WO2022124079A1 - Oil-in-water type emulsion composition containing platinum catalyst and method of using same - Google Patents

Oil-in-water type emulsion composition containing platinum catalyst and method of using same Download PDF

Info

Publication number
WO2022124079A1
WO2022124079A1 PCT/JP2021/043041 JP2021043041W WO2022124079A1 WO 2022124079 A1 WO2022124079 A1 WO 2022124079A1 JP 2021043041 W JP2021043041 W JP 2021043041W WO 2022124079 A1 WO2022124079 A1 WO 2022124079A1
Authority
WO
WIPO (PCT)
Prior art keywords
agent
less
mass
terminated
organopolysiloxane
Prior art date
Application number
PCT/JP2021/043041
Other languages
French (fr)
Japanese (ja)
Inventor
俊 久保田
知子 佐藤
英夫 秦
Original Assignee
株式会社 資生堂
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社 資生堂 filed Critical 株式会社 資生堂
Priority to JP2022568170A priority Critical patent/JPWO2022124079A1/ja
Priority to CN202180074880.5A priority patent/CN116437972A/en
Publication of WO2022124079A1 publication Critical patent/WO2022124079A1/en

Links

Classifications

    • 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
    • A61K8/23—Sulfur; Selenium; Tellurium; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
    • A61L27/04—Metals or alloys
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/14—Macromolecular materials
    • A61L27/16—Macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/14—Macromolecular materials
    • A61L27/18—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/60—Materials for use in artificial skin

Definitions

  • the present disclosure relates to an oil-in-water emulsified composition containing a platinum catalyst and a method for using the same.
  • platinum catalysts have been used in various applications such as polymer polymerization.
  • Patent Document 1 describes a formulation for application to the skin, a) (i) a highly viscous vinyl-terminated organopoly having a viscosity of 100,000-500,000 cst or cP at 25 ° C. Reactions comprising at least one siloxane, at least one low-viscosity vinyl-terminated organopolysiloxane having a viscosity of 500-50,000 cst or cP at 25 ° C., and at least one hydride-functionalized polysiloxane.
  • It contains a sex element; and (ii) a reactive reinforcing component containing a reinforcing element; and b) a cross-linking component containing a platinum catalyst; the cross-linking component promotes cross-linking of the reactive reinforcing component in situ, resulting in a film.
  • formulations that form on the skin.
  • the platinum catalyst is typically an unstable catalyst with poor storage stability, it is generally stored in a cool and dark place in a state of being dispersed in oil and purged with nitrogen.
  • the platinum catalyst In order to increase the variation of the usage pattern of the platinum catalyst, for example, it is conceivable to use an aqueous phase in combination with the platinum catalyst and the oil phase.
  • the platinum catalyst is sensitive to water, and it has been difficult to stabilize the platinum catalyst in a system containing water. Furthermore, in a system containing water, it was even more difficult to improve the storage stability in a high temperature environment.
  • the subject of the present disclosure is to provide an oil-in-water emulsified composition containing a platinum catalyst, which is excellent in storage stability of the platinum catalyst at high temperatures.
  • An oil-in-water emulsified composition comprising a dispersion medium containing water and oil droplets dispersed in the dispersion medium.
  • the oil droplets contain an oil, an emulsifier, and a catalyst.
  • the oil contains the first unsaturated organopolysiloxane and contains
  • the catalyst contains a platinum complex coordinated with 1,3-divinyltetramethyldisiloxane, and The mass ratio of the first unsaturated organopolysiloxane to the total amount of platinum in the platinum complex is 200 or more.
  • Oil-in-water emulsified composition ⁇ Aspect 2> The composition according to aspect 1, wherein the emulsifier contains a polymer emulsifier.
  • the polymer emulsifiers are (Acrylate / alkyl acrylate (C10-30)) cross-polymer, (acryloyldimethyltaurinammonium ammonium methacrylate / behenes-25 methacrylate) cross-polymer, (hydroxyethyl acrylate / acryloyldimethyltaurine Na) copolymer, PEG.
  • the composition according to aspect 2 which is at least one selected from modified crosspolymer / copolymer siloxane, polyether modified crosspolymer / copolymer siloxane, and polyoxyethylene.
  • the first unsaturated organopolysiloxane is at least one selected from an organopolysiloxane having a vinyl group, a vinyl-terminated organopolysiloxane, and an organopolysiloxane having a vinylized branched chain.
  • the first agent comprises a second unsaturated organopolysiloxane and a hydride-functionalized polysiloxane.
  • the second agent is the oil-in-water emulsified composition according to any one of aspects 1 to 8.
  • ⁇ Aspect 10> Aspect in which the second unsaturated organopolysiloxane is at least one selected from an organopolysiloxane having a vinyl group, a vinyl-terminated organopolysiloxane, and an organopolysiloxane having a vinylized branched chain. 9. The artificial skin forming agent according to 9.
  • the second unsaturated organopolysiloxane is vinyl-terminated polydimethylsiloxane, vinyl-terminated diphenylsiloxane-dimethylsiloxane copolymer, vinyl-terminated polyphenylmethylsiloxane, vinylphenylmethyl-terminated vinylphenylsiloxane-phenylmethylsiloxane copolymer, vinyl-terminated trifluoro.
  • the artificial skin-forming agent according to aspect 10 which is at least one selected from a polymer, a vinyl T-structure polymer, a monovinyl-terminated polydimethylsiloxane, a vinylmethylsiloxane tarpolymer, and a vinylmethoxysilane homopolymer.
  • the hydride-functionalized polysiloxanes are hydride-terminated polydimethylsiloxane, hydride-terminated polyphenyl- (dimethylhydrosiloxy) siloxane, hydride-terminated methylhydrosiloxane-phenylmethylsiloxane copolymer, trimethylsiloxy-terminated methylhydrosiloxane-dimethylsiloxane copolymer, and polymethyl.
  • Skin forming agent ⁇ Aspect 14> One of embodiments 9-13, wherein the first agent, the second agent, or both of them comprises at least one selected from fibers, pigments, dyes, thickeners, protective colloid agents, and fillers. The artificial skin-forming agent described.
  • the first agent and the second agent according to any one of embodiments 9 to 14 are encapsulated in separate containers, or separately encapsulated in each compartment of a container having two or more compartments. ,kit.
  • ⁇ Aspect 16> A method of using the artificial skin forming agent according to any one of aspects 9 to 14. After the first agent is applied to the body surface to form the first agent layer, the second agent is applied onto the first agent layer and crosslinked to form an artificial skin. After the second agent is applied to the body surface to form the second agent layer, the first agent is applied onto the second agent layer and crosslinked to form an artificial skin, or After preparing a mixture by mixing the first agent and the second agent, the mixture is applied to the body surface and crosslinked to form an artificial skin. how to use.
  • an oil-in-water emulsified composition containing a platinum catalyst which is excellent in storage stability of the platinum catalyst at high temperatures.
  • the oil-in-water emulsifying composition of the present disclosure is an oil-in-water emulsifying composition containing a dispersion medium containing water and oil droplets dispersed in the dispersion medium, wherein the oil droplets are an oil component, an emulsifier, and the like.
