmetics of the cosmetic composition of the present invention is not particularly limited, and includes toiletry products such as shampoos and conditioners, such as lotions, lotions, milky lotions, creams, facial cleansing foams, and cleansing products. Milk, cleansing lotion, hair tonic, hair liquid, setting lotion, hair bleach, color rinse, permanent wave liquid, lipstick, face pack, foundation, cologne, shampoo, conditioner, treatment, sunscreen, deodorant, perfume, cleansing oil, and cosmetic oil etc.
　本発明の化粧料組成物は、（ＰＰＧ－１２／ＳＭＤＩ）コポリマー（Ａ）と、シリカ粒子（Ｂ）と、ポリグリセリン脂肪酸エステル（Ｃ）とを、油成分（Ｄ）に混合する際、又は混合した後に、目的に応じて、保存時、使用時、使用後にて各種特性（溶解性、分散性、安定性、使用感、塗布性、浸透性、保湿性、安全性、意匠性、光学特性、芳香性、美白性等）を向上又は改善させるために、化粧料組成物で一般に使用されるその他の添加剤を更に混合して得られた化粧料組成物であってもよい。また、その他の添加剤を混合した油成分を用いて得られた化粧料組成物であってもよい。その他の添加剤としては、例えば、ロウ、粉末成分（シリカ粒子（Ｂ）を除く）、高級脂肪酸、アニオン界面活性剤、カチオン界面活性剤、両性界面活性剤、非イオン界面活性剤（ポリグリセリン脂肪酸エステル（Ｃ）を除く）、保湿剤、水溶性高分子、キレート剤、低級アルコール、多価アルコール、糖、アミノ酸及びその誘導体、有機アミン、ｐＨ調整剤、ビタミン、酸化防止剤、その他の配合可能成分等が挙げられ、これらの中から１種又は２種以上を任意に配合することができる。 The cosmetic composition of the present invention can be prepared by mixing a (PPG-12/SMDI) copolymer (A), silica particles (B), and a polyglycerin fatty acid ester (C) into an oil component (D), or After mixing, various properties (solubility, dispersibility, stability, usability, applicability, permeability, moisture retention, safety, design, optical properties) are determined depending on the purpose during storage, during use, and after use. The cosmetic composition may also be obtained by further mixing other additives commonly used in cosmetic compositions in order to enhance or improve the cosmetic composition, fragrance, whitening properties, etc.). Alternatively, the cosmetic composition may be obtained using an oil component mixed with other additives. Other additives include, for example, wax, powder components (excluding silica particles (B)), higher fatty acids, anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants (polyglycerin fatty acids (excluding ester (C)), humectants, water-soluble polymers, chelating agents, lower alcohols, polyhydric alcohols, sugars, amino acids and their derivatives, organic amines, pH adjusters, vitamins, antioxidants, and other ingredients can be added. One or more of these components may be optionally blended.
　ロウとしては、例えば、ミツロウ、カンデリラロウ、綿ロウ、カルナウバロウ、ベイベリーロウ、イボタロウ、鯨ロウ、モンタンロウ、ヌカロウ、ラノリン、カポックロウ、酢酸ラノリン、液状ラノリン、サトウキビロウ、ラノリン脂肪酸イソプロピル、還元ラノリン、ジョジョバロウ、硬質ラノリン、セラックロウ、ＰＯＥラノリンアルコールエーテル、ＰＯＥラノリンアルコールアセテート、ＰＯＥコレステロールエーテル、ラノリン脂肪酸ポリエチレングリコール、ＰＯＥ水素添加ラノリンアルコールエーテル等が挙げられる。 Examples of the wax include beeswax, candelilla wax, cotton wax, carnauba wax, bayberry wax, privet wax, spermaceti wax, montan wax, bran wax, lanolin, kapok wax, acetic acid lanolin, liquid lanolin, sugarcane wax, lanolin fatty acid isopropyl, reduced lanolin, jojoba wax, and hard wax. Examples include lanolin, shellac wax, POE lanolin alcohol ether, POE lanolin alcohol acetate, POE cholesterol ether, lanolin fatty acid polyethylene glycol, and POE hydrogenated lanolin alcohol ether.
　粉末成分としては、例えば、無機粉末（例えば、タルク、カオリン、雲母、絹雲母（セリサイト）、白雲母、金雲母、合成雲母、紅雲母、黒雲母、パーミキュライト、炭酸マグネシウム、炭酸カルシウム、ケイ酸アルミニウム、ケイ酸バリウム、ケイ酸カルシウム、ケイ酸マグネシウム、ケイ酸ストロンチウム、タングステン酸金属塩、マグネシウム、ゼオライト、硫酸バリウム、焼成硫酸カルシウム（焼セッコウ）、リン酸カルシウム、弗素アパタイト、ヒドロキシアパタイト、セラミックパウダー、金属石鹸（例えば、ミリスチン酸亜鉛、パルミチン酸カルシウム、ステアリン酸アルミニウム）、窒化ホウ素等）；有機粉末（例えば、ポリアミド樹脂粉末（ナイロン粉末）、ポリエチレン粉末、ポリメタクリル酸メチル粉末、ポリスチレン粉末、スチレンとアクリル酸の共重合体樹脂粉末、ベンゾグアナミン樹脂粉末、ポリ四弗化エチレン粉末、セルロース粉末等）；無機白色顔料（例えば、二酸化チタン、酸化亜鉛等）；無機赤色系顔料（例えば、酸化鉄（ベンガラ）、チタン酸鉄等）；無機褐色系顔料（例えば、γ－酸化鉄等）；無機黄色系顔料（例えば、黄酸化鉄、黄土等）；無機黒色系顔料（例えば、黒酸化鉄、低次酸化チタン等）；無機紫色系顔料（例えば、マンガンバイオレット、コバルトバイオレット等）；無機緑色系顔料（例えば、酸化クロム、水酸化クロム、チタン酸コバルト等）；無機青色系顔料（例えば、群青、紺青等）；パール顔料（例えば、酸化チタンコーテッドマイカ、酸化チタンコーテッドオキシ塩化ビスマス、酸化チタンコーテッドタルク、着色酸化チタンコーテッドマイカ、オキシ塩化ビスマス、魚鱗箔等）；金属粉末顔料（例えば、アルミニウムパウダー、カッパーパウダー等）；ジルコニウム、バリウム又はアルミニウムレーキ等の有機顔料（例えば、赤色２０１号、赤色２０２号、赤色２０４号、赤色２０５号、赤色２２０号、赤色２２６号、赤色２２８号、赤色４０５号、橙色２０３号、橙色２０４号、黄色２０５号、黄色４０１号、及び青色４０４号等の有機顔料、赤色３号、赤色１０４号、赤色１０６号、赤色２２７号、赤色２３０号、赤色４０１号、赤色５０５号、橙色２０５号、黄色４号、黄色５号、黄色２０２号、黄色２０３号、緑色３号及び青色１号等）；天然色素（例えば、クロロフィル、β－カロチン等）等が挙げられる。 Examples of powder components include inorganic powders (such as talc, kaolin, mica, sericite, muscovite, phlogopite, synthetic mica, rhodochite, biotite, permiculite, magnesium carbonate, calcium carbonate, and silicic acid). Aluminum, barium silicate, calcium silicate, magnesium silicate, strontium silicate, metal tungstate, magnesium, zeolite, barium sulfate, calcined calcium sulfate (calcined gypsum), calcium phosphate, fluoroapatite, hydroxyapatite, ceramic powder, metal soaps (e.g. zinc myristate, calcium palmitate, aluminum stearate), boron nitride, etc.); organic powders (e.g. polyamide resin powder (nylon powder), polyethylene powder, polymethyl methacrylate powder, polystyrene powder, styrene and acrylic Acid copolymer resin powder, benzoguanamine resin powder, polytetrafluoroethylene powder, cellulose powder, etc.); Inorganic white pigments (e.g., titanium dioxide, zinc oxide, etc.); Inorganic red pigments (e.g., iron oxide (red iron oxide)) , iron titanate, etc.); Inorganic brown pigments (e.g., γ-iron oxide, etc.); Inorganic yellow pigments (e.g., yellow iron oxide, ocher, etc.); Inorganic black pigments (e.g., black iron oxide, lower oxidation titanium, etc.); inorganic purple pigments (e.g., manganese violet, cobalt violet, etc.); inorganic green pigments (e.g., chromium oxide, chromium hydroxide, cobalt titanate, etc.); inorganic blue pigments (e.g., ultramarine, navy blue, etc.) ); Pearl pigments (e.g. titanium oxide coated mica, titanium oxide coated bismuth oxychloride, titanium oxide coated talc, colored titanium oxide coated mica, bismuth oxychloride, fish scale foil, etc.); Metal powder pigments (e.g. aluminum powder, copper powder) etc.); organic pigments such as zirconium, barium or aluminum lake (e.g. Red No. 201, Red No. 202, Red No. 204, Red No. 205, Red No. 220, Red No. 226, Red No. 228, Red No. 405, Orange 203); organic pigments such as Orange No. 204, Yellow No. 205, Yellow No. 401, and Blue No. 404, Red No. 3, Red No. 104, Red No. 106, Red No. 227, Red No. 230, Red No. 401, and Red No. 505. , Orange No. 205, Yellow No. 4, Yellow No. 5, Yellow No. 202, Yellow No. 203, Green No. 3, Blue No. 1, etc.); and natural pigments (for example, chlorophyll, β-carotene, etc.).
