WO2023238715A1 - Composition d'émulsion de type huile dans l'eau - Google Patents

Composition d'émulsion de type huile dans l'eau Download PDF

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WO2023238715A1
WO2023238715A1 PCT/JP2023/019846 JP2023019846W WO2023238715A1 WO 2023238715 A1 WO2023238715 A1 WO 2023238715A1 JP 2023019846 W JP2023019846 W JP 2023019846W WO 2023238715 A1 WO2023238715 A1 WO 2023238715A1
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oil
emulsion composition
water emulsion
general formula
composition according
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PCT/JP2023/019846
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English (en)
Japanese (ja)
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一幸 竹脇
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信越化学工業株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/01—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/549—Silicon-containing compounds containing silicon in a ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/22—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers modified by chemical after-treatment

Definitions

  • the present invention relates to oil-in-water emulsion compositions.
  • Polyvinyl alcohol is a thermoplastic polymer material with excellent gas barrier properties and transparency. Its glass transition temperature is relatively low at about 80 degrees, and it has excellent heat moldability, so it is widely used as a raw material for films, sheets, containers, etc. It is also used to improve oil resistance and gas barrier properties by being coated with other resin films or sheets.
  • polyvinyl alcohol has excellent properties such as transparency, emulsification, low skin irritation, film softness, and biocompatibility, and is therefore incorporated into various cosmetics.
  • polyvinyl alcohol has poor solubility in general oil-based ingredients, and has poor compatibility with hydrocarbon solvents, oils and fats, silicone materials, etc. that are often included in cosmetics, etc., and when dried on the skin.
  • Polyvinyl alcohol also has poor reactivity with modifiers for imparting new functions, making it difficult to modify the material. Therefore, there has been a desire for polyvinyl alcohol that maintains the properties unique to polyvinyl alcohol and has excellent compatibility with oily components.
  • silicone resins that are compatible with oily components and have film-forming properties are often used in similar applications.
  • Film-forming silicone resins used in cosmetics include silicone resins (Patent Document 1) and silicone crosslinked products obtained by addition polymerization of organohydrogenpolysiloxane and vinyl group-containing organopolysiloxane (Patent Document 2). , acrylic-silicone graft copolymer (Patent Document 3), etc., but new materials are being sought to further improve properties.
  • Patent Document 4 proposes a polymer having an alkoxy group in its side chain.
  • the solvent solubility can be improved, the side chain alkoxy group bonded to Si is highly hydrolyzable, causing another problem regarding stability.
  • solubility in highly safe silicone oils and hydrocarbon oils.
  • Patent Document 5 proposes a polymer having a linear siloxane in its side chain.
  • this polymer has improved solubility in aromatic hydrocarbon solvents such as toluene and xylene, and polar solvents such as N,N-dimethylformamide (DMF) and methyl ethyl ketone (MEK), it has a high solubility in silicone oil and hydrocarbons, which are highly safe. It has poor solubility in oil, and the fundamental solution to the above problem has not yet been reached.
  • aromatic hydrocarbon solvents such as toluene and xylene
  • polar solvents such as N,N-dimethylformamide (DMF) and methyl ethyl ketone (MEK)
  • Patent Document 6 discloses that polyvinyl alcohol has high solubility in organic solvents by modifying silicone having a branched structure while maintaining its general properties such as film-forming properties, toughness, excellent gas barrier properties, and transparency.
  • Substituted silylalkyl carbamic acid polyvinyl alcohol has been proposed as a material that also has excellent handling properties as a liquid material.
  • the reactivity of general polyvinyl alcohol and silicone modifiers is low, and in order to obtain substituted silylalkyl carbamic acid polyvinyl alcohol with a high modification rate, an excessive amount of silicone modifier must be used, resulting in high production costs. , it is often not suitable for the intended use.
  • Patent Document 7 by modifying polyvinyl alcohol having a specific structural unit with silicone having a branched structure, it is possible to improve the general properties of polyvinyl alcohol such as film-forming properties and transparency, high solubility in organic solvents, and liquid form. Materials that also have excellent handling properties have been proposed. However, since the solubility and dispersibility in water is low, when added to an aqueous formulation, it has the disadvantage that it separates in the formulation due to insufficient dispersibility.
  • the present invention was made in view of the above problems, and the organosiloxane grafted polyvinyl alcohol polymer blended as the main component maintains the general properties of polyvinyl alcohol, such as film-forming properties, and has an oily component, In particular, it has good compatibility with hydrocarbon solvents, oils and fats, silicone materials, etc. that are often included in cosmetics, etc., and in addition to forming a uniform film when dried on the skin, it also evaporates.