  • a catalyst the oil content contains the first unsaturated organopolysiloxane, the catalyst contains a platinum complex coordinated with 1,3-divinyltetramethyldisiloxane, and the first relative to the total amount of platinum in the platinum complex.
  • the mass ratio of the unsaturated organopolysiloxane of 1 is 200 or more.
  • the oil-in-water emulsified composition of the present disclosure has excellent storage stability of the platinum catalyst at high temperatures, and blackening, reduction of catalytic activity, etc. due to aggregation of the platinum catalyst, etc.
  • the principle of action that can reduce or prevent defects is considered to be as follows.
  • the platinum catalyst of the present disclosure is intended to be a platinum complex represented by the following formula 1 in which 1,3-divinyltetramethyldisiloxane is coordinated with respect to platinum:
  • 1,3-divinyltetramethyldisiloxane is coordinated with respect to platinum, which causes steric hindrance and suppresses aggregation of the platinum catalyst as compared with platinum having no ligand. can do.
  • a platinum catalyst having such a ligand is mixed with a high-viscosity silicone oil, for example, if it is not stored in a cool and dark place with nitrogen purge, the platinum catalyst will aggregate and turn black. Resulting in. Aggregation of the platinum catalyst leads to an increase in the particle size of the platinum catalyst, that is, a decrease in the surface area, which may cause a decrease in the catalytic activity.
  • 1,3-divinyltetramethyldisiloxane which is a ligand, becomes easy to be attached to and detached from platinum because its thermal motion becomes active as the temperature rises.
  • the surface of platinum tends to be temporarily exposed, and when it comes into contact with adjacent platinum, it tends to aggregate, so it is considered that blackening progresses especially at high temperatures.
  • the present inventor has added a predetermined amount of a platinum catalyst to the first unsaturated organopoly, even in the case of an oil-in-water emulsified composition which is a water-containing system, which is generally said to have worse storage stability. Surprisingly, it was found that the storage stability of the platinum catalyst at high temperatures was improved when it was added to the oil phase together with siloxane.
  • the first unsaturated organopolysiloxane which is simultaneously blended in the oil phase, also has the ability to coordinate with platinum. Therefore, even if 1,3-divinyltetramethyldisiloxane deviates from platinum as the temperature rises, the first unsaturated organopolysiloxane complements the site and suppresses the progress of aggregation of the platinum catalyst. It is thought that it can be done.
  • the fact that the oil phase is dispersed in the form of fine emulsified particles (oil droplets) is considered to be one of the factors that suppress the progress of aggregation of the platinum catalyst. ing. That is, even if the complementary action of the first unsaturated organopolysiloxane occurs, the newly coordinated first unsaturated organopolysiloxane is also detached from the platinum catalyst by thermal motion, so that the surface of platinum is exposed. Can be. In the case of a single phase containing only an oil phase, since the oil phase in which the platinum catalyst is present is a continuous phase, it is considered that there is a relatively high possibility that platinum having a bare surface comes into contact with each other.
  • the oil phase is dispersed in the form of emulsified particles, and is separated from the platinum catalyst in other emulsified particles via the aqueous phase.
  • the possibility of platinum having bare surfaces coming into contact with each other is lower than in the case of a single phase containing only an oil phase.
  • the complementary action of the predetermined amount of the first unsaturated organopolysiloxane blended in the oil phase and the separating action of the platinum catalyst by the emulsified particles are synergistic. Therefore, it is thought that the storage stability of the platinum catalyst at high temperatures can be improved. Needless to say, if the storage stability at a high temperature is excellent, the storage stability at a low temperature is more excellent than that.
  • high temperature can be intended to be 50 ° C. or higher, 60 ° C. or higher, or 70 ° C. or higher, and 90 ° C. or lower, 85 ° C. or lower, or 80 ° C. or lower.
  • viscosity refers to a measure of the resistance of a fluid being deformed by either shear stress or tensile stress.
  • the viscosities of the first and second agents in an artificial skin forming agent affect the thickness, spreadability, and uniformity and / or uniformity of the layers formed on the substrate.
  • Viscosity is dynamic viscosity (also known as absolute viscosity, typical units are Pa ⁇ s, Poise, P, cP) or kinematic viscosity (typical units are cm 2 / s, Stoke, St, It can be reported as any of cst), and this kinematic viscosity is the dynamic viscosity divided by the density of the measured fluid.
  • the viscosity range of the components disclosed herein is generally a unit of kinematic viscosity (eg,) as measured by the supplier of each component using a leometer or a Canon-Fenske tube viscometer. , Cst), but the viscosity of the fluid may be, for example, a leometer (eg, a linear shear leometer or a dynamic shear leometer) or a viscometer (viscosity meter, eg, a capillary viscometer or a rotational viscometer). It can also be measured using (called).
  • a leometer eg, a linear shear leometer or a dynamic shear leometer
  • viscometer viscosity meter, eg, a capillary viscometer or a rotational viscometer
  • crosslinking in the present disclosure also includes the concept generally referred to as “curing”.
  • body surface means the skin surface of the body.
  • Oil-in-water emulsification composition >> The oil-in-water emulsified composition containing the platinum catalyst of the present disclosure (sometimes referred to simply as "composition") is excellent in storage stability of the platinum catalyst at high temperatures.
  • compositions of the present disclosure are selected from at least one temperature selected from 50 ° C, 60 ° C, and 70 ° C, and from 8 hours, 1 day, 7 days, and 14 days.
  • a D rating, a C rating, a B rating, or an A rating can be obtained in a storage stability test described later for at least one period.
  • the oil-in-water emulsified composition of the present disclosure is 5,000 cst or more immediately after preparation of the composition, for example, from the viewpoint of usability, emulsification stability, storage stability of platinum catalyst, and the like. It can be 6,000 cst or more, 7,000 cst or more, or 8,000 cst or more.
  • the upper limit of the viscosity is not particularly limited and may be, for example, 20,000 cst or less, 18,000 cst or less, or 15,000 cst or less.
  • the viscosity is a value measured with a B-type viscometer (Bismetron manufactured by Shibaura System Co., Ltd.) at 25 ° C. and 12 rotations / minute (rotor No. 3 or No. 4) for 60 seconds.
  • the dispersion medium in the oil-in-water emulsified composition of the present disclosure contains water.
  • the amount of water to be blended is not particularly limited. For example, from the viewpoint of usability, emulsion stability, storage stability of platinum catalyst, etc., 15% by mass or more, 20% by mass or more, and 30% by mass with respect to the total amount of the composition. % Or more, 40% by mass or more, 50% by mass or more, 60% by mass or more, 70% by mass or more, or 80% by mass or more, and 90% by mass or less, 80% by mass or less, 70% by mass or less. , 60% by mass or less, or 50% by mass or less.
  • the water that can be used in the oil-in-water emulsified composition of the present disclosure is not particularly limited, but water used for cosmetics, quasi-drugs, etc. can be used.
  • water used for cosmetics, quasi-drugs, etc. can be used.
  • ion-exchanged water, distilled water, ultrapure water, tap water and the like can be used.