　高級脂肪酸としては、例えば、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、ベヘニン酸、オレイン酸、ウンデシレン酸、トール油脂肪酸、イソステアリン酸、リノール酸、リノレイン酸、エイコサペンタエン酸（ＥＰＡ）、ドコサヘキサエン酸（ＤＨＡ）等が挙げられる。 Examples of higher fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, undecylenic acid, tall oil fatty acid, isostearic acid, linoleic acid, linoleic acid, eicosapentaenoic acid (EPA), and docosahexaenoic acid. (DHA) and the like.
　高級アルコールとしては、例えば、直鎖アルコール（例えば、ラウリルアルコール、セチルアルコール、ステアリルアルコール、ベヘニルアルコール、ミリスチルアルコール、オレイルアルコール、セトステアリルアルコール等）；分枝鎖アルコール（例えば、２－デシルテトラデシノール、ラノリンアルコール、コレステロール、フィトステロール、ヘキシルドデカノール、イソステアリルアルコール、オクチルドデカノール等）等が挙げられる。 Examples of higher alcohols include straight chain alcohols (for example, lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, cetostearyl alcohol, etc.); branched chain alcohols (for example, 2-decyltetradecinol, lanolin alcohol, cholesterol, phytosterol, hexyldodecanol, isostearyl alcohol, octyldodecanol, etc.).
　アニオン界面活性剤としては、例えば、脂肪酸セッケン（例えば、ラウリン酸ナトリウム、パルミチン酸ナトリウム等）；高級アルキル硫酸エステル塩（例えば、ラウリル硫酸ナトリウム、ラウリル硫酸カリウム等）；アルキルエーテル硫酸エステル塩（例えば、ＰＯＥ－ラウリル硫酸トリエタノールアミン、ＰＯＥ－ラウリル硫酸ナトリウム等）；Ｎ－アシルサルコシン酸（例えば、ラウロイルサルコシンナトリウム等）；高級脂肪酸アミドスルホン酸塩（例えば、Ｎ－ミリストイル－Ｎ－メチルタウリンナトリウム、ヤシ油脂肪酸メチルタウリンナトリウム、ラウリルメチルタウリンナトリウム等）；リン酸エステル塩（ＰＯＥ－オレイルエーテルリン酸ナトリウム、ＰＯＥ－ステアリルエーテルリン酸等）；スルホコハク酸塩（例えば、ジ－２－エチルヘキシルスルホコハク酸ナトリウム、モノラウロイルモノエタノールアミドポリオキシエチレンスルホコハク酸ナトリウム、ラウリルポリプロピレングリコールスルホコハク酸ナトリウム等）；アルキルベンゼンスルホン酸塩（例えば、リニアドデシルベンゼンスルホン酸ナトリウム、リニアドデシルベンゼンスルホン酸トリエタノールアミン、リニアドデシルベンゼンスルホン酸等）；高級脂肪酸エステル硫酸エステル塩（例えば、硬化ヤシ油脂肪酸グリセリン硫酸ナトリウム等）；Ｎ－アシルグルタミン酸塩（例えば、Ｎ－ラウロイルグルタミン酸モノナトリウム、Ｎ－ステアロイルグルタミン酸ジナトリウム、Ｎ－ミリストイル－Ｌ－グルタミン酸モノナトリウム等）；硫酸化油（例えば、ロート油等）；ＰＯＥ－アルキルエーテルカルボン酸；ＰＯＥ－アルキルアリルエーテルカルボン酸塩；α－オレフィンスルホン酸塩；高級脂肪酸エステルスルホン酸塩；二級アルコール硫酸エステル塩；高級脂肪酸アルキロールアミド硫酸エステル塩；ラウロイルモノエタノールアミドコハク酸ナトリウム；Ｎ－パルミトイルアスパラギン酸ジトリエタノールアミン；カゼインナトリウム等が挙げられる。 Examples of anionic surfactants include fatty acid soaps (e.g., sodium laurate, sodium palmitate, etc.); higher alkyl sulfate salts (e.g., sodium lauryl sulfate, potassium lauryl sulfate, etc.); alkyl ether sulfate salts (e.g., POE-triethanolamine lauryl sulfate, POE-sodium lauryl sulfate, etc.); N-acyl sarcosinate (e.g. sodium lauroyl sarcosine, etc.); Higher fatty acid amide sulfonates (e.g. sodium myristoyl-N-methyltaurate, oil fatty acid methyl taurate sodium, lauryl methyl taurate sodium, etc.); phosphate ester salts (POE-sodium oleyl ether phosphate, POE-stearyl ether phosphate, etc.); sulfosuccinates (for example, sodium di-2-ethylhexyl sulfosuccinate, monolauroyl monoethanolamide polyoxyethylene sodium sulfosuccinate, lauryl polypropylene glycol sodium sulfosuccinate, etc.); alkylbenzene sulfonates (e.g., sodium linear dodecylbenzenesulfonate, linear dodecylbenzenesulfonic acid triethanolamine, linear dodecylbenzenesulfonic acid, etc.) ); higher fatty acid ester sulfate salts (e.g. hydrogenated coconut oil fatty acid sodium glycerol sulfate, etc.); N-acylglutamates (e.g. monosodium N-lauroylglutamate, disodium N-stearoylglutamate, N-myristoyl-L-glutamic acid); monosodium, etc.); sulfated oil (e.g., funnel oil, etc.); POE-alkyl ether carboxylic acid; POE-alkyl allyl ether carboxylate; α-olefin sulfonate; higher fatty acid ester sulfonate; secondary alcohol sulfuric acid Examples include ester salts; higher fatty acid alkylolamide sulfate ester salts; sodium lauroyl monoethanolamide succinate; N-palmitoylaspartic acid ditriethanolamine; sodium caseinate and the like.
　カチオン界面活性剤としては、例えば、アルキルトリメチルアンモニウム塩（例えば、塩化ステアリルトリメチルアンモニウム、塩化ラウリルトリメチルアンモニウム等）；アルキルピリジニウム塩（例えば、塩化セチルピリジニウム等）；ジアルキルジメチルアンモニウム塩（塩化ジステアリルジメチルアンモニウム等）；アルキル四級アンモニウム塩；アルキルジメチルベンジルアンモニウム塩；アルキルイソキノリニウム塩；ジアルキルモルホリニウム塩；ＰＯＥ－アルキルアミン；アルキルアミン塩；アミルアルコール脂肪酸誘導体；塩化ベンザルコニウム；塩化ベンゼトニウム等が挙げられる。 Examples of cationic surfactants include alkyltrimethylammonium salts (e.g., stearyltrimethylammonium chloride, lauryltrimethylammonium chloride, etc.); alkylpyridinium salts (e.g., cetylpyridinium chloride, etc.); dialkyldimethylammonium salts (distearyldimethylammonium chloride, etc.); etc.); Alkyl quaternary ammonium salt; Alkyldimethylbenzylammonium salt; Alkylisoquinolinium salt; Dialkylmorpholinium salt; POE-alkylamine; Alkylamine salt; Amyl alcohol fatty acid derivative; Benzalkonium chloride; Benzethonium chloride, etc. can be mentioned.