  • a solution dissolved in a water-based oil it can be used as a raw material for an oil-in-water emulsion, and by forming an oil-in-water emulsion composition, it can be incorporated into an aqueous formulation.
  • the purpose is to provide something.
  • An oil-in-water emulsion composition containing the following components (A) to (C) is provided.
  • A-1) An organosiloxane grafted polyvinyl alcohol polymer characterized by having a structural unit represented by the following general formula (1) (In the formula, M 1 and M 2 are hydrogen atoms, acetyl groups, or siloxane groups represented by the following general formula (2), and at least one of M 1 and M 2 is represented by the following general formula (2).
  • R 1 is a monovalent organic group having 1 to 6 carbon atoms
  • R 2 , R 3 , and R 4 are each a monovalent organic group having 1 to 6 carbon atoms or -OSiR 5
  • R 6 R 7 is a siloxy group
  • R 5 , R 6 , and R 7 are each a monovalent organic group having 1 to 6 carbon atoms.
  • n is an integer of 1 to 10
  • a is an integer of 0 to 2.
  • B At least one surfactant selected from nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants: 2 to 30 mass Department
  • C Water: 10 to 2,000 parts by mass.
  • the organosiloxane-grafted polyvinyl alcohol-based polymer blended as a main component has the general properties such as film-forming properties that polyvinyl alcohol has. It retains its properties and has excellent compatibility with oily components, especially hydrocarbon oils and silicone-based materials, and is a material that can be incorporated into water-based formulations. Therefore, it can be suitably used as a material for water-based cosmetics, adhesives, paints, etc.
  • a in the general formula (1) is a single bond.
  • the organosiloxane grafted polyvinyl alcohol polymer of the component (A-1) further has a structural unit represented by the following general formula (3), and has a number average molecular weight (Mn) in terms of polystyrene measured by GPC. It is preferably from 5,000 to 500,000.
  • M3 is a hydrogen atom, an acetyl group, or a siloxane group represented by the above general formula (2).
  • Such component (A-1) more reliably maintains the general properties of polyvinyl alcohol, such as film-forming properties, and has excellent compatibility with oily components, especially hydrocarbon oils and silicone-based materials. Becomes a material.
  • n 3
  • R 2 , R 3 and R 4 are methyl groups
  • a 0.
  • the volatile oil of component (A-2) is preferably a silicone oil and/or a hydrocarbon oil having a viscosity of less than 6 mm 2 /s at 25°C.
  • the component (A-2) when the oil-in-water emulsion composition is applied, the component (A-2) evaporates immediately and a good film can be obtained.
  • the component (B) contains a nonionic surfactant.
  • This oil-in-water emulsion composition will have better stability if it contains a nonionic surfactant.
  • nonionic surfactant is one or more selected from polyoxyalkylene alkyl ether and polyoxyethylene sorbitan fatty acid ester.
  • the oil-in-water emulsion composition has even better stability.
  • the average particle diameter of the emulsified particles in the oil-in-water emulsion composition is 500 nm or less.
  • this oil-in-water emulsion composition will have even better stability.
  • the oil-in-water emulsion composition of the present invention retains the general properties of polyvinyl alcohol, such as film-forming properties, and has excellent compatibility with oily components, particularly hydrocarbon oils and silicone materials, so it can be made into a solution.
  • This makes it possible to handle it as a liquid substance, and by making it into an oil-in-water emulsion composition, it becomes a material that can be incorporated into water-based formulations. Therefore, it can be suitably used as a material for water-based cosmetics, adhesives, paints, etc.
  • the oil-based emulsion composition retains the general properties of polyvinyl alcohol such as film-forming properties, has excellent compatibility with oil-based components, especially hydrocarbon oils and silicone-based materials, and is a material that can be incorporated into water-based formulations. They have discovered that this is the case and have completed the present invention.
  • the present invention This is an oil-in-water emulsion composition containing the following components (A) to (C).
  • A-1) An organosiloxane grafted polyvinyl alcohol polymer characterized by having a structural unit represented by the following general formula (1) (In the formula, M 1 and M 2 are hydrogen atoms, acetyl groups, or siloxane groups represented by the following general formula (2), and at least one of M 1 and M 2 is represented by the following general formula (2).
  • R 1 is a monovalent organic group having 1 to 6 carbon atoms
  • R 2 , R 3 , and R 4 are each a monovalent organic group having 1 to 6 carbon atoms or -OSiR 5
  • R 6 R 7 is a siloxy group
  • R 5 , R 6 , and R 7 are each a monovalent organic group having 1 to 6 carbon atoms.
  • n is an integer of 1 to 10
  • a is an integer of 0 to 2.
  • B At least one surfactant selected from nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants: 2 to 30 mass Department
  • C Water: 10 to 2,000 parts by mass.