  • oil droplets as an oil phase or a dispersed phase in an oil-in-water emulsified composition contain an oil component, an emulsifier, and a catalyst.
  • the blending amount of the oil is not particularly limited, and for example, from the viewpoint of usability, emulsion stability, storage stability of the platinum catalyst, etc., 1% by mass or more, 3% by mass or more, and 5% by mass with respect to the total amount of the composition. % Or more, 10% by mass or more, 15% by mass or more, or 20% by mass or more, and 50% by mass or less, 40% by mass or less, 30% by mass or less, 20% by mass or less, 15% by mass or less. , Or 10% by mass or less.
  • the oil content is not particularly limited, and examples thereof include liquid fats and oils, solid fats and oils, waxes, hydrocarbon oils, silicone oils, and polar oils.
  • the oil content can be used alone or in combination of two or more.
  • silicone oil is preferable from the viewpoint of compatibility with 1,3-divinyltetramethyldisiloxane, which is coordinated with the catalyst blended in the oil droplets.
  • the ratio of silicone oil in the oil content is not particularly limited, and is, for example, 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, or 90% by mass or more with respect to the total amount of oil content. Is preferable.
  • the upper limit of such a ratio is not particularly limited, but may be, for example, 100% by mass or less, less than 100% by mass, 98% by mass or less, or 95% by mass or less.
  • composition of the present disclosure contains, as an oil component, a first unsaturated organopolysiloxane which is a kind of silicone oil.
  • the first unsaturated organopolysiloxane also has a function as a dispersant for a platinum catalyst.
  • the first unsaturated organopolysiloxane is not particularly limited as long as it has the ability to improve the storage stability of the catalyst.
  • an organopolysiloxane having a vinyl group, a vinyl-terminated organopolysiloxane, and a vinylized organopolysiloxane At least one unsaturated organopolysiloxane selected from organopolysiloxanes having a branched chain can be used.
  • vinyl-terminated polydimethylsiloxane vinyl-terminated diphenylsiloxane-dimethylsiloxane copolymer
  • vinyl-terminated polyphenylmethylsiloxane vinylphenylmethyl-terminated vinylphenylsiloxane-phenylmethylsiloxane copolymer
  • vinyl-terminated trifluoropropylmethylsiloxane- vinyl-terminated polydimethylsiloxane, vinyl-terminated diphenylsiloxane-dimethylsiloxane copolymer, vinyl-terminated polyphenylmethylsiloxane, vinylphenylmethyl-terminated vinylphenylsiloxane-phenylmethylsiloxane copolymer, vinyl-terminated trifluoropropylmethylsiloxane-.
  • Dimethylsiloxane Polymer Vinyl-Terminated diethylsiloxane-Dimethylsiloxane Polymeric, Vinylmethylsiloxane-Dimethylsiloxane Polymeri, trimethylsiloxy-Terminated Vinylmethylsiloxane-Dimethylsiloxane Polymeric, Cyranol-Terminated Vinylmethylsiloxane-Dimethylsiloxane Polymericator, Vinylmethylsiloxane Homopolymer, Vinyl T -Structural polymers, vinyl Q-structural polymers, monovinyl-terminated polydimethylsiloxanes, vinylmethylsiloxane terpolymers, and vinylmethoxysilane homopolymers can be mentioned.
  • the first unsaturated organopolysiloxane can be used alone or in combination of two or more.
  • vinyl-terminated polydimethylsiloxane is preferable, and divinyldimethicone and 1,3-divinyltetramethyldisiloxane are more preferable, from the viewpoint of the complementing performance of the ligand to the catalyst and the storage stability of the catalyst.
  • the term "end” is intended to be either one end or both ends. When distinguishing these, for example, it can be expressed as "vinyl single end" or "vinyl both ends".
  • the first unsaturated organopolysiloxane is contained so that the mass ratio of the first unsaturated organopolysiloxane to the total amount of platinum in the platinum complex described later is 200 or more. ..
  • the mass ratio is preferably 230 or more, 250 or more, 270 or more, 300 or more, 350 or more, 400 or more, 450 or more, or 500 or more.
  • the upper limit of the mass ratio is not particularly limited, but may be, for example, 2,000 or less, 1,500 or less, 1,000 or less, 900 or less, 800 or less, 700 or less, 600 or less, or 500 or less. can.
  • the portion thereof is designated as the first unsaturated organopolysiloxane.
  • the storage stability of the catalyst under high temperature can be improved.
  • the mixing ratio of the first unsaturated organopolysiloxane in the oil is, for example, 50% by mass or more with respect to the total amount of the oil from the viewpoint of the complementing performance of the ligand to the catalyst and the storage stability of the catalyst. , 60% by mass or more, 70% by mass or more, 80% by mass or more, or 90% by mass or more.
  • the upper limit of such a ratio is not particularly limited, but may be, for example, 100% by mass or less, less than 100% by mass, 98% by mass or less, or 95% by mass or less.
  • the size of the first unsaturated organopolysiloxane can be indirectly specified by the viscosity. That is, it can be said that if the viscosity is small, the size is also small, and if the viscosity is large, the size is also large.
  • the viscosity of the first unsaturated organopolysiloxane at 25 ° C. is less than 1,000 cst, 700 cst or less, 500 cst or less, or 300 cst or less from the viewpoint of the complementing performance of the ligand to the catalyst and the storage stability of the catalyst. It is preferably 50 cst or more, 100 cst or more, or 150 cst or more.
  • the viscosity is a value measured with a B-type viscometer (Bismetron manufactured by Shibaura System Co., Ltd.) at 25 ° C. and 12 rotations / minute (rotor No. 3 or No. 4) for 60 seconds.
  • the first unsaturated organopolysiloxane having a viscosity of less than 1,000 cst When such a first unsaturated organopolysiloxane having a viscosity of less than 1,000 cst is used, the first unsaturated organopolysiloxane having a viscosity of less than 1,000 cst with respect to the total amount of platinum in the platinum complex is used.
  • the mass ratio is preferably more than 150, 155 or more, 160 or more, 180 or more, 200 or more, 230 or more, 250 or more, 270 or more, 300 or more, 350 or more, 400 or more, 450 or more, or 500 or more.
  • the upper limit of the mass ratio is not particularly limited, but may be, for example, 2,000 or less, 1,500 or less, 1,000 or less, 900 or less, 800 or less, 700 or less, 600 or less, or 500 or less. can.
  • the first unsaturated organopolysiloxane it is preferable to use an unsaturated organopolysiloxane having a viscosity at 25 ° C. of 50 cst or more and less than 1,000 cst.
  • an unsaturated organopolysiloxane having a viscosity at 25 ° C. of less than 50 cst is used.
  • Saturated organopolysiloxane and / or unsaturated organopolysiloxane of 1,000 cst or more may be used or used in combination.
  • the blending ratio of the unsaturated organopolysiloxane of 50 cst or more and less than 1,000 cst in the first unsaturated organopolysiloxane is, for example, 30 with respect to the total amount of the first unsaturated organopolysiloxane. It can be mass% or more, 40% by mass or more, 50% by mass or more, 60% by mass or more, 70% by mass or more, or 80% by mass or more, and less than 100% by mass, 98% by mass or less, or 95% by mass. It can be less than or equal to%.