　両性界面活性剤としては、例えば、イミダゾリン系両性界面活性剤（例えば、２－ウンデシル－Ｎ，Ｎ，Ｎ－（ヒドロキシエチルカルボキシメチル）－２－イミダゾリンナトリウム、２－ココイル－２－イミダゾリニウムヒドロキサイド－１－カルボキシエチロキシ２ナトリウム塩等）；ベタイン系界面活性剤（例えば、２－アルキル－Ｎ－カルボキシメチル－Ｎ－ヒドロキシエチルイミダゾリニウムベタイン（ココアンホ酢酸Ｎａ）、ラウリルジメチルアミノ酢酸ベタイン、アルキルベタイン、アミドベタイン、スルホベタイン等）等が挙げられる。 Examples of amphoteric surfactants include imidazoline-based amphoteric surfactants (for example, 2-undecyl-N,N,N-(hydroxyethylcarboxymethyl)-2-imidazoline sodium, 2-cocoyl-2-imidazolinium hydroxide), side-1-carboxyethyloxy disodium salt, etc.); betaine surfactants (for example, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine (sodium cocoamphoacetate), lauryldimethylaminoacetic acid betaine, Alkylbetaine, amidobetaine, sulfobetaine, etc.).
　非イオン界面活性剤としては、例えば、ソルビタン脂肪酸エステル類（例えば、ソルビタンモノオレエート、ソルビタンモノイソステアレート、ソルビタンモノラウレート、ソルビタンモノパルミテート、ソルビタンモノステアレート、ソルビタンセスキオレエート、ソルビタントリオレエート、ペンタ－２－エチルヘキシル酸ジグリセロールソルビタン、テトラ－２－エチルヘキシル酸ジグリセロールソルビタン等）；プロピレングリコール脂肪酸エステル類（例えば、モノステアリン酸プロピレングリコール等）；硬化ヒマシ油誘導体；グリセリンアルキルエーテル；ＰＯＥ－ソルビタン脂肪酸エステル類（例えば、ＰＯＥ－ソルビタンモノオレエート、ＰＯＥ－ソルビタンモノステアレート、ＰＯＥ－ソルビタンテトラオレエート等）；ＰＯＥソルビット脂肪酸エステル類（例えば、ＰＯＥ－ソルビットモノラウレート、ＰＯＥ－ソルビットモノオレエート、ＰＯＥ－ソルビットペンタオレエート、ＰＯＥ－ソルビットモノステアレート等）；ＰＯＥ－グリセリン脂肪酸エステル類（例えば、ＰＯＥ－グリセリンモノステアレート、ＰＯＥ－グリセリンモノイソステアレート、ＰＯＥ－グリセリントリイソステアレート等）；ＰＯＥ－脂肪酸エステル類（例えば、ＰＯＥ－ジステアレート、ＰＯＥ－モノジオレエート、ジステアリン酸エチレングリコール等）；ＰＯＥ－アルキルエーテル類（例えば、ＰＯＥ－ラウリルエーテル、ＰＯＥ－オレイルエーテル、ＰＯＥ－ステアリルエーテル、ＰＯＥ－ベヘニルエーテル、ＰＯＥ－２－オクチルドデシルエーテル、ＰＯＥ－コレスタノールエーテル等）；プルロニック（登録商標）型類（例えば、プルロニック（登録商標）等）；ＰＯＥ／ＰＯＰ－アルキルエーテル類（例えば、ＰＯＥ／ＰＯＰ－セチルエーテル、ＰＯＥ／ＰＯＰ－２－デシルテトラデシルエーテル、ＰＯＥ／ＰＯＰ－モノブチルエーテル、ＰＯＥ／ＰＯＰ－水添ラノリン、ＰＯＥ／ＰＯＰ－グリセリンエーテル等）；テトラＰＯＥ／テトラＰＯＰ－エチレンジアミン縮合物類（例えば、テトロニック等）；ＰＯＥ－ヒマシ油硬化ヒマシ油誘導体（例えば、ＰＯＥ－ヒマシ油、ＰＯＥ－硬化ヒマシ油、ＰＯＥ－硬化ヒマシ油モノイソステアレート、ＰＯＥ－硬化ヒマシ油トリイソステアレート、ＰＯＥ－硬化ヒマシ油モノピログルタミン酸モノイソステアリン酸ジエステル、ＰＯＥ－硬化ヒマシ油マレイン酸等）；ＰＯＥ－ミツロウ／ラノリン誘導体（例えば、ＰＯＥ－ソルビットミツロウ等）；アルカノールアミド（例えば、ヤシ油脂肪酸ジエタノールアミド、ラウリン酸モノエタノールアミド、脂肪酸イソプロパノールアミド等）；ＰＯＥ－プロピレングリコール脂肪酸エステル；ＰＯＥ－アルキルアミン；ＰＯＥ－脂肪酸アミド；ショ糖脂肪酸エステル；アルキルエトキシジメチルアミンオキシド；トリオレイルリン酸等が挙げられる。 Examples of nonionic surfactants include sorbitan fatty acid esters (e.g., sorbitan monooleate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquioleate, sorbitan trioleate). ate, diglycerol sorbitan pent-2-ethylhexylate, diglycerol sorbitan tetra-2-ethylhexylate, etc.); Propylene glycol fatty acid esters (e.g. propylene glycol monostearate, etc.); Hydrogenated castor oil derivatives; Glycerin alkyl ethers; POE - Sorbitan fatty acid esters (for example, POE-sorbitan monooleate, POE-sorbitan monostearate, POE-sorbitan tetraoleate, etc.); POE-sorbitan fatty acid esters (for example, POE-sorbitan monolaurate, POE-sorbitan monolaurate, oleate, POE-sorbitolpentaoleate, POE-sorbitol monostearate, etc.); POE-glycerol fatty acid esters (e.g., POE-glycerol monostearate, POE-glycerol monoisostearate, POE-glycerol triisostearate) ); POE-fatty acid esters (e.g., POE-distearate, POE-monodioleate, ethylene glycol distearate, etc.); POE-alkyl ethers (e.g., POE-lauryl ether, POE-oleyl ether, POE-stearyl ether, POE -behenyl ether, POE-2-octyldodecyl ether, POE-cholestanol ether, etc.); Pluronic (registered trademark) types (e.g., Pluronic (registered trademark), etc.); POE/POP-alkyl ethers (e.g., POE/ POP-cetyl ether, POE/POP-2-decyltetradecyl ether, POE/POP-monobutyl ether, POE/POP-hydrogenated lanolin, POE/POP-glycerin ether, etc.); Tetra-POE/tetra-POP-ethylenediamine condensates (e.g., Tetronic, etc.); POE-castor oil hydrogenated castor oil derivatives (e.g., POE-castor oil, POE-hydrogenated castor oil, POE-hydrogenated castor oil monoisostearate, POE-hydrogenated castor oil triisostearate, POE-hydrogenated castor oil monopyroglutamic acid monoisostearate diester, POE-hydrogenated castor oil maleic acid, etc.); POE-beeswax/lanolin derivatives (e.g. POE-sorbit beeswax, etc.); alkanolamides (e.g. coconut oil fatty acid diethanolamide, (lauric acid monoethanolamide, fatty acid isopropanolamide, etc.); POE-propylene glycol fatty acid ester; POE-alkylamine; POE-fatty acid amide; sucrose fatty acid ester; alkyl ethoxydimethylamine oxide; trioleyl phosphoric acid.
　保湿剤としては、例えば、ポリエチレングリコール、キシリトール、ソルビトール、マルチトール、コンドロイチン硫酸、ヒアルロン酸、ムコイチン硫酸、カロニン酸、アテロコラーゲン、コレステリル－１２－ヒドロキシステアレート、乳酸ナトリウム、胆汁酸塩、ｄｌ－ピロリドンカルボン酸塩、短鎖可溶性コラーゲン、ジグリセリン（ＥＯ）ＰＯ付加物、イザヨイバラ抽出物、セイヨウノコギリソウ抽出物、メリロート抽出物等が挙げられる。 Examples of moisturizing agents include polyethylene glycol, xylitol, sorbitol, maltitol, chondroitin sulfate, hyaluronic acid, mucoitin sulfate, caronic acid, atelocollagen, cholesteryl-12-hydroxystearate, sodium lactate, bile salts, dl-pyrrolidone carvone. Examples include acid salts, short-chain soluble collagen, diglycerin (EO) PO adducts, Izayoi rosea extract, Yarrow extract, Melilot extract, and the like.
　天然の水溶性高分子としては、例えば、植物系高分子（例えば、アラビアガム、トラガカントガム、ガラクタン、グアーガム、キャロブガム、カラヤガム、カラギーナン、ペクチン、カンテン、クインスシード（マルメロ）、アルゲコロイド（カッソウエキス）、デンプン（コメ、トウモロコシ、バレイショ、コムギ）、グリチルリチン酸）；微生物系高分子（例えば、キサンタンガム、デキストラン、サクシノグルカン、ブルラン、ジェランガム等）；動物系高分子（例えば、コラーゲン、カゼイン、アルブミン、ゼラチン等）等が挙げられる。 Examples of natural water-soluble polymers include plant-based polymers (e.g., gum arabic, gum tragacanth, galactan, guar gum, carob gum, gum karaya, carrageenan, pectin, agar, quince seed (quince), algae colloid (cassou extract), starch). (rice, corn, potato, wheat), glycyrrhizic acid); Microbial polymers (e.g., xanthan gum, dextran, succinoglucan, bull run, gellan gum, etc.); Animal-based polymers (e.g., collagen, casein, albumin, gelatin, etc.) ) etc.