  • the component (A) in the present invention has a structure represented by the following general formula (1). This is a composition prepared by mixing an organosiloxane-grafted polyvinyl alcohol-based polymer (A-1) having units and a volatile oil (A-2) to form a solution.
  • A-1) An organosiloxane grafted polyvinyl alcohol polymer characterized by having a structural unit represented by the following general formula (1) (In the formula, M 1 and M 2 are hydrogen atoms, acetyl groups, or siloxane groups represented by the following general formula (2), and at least one of M 1 and M 2 is represented by the following general formula (2).
  • R 1 is a monovalent organic group having 1 to 6 carbon atoms
  • R 2 , R 3 , and R 4 are each a monovalent organic group having 1 to 6 carbon atoms or -OSiR 5
  • R 6 R 7 is a siloxy group
  • R 5 , R 6 , and R 7 are each a monovalent organic group having 1 to 6 carbon atoms.
  • n is an integer of 1 to 10
  • a is an integer of 0 to 2. be.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 in the above general formula (2) present as a side chain of the compound of the above general formula (1) representing the component (A- 1 ) , and R 7 are monovalent organic groups having 1 to 6 carbon atoms, specifically, alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, hexyl group, etc.
  • Cycloalkyl groups such as cyclopentyl group and cyclohexyl group
  • Aryl groups such as phenyl group
  • Alkenyl groups such as vinyl group, allyl group, and 5-hexenyl group
  • chloromethyl group 3,3,3-trifluoropropyl group, etc.
  • Examples include substituted hydrocarbon groups, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 may be the same or different.
  • R 2 , R 3 and R 4 may each be a siloxy group represented by -OSiR 5 R 6 R 7 , and examples of this siloxy group include trimethylsiloxy group, ethyldimethylsiloxy group, phenyldimethylsiloxy group, Examples include vinyldimethylsiloxy group, chloromethyldimethylsiloxy group, and 3,3,3-trifluoropropyldimethylsiloxy group.
  • a in the above general formula (2) is an integer of 0 to 2, preferably, in the above general formula (2), n is 3 and R 2 , R 3 and R 4 are methyl groups, Preferably, a is 0.
  • a in the above general formula (1) is a single bond.
  • Such component (A-1) more reliably maintains the general properties of polyvinyl alcohol, such as film-forming properties, and has excellent compatibility with oily components, especially hydrocarbon oils and silicone-based materials. Becomes a material.
  • the organosiloxane grafted polyvinyl alcohol polymer as component (A-1) has a polystyrene equivalent number average molecular weight (Mn) measured by GPC of 5,000 to 500,000.
  • the molecular weight of the organosiloxane grafted polyvinyl alcohol polymer of component (A-1) is such that the number average molecular weight (Mn) in terms of polystyrene is 5,000 to 500,000 as measured by GPC using tetrahydrofuran (THF) as a solvent. It may be within any range, preferably 7,000 to 300,000, more preferably 10,000 to 100,000. If the number average molecular weight is 5,000 or more, it is excellent in terms of film strength, and if the number average molecular weight is 500,000 or less, it is good in terms of handleability and solubility.
  • Mn number average molecular weight in terms of polystyrene
  • THF tetrahydrofuran
  • the component (A-1) is like this, as in the case where A is a single bond, it will more reliably maintain the general properties of polyvinyl alcohol such as film-forming properties, and will also be able to retain oily components, especially hydrocarbon oil. It becomes a material with excellent compatibility with silicone-based materials.
  • M3 is a hydrogen atom, an acetyl group, or a siloxane group represented by the above general formula (2).
  • organosiloxane grafted polyvinyl alcohol polymer (Method for producing organosiloxane grafted polyvinyl alcohol polymer)
  • the organosiloxane grafted polyvinyl alcohol polymer of component (A-1) is a polyvinyl alcohol resin compound containing a structural unit represented by the following general formula (4) and an isocyanate represented by the following general formula (5). Obtained by reacting with a group-containing organosiloxane.
  • A represents a single bond or a connecting group.
  • R 1 is a monovalent organic group having 1 to 6 carbon atoms
  • R 2 , R 3 , and R 4 are each a monovalent organic group having 1 to 6 carbon atoms or -OSiR 5
  • R 6 R 7 is a siloxy group
  • R 5 , R 6 , and R 7 are each a monovalent organic group having 1 to 6 carbon atoms.
  • n is an integer of 1 to 10
  • a is an integer of 0 to 2. be.
  • the polyvinyl alcohol resin compound that is the raw material for the organosiloxane grafted polyvinyl alcohol polymer
  • the polyvinyl alcohol resin compound has a high resistance to oil-based materials.