  • the silicone oils other than the first unsaturated organopolysiloxane are not particularly limited, and for example, chain silicones such as dimethylpolysiloxane (dimethicone), methylphenylpolysiloxane, and methylhydrogenpolysiloxane; Cyclic silicones such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane can be used.
  • Other silicone oils can be used alone or in combination of two or more.
  • the emulsifier in the present disclosure is intended to be an agent having an emulsifying function (surfactant ability), and may also include an agent generally referred to as a surfactant.
  • the amount of the emulsifier to be blended is not particularly limited.
  • emulsifier for example, anionic, cationic, amphoteric, or nonionic emulsifiers can be used.
  • the emulsifier can be used alone or in combination of two or more.
  • polymer emulsifiers are preferable from the viewpoint of storage stability of the platinum catalyst.
  • the polymer emulsifier can typically be intended as an emulsifier (surfactant) having a large molecular weight and a low emulsifying ability as compared with a general emulsifier (surfactant).
  • an emulsifier having a high emulsifying ability is generally used.
  • the present inventor finds that the use of a polymer emulsifier having a relatively low emulsifying ability is even more excellent in the storage stability of the platinum catalyst. I found.
  • the effect of further improving the storage stability of the platinum catalyst by using the polymer emulsifier is considered as follows.
  • a general emulsifier (surfactant) having a high emulsifying ability other than a polymer emulsifier is used, the emulsified particles become finer, so that the emulsified composition is usually stabilized.
  • 1,3-divinyltetramethyldisiloxane is coordinated on the surface of the catalyst.
  • the emulsifier having a high emulsifying ability acts to pull out the platinum catalyst from the oil phase to the aqueous phase, so that the platinum catalyst moved to the aqueous phase side becomes unstable, aggregates, and becomes easy to blacken. thinking.
  • the polymer emulsifier having a low emulsifying ability can stably store the platinum catalyst in the oil phase because the pulling action of the platinum catalyst into the aqueous phase is weak.
  • the weight average molecular weight of the polymer emulsifier can be 500 or more, 700 or more, 1,000 or more, 1,500 or more, or 2,000 or more from the viewpoint of emulsion stability, storage stability of the platinum catalyst, and the like. ..
  • the upper limit of the weight average molecular weight of the polymer emulsifier is not particularly limited, and may be, for example, 1,000,000 or less, 100,000 or less, 10,000 or less, or 5,000 or less.
  • dissolve the emulsifier in N, N-dimethylformamide (DMF) dissolve the emulsifier in N, N-dimethylformamide (DMF) to prepare a 0.5% solution, and use this to prepare a 0.5% solution by GPC (gel permeation chromatography) under the following conditions.
  • DMF N, N-dimethylformamide
  • the polymer emulsifier is not particularly limited, and is, for example, (Acrylate / alkyl acrylate (C10-30)) crosspolymer, (acryloyldimethyltaurineammonium / behenes-25 methacrylate) crosspolymer, (hydroxyethyl acrylate / acryloyldimethyl).
  • At least one selected from taurine Na) copolymer, PEG-modified crosspolymer / copolymer siloxane, polyether-modified crosspolymer / copolymer siloxane, and polyoxyethylene can be mentioned.
  • (Acrylate / alkyl acrylate (C10-30)) crosspolymer is preferable from the viewpoint of emulsion stability, storage stability of platinum catalyst and the like.
  • the amount of general emulsifiers (surfactants) other than polymer emulsifiers (surfactants), especially silicone emulsifiers is small from the viewpoint of storage stability of the platinum catalyst.
  • the blending amount of such an emulsifier is, for example, less than 1% by mass, 0.7% by mass or less, 0.5% by mass or less, 0.3% by mass or less, or 0.1 by mass with respect to the total amount of the composition. It is preferably not more than% by mass, and it is more preferable that such an emulsifier is not contained in the composition.
  • the weight average molecular weight of general emulsifiers (surfactants) other than polymer emulsifiers can be less than 500, 450 or less, or 400 or less, and 100 or more, 150 or more, or 200 or more. Can be done.
  • the HLB of a general emulsifier (surfactant) other than a polymer emulsifier can be 2.0 or more, 3.0 or more, or 4.0 or more, and 10.0 or less, 9.0. It can be less than or equal to or less than 8.0.
  • the emulsified composition of the present disclosure contains, as a catalyst, at least a platinum complex coordinated with 1,3-divinyltetramethyldisiloxane represented by the following formula 1.
  • the content of the platinum complex is not particularly limited, and is 0.01% by mass or more, 0.05% by mass or more, 0.10% by mass or more, 0.15% by mass or more, or 0.15% by mass or more, based on the total amount of the composition. It can be 0.20% by mass or more.
  • the upper limit of the content is not particularly limited, and is 3.0% by mass or less, 2.5% by mass or less, 2.0% by mass or less, 1.5% by mass or less, 1.0% by mass or less, 0.70. It can be mass% or less, 0.50 mass% or less, or 0.30 mass% or less.
  • the content of platinum itself in the platinum complex is not particularly limited, and is 0.001% by mass or more, 0.005% by mass or more, 0.010% by mass or more, and 0.015% by mass with respect to the total amount of the composition.
  • the above, or 0.020% by mass or more can be used.
  • the upper limit of the content is not particularly limited and may be 1.0% by mass or less, 0.50% by mass or less, 0.10% by mass or less, or 0.050% by mass or less.
  • the emulsified composition of the present disclosure may contain other catalysts in addition to the above-mentioned platinum complex as long as the effects of the present disclosure are not affected.
  • catalysts examples include Group VIII metal catalysts, such as platinum catalysts other than the platinum complex, rhodium catalysts, palladium catalysts, cobalt catalysts, nickel catalysts, ruthenium catalysts, osmium catalysts, and iridium catalysts, and IVA.
  • Group metal catalysts such as germanium catalysts and tin catalysts can be mentioned.
  • Other catalysts can be used alone or in combination of two or more.
  • platinum catalysts other than the platinum complex include platinum carbonylcyclovinylmethylsiloxane complex, platinumcyclovinylmethylsiloxane complex, platinum octanealdehyde / octanol complex, and other Pt (0) catalysts, such as Karlstead catalyst.
  • Platinum-alcohol complex platinum-alkoxide complex, platinum-ether complex, platinum-aldehyde complex, platinum-ketone complex, platinum-halogen complex, platinum-sulfur complex, platinum-nitrogen complex, platinum-phosphorus complex, platinum-carbon double Bonded complex, platinum carbon triple bond complex, platinum-imide complex, platinum-amide complex, platinum-ester complex, platinum-phosphate ester complex, platinum-thiol ester complex, platinum isolated electron pair complex, platinum-aromatic complex, platinum ⁇ -Electronic complexes and combinations thereof can be mentioned.
  • rhodium catalyst examples include tris trichloride (dibutyl sulfide) rhodium and rhodium trichloride hydrate.
  • tin catalyst examples include tin octanoate (II), tin neodecanoate (II), dibutyltin diisooctylmaleate, di-n-butylbis (2,4-pentandionate) tin, and di-n-butylbutoxy. Included are chlorotin, dibutyltin dilaurate, dimethyltin dineodecanoate, dimethylhydroxy (oleate) tin, and tin oleate (II).