　水溶性高分子としては、例えば、デンプン系高分子（例えば、カルボキシメチルデンプン、メチルヒドロキシプロピルデンプン等）；セルロース系高分子（メチルセルロース、エチルセルロース、メチルヒドロキシプロピルセルロース、ヒドロキシエチルセルロース、セルロース硫酸ナトリウム、ヒドロキシプロピルセルロース、カルボキシメチルセルロース、カルボキシメチルセルロースナトリウム、結晶セルロース、セルロース末等）；アルギン酸系高分子（例えば、アルギン酸ナトリウム、アルギン酸プロピレングリコールエステル等）；ビニル系高分子（例えば、ポリビニルアルコール、ポリビニルメチルエーテル、ポリビニルピロリドン、カルボキシビニルポリマー等）；ポリオキシエチレン系高分子（例えば、ポリエチレングリコール２０，０００、ポリエチレングリコール４０，０００、ポリエチレングリコール６０，０００等のポリオキシエチレンポリオキシプロピレン共重合体等）；アクリル系高分子（例えば、ポリアクリル酸ナトリウム、ポリエチルアクリレート、ポリアクリルアミド等）；ポリエチレンイミン；カチオンポリマー等が挙げられる。 Examples of water-soluble polymers include starch-based polymers (e.g., carboxymethyl starch, methylhydroxypropyl starch, etc.); cellulose-based polymers (methyl cellulose, ethyl cellulose, methyl hydroxypropyl cellulose, hydroxyethyl cellulose, sodium cellulose sulfate, hydroxypropyl Cellulose, carboxymethylcellulose, sodium carboxymethylcellulose, crystalline cellulose, cellulose powder, etc.); Alginic acid polymers (e.g. sodium alginate, alginate propylene glycol ester, etc.); Vinyl polymers (e.g. polyvinyl alcohol, polyvinyl methyl ether, polyvinyl pyrrolidone) , carboxyvinyl polymer, etc.); polyoxyethylene polymers (e.g., polyoxyethylene polyoxypropylene copolymers such as polyethylene glycol 20,000, polyethylene glycol 40,000, polyethylene glycol 60,000, etc.); acrylic polymers Molecules (eg, sodium polyacrylate, polyethyl acrylate, polyacrylamide, etc.); polyethyleneimine; cationic polymers, and the like.
　キレート剤としては、例えば、１－ヒドロキシエタン－１，１－ジフォスホン酸、１－ヒドロキシエタン－１，１－ジフォスホン酸四ナトリウム塩、エデト酸二ナトリウム、エデト酸三ナトリウム、エデト酸四ナトリウム、ポリリン酸ナトリウム、メタリン酸ナトリウム、リン酸、アスコルビン酸、コハク酸、エデト酸等が挙げられる。 Examples of the chelating agent include 1-hydroxyethane-1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid tetrasodium salt, edetate disodium, edetate trisodium, edetate tetrasodium, polyphosphoric acid. Examples include sodium acid, sodium metaphosphate, phosphoric acid, ascorbic acid, succinic acid, edetate, and the like.
　低級アルコールとしては、例えば、エタノール、プロパノール、イソプロパノール、イソブチルアルコール、ｔ－ブチルアルコール等が挙げられる。 Examples of lower alcohols include ethanol, propanol, isopropanol, isobutyl alcohol, and t-butyl alcohol.
　多価アルコールとしては、例えば、２価のアルコール（例えば、１，２－エタンジオール、１，２－プロパンジオール、１，３－プロパンジオール、１，２－ブタンジオール、１，３－ブタンジオール、１，４－ブタンジオール、２，３－ブタンジオール、１，２－ペンタンジオール、１，５－ペンタンジオール、２，４－ペンタンジオール等）；３価のアルコール（例えば、グリセリン、トリメチロールプロパン等）；４価アルコール（例えば、１，２，５，６－ヘキサンテトラオール等のペンタエリスリトール等）；５価アルコール（例えば、キシリトール等）；６価アルコール（例えば、ソルビトール、マンニトール等）；多価アルコール重合体（例えば、ジエチレングリコール、トリエチレングリコール、ジプロピレングリコール、ポリプロピレングリコール、テトラエチレングリコール、ジグリセリン、ポリエチレングリコール、トリグリセリン、テトラグリセリン、ポリグリセリン等）；（アルキルグリセリルエーテル（例えば、プロピルグリセリルエーテル、ブチルグリセリルエーテル、ペンチルグリセリルエーテル、ヘキシルグリセリルエーテル、シクロヘキシルグリセリルエーテル、ヘプチルグリセリルエーテル、オクチルグリセリルエーテル、エチルヘキシルグリセリルエーテル、ノニルグリセリルエーテル、デシルグリセリルエーテル、ヘキサデシルグリセリルエーテル、オレイルグリセリルエーテル、オクタデシルグリセリルエーテル、イソステアリルグリセリルエーテル等）；アルコールアルキルエーテル（例えば、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールモノフェニルエーテル、エチレングリコールモノヘキシルエーテル、エチレングリコールモノ２－メチルヘキシルエーテル、エチレングリコールイソアミルエーテル、エチレングリコールベンジルエーテル、エチレングリコールイソプロピルエーテル、エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、エチレングリコールジブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールブチルエーテル、ジエチレングリコールメチルエチルエーテル、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノブチルエーテル、プロピレングリコールイソプロピルエーテル、ジプロピレングリコールメチルエーテル、ジプロピレングリコールエチルエーテル、ジプロピレングリコールブチルエーテル等）；２価アルコールエーテルエステル（例えば、エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、エチレングリコールモノブチルエーテルアセテート、エチレングリコールモノフェニルエーテルアセテート、エチレングリコールジアジベート、エチレングリコールジサクシネート、ジエチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノブチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノプロピルエーテルアセテート、プロピレングリコールモノフェニルエーテルアセテート等）；糖アルコール（例えば、ソルビトール、マルチトール、マルトトリオース、マンニトール、エリトリトール、グルコース、フルクトース、デンプン分解糖、マルトース、キシリトース、デンプン分解糖還元アルコール等）；グリソリッド；テトラハイドロフルフリルアルコール；ＰＯＥ－テトラハイドロフルフリルアルコール；ＰＯＰ－ブチルエーテル；ＰＯＰ／ＰＯＥ－ブチルエーテル；トリポリオキシプロピレングリセリンエーテル；ＰＯＰ－グリセリンエーテル；ＰＯＰ－グリセリンエーテルリン酸；ＰＯＰ／ＰＯＥ－ペンタンエリスリトールエーテル等が挙げられる。 Examples of polyhydric alcohols include dihydric alcohols (for example, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2-pentanediol, 1,5-pentanediol, 2,4-pentanediol, etc.); trihydric alcohols (for example, glycerin, trimethylolpropane, etc.) ); Tetrahydric alcohols (e.g., pentaerythritol such as 1,2,5,6-hexanetetraol, etc.); Pentahydric alcohols (e.g., xylitol, etc.); Hexahydric alcohols (e.g., sorbitol, mannitol, etc.); Polyhydric alcohols Alcohol polymers (e.g. diethylene glycol, triethylene glycol, dipropylene glycol, polypropylene glycol, tetraethylene glycol, diglycerin, polyethylene glycol, triglycerin, tetraglycerin, polyglycerin, etc.); (alkyl glyceryl ethers (e.g. propyl glyceryl ether) , butyl glyceryl ether, pentyl glyceryl ether, hexyl glyceryl ether, cyclohexyl glyceryl ether, heptyl glyceryl ether, octyl glyceryl ether, ethylhexyl glyceryl ether, nonyl glyceryl ether, decyl glyceryl ether, hexadecyl glyceryl ether, oleyl glyceryl ether, octadecyl glyceryl ether, isostearyl glyceryl ether, etc.); alcohol alkyl ethers (e.g., ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, ethylene glycol monohexyl ether, ethylene glycol mono-2-methylhexyl ether, Ethylene glycol isoamyl ether, ethylene glycol benzyl ether, ethylene glycol isopropyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol Butyl ether, diethylene glycol methyl ethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol isopropyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol butyl ether, etc.); dihydric alcohol ether esters (e.g., ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, ethylene glycol diadibate, ethylene glycol disuccinate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monophenyl ether acetate, etc.); sugar alcohols (e.g. , sorbitol, maltitol, maltotriose, mannitol, erythritol, glucose, fructose, starch-degrading sugar, maltose, xylitose, starch-degrading sugar reducing alcohol, etc.); Glysolid; Tetrahydrofurfuryl alcohol; POE-tetrahydrofurfuryl alcohol ; POP-butyl ether; POP/POE-butyl ether; tripolyoxypropylene glycerin ether; POP-glycerin ether; POP-glycerin ether phosphoric acid; POP/POE-pentane erythritol ether.