  • the compatibility is improved, and the reaction rate with the isocyanate group-containing organosiloxane represented by the above general formula (5) can be significantly improved.
  • polyvinyl alcohol resin compound it is preferable to use one further containing a structural unit represented by the following formula (6).
  • a polyvinyl alcohol resin compound containing a structural unit represented by the above general formula (4) and further a structural unit represented by the above formula (6) may include, for example, a structural unit represented by the following general formula (7) and a structural unit represented by the following general formula (7). It can be obtained by saponifying a polyvinyl acetate resin compound containing a structural unit represented by the following formula (8). (In the formula, A represents a single bond or a connecting group.)
  • the polyvinyl alcohol resin compound which is the raw material for the organosiloxane grafted polyvinyl alcohol polymer, can be obtained by saponifying a polyvinyl acetate compound, but the polyvinyl alcohol resin compound is partially saponified. You can also use the
  • organosiloxane grafted polyvinyl alcohol polymer is synthesized using a partially saponified polyvinyl alcohol resin compound, the structural unit represented by the above general formula (7) and the above formula ( It can be an organosiloxane-grafted polyvinyl alcohol polymer containing the structural unit shown in 8).
  • a polyvinyl acetate resin compound containing the structural unit represented by the above general formula (7) and further the structural unit represented by the above formula (8) is a compound represented by the following general formula (9) and the following formula ( It can be obtained by polymerizing the compound represented by 10). (In the formula, A represents a single bond or a connecting group.)
  • the molecular weight of the polyvinyl alcohol resin compound described above is such that the molecular weight of the organosiloxane grafted polyvinyl alcohol polymer of the present invention (that is, the number average molecular weight (Mn) in terms of polystyrene measured by GPC) is 5,000 to 500, It is possible to appropriately select a value within the range of 000.
  • the above-mentioned polyvinyl alcohol-based resin compound is manufactured and sold as G-Polymer TM by Nippon Gosei Kagaku Kogyo and can be obtained. Specifically, it can be selected from among AZF8035W, OKS-6026, OKS-1011, OKS-8041, OKS-8049, OKS-1028, OKS-1027, OKS-1109, and OKS-1083.
  • the method for producing the organosiloxane-grafted polyvinyl alcohol polymer as component (A-1) is carried out by reacting the hydroxyl group of a polyvinyl alcohol resin compound with an isocyanate group-containing organosiloxane as described above.
  • the containing organosiloxane is particularly tristrimethylsiloxysilylpropylisocyanate (i.e., in the above general formula (5), n is 3, R 2 , R 3 and R 4 are methyl groups, and a is 0).
  • a tristrimethylsiloxysilylpropyl carbamic acid polyvinyl alcohol polymer By reacting tristrimethylsiloxysilylpropyl isocyanate with a polyvinyl alcohol resin compound, a tristrimethylsiloxysilylpropyl carbamic acid polyvinyl alcohol polymer can be obtained.
  • This has a structural unit represented by the following general formula (11).
  • L 1 and L 2 are a hydrogen atom, an acetyl group, or a siloxane group represented by the following formula (12), and at least one of L 1 and L 2 is a siloxane group represented by the following formula (12).
  • A represents a single bond or a connecting group.
  • the method for producing the organosiloxane-grafted polyvinyl alcohol polymer as component (A-1) is carried out by reacting the hydroxyl groups of the polyvinyl alcohol resin compound with the isocyanate group-containing organosiloxane as described above. It is preferable that the resin compound contains a polybutene diol structure (that is, in the above general formula (4), A is a single bond). If it contains a polybutene diol structure, it is possible to efficiently obtain an organosiloxane-grafted polyvinyl alcohol polymer that has high solubility in organic solvents and a high modification rate. This has a structural unit represented by the following general formula (13). (In the formula, L 1 and L 2 are the same as above.)
  • the method for producing the organosiloxane-grafted polyvinyl alcohol polymer as component (A-1) is a method for producing the urethane bond-forming reaction between the hydroxyl groups of the polyvinyl alcohol resin compound and the isocyanate group-containing organosiloxane, so special preparations are required.
  • a solvent for mixing the polyvinyl alcohol resin compound and isocyanate group-containing organosiloxane, reaction efficiency, and reaction control is preferable to use a solvent for mixing the polyvinyl alcohol resin compound and isocyanate group-containing organosiloxane, reaction efficiency, and reaction control.
  • this solvent examples include esters such as methyl acetate, ethyl acetate, and butyl acetate; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; aromatic hydrocarbons such as toluene and xylene; ethers such as diethyl ether and tetrahydrofuran; Examples include amides such as N-dimethylformamide and N-methylpyrrolidone, and sulfoxides such as dimethylsulfoxide, and these may be used alone or in combination of two or more.