  • the blending amount of the catalyst other than the platinum complex may be less than 50% by mass, 30% by mass or less, 10% by mass or less, 5% by mass or less, or 1% by mass or less with respect to the total amount of the catalyst. .. From the viewpoint of emulsion stability, storage stability of the platinum catalyst, etc., it is preferable that other catalysts are not contained in the emulsified composition.
  • the oil-in-water emulsified composition of the present disclosure may appropriately contain various components as long as it does not affect the effects of the present disclosure.
  • Such optional components include, for example, moisturizing agents, emollients, thickeners, water-soluble polymers, oil-soluble polymers, film-forming agents such as siliconeized polysaccharides, higher fatty acids such as isostearic acid, and metal ion sequestering agents.
  • Lower alcohols such as ethanol, higher alcohols such as stearyl alcohol, polyhydric alcohols such as 1,3-butylene glycol, various extracts, sugars, amino acids, organic amines, chelating agents, ultraviolet absorbers, pH adjusters, skin nutrition
  • Water-soluble agents applicable to agents, vitamins, pharmaceuticals, non-pharmaceutical products, cosmetics, etc., buffers, anti-fading agents, preservatives, propellants, organic powders, pigments, dyes, pigments, fragrances, etc. can.
  • the optional ingredients can be used alone or in combination of two or more.
  • the oil-in-water emulsified composition of the present disclosure described above can be used for various purposes. Although not limited to the following uses, the oil-in-water emulsified composition of the present disclosure has excellent storage stability of the platinum catalyst, and can reduce or suppress defects such as discoloration, so that it is possible to prevent changes in color tone. It can be suitably used as a second agent of an artificial skin forming agent containing a first agent and a second agent, for example, in a desired application. Such an artificial skin forming agent is obtained, for example, by applying the first agent to the body surface to form the first agent layer and then applying the second agent to the first agent layer to crosslink the first agent layer. Artificial skin can be formed.
  • the application performance of the artificial skin forming agent can be evaluated by the viscosity using a B-type viscometer (Shibaura System Co., Ltd., Bismetron).
  • the viscosities of the first and second agents of the artificial skin forming agent of the present disclosure measured under the conditions of 25 ° C. and 60 rotations / minute (rotor No. 3 or No. 4) immediately after preparation are, for example, 100 mPa ⁇ s or more.
  • 500 mPa ⁇ s or more, 1,000 mPa ⁇ s or more, 2,000 mPa ⁇ s or more, 5,000 mPa ⁇ s or more, 7,500 mPa ⁇ s or more, 10,000 mPa ⁇ s or more, or 15,000 mPa ⁇ s or more Can be 1,000,000 mPa ⁇ s or less, 750,000 mPa ⁇ s or less, 500,000 mPa ⁇ s or less, 250,000 mPa ⁇ s or less, 200,000 mPa ⁇ s or less, 175,000 mPa ⁇ s or less, 150, It can be 000 mPa ⁇ s or less, 125,000 mPa ⁇ s or less, 100,000 mPa ⁇ s or less, or 80,000 mPa ⁇ s or less.
  • the artificial skin forming agent has a viscosity of 20,000 mPa ⁇ s or less, 15,000 mPa ⁇ s or less, or 10,000 mPa ⁇ s or less from the viewpoint of smooth application performance and suppression of dripping from the skin. It is preferable to have a viscosity of 3,000 mPa ⁇ s or more, 5,000 mPa ⁇ s or more, or 7,000 mPa ⁇ s or more.
  • the viscosities of the first agent and the second agent in the artificial skin forming agent of the present disclosure measured under the conditions of 25 ° C. and 60 rpm (rotor No. 3) after 2 weeks are determined. From the viewpoint of smooth application performance and suppression of dripping from the skin, it is preferably 50,000 mPa ⁇ s or less, 30,000 mPa ⁇ s or less, or 15,000 mPa ⁇ s or less, preferably 5,000 mPa ⁇ s or more. It is preferably 7,000 mPa ⁇ s or more, or 10,000 mPa ⁇ s or more.
  • the film performance of the artificial skin can be evaluated, for example, by the presence or absence of tearing of the artificial skin when peeled from the skin. For example, when the tearing of the applied artificial skin is 15% or less, 10% or less, or 5% or less of the whole, it can be said that the film performance is excellent.
  • the lower limit of tearing is not particularly limited, but may be, for example, 0% or more or more than 0%.
  • the film performance can be evaluated based on the tensile strength and elongation at break, which will be described later.
  • the first agent constituting the artificial skin forming agent of the present disclosure contains a second unsaturated organopolysiloxane and a hydride-functionalized polysiloxane.
  • the first agent may be, for example, in the form of an anhydrous form, or may be in the form of an oil-in-water type or a water-in-oil type emulsion, but the drying property after the first agent is applied to the body surface. From the viewpoint of crosslinkability and the like, it is advantageous that the first agent is in an anhydrous form.
  • anhydrous form usually does not require a preservative against bacteria or mold, so it can be stored for a longer period of time than an emulsion with similar components.
  • anhydrous means that the composition does not contain water, and the content of water is low, that is, 10% by mass or less, 5% by mass or less. It is also intended to be 2% by mass or less, 1% by mass or less, or 0.1% by mass or less.
  • the first agent is applied to the body surface by coating or the like, it is preferable to have a glass transition temperature equal to or lower than the body temperature from the viewpoint of coating performance.
  • the glass transition temperature can be 37 ° C. or lower, 25 ° C. or lower, 10 ° C. or lower, or 0 ° C. or lower.
  • the lower limit of the glass transition temperature is not particularly limited, but may be, for example, ⁇ 30 ° C. or higher, ⁇ 20 ° C. or higher, or ⁇ 10 ° C. or higher.
  • the "glass transition temperature” refers to the temperature at which the transition from the solid state to the liquid state occurs, and can be measured using, for example, a differential scanning calorimeter (DSC) compliant with ASTM D3418-03.
  • DSC differential scanning calorimeter
  • the second unsaturated organopolysiloxane is not particularly limited, and examples thereof include one or more organopolysiloxanes having at least two carbon-carbon double bonds or at least one carbon-carbon triple bond in the molecule. can.
  • the second unsaturated organopolysiloxane is preferably one or more organopolysiloxanes having at least two alkenyl functional groups on average and a viscosity of 10,000-2,000,000 cst at 25 ° C. be able to.
  • "carbon-carbon double bond” and “carbon-carbon triple bond” may be simply referred to as "double bond” and "triple bond".
  • the second unsaturated organopolysiloxane can be used alone or in combination of two or more.
  • Such organopolysiloxanes may contain double or triple bonds in the terminal units of the polymer, in the non-terminal monomer units of the polymer, or in combinations thereof, among others, in the non-terminal monomer units of the polymer. Is preferable.
  • the double bond-containing monomer units in the organopolysiloxane averaged 40 monomer units or more, 200 monomer units or more, 400 monomer units or more, 1,000 monomer units or more, or 2,000 monomer units. It may be separated by more than that.