　単糖としては、例えば、三炭糖（例えば、Ｄ－グリセリルアルデヒド、ジヒドロキシアセトン等）；四炭糖（例えば、Ｄ－エリトロース、Ｄ－エリトルロース、Ｄ－トレオース、エリスリトール等）；五炭糖（例えば、Ｌ－アラビノース、Ｄ－キシロース、Ｌ－リキソース、Ｄ－アラビノース、Ｄ－リボース、Ｄ－リブロース、Ｄ－キシルロース、Ｌ－キシルロース等）；六炭糖（例えば、Ｄ－グルコース、Ｄ－タロース、Ｄ－ブシコース、Ｄ－ガラクトース、Ｄ－フルクトース、Ｌ－ガラクトース、Ｌ－マンノース、Ｄ－タガトース等）；七炭糖（例えば、アルドヘプトース、ヘプロース等）；八炭糖（例えば、オクツロース等）；デオキシ糖（例えば、２－デオキシ－Ｄ－リボース、６－デオキシ－Ｌ－ガラクトース、６－デオキシ－Ｌ－マンノース等）；アミノ糖（例えば、Ｄ－グルコサミン、Ｄ－ガラクトサミン、シアル酸、アミノウロン酸、ムラミン酸等）；ウロン酸（例えば、Ｄ－グルクロン酸、Ｄ－マンヌロン酸、Ｌ－グルロン酸、Ｄ－ガラクツロン酸、Ｌ－イズロン酸等）等が挙げられる。 Examples of monosaccharides include tricarbons (e.g., D-glycerylaldehyde, dihydroxyacetone, etc.); tetracarbons (e.g., D-erythrose, D-erythrulose, D-threose, erythritol, etc.); pentose (e.g., , L-arabinose, D-xylose, L-lyxose, D-arabinose, D-ribose, D-ribulose, D-xylulose, L-xylulose, etc.); hexoses (e.g., D-glucose, D-talose, D - Bucicose, D-galactose, D-fructose, L-galactose, L-mannose, D-tagatose, etc.); Seven carbon sugars (e.g., aldoheptose, heprose, etc.); Octose sugars (e.g., octulose, etc.); Deoxy sugars ( For example, 2-deoxy-D-ribose, 6-deoxy-L-galactose, 6-deoxy-L-mannose, etc.); Amino sugars (for example, D-glucosamine, D-galactosamine, sialic acid, aminouronic acid, muramic acid, etc.) ); uronic acids (eg, D-glucuronic acid, D-mannuronic acid, L-guluronic acid, D-galacturonic acid, L-iduronic acid, etc.);
　オリゴ糖としては、例えば、ショ糖、ウンベリフェロース、ラクトース、プランテオース、イソリクノース類、α，α－トレハロース、ラフィノース、リクノース類、ウンビリシン、スタキオース、ベルバスコース類等が挙げられる。
　多糖としては、例えば、セルロース、クインスシード、コンドロイチン硫酸、デンプン、ガラクタン、デルマタン硫酸、グリコーゲン、アラビアガム、ヘパラン硫酸、ヒアルロン酸、トラガントガム、ケラタン硫酸、コンドロイチン、キサンタンガム、ムコイチン硫酸、グアーガム、デキストラン、ケラト硫酸、ローカストビンガム、サクシノグルカン、カロニン酸等が挙げられる。 Examples of oligosaccharides include sucrose, umbelliferose, lactose, planteose, isoliqunose, α,α-trehalose, raffinose, lichnose, umbilicin, stachyose, verbascose, and the like.
Examples of polysaccharides include cellulose, quince seed, chondroitin sulfate, starch, galactan, dermatan sulfate, glycogen, gum arabic, heparan sulfate, hyaluronic acid, gum tragacanth, keratan sulfate, chondroitin, xanthan gum, mucoitin sulfate, guar gum, dextran, and keratosulfate. , locust Bingham, succinoglucan, caronic acid, and the like.
　アミノ酸としては、例えば、中性アミノ酸（例えば、スレオニン、システイン等）；塩基性アミノ酸（例えば、ヒドロキシリジン等）等が挙げられる。また、アミノ酸誘導体として、例えば、アシルサルコシンナトリウム（ラウロイルサルコシンナトリウム）、アシルグルタミン酸塩、アシルβ－アラニンナトリウム、グルタチオン、ピロリドンカルボン酸等が挙げられる。 Examples of amino acids include neutral amino acids (eg, threonine, cysteine, etc.); basic amino acids (eg, hydroxylysine, etc.). Further, examples of amino acid derivatives include sodium acylsarcosine (sodium lauroylsarcosine), acylglutamate, sodium acyl β-alanine, glutathione, and pyrrolidone carboxylic acid.
　有機アミンとしては、例えば、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、モルホリン、トリイソプロパノールアミン、２－アミノ－２－メチル－１，３－プロパンジオール、２－アミノ－２－メチル－１－プロパノール等が挙げられる。 Examples of organic amines include monoethanolamine, diethanolamine, triethanolamine, morpholine, triisopropanolamine, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-methyl-1-propanol, etc. can be mentioned.
　ｐＨ調整剤としては、例えば、乳酸－乳酸ナトリウム、コハク酸－コハク酸ナトリウム、クエン酸－クエン酸ナトリウム、炭酸水素ナトリウム等が挙げられる。本発明の化粧料組成物のｐＨは用途に応じて適宜調節すればよいが、肌への適用性等の観点から、２．０～１２．０であることが好ましい。 Examples of the pH adjuster include lactic acid-sodium lactate, succinic acid-sodium succinate, citric acid-sodium citrate, and sodium hydrogen carbonate. The pH of the cosmetic composition of the present invention may be adjusted as appropriate depending on the intended use, but from the viewpoint of applicability to the skin, it is preferably 2.0 to 12.0.
　ビタミンとしては、例えば、ビタミンＡ、Ｂ１、Ｂ２、Ｂ６、Ｃ、Ｅ及びその誘導体、パントテン酸及びその誘導体、ビオチン等が挙げられる。
　酸化防止剤としては、例えば、トコフェロール類、ジブチルヒドロキシトルエン、ブチルヒドロキシアニソール、没食子酸エステル類等が挙げられる。 Examples of vitamins include vitamins A, B1, B2, B6, C, E and their derivatives, pantothenic acid and its derivatives, biotin, and the like.
Examples of the antioxidant include tocopherols, dibutylhydroxytoluene, butylhydroxyanisole, gallic acid esters, and the like.