  • this reaction is usually carried out at 20 to 150°C for 1 to 24 hours.
  • triethylamine, triethylenediamine, N-methylmorpholine, etc. are Known catalysts used in forming urethane bonds, such as amines, organometallic compounds such as di-n-butyltin dilaurate, and stannous oleate, may be added.
  • the desired organosiloxane-grafted polyvinyl alcohol polymer can be obtained by washing and drying.
  • Volatile oils include silicone oils with a viscosity of less than 6 mm 2 /s at 25°C; hydrocarbon oils such as hexane, octane, isododecane, ⁇ -olefin oligomers, light isoparaffins, light liquid isoparaffins, liquid paraffins, liquid isoparaffins; methyl ethyl ketone; Ketone compounds such as , methyl isobutyl ketone; Ester compounds such as ethyl acetate and isobutyl acetate; Alcohols such as methanol, ethanol, isopropanol, butanol, isobutanol, and t-butanol; Aromatic hydrocarbons such as toluene and xylene, etc.
  • hydrocarbon oils such as hexane, octane, isododecane, ⁇ -olefin oligomers, light isoparaffins, light liquid
  • silicone oils can be appropriately selected from those having a boiling point of 260° C. or lower at normal pressure and 25° C., and can be used alone or in an appropriate combination of two or more.
  • substances that can be used in cosmetics include silicone oils, hydrocarbon oils, ketone compounds, ester compounds, and alcohols. From the viewpoint of safety and versatility, silicone oils, hydrocarbon oils, and ester compounds are preferred. More preferred are silicone oil and hydrocarbon oil.
  • the silicone oil one having a viscosity of less than 6 mm 2 /s at 25° C. is used. Note that this viscosity is a kinematic viscosity, and is a value measured at 25° C. using an Ostwald viscometer (the same applies hereinafter). If the viscosity is less than 6 mm 2 /s, it will be volatile at 25°C, the silicone oil will not remain in the film, and a tacky feeling will appear when the oil-in-water emulsion composition is blended into cosmetics, etc. There is no such thing.
  • the lower limit of the viscosity of silicone oil at 25° C. is not particularly limited, but may be, for example, 0.65 mm 2 /s. Examples of the silicone oil include those represented by the following general formula. (In the formula, b is an integer of 1 to 3, R 8 is the same or different monovalent organic group having 1 to 10 carbon atoms, and c is an integer of 4 to 6.)
  • hydrocarbon oils examples include linear or branched volatile hydrocarbon oils. Specific examples thereof include isododecane, ⁇ -olefin oligomer, light isoparaffin, light liquid isoparaffin, liquid paraffin, liquid isoparaffin, and the like. Although it may be selected as appropriate depending on the desired feeling of use, etc., isododecane, isoparaffin, etc. are preferred from the viewpoint of versatility.
  • ester compounds include ethyl acetate, butyl acetate, isopropyl acetate, and the like.
  • the viscosity of the solution of the organosiloxane grafted polyvinyl alcohol polymer (A) is not particularly limited, but is preferably 1 to 100,000 mm 2 /s, more preferably 2 to 50,000 mm 2 /s, even more preferably is 5 to 30,000 mm 2 /s, particularly preferably 10 to 10,000 mm 2 /s. If the viscosity is 1 mm 2 /s or more, it is easy to emulsify with a general stirrer such as a homomixer or homodisper, and the emulsified particles of the oil-in-water emulsion composition become finer, so the storage stability does not deteriorate over time. There is no risk of light and shade separation occurring. Moreover, if the viscosity is 100,000 mm 2 /s or less, handling properties will not deteriorate.
  • the surfactant as component (B) is not particularly limited as long as it can emulsify and disperse component (A) in water, but it is preferably one that includes a nonionic surfactant.
  • examples include polyoxyalkylene alkyl ethers such as polyoxyethylene alkyl ether and polyoxyethylene oxypropylene alkyl ether; sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and polyoxyethylene fatty acid ester; From the viewpoint of stability and safety of the emulsion composition, polyoxyalkylene alkyl ether and polyoxyethylene sorbitan fatty acid ester are particularly preferred.
  • polyoxyethylene octyl ether examples include polyoxyethylene octyl ether, polyoxyethylene nonyl ether, polyoxyethylene decyl ether, polyoxyethylene oxypropylene decyl ether, polyoxyethylene lauryl ether, polyoxyethylene oxypropylene lauryl ether, polyoxyethylene Tridecyl ether, polyoxyethylene oxypropylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene Examples include sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, and polyoxyethylene sorbitan trioleate.
  • these nonionic surfactants can be used alone or in combination of two or more.
  • anionic surfactants such as alkyl sulfates, alkylbenzene sulfonates, alkyl sulfosuccinates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, quaternary ammonium salts, alkylamine acetates, etc.