  • the amount of double or triple bond containing monomer units of an organopolysiloxane having a double or triple bond can be, for example, 0.01% by weight or more or 0.03% by weight or more. , 2% by mass or less or 0.6% by mass or less.
  • the vinyl equivalent of the organopolysiloxane having a double or triple bond can be, for example, 0.005 or more or 0.01 or more per kilogram, 0.5 or less or 0.25. It can be:
  • the approximate molar amount of double or triple bonds in an organopolysiloxane can be calculated based on the average molecular weight of the organopolysiloxane.
  • the average molecular weight or molecular mass of each component in the artificial skin-forming agent disclosed herein is generally provided by the supplier of each component and is in units of dalton (Da) or equivalent g / mol. Can be represented.
  • the second unsaturated organopolysiloxane can have a viscosity of 10,000-2,000,000 cst at 25 ° C.
  • the lower limit of the viscosity is preferably 20,000 cst or more, 40,000 cst or more, 60,000 cst or more, 80,000 cst or more, or 100,000 cst or more, and 125,000 cst or more or 150,000 cst or more. Is more preferable.
  • the upper limit of the viscosity is preferably 1,000,000 cst or less, 500,000 cst or less, 450,000 cst or less, 400,000 cst or less, 350,000 cst or less, 300,000 cst or less, or 250,000 cst or less. It is more preferably 200,000 cst or less or 180,000 cst or less, and further preferably 165,000 cst or less.
  • the second unsaturated organopolysiloxane can have an average molecular weight of 60,000 Da to 500,000 Da.
  • the lower limit of the average molecular weight is preferably 72,000 Da or more, 84,000 Da or more, 96,000 Da or more, or 100,000 Da or more, and more preferably 140,000 Da or more or 150,000 Da or more. ..
  • the upper limit of the average molecular weight is preferably 200,000 Da or less, 190,000 Da or less, 180,000 Da, or 170,000 Da or less, more preferably 160,000 Da or less, and further preferably 155,000 Da or less. preferable.
  • the second unsaturated organopolysiloxane for example, at least one selected from an organopolysiloxane having a vinyl group, a vinyl-terminated organopolysiloxane, and an organopolysiloxane having a vinylized branched chain is mentioned. Can be done.
  • Such a second unsaturated organopolysiloxane include vinyl-terminated polydimethylsiloxane, vinyl-terminated diphenylsiloxane-dimethylsiloxane copolymer, vinyl-terminated polyphenylmethylsiloxane, and vinylphenylmethyl-terminated vinylphenylsiloxane.
  • -Phenylmethylsiloxane copolymer vinyl-terminated trifluoropropylmethylsiloxane-dimethylsiloxane copolymer, vinyl-terminated diethylsiloxane-dimethylsiloxane copolymer, vinylmethylsiloxane-dimethylsiloxane copolymer, trimethylsiloxy-terminated vinylmethylsiloxane-dimethylsiloxane copolymer, silanol-terminated vinylmethyl At least one selected from a siloxane-dimethylsiloxane copolymer, a vinylmethylsiloxane homopolymer, a vinyl T-structure polymer, a monovinyl-terminated polydimethylsiloxane, a vinylmethylsiloxane tarpolymer, and a vinylmethoxysilane homopolymer can be employed.
  • vinyl-terminated polydimethylsiloxane is preferable, and
  • the blending amount of the second unsaturated organopolysiloxane in the first agent may be appropriately adjusted according to the required coating performance and the like, and is not particularly limited.
  • the blending amount of the second unsaturated organopolysiloxane is 5% by mass or more, 10% by mass or more, 20% by mass or more, 30% by mass or more, 35% by mass or more, or 40 with respect to the entire first agent. It can be 90% by mass or less, 80% by mass or less, 70% by mass or less, 60% by mass or less, 50% by mass or less, or 45% by mass or less.
  • Hydride-functionalized polysiloxane is not particularly limited, and examples thereof include compounds of the following formula 2. Hydride-functionalized polysiloxanes can be used alone or in combination of two or more:
  • R 1b , R 2b , R 3b , R 4b , R 5b , R 6b , R 7b , R 8b , R 9b and R 10b are independently hydrogen, C 1-20 alkyl and C 2 respectively. Selected from -20 alkenyl, C 5-10 aryl, hydroxyl, or C 1-20 alkoxy, m and n are independently integers from 10 to 6000. However, at least one of R 1b , R 2b , R 3b , R 4b , R 5b , R 6b , R 7b , R 8b , R 9b and R 10b is hydrogen.
  • At least one of R 1b , R 2b , R 3b , R 4b , R 5b , R 6b , R 7b , R 8b , R 9b and R 10b is hydrogen and the rest is C 1- . It is 20 alkyl.
  • At least two of R 1b , R 2b , R 3b , R 4b , R 5b , R 6b , R 7b , R 8b , R 9b and R 10b are hydrogen (eg, functionalized hydrides). 2 Si—H units per polysiloxane molecule).
  • R 1b , R 2b , R 3b , R 4b , R 5b , R 6b , R 7b , R 8b , R 9b and R 10b are hydrogen (eg, a functionalized hydride polysiloxane molecule). 3 Si—H units per unit).
  • At least two of R 1b , R 2b , R 3b , R 4b , R 5b , R 6b , R 7b , R 8b , R 9b and R 10b are hydrogen (eg, functionalized hydride polysiloxane). 2 Si—H units per molecule), with the rest being C 1-20 alkyl.
  • R 1b , R 2b , R 3b , R 4b , R 5b , R 6b , R 7b , R 8b , R 9b and R 10b are hydrogen (eg, a functionalized hydride polysiloxane molecule). 3 per Si—H unit), the rest are C 1-20 alkyl.
  • At least two of R 4b , R 5b , R 9b and R 10b are hydrogen (eg, two Si—H units per functionalized hydride polysiloxane molecule) and the rest are C 1- . It is 20 alkyl.
  • At least three of R 4b , R 5b , R 9b and R 10b are hydrogen (eg, 3 Si—H units per functionalized hydride polysiloxane molecule) and the rest are C 1-20 . It is alkyl.
  • the sum of m and n is 10-1,300, 10-1,100, 10-600, 15-500, 15-400, 20-300, 20-200, 25-100, It is an integer of 25 to 75, 30 to 50, or 40 to 45.
  • the hydride-functionalized polysiloxane can include a non-terminal and / or terminally hydroxylated organopolysiloxane, and one or more having at least two Si—H units in the molecule.
  • a non-terminal and / or terminally hydroxylated organopolysiloxane can be mentioned, preferably, one or more organopolysiloxanes composed of the organopolysiloxanes of the above, preferably having at least two Si—H units on average and having a viscosity of 2 to 100,000 cst at 25 ° C.
  • the organopolysiloxane having Si—H units may contain such Si—H units in the terminal units of the polymer, in the non-terminal monomer units of the polymer, or in combinations thereof.
  • the Si—H unit is preferably contained in the non-terminal monomer unit of the polymer.
  • the hydride-functionalized polysiloxane in this case may be alkyl-terminated.
  • R 2b and R 7b may be C 1-20 alkyl.