　その他の配合可能成分としては、例えば、消炎剤（例えば、グリチルリチン酸誘導体、グリチルレチン酸誘導体、サリチル酸誘導体、ヒノキチオール、酸化亜鉛、アラントイン等）；美白剤（例えば、ユキノシタ抽出物、アルブチン等）；各種抽出物（例えば、オウバク、オウレン、シコン、シャクヤク、センブリ、バーチ、セージ、ビワ、ニンジン、アロエ、ゼニアオイ、アイリス、ブドウ、ヨクイニン、ヘチマ、ユリ、サフラン、センキュウ、ショウキョウ、オトギリソウ、オノニス、ニンニク、トウガラシ、チンピ、トウキ、海藻等）、賦活剤（例えば、ローヤルゼリー、感光素、コレステロール誘導体等）；血行促進剤（例えば、ニコチン酸ベンジルエステル、ニコチン酸β－ブトキシエチルエステル、カプサイシン、ジンゲロン、カンタリスチンキ、イクタモール、タンニン酸、α－ボルネオール、ニコチン酸トコフェロール、イノシトールヘキサニコチネート、シクランデレート、シンナリジン、トラゾリン、アセチルコリン、ベラパミル、セファランチン、γ－オリザノール等）；抗脂漏剤（例えば、硫黄、チアントール等）；抗炎症剤（例えば、トラネキサム酸、チオタウリン、ヒポタウリン等）等が挙げられる。 Other ingredients that can be blended include, for example, anti-inflammatory agents (e.g., glycyrrhizic acid derivatives, glycyrrhetinic acid derivatives, salicylic acid derivatives, hinokitiol, zinc oxide, allantoin, etc.); skin whitening agents (e.g., saxifrage extract, arbutin, etc.); various extracts. Things (e.g., sagebrush, sage, loquat, carrot, aloe, mallow, iris, grape, sagebrush, loofah, lily, saffron, nematode, ginger, hypericum, hypericum, ononis, garlic, chili pepper) , Chimpi, Touki, seaweed, etc.), activators (e.g., royal jelly, photosensors, cholesterol derivatives, etc.); blood circulation promoters (e.g., benzyl nicotinic acid ester, β-butoxyethyl nicotinic acid ester, capsaicin, zingerone, cantharis tincture) , ictamol, tannic acid, α-borneol, tocopherol nicotinate, inositol hexanicotinate, cyclanderate, cinnarizine, tolazoline, acetylcholine, verapamil, cephalanthine, γ-oryzanol, etc.); antiseborrheic agents (for example, sulfur, thianthol, etc.) ); anti-inflammatory agents (eg, tranexamic acid, thiotaurine, hypotaurine, etc.);
　本発明の化粧料組成物の粘度は特に限定されず、具体的な化粧料の種類及び目的に応じて調整することができるが、化粧料組成物の使用感の観点から、例えば、本発明の化粧料組成物の２５℃での粘度は、１００～１００，０００ｍＰａ・ｓであることが好ましく、２００～８０，０００ｍＰａ・ｓであることがより好ましく、３００～５０，０００ｍＰａ・ｓであることが更により好ましい。本発明において、２５℃での粘度は、ＪＩＳ　Ｋ　７１１７に準拠して測定される。 The viscosity of the cosmetic composition of the present invention is not particularly limited and can be adjusted depending on the specific type and purpose of the cosmetic composition. The viscosity of the cosmetic composition at 25°C is preferably 100 to 100,000 mPa·s, more preferably 200 to 80,000 mPa·s, and preferably 300 to 50,000 mPa·s. Even more preferred. In the present invention, the viscosity at 25°C is measured in accordance with JIS K 7117.
４．その他
　本発明においては、以下の態様が挙げられる。 4. Others The present invention includes the following aspects.
［１］（ＰＰＧ－１２／ＳＭＤＩ）コポリマー（Ａ）と、シリカ粒子（Ｂ）と、グリセリンの重合度が２～２０であるポリグリセリンと炭素原子数が８～２０である脂肪酸とのモノエステル又はジエステルであるポリグリセリン脂肪酸エステル（Ｃ）とを、エステル油、炭化水素油及びシリコーン油から選ばれる１種又は２種以上の油成分（Ｄ）に混合することを含む、油成分を増粘する方法。 [1] Monoester of (PPG-12/SMDI) copolymer (A), silica particles (B), polyglycerin whose degree of polymerization is 2 to 20, and fatty acid having 8 to 20 carbon atoms or thickening the oil component, which includes mixing polyglycerol fatty acid ester (C), which is a diester, with one or more oil components (D) selected from ester oil, hydrocarbon oil, and silicone oil. how to.
［２］油成分（Ｄ）に混合するポリグリセリン脂肪酸エステル（Ｃ）の質量が、油成分（Ｄ）１００質量部に対して１～１００質量部である、請求項１に記載の油成分を増粘する方法。 [2] The oil component according to claim 1, wherein the mass of the polyglycerin fatty acid ester (C) mixed with the oil component (D) is 1 to 100 parts by mass based on 100 parts by mass of the oil component (D). How to thicken.
［３］油成分（Ｄ）に混合する（ＰＰＧ－１２／ＳＭＤＩ）コポリマー（Ａ）とポリグリセリン脂肪酸エステル（Ｃ）の比率が、質量比で１：０．０５～１：５００である、請求項１又は２に記載の油成分を増粘する方法。 [3] A claim in which the ratio of the (PPG-12/SMDI) copolymer (A) and polyglycerin fatty acid ester (C) mixed in the oil component (D) is 1:0.05 to 1:500 in mass ratio A method for thickening an oil component according to item 1 or 2.
［４］油成分（Ｄ）に混合するシリカ粒子（Ｂ）とポリグリセリン脂肪酸エステル（Ｃ）の比率が、質量比で１：０．５～１：２００である、請求項１～３のいずれか一項に記載の油成分を増粘する方法。 [4] Any of claims 1 to 3, wherein the ratio of the silica particles (B) and the polyglycerin fatty acid ester (C) to be mixed with the oil component (D) is 1:0.5 to 1:200 in mass ratio. A method for thickening an oil component according to item (1).
［５］油成分（Ｄ）がエステル油を含む、請求項１～４のいずれか一項に記載の油成分を増粘する方法。 [5] The method for thickening an oil component according to any one of claims 1 to 4, wherein the oil component (D) contains an ester oil.
［６］（ＰＰＧ－１２／ＳＭＤＩ）コポリマー（Ａ）と、シリカ粒子（Ｂ）と、グリセリンの重合度が２～２０であるポリグリセリンと炭素原子数が８～２０である脂肪酸とのモノエステル又はジエステルであるポリグリセリン脂肪酸エステル（Ｃ）と、エステル油、炭化水素油及びシリコーン油から選ばれる１種又は２種以上の油成分（Ｄ）と、を含む油成分含有組成物。 [6] Monoester of (PPG-12/SMDI) copolymer (A), silica particles (B), polyglycerin with a degree of polymerization of glycerin of 2 to 20, and fatty acid with a carbon number of 8 to 20 or a polyglycerol fatty acid ester (C) which is a diester, and one or more oil components (D) selected from ester oils, hydrocarbon oils, and silicone oils.
［７］前記油成分含有組成物が化粧料組成物である、請求項６に記載の油成分含有組成物。 [7] The oil component-containing composition according to claim 6, wherein the oil component-containing composition is a cosmetic composition.
［８］シリカ粒子（Ｂ）と、グリセリンの重合度が２～２０であるポリグリセリンと炭素原子数が８～２０である脂肪酸とのモノエステル又はジエステルであるポリグリセリン脂肪酸エステル（Ｃ）と共に、エステル油、炭化水素油及びシリコーン油から選ばれる１種又は２種以上の油成分（Ｄ）に混合するための、（ＰＰＧ－１２／ＳＭＤＩ）コポリマー（Ａ）を含む増粘剤組成物。 [8] Silica particles (B) and polyglycerin fatty acid ester (C) which is a monoester or diester of polyglycerin whose polymerization degree is 2 to 20 and a fatty acid having 8 to 20 carbon atoms, A thickener composition containing a (PPG-12/SMDI) copolymer (A) for mixing with one or more oil components (D) selected from ester oils, hydrocarbon oils, and silicone oils.
　以下、実施例及び比較例により本発明の詳細を説明するが、これらによって本発明が限定されるものではない。なお、以下の実施例等において、％は特に記載がない限り質量基準である。 The details of the present invention will be explained below with reference to Examples and Comparative Examples, but the present invention is not limited by these. In addition, in the following examples etc., % is based on mass unless otherwise specified.
［（ＰＰＧ－１２／ＳＭＤＩ）コポリマー１の製造］
　撹拌機、冷却管、窒素導入管を有するガラス製反応容器に、ＰＰＧ－１２を８７２．７ｇ（１．２５モル）、ジシクロヘキシルメタン４，４’－ジイソシアネートを１３５．１５ｇ（０．４０モル）入れて、撹拌した状態で、１２０℃で１時間反応させ、赤外線吸収スペクトルによりＮＣＯの吸収がないことを確認して反応を終了することで、（ＰＰＧ－１２／ＳＭＤＩ）コポリマー１を製造した。得られた（ＰＰＧ－１２／ＳＭＤＩ）コポリマー１のゲル浸透クロマトグラフィー（ＧＰＣ）により測定し、スチレン換算で求めた重量平均分子量は４６００であった。 [Production of (PPG-12/SMDI) copolymer 1]
872.7 g (1.25 mol) of PPG-12 and 135.15 g (0.40 mol) of dicyclohexylmethane 4,4'-diisocyanate were placed in a glass reaction vessel equipped with a stirrer, a cooling tube, and a nitrogen introduction tube. (PPG-12/SMDI) copolymer 1 was produced by reacting at 120° C. for 1 hour with stirring and terminating the reaction after confirming the absence of NCO absorption by infrared absorption spectrum. The weight average molecular weight of the obtained (PPG-12/SMDI) copolymer 1 measured by gel permeation chromatography (GPC) was 4,600 in terms of styrene.