  • Cationic surfactants such as, and amphoteric surfactants such as alkyl betaines and alkylimidazolines can also be used.
  • the amount of component (B) added is 2 to 30 parts by mass per 100 parts by mass of component (A).
  • the amount added is preferably 2.5 to 25 parts by weight, more preferably 3 to 20 parts by weight, and still more preferably 4 to 15 parts by weight. If the amount added is less than 2 parts by mass, the stability of the oil-in-water emulsion composition will deteriorate, and if the amount added exceeds 30 parts by mass, the film properties of the film formed from the oil-in-water emulsion composition will deteriorate. becomes worse.
  • the above surfactant preferably has an HLB value of 3.0 to 19.0.
  • the weighted average of the HLB values is preferably 7.0 to 17.0.
  • the oil-in-water emulsion composition of the present invention can be prepared by mixing water, which is the component (C), with the above-mentioned components (A) and (B), and emulsifying and dispersing the mixture according to a conventional method.
  • Water is preferably ion-exchanged water.
  • the content of water (C) is 10 to 2,000 parts by weight, preferably 50 to 1,000 parts by weight, per 100 parts by weight of component (A).
  • An oil-in-water emulsion composition is obtained by mixing and emulsifying and dispersing the above components (A) to (C).
  • the result is a white emulsion, but if the average particle diameter of the emulsified particles is 200 nm or less, the microemulsion may have a bluish-white or transparent appearance.
  • the obtained oil-in-water emulsion composition can be diluted by further adding water.
  • the amount of water for dilution is not particularly limited and may be adjusted as appropriate depending on the application.
  • the emulsification temperature is not particularly limited, but it is preferably set to below the flash point of the oil-in-water emulsion composition of the present invention.
  • the temperature is preferably 0 to 80°C, more preferably 0 to 40°C. By setting the temperature to 0 to 80°C, emulsification becomes easier and the emulsified composition becomes more stable.
  • the stirring speed is preferably 100 to 10,000 rpm, more preferably 500 to 5,000 rpm.
  • the emulsification time is not particularly limited, but it is preferably 1 to 240 minutes when produced using a batch-type emulsifier, and 1 minute or less when produced using a continuous-type emulsifier.
  • the pressure during emulsification may be not only normal pressure but also reduced pressure or increased pressure. When stirring under reduced pressure or increased pressure, bubbles may be less likely to be mixed in and more effective emulsification may be possible.
  • the pressure is set higher than the vapor pressure of the raw material to prevent the raw material from volatilizing.
  • emulsifiers examples include Homo Mixer (Primix), Homo Disper (Primix), Ajihomo Mixer (Primix), and Combimix, which is a three-shaft dispersion kneader that combines a Homomixer, Homodisper, and Anchor mixer.
  • Primarymix a colloid mill with a stirring section consisting of a rotor and a stator (IKA, PUC, Nippon Seiki, Iwaki), a high-shear mixer (Silverson, Primix), and a revolving motion of two blades. It is possible to use a Hivis Dispermix 3D-5 model (Primix Co., Ltd.), which is an agitator that uses rotational motion and high-speed rotation of tooth-shaped blades.
  • the viscosity of the oil-in-water emulsion composition is not particularly specified, but is preferably 5 to 20,000 mPa ⁇ s, more preferably 10 to 5,000 mPa ⁇ s, and even more preferably 20 to 2,000 mPa ⁇ s. If the absolute viscosity is 5 mPa ⁇ s or more, there is no fear that the storage stability will deteriorate or that the film will be repelled. On the other hand, if the absolute viscosity is 20,000 mPa ⁇ s or less, it will be easier to handle.
  • the absolute viscosity of the oil-in-water emulsion composition is the value at 25° C. measured using a BM rotational viscometer.
  • the average particle diameter of the emulsified particles in the oil-in-water emulsion composition is preferably 500 nm or less, more preferably 400 nm or less. If the average particle size is 500 nm or less, separation will not occur immediately. Note that the lower limit of the average particle diameter is not particularly limited, but it can usually be 100 nm or more, particularly 150 nm or more.
  • the average particle size can be measured by a dynamic light scattering method or a laser diffraction method, but in the present invention, the volume average particle size (cumulative average diameter D50 (median diameter)) is measured by a laser diffraction method. be.
  • Examples of devices for dynamic light scattering include N4PLUS (BECKMAN COULTER), DelsaMax CORE (BECKMAN COULTER), and DelsaMax Pro (BECKMAN COULTER); examples of devices for laser diffraction include LA-920 ( (manufactured by Horiba, Ltd.), LA-960 (manufactured by Horiba, Ltd.), and Partica LA-960V2 (manufactured by Horiba, Ltd.).