  • R 1b , R 2b , R 3b , R 6b , R 7b and R 8b are C 1-20 alkyl. May be.
  • R 1b , R 2b , R 3b , R 4b , R 5b , R 6b , R 7b , R 8b and R 10b are C 1-20 alkyl, eg, C 1 alkyl (eg, methyl), respectively.
  • R 9b may be hydrogen.
  • R 1b , R 2b , R 3b , R 4b , R 5b , R 6b , R 7b , R 8b and R 9b are C 1-20 alkyl, eg, C 1 alkyl (eg, methyl), respectively.
  • R 10b may be hydrogen.
  • the Si—H-containing monomer unit in the organopolysiloxane averages 1 monomer unit or more, 2 monomer units or more, 5 monomer units or more, 10 monomer units or more, 20 monomer units or more, and 40 monomer units. As mentioned above, it may be separated by 200 monomer units or more, 400 monomer units or more, 1,000 monomer units or more, or 2,000 monomer units or more.
  • the Si—H-containing monomer unit amount of the organopolysiloxane having Si—H units is 0.003% by mass or more, 0.01% by mass or more, 0.1% by mass or more, and 1% by mass or more. It can be 3% by mass or more, 5% by mass or more, 10% by mass or more, 20% by mass or more, or 26% by mass or more, and 50% by mass or less, 45% by mass or less, 40% by mass or less, 35% by mass. % Or less, 30% by mass or less, or 27% by mass or less.
  • the Si—H content of the organopolysiloxane having the Si—H unit is 0.1 mmol / g or more, 0.5 mmol / g or more, 1 mmol / g or more, 2 mmol / g or more, 3 mmol / g or more. , Or 4 mmol / g or more, 20 mmol / g or less, 10 mmol / g or less, 9 mmol / g or less, 8 mmol / g or less, 7 mmol / g or less, 6 mmol / g or less, or 5 mmol / g or less. Can be done.
  • the approximate molar amount of Si—H units in the organopolysiloxane can be calculated based on the average molecular weight of the organopolysiloxane.
  • the hydride functionalized polysiloxane can have a viscosity of 2 to 500,000 cst at 25 ° C.
  • the lower limit of the viscosity is preferably 3 cst or more, 4 cst or more, 5 cst or more, 10 cst or more, 12 cst or more, 15 cst or more, 20 cst or more, 25 cst or more, or 30 cst or more, and more preferably 40 cst or more.
  • the upper limit of the viscosity shall be 200,000 cst or less, 100,000 cst or less, 50,000 cst or less, 20,000 cst or less, 10,000 cst or less, 5,000 cst or less, 2,000 cst or less, or 1,000 cst or less. Is preferable, and 500 cst or less is more preferable.
  • the viscosity of the hydride-functionalized polysiloxane is particularly preferably in the range of 45 to 100 cst or 45 to 50 cst at 25 ° C.
  • the hydride functionalized polysiloxane can have an average molecular weight of 400-500,000 Da.
  • the lower limit of the average molecular weight is 500 Da or more, 800 Da or more, 900 Da or more, 1,000 Da or more, 1,200 Da or more, 1,400 Da or more, 1,600 Da or more, 1,800 Da or more, 2,000 Da or more, or 2 , 200 Da or more, more preferably 2,300 Da or more.
  • the upper limit of the average molecular weight is 250,000 Da or less, 140,000 Da or less, 100,000 Da or less, 72,000 Da or less, 62,700 Da or less, 60,000 Da or less, 50,000 Da or less, 49,500 Da or less, 36, It is preferably 000 Da or less, 28,000 Da or less, 25,000 Da or less, 20,000 Da or less, 15,000 Da or less, 10,000 Da or less, 5,000 Da or less, or 4,000 Da or less, preferably 2,500 Da or less. Is more preferable.
  • Hydride-functionalized polysiloxanes are, but are not limited to, for example, hydride-terminated polydimethylsiloxanes, hydride-terminated polyphenyl- (dimethylhydrosiloxy) siloxanes, hydride-terminated methylhydrosiloxane-phenylmethylsiloxane copolymers, trimethylsiloxy-terminated methyls.
  • hydrosiloxane-dimethylsiloxane copolymer polymethylhydrosiloxane
  • trimethylsiloxy-terminated polyethylhydrosiloxane triethylsiloxane
  • methylhydrosiloxane-phenyloctylmethylsiloxane copolymer methylhydrosiloxane-phenyloctylmethylsiloxane tarpolymer.
  • the blending amount of the hydride-functionalized polysiloxane in the first agent may be appropriately adjusted according to the required film performance and the like, and is not particularly limited.
  • the blending amount of the hydride-functionalized polysiloxane can be 1% by mass or more, 3% by mass or more, or 5% by mass or more, and 75% by mass or less, 60% by mass or less, based on the entire first agent. , 50% by mass or less, 40% by mass or less, 30% by mass or less, 20% by mass or less, or 10% by mass or less.
  • the first agent can optionally include other polymers.
  • Other polymers can be used alone or in combination of two or more.
  • the other polymer can have a viscosity of 0.7 cst to 50,000 cst at 25 ° C.
  • the lower limit of the viscosity is 1 cst or more, 6 cst or more, 10 cst or more, 20 cst or more, 50 cst or more, 100 cst or more, 200 cst or more, 300 cst or more, 400 cst or more, 750 cst or more, 1,000 cst or more, 1,500 cst or more, 2, It can be 000 cst or more, 2,500 cst or more, 3,000 cst or more, 3,500 cst or more, or 4000 cst or more.
  • the upper limit of the viscosity is 45,000 cst or less, 40,000 cst or less, 35,000 cst or less, 30,000 cst or less, 25,000 cst or less, 20,000 cst or less, 15,000 cst or less, 12,000 cst or less, 10,000 cst or less.
  • it can be 5,000 cst or less, 4,000 cst or less, 2,000 cst or less, 1,500 cst or less, or 1,000 cst or less.
  • the other polymer can have an average molecular weight of 180Da-80,000Da.
  • the lower limit of the average molecular weight is 500 Da or more, 800 Da or more, 1,500 Da or more, 3,000 Da or more, 6,000 Da or more, 9,400 Da or more, 10,000 Da or more, 15,000 Da or more, 20,000 Da or more, It can be 30,000 Da or more, 40,000 Da or more, 50,000 Da or more, 55,000 Da or more, 60,000 Da or more, or 62,000 Da or more.
  • the upper limit of the average molecular weight can be 75,000 Da or less, 70,000 Da or less, 65,000 Da or less, or 63,000 Da or less.
  • one or more organopolysiloxanes having at least one alkenyl functional group on average and having a viscosity of 0.7 to 50,000 cst at 25 ° C. can be mentioned.
  • vinyl-terminated polydimethylsiloxane for example, vinyl-terminated diphenylsiloxane-dimethylsiloxane copolymer, vinyl-terminated polyphenylmethylsiloxane, vinylphenylmethyl-terminated vinylphenylsiloxane-phenylmethylsiloxane copolymer, vinyl-terminated tori.