［使用した化合物］
＜（ＰＰＧ－１２／ＳＭＤＩ）コポリマー（Ａ）＞
　（ＰＰＧ－１２／ＳＭＤＩ）コポリマー１：上述の方法により製造された、重量平均分子量が４６００である（ＰＰＧ－１２／ＳＭＤＩ）コポリマー
＜シリカ粒子（Ｂ）＞
　シリカ粒子１：ジメチルシリル化処理がされた、平均一次粒子径１６ｎｍの疎水性シリカ粒子（ＥＶＯＮＩＫ社製、ＡＥＲＯＳＩＬ（登録商標）　Ｒ９７２）
＜ポリグリセリン脂肪酸エステル（Ｃ）＞
　ポリグリセリン脂肪酸エステル１：ラウリン酸ポリグリセリル－１０（ＨＬＢ＝１７．１）
　ポリグリセリン脂肪酸エステル２：ジカプリン酸ポリグリセリル－６（ＨＬＢ＝１０．２）
　ポリグリセリン脂肪酸エステル３：ジイソステアリン酸ポリグリセリル－１０（ＨＬＢ＝１０．０）
　ポリグリセリン脂肪酸エステル４：ジオレイン酸ポリグリセリル－１０（ＨＬＢ＝１１．５）
　ポリグリセリン脂肪酸エステル５：カプリル酸ポリグリセリル－６（ＨＬＢ＝１３．０）
　ポリグリセリン脂肪酸エステル６：カプリン酸ポリグリセリル－２（ＨＬＢ＝９．５）
　ポリグリセリン脂肪酸エステル７：ラウリン酸ポリグリセリル－５（ＨＬＢ＝１５．８）
＜ポリグリセリン脂肪酸エステル（Ｃ'）＞
　ポリグリセリン脂肪酸エステル８（比較化合物）：カプリル酸グリセリル （ＨＬＢ＝５．５）
　ポリグリセリン脂肪酸エステル９（比較化合物）：トリイソステアロイルポリグリセリル－３二量体ジリノレエート（ＨＬＢ＝３．０）
＜油成分（Ｄ）＞
　油成分１：イソノナン酸イソノニル（２５℃での粘度：７．０ｍＰａ・ｓ） [Compounds used]
<(PPG-12/SMDI) copolymer (A)>
(PPG-12/SMDI) copolymer 1: (PPG-12/SMDI) copolymer <silica particles (B)> with a weight average molecular weight of 4600, produced by the above method
Silica particles 1: Hydrophobic silica particles with an average primary particle diameter of 16 nm that have been subjected to dimethylsilylation treatment (manufactured by EVONIK, AEROSIL (registered trademark) R972)
<Polyglycerin fatty acid ester (C)>
Polyglycerin fatty acid ester 1: Polyglyceryl-10 laurate (HLB=17.1)
Polyglycerin fatty acid ester 2: Polyglyceryl-6 dicaprate (HLB=10.2)
Polyglycerin fatty acid ester 3: Polyglyceryl-10 diisostearate (HLB=10.0)
Polyglycerin fatty acid ester 4: polyglyceryl dioleate-10 (HLB=11.5)
Polyglycerin fatty acid ester 5: polyglyceryl-6 caprylate (HLB=13.0)
Polyglycerin fatty acid ester 6: polyglyceryl-2 caprate (HLB=9.5)
Polyglycerin fatty acid ester 7: Polyglyceryl-5 laurate (HLB=15.8)
<Polyglycerin fatty acid ester (C')>
Polyglycerin fatty acid ester 8 (comparative compound): Glyceryl caprylate (HLB=5.5)
Polyglycerin fatty acid ester 9 (comparative compound): triisostearoyl polyglyceryl-3 dimer dilinoleate (HLB=3.0)
<Oil component (D)>
Oil component 1: isononyl isononanoate (viscosity at 25°C: 7.0 mPa・s)
［実施例１～７及び比較例１～１０］
　実施例１～７として、（ＰＰＧ－１２／ＳＭＤＩ）コポリマー１（Ａ）と、シリカ粒子１（Ｂ）と、ポリグリセリン脂肪酸エステル１～７（Ｃ）を、以下の表１に示す質量％でそれぞれ油成分１（Ｄ）に加え、常温でディスパーを用いて撹拌することにより混合し、油成分含有組成物を調製した。また、比較例１～１０として、（ＰＰＧ－１２／ＳＭＤＩ）コポリマー１（Ａ）と、シリカ粒子１（Ｂ）と、ポリグリセリン脂肪酸エステル１～４（Ｃ）又はポリグリセリン脂肪酸エステル８、９（Ｃ’）を、以下の表２に示す質量％でそれぞれ油成分１（Ｄ）に加え、実施例と同様に油成分含有組成物を調製した。各油成分含有組成物の粘度を、ＪＩＳ　Ｋ　７１１７に準拠してＢ型粘度計を用いて２５℃、回転数５ｒｐｍの条件で測定した結果をそれぞれ表１及び２に示す。また、実施例１～７において、各油成分含有組成物の粘度が、ポリグリセリン脂肪酸エステルを混合しなかった場合（比較例２）の油成分含有組成物の粘度と比較して何倍に増粘されたかを、増粘倍率としてそれぞれ算出した。算出結果を表１に併せて示す。 [Examples 1 to 7 and Comparative Examples 1 to 10]
As Examples 1 to 7, (PPG-12/SMDI) copolymer 1 (A), silica particles 1 (B), and polyglycerin fatty acid esters 1 to 7 (C) were mixed in the mass% shown in Table 1 below. Each was added to oil component 1 (D) and mixed by stirring using a disper at room temperature to prepare an oil component-containing composition. In addition, as Comparative Examples 1 to 10, (PPG-12/SMDI) copolymer 1 (A), silica particles 1 (B), polyglycerol fatty acid esters 1 to 4 (C) or polyglycerol fatty acid esters 8, 9 ( C') was added to oil component 1 (D) in the mass % shown in Table 2 below, and an oil component-containing composition was prepared in the same manner as in the example. The viscosity of each oil component-containing composition was measured using a B-type viscometer according to JIS K 7117 at 25° C. and 5 rpm, and the results are shown in Tables 1 and 2, respectively. Furthermore, in Examples 1 to 7, the viscosity of each oil component-containing composition was increased by several times compared to the viscosity of the oil component-containing composition when the polyglycerin fatty acid ester was not mixed (Comparative Example 2). The degree of viscosity was calculated as the thickening ratio. The calculation results are also shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
［実施例８～１０及び比較例１１～１３］
　実施例８～１０として、（ＰＰＧ－１２／ＳＭＤＩ）コポリマー（Ａ）と、シリカ粒子（Ｂ）と、ポリグリセリン脂肪酸エステルと１～３（Ｃ）を、以下の表３に示す質量％でそれぞれ油成分（Ｄ）に加え、常温でディスパーを用いて撹拌することにより混合し、油成分含有組成物を調製した。また、比較例１１～１３として、（ＰＰＧ－１２／ＳＭＤＩ）コポリマー１（Ａ）と、シリカ粒子１（Ｂ）と、ポリグリセリン脂肪酸エステル８（Ｃ’）を、以下の表３に示す質量％でそれぞれ油成分（Ｄ）に加え、実施例と同様に油成分含有組成物を調製した。各油成分含有組成物の粘度を、ＪＩＳ　Ｋ　７１１７に準拠してＢ型粘度計を用いて２５℃、回転数５ｒｐｍの条件で測定した結果をそれぞれ表３に示す。また、実施例８～１０において、各混合後の粘度が、ポリグリセリン脂肪酸エステルを混合しなかった場合（比較例１２）の油成分含有組成物の粘度と比較して何倍に増粘されたかを、増粘倍率としてそれぞれ算出した。算出結果を表３に併せて示す。 [Examples 8 to 10 and Comparative Examples 11 to 13]
As Examples 8 to 10, (PPG-12/SMDI) copolymer (A), silica particles (B), polyglycerin fatty acid ester, and 1 to 3 (C) were each added in the mass % shown in Table 3 below. In addition to the oil component (D), the mixture was mixed by stirring using a disper at room temperature to prepare an oil component-containing composition. In addition, as Comparative Examples 11 to 13, (PPG-12/SMDI) copolymer 1 (A), silica particles 1 (B), and polyglycerin fatty acid ester 8 (C') were mixed in the mass percentage shown in Table 3 below. In addition to the oil component (D), an oil component-containing composition was prepared in the same manner as in the example. The viscosity of each oil component-containing composition was measured using a B-type viscometer according to JIS K 7117 at 25° C. and 5 rpm, and the results are shown in Table 3. Also, in Examples 8 to 10, how many times the viscosity after each mixing increased compared to the viscosity of the oil component-containing composition when the polyglycerin fatty acid ester was not mixed (Comparative Example 12)? were each calculated as the thickening ratio. The calculation results are also shown in Table 3.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　上記の結果から、本発明の油成分を増粘する方法によれば、（ＰＰＧ－１２／ＳＭＤＩ）コポリマー（Ａ）と、シリカ粒子（Ｂ）と、特定のポリグリセリン脂肪酸エステル（Ｃ）とを油成分（Ｄ）に混合することで、顕著に油成分（Ｄ）を増粘できることが示された。一方、（ＰＰＧ－１２／ＳＭＤＩ）コポリマー（Ａ）とシリカ粒子（Ｂ）のみ、又はシリカ粒子（Ｂ）と特定のポリグリセリン脂肪酸エステル（Ｃ）のみを油成分に混合した場合においては、本発明の実施例と比較して、いずれも油成分（Ｄ）の増粘効果に劣っていた。