  • additives In addition to the above-mentioned components (A) to (C), various additives may be added to the emulsion water repellent composition of the present invention, if necessary.
  • it may contain a thickener, an antifreeze agent, a preservative, a rust preventive, an antioxidant, an ultraviolet absorber, and the like.
  • the average particle diameter is a volume average particle diameter (cumulative average diameter D50 (median diameter)), and is a value measured using a laser diffraction/scattering particle size distribution analyzer LA-960 manufactured by Horiba, Ltd.
  • the viscosity is an absolute viscosity measured at 25° C. using a B-type rotational viscometer, and is a value measured using a TVB-10 type viscometer manufactured by Toki Sangyo.
  • the mixture was stirred with a homomixer at 1,500 rpm for 3 minutes to obtain an oil-in-water emulsion composition (2).
  • the average particle diameter of the emulsified particles of emulsion composition (2) was 300 nm, and the viscosity was 170 mPa ⁇ s.
  • Example 3 75.0 g of organosiloxane grafted polyvinyl alcohol polymer solution (A [II]), 7.5 g of polyoxyethylene [20] sorbitan monostearate (B [IV]) and (C) 22.5 g of ion-exchanged water.
  • Blend, T. K. Homo mixer (Primix) was stirred for 3 minutes at 3,000 rpm to emulsify, and T. K. The mixture was stirred at 1,500 rpm for 15 minutes (Homodisper (Primix)). Thereafter, (C) 43.95 g of water, 0.75 g of sodium benzoate as a preservative, and 0.3 g of citric acid were added, and T. K.
  • the mixture was stirred for 3 minutes at 1,500 rpm using a homomixer to obtain an oil-in-water emulsion composition (3).
  • the average particle diameter of the emulsified particles of emulsion composition (3) was 450 nm, and the viscosity was 150 mPa ⁇ s.
  • Organosiloxane grafted polyvinyl alcohol polymer solution (A[I]) 66.0g, polyoxyethylene[4]lauryl ether (B[I]) 1.32g, polyoxyethylene[23]lauryl ether (B[II]) ]) 1.98g and (C) 16.5g of ion-exchanged water were blended, and T. K. Homo mixer (Primix) was stirred for 3 minutes at 3,000 rpm to emulsify, and T. K. The mixture was stirred at 1,500 rpm for 15 minutes (Homodisper (Primix)).
  • the evaluation results of properties, water dispersibility, coating properties, drying properties, and cracking properties are shown in the table below.
  • the average particle diameter is a volume average particle diameter (cumulative average diameter D50 (median diameter)), and is a value measured using a laser diffraction/scattering particle size distribution analyzer LA-960 manufactured by Horiba, Ltd.
  • the viscosity is an absolute viscosity measured at 25° C. using a B-type rotational viscometer, and is a value measured using a TVB-10 type viscometer manufactured by Toki Sangyo.
  • Comparative Example 1 in which dimethylpolysiloxane (viscosity 6 mm 2 /s) was used as the component (A-2) had poor drying properties and resulted in a tacky feeling in the film.
  • Comparative Example 2 in which the amount of component (B) added was 1.4 parts by mass had a large average particle diameter and poor centrifugal stability.
  • A-1) An organosiloxane grafted polyvinyl alcohol polymer characterized by having a structural unit represented by the following general formula (1) (In the formula, M 1 and M 2 are hydrogen atoms, acetyl groups, or siloxane groups represented by the following general formula (2), and at least one of M 1 and M 2 is represented by the following general formula (2).
  • R 1 is a monovalent organic group having 1 to 6 carbon atoms
  • R 2 , R 3 , and R 4 are each a monovalent organic group having 1 to 6 carbon atoms or -OSiR 5
  • R 6 R 7 is a siloxy group
  • R 5 , R 6 , and R 7 are each a monovalent organic group having 1 to 6 carbon atoms.
  • n is an integer of 1 to 10
  • a is an integer of 0 to 2.
  • A-2) Volatile oil
  • B At least one surfactant selected from nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants: 2 to 30 mass Department
  • C Water: 10 to 2,000 parts by mass.
  • M3 is a hydrogen atom, an acetyl group, or a siloxane group represented by the above general formula (2).
  • the volatile oil of the component (A-2) is a silicone oil and/or a hydrocarbon oil having a viscosity of less than 6 mm 2 /s at 25°C. 4].
  • [6] The oil-in-water emulsion composition according to any one of [1] to [5] above, wherein the component (B) contains a nonionic surfactant.
  • [7] The oil-in-water emulsion composition according to [6] above, wherein the nonionic surfactant is one or more selected from polyoxyalkylene alkyl ether and polyoxyethylene sorbitan fatty acid ester.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
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Abstract

La présente invention concerne une composition d'émulsion de type huile dans l'eau caractérisée en ce qu'elle contient les composants (A) à (C) suivants. (A) Une solution obtenue par mélange du composant (A-1) et du composant (A-2) suivants. (A-1) Un polymère à base d'alcool polyvinylique greffé d'organosiloxane ayant un motif structural représenté par la formule générale (1). (A-2) Une huile volatile. (B) Au moins un tensioactif choisi parmi des tensioactifs non ioniques, des tensioactifs anioniques, des tensioactifs cationiques et des tensioactifs amphotères. (C) De l'eau. Par conséquent, le polymère à base d'alcool polyvinylique conserve des caractéristiques telles qu'une capacité de formation de film de revêtement, et obtient une excellente compatibilité par rapport à des composants huileux. En conséquence, le polymère à base d'alcool polyvinylique peut être utilisé en tant que matière première pour une émulsion de type huile dans l'eau, et, lorsqu'il est transformé en une composition d'émulsion de type huile dans l'eau, il est possible de fournir une composition qui peut être mélangée dans une formulation aqueuse. (Dans la formule (1), M1 et M2 représentent chacun un atome d'hydrogène, un groupe acétyle ou un groupe siloxane représenté par la formule générale (2).)
PCT/JP2023/019846 2022-06-09 2023-05-29 Composition d'émulsion de type huile dans l'eau WO2023238715A1 (fr)

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Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1029910A (ja) * 1996-05-16 1998-02-03 Shiseido Co Ltd 化粧料
JPH11106310A (ja) * 1997-09-30 1999-04-20 Shiseido Co Ltd Ｗ／ｏ乳化組成物
JP2001278729A (ja) * 2000-03-28 2001-10-10 Shiseido Co Ltd 油中水型乳化組成物
JP2011246642A (ja) * 2010-05-28 2011-12-08 Shin-Etsu Chemical Co Ltd 置換シリルアルキルカルバミド酸ポリビニルアルコール及びその製造方法
JP2013216583A (ja) * 2012-04-04 2013-10-24 Shin-Etsu Chemical Co Ltd 化粧料
JP2016508165A (ja) * 2012-12-14 2016-03-17 ノバルティス アーゲー 両親媒性シロキサン含有ビニルモノマー及びこれらの使用
JP2017203127A (ja) * 2016-05-12 2017-11-16 信越化学工業株式会社 オルガノシロキサングラフトポリビニルアルコール系重合体及びその製造方法
JP2018002664A (ja) * 2016-07-04 2018-01-11 信越化学工業株式会社 化粧料
JP2018043938A (ja) * 2016-09-13 2018-03-22 信越化学工業株式会社 化粧料及び化粧料の製造方法
WO2021187306A1 (fr) * 2020-03-18 2021-09-23 信越化学工業株式会社 Composition cosmétique
WO2022259964A1 (fr) * 2021-06-08 2022-12-15 信越化学工業株式会社 Composé de cyclodextrine modifiée par un organopolysiloxane et produits cosmétiques le contenant

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1029910A (ja) * 1996-05-16 1998-02-03 Shiseido Co Ltd 化粧料
JPH11106310A (ja) * 1997-09-30 1999-04-20 Shiseido Co Ltd Ｗ／ｏ乳化組成物
JP2001278729A (ja) * 2000-03-28 2001-10-10 Shiseido Co Ltd 油中水型乳化組成物
JP2011246642A (ja) * 2010-05-28 2011-12-08 Shin-Etsu Chemical Co Ltd 置換シリルアルキルカルバミド酸ポリビニルアルコール及びその製造方法
JP2013216583A (ja) * 2012-04-04 2013-10-24 Shin-Etsu Chemical Co Ltd 化粧料
JP2016508165A (ja) * 2012-12-14 2016-03-17 ノバルティス アーゲー 両親媒性シロキサン含有ビニルモノマー及びこれらの使用
JP2017203127A (ja) * 2016-05-12 2017-11-16 信越化学工業株式会社 オルガノシロキサングラフトポリビニルアルコール系重合体及びその製造方法
JP2018002664A (ja) * 2016-07-04 2018-01-11 信越化学工業株式会社 化粧料
JP2018043938A (ja) * 2016-09-13 2018-03-22 信越化学工業株式会社 化粧料及び化粧料の製造方法
WO2021187306A1 (fr) * 2020-03-18 2021-09-23 信越化学工業株式会社 Composition cosmétique
WO2022259964A1 (fr) * 2021-06-08 2022-12-15 信越化学工業株式会社 Composé de cyclodextrine modifiée par un organopolysiloxane et produits cosmétiques le contenant

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