また、本発明の油成分を増粘する方法に用いられる特定のポリグリセリン脂肪酸エステル（Ｃ）以外のポリグリセリン脂肪酸エステル（Ｃ’）を混合した場合においても、本発明の実施例と比較して油成分の増粘効果に劣ることが確認された。よって、本発明の油成分を増粘する方法によれば、油成分を含む塗料、洗浄剤、接着剤、化粧品、医薬品、農薬、インク、染料等に用いることで、それぞれの製品に適した粘度に容易に調整することができる。 From the above results, according to the method of thickening an oil component of the present invention, the (PPG-12/SMDI) copolymer (A), the silica particles (B), and the specific polyglycerol fatty acid ester (C) are combined. It has been shown that by mixing with oil component (D), the viscosity of oil component (D) can be significantly increased. On the other hand, when only (PPG-12/SMDI) copolymer (A) and silica particles (B), or only silica particles (B) and specific polyglycerin fatty acid ester (C) are mixed in the oil component, the present invention In all cases, the thickening effect of the oil component (D) was inferior to those in Examples. Furthermore, even when a polyglycerol fatty acid ester (C') other than the specific polyglycerol fatty acid ester (C) used in the method of thickening an oil component of the present invention is mixed, compared to the examples of the present invention, It was confirmed that the thickening effect of the oil component was inferior. Therefore, according to the method of thickening an oil component of the present invention, it can be used in paints, cleaning agents, adhesives, cosmetics, pharmaceuticals, agricultural chemicals, inks, dyes, etc. containing oil components, so that the viscosity is suitable for each product. can be easily adjusted.

Claims (8)

  1. 　（ＰＰＧ－１２／ＳＭＤＩ）コポリマー（Ａ）と、シリカ粒子（Ｂ）と、グリセリンの重合度が２～２０であるポリグリセリンと炭素原子数が８～２０である脂肪酸とのモノエステル又はジエステルであるポリグリセリン脂肪酸エステル（Ｃ）とを、エステル油、炭化水素油及びシリコーン油から選ばれる１種又は２種以上の油成分（Ｄ）に混合することを含む、油成分を増粘する方法。 (PPG-12/SMDI) A monoester or diester of copolymer (A), silica particles (B), polyglycerin whose degree of polymerization is 2 to 20, and fatty acid having 8 to 20 carbon atoms. A method for thickening an oil component, which comprises mixing a certain polyglycerin fatty acid ester (C) with one or more oil components (D) selected from ester oils, hydrocarbon oils, and silicone oils.
  2. 　油成分（Ｄ）に混合するポリグリセリン脂肪酸エステル（Ｃ）の質量が、油成分（Ｄ）１００質量部に対して１～１００質量部である、請求項１に記載の油成分を増粘する方法。 Thickening the oil component according to claim 1, wherein the mass of the polyglycerin fatty acid ester (C) mixed with the oil component (D) is 1 to 100 parts by mass based on 100 parts by mass of the oil component (D). Method.
  3. 　油成分（Ｄ）に混合する（ＰＰＧ－１２／ＳＭＤＩ）コポリマー（Ａ）とポリグリセリン脂肪酸エステル（Ｃ）の比率が、質量比で１：０．０５～１：５００である、請求項１又は２に記載の油成分を増粘する方法。 Claim 1 or 2, wherein the ratio of the (PPG-12/SMDI) copolymer (A) and the polyglycerin fatty acid ester (C) mixed in the oil component (D) is 1:0.05 to 1:500 in terms of mass ratio. 2. The method of thickening an oil component according to 2.
  4. 　油成分（Ｄ）に混合するシリカ粒子（Ｂ）とポリグリセリン脂肪酸エステル（Ｃ）の比率が、質量比で１：０．５～１：２００である、請求項１又は２に記載の油成分を増粘する方法。 The oil component according to claim 1 or 2, wherein the ratio of the silica particles (B) and the polyglycerin fatty acid ester (C) to be mixed in the oil component (D) is 1:0.5 to 1:200 in mass ratio. How to thicken.
  5. 　油成分（Ｄ）がエステル油を含む、請求項１又は２に記載の油成分を増粘する方法。 The method for thickening an oil component according to claim 1 or 2, wherein the oil component (D) contains an ester oil.
  6. 　（ＰＰＧ－１２／ＳＭＤＩ）コポリマー（Ａ）と、シリカ粒子（Ｂ）と、グリセリンの重合度が２～２０であるポリグリセリンと炭素原子数が８～２０である脂肪酸とのモノエステル又はジエステルであるポリグリセリン脂肪酸エステル（Ｃ）と、エステル油、炭化水素油及びシリコーン油から選ばれる１種又は２種以上の油成分（Ｄ）と、を含む油成分含有組成物。 (PPG-12/SMDI) A monoester or diester of copolymer (A), silica particles (B), polyglycerin whose degree of polymerization is 2 to 20, and fatty acid having 8 to 20 carbon atoms. An oil component-containing composition comprising a certain polyglycerin fatty acid ester (C) and one or more oil components (D) selected from ester oils, hydrocarbon oils, and silicone oils.
  7. 　前記油成分含有組成物が化粧料組成物である、請求項６に記載の油成分含有組成物。 The oil component-containing composition according to claim 6, wherein the oil component-containing composition is a cosmetic composition.
  8. 　シリカ粒子（Ｂ）と、グリセリンの重合度が２～２０であるポリグリセリンと炭素原子数が８～２０である脂肪酸とのモノエステル又はジエステルであるポリグリセリン脂肪酸エステル（Ｃ）と共に、エステル油、炭化水素油及びシリコーン油から選ばれる１種又は２種以上の油成分（Ｄ）に混合するための、（ＰＰＧ－１２／ＳＭＤＩ）コポリマー（Ａ）を含む増粘剤組成物。 Silica particles (B) and polyglycerin fatty acid ester (C) which is a monoester or diester of polyglycerin having a polymerization degree of glycerin of 2 to 20 and a fatty acid having 8 to 20 carbon atoms, together with an ester oil, A thickener composition containing a (PPG-12/SMDI) copolymer (A) for mixing with one or more oil components (D) selected from hydrocarbon oils and silicone oils.
PCT/JP2023/010344 2022-03-22 2023-03-16 Method for thickening oily component and composition containing oily component WO2023182149A1 (en)

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US20160008263A1 (en) * 2014-07-11 2016-01-14 Mary Kay Inc. Cosmetic compositions
JP2016074637A (en) * 2014-10-08 2016-05-12 クラシエホームプロダクツ株式会社 Oily liquid skin detergent composition
JP2019014709A (en) * 2017-07-07 2019-01-31 ポーラ化成工業株式会社 Skin care composition
JP2019019077A (en) * 2017-07-18 2019-02-07 ポーラ化成工業株式会社 Skin external composition
WO2021182500A1 (en) * 2020-03-13 2021-09-16 株式会社Adeka Oily composition and cosmetics composition containing said oily composition

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010513540A (en) * 2006-12-20 2010-04-30 エイボン プロダクツ インコーポレーテッド Gel-based lipstick with improved rheology
US20160008263A1 (en) * 2014-07-11 2016-01-14 Mary Kay Inc. Cosmetic compositions
JP2016074637A (en) * 2014-10-08 2016-05-12 クラシエホームプロダクツ株式会社 Oily liquid skin detergent composition
JP2019014709A (en) * 2017-07-07 2019-01-31 ポーラ化成工業株式会社 Skin care composition
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