  • Fluoropropylmethylsiloxane-dimethylsiloxane polymer vinyl-terminated diethylsiloxane-dimethylsiloxane copolymer, vinylmethylsiloxane-dimethylsiloxane copolymer, trimethylsiloxy-terminated vinylmethylsiloxane-dimethylsiloxane copolymer, silanol-terminated vinylmethylsiloxane-dimethylsiloxane copolymer, vinyl-terminated vinyl rubber , Vinyl Methylsiloxane Homopolymer, Vinyl T-Structural Polymer, Vinyl Q-Structural Polymer, Unsaturated Organic Polymer (eg, Unsaturated Fat Alcohol, Unsaturated Fatty Acid, Unsaturated Fat Ester, Unsaturated Fat Amid, Unsaturated Fat Urethane, Unsaturated fatty ureas, ceramides, crosetins, lecithins
  • the blending amount of the other polymer in the first agent may be appropriately adjusted according to the required coating performance and the like, and is not particularly limited.
  • the blending amount of the other polymer may be 0.01% by mass or more, 0.1% by mass or more, 0.3% by mass or more, or 0.5% by mass or more with respect to the entire first agent. It can be 20% by mass or less, 15% by mass or less, or 10% by mass or less.
  • the molar ratio of the Si—H functional group derived from the hydride-functionalized polysiloxane to the alkenyl functional group derived from the second unsaturated organopolysiloxane is preferably 60: 1 to 1: 5. , 45: 1 to 15: 1, more preferably.
  • the molar ratio of Si—H functional groups derived from hydride-functionalized polysiloxane to alkenyl functional groups derived from other polymers is preferably 60: 1 to 1: 5, preferably 45: 1 to 45. It is more preferably 15: 1.
  • the molar ratio of the alkenyl functional group derived from the second unsaturated organopolysiloxane to the alkenyl functional group derived from the other polymer is preferably 100: 1 to 1: 100, 10: 1. It is more preferably ⁇ 1:10.
  • the oil-in-water emulsified composition of the present disclosure described above can be used as a second agent of an artificial skin forming agent.
  • the catalyst contained in such a composition can promote the cross-linking of the above-mentioned second unsaturated organopolysiloxane and hydride-functionalized polysiloxane.
  • the artificial skin forming agent of the present disclosure may contain one or more arbitrary components with respect to the first agent and / or the second agent as long as the effects of the present disclosure are not affected.
  • the optional component is not particularly limited, but for example, a feel modifier, a tackifier modifier, a spread accelerator, a diluent, an adhesion modifier, an emulsifier, an emollient agent, a surfactant, a solvent, a film forming agent, etc.
  • Emulsifiers preservatives, fibers, pigments, dyes, thickeners, protective colloids, fillers, skin permeation enhancers, optical modifiers, scatterers, adsorbents, magnetic materials, gas transport modifiers, liquids Examples include transport modifiers, pH modifiers, sensitizer modifiers, and aesthetic modifiers.
  • Fillers include, for example, carbon, silver, mica, zinc sulfide, zinc oxide, titanium dioxide, aluminum oxide, clay, chalk, talc, calculus (eg CaCO 3 ), barium sulfate, zirconium dioxide, polymer beads, silica (eg, CaCO 3).
  • silica eg, CaCO 3
  • fumed silica, silicic acid, or anhydrous silica silica aluminate
  • calcium silicate can be mentioned, which may be surface treated.
  • Such a filler can improve the physical properties (eg strength) of the coating (artificial skin) and can also serve as a viscosity modifier.
  • surface-treated silica for example, silica treated with a surface-treating agent such as hexamethyldisilazane, polydimethylsiloxane, hexadecylsilane, or methacrylsilane is preferable.
  • fumed silica is also preferable, and for example, fumed silica surface-treated with hexamethyldisilazane or the like can also be preferably used.
  • the filler can have a specific surface area of 50-500 m 2 / g.
  • the specific surface area of the filler is preferably 100 to 350 m 2 / g, more preferably 135 to 250 m 2 / g.
  • the specific surface area of the filler can be calculated using the BET method.
  • the filler can have a particle size equivalent to an area circle of 1 nm to 20 ⁇ m.
  • the particle size corresponding to the area circle of the filler is preferably 2 nm to 1 ⁇ m, and more preferably 5 nm to 50 nm.
  • the particle size equivalent to the area circle of the filler is intended to be, for example, the particle size when converted into circular particles having the same area as the projected area of the filler particles observed with a transmission electron microscope. can.
  • the particle size corresponding to the area circle can be defined as an average value of 10 or more particles.
  • the blending amount may be, for example, 1% by mass or more, 3% by mass or more, or 5% by mass or more, and 25% by mass, based on the entire first agent. Hereinafter, it can be 15% by mass or less, or 10% by mass or less.
  • the mass ratio of the total amount of the second unsaturated organopolysiloxane, hydride-functionalized polysiloxane and other polymers to the filler is 100: 1 to 1: 1. It can be preferably 50: 1 to 2: 1, more preferably 15: 1 to 3: 1, still more preferably 10: 1 to 4: 1, and particularly preferably 5. 1 to 9: 1.
  • At least one selected from pigments, dyes and fillers is preferably added to the first agent.
  • pigments and dyes when these are blended in the second agent, if this second agent is applied to the application surface of the first agent, it will harden in the middle and the pigment or dye will be formed. Color unevenness may occur because it is easy to localize. From the viewpoint of suppressing color unevenness, it is advantageous to add the pigment and the dye to the first agent.
  • the second agent may contain a pigment, a dye and a filler as long as color unevenness does not occur, but it is advantageous that these are not included in the second agent.
  • compositions of the present disclosure may further comprise one or more agents with respect to the first and / or second agent.
  • agents include cosmetics, therapeutic agents, stimulant responsive agents, and drug delivery agents.
  • Suitable cosmetic agents include, for example, moisturizers, UV absorbers, skin protectants, skin soothing agents, skin whitening agents, skin brighteners, skin softening agents, skin smoothing agents, skin bleaching agents, skin keratin removers, etc.
  • Suitable therapeutic agents include, for example, pain relievers, analgesics, antipruritic agents, anti-sciatic agents (eg, ⁇ -hydroxy acid, salicylic acid, benzoyl peroxide), anti-inflammatory agents, anti-histamine agents, corticosteroids.
  • NSAID non-steroidal anti-inflammatory drug
  • preservatives antibiotics, antibacterial agents, antifungal agents, antiviral agents, antiallergic agents, antistimulants, insect repellents, phototherapy agents, blood coagulants, anti-new
  • biopharmaceuticals include biopharmaceuticals, immune system enhancers, immune system suppressants, coaltal, anthraline, fluorinide, methotrexate, cyclosporin, pimechlorimus, tachlorimus, azathiopurine, fluorouracil, ceramide, anti-inflammatory agents, and skin cooling compounds.
  • Suitable agents include, for example, whitening agents, activators, blood circulation promoters, anti-inflammatory agents, antioxidants, enzymes, vitamins, hormones, antibacterial agents, anti-fat leak agents, amino acids and their derivatives, sugar alcohols and Examples thereof include derivatives thereof, fat-soluble agents, fat-soluble treated agents, and hair-growth agents. These can be used alone or in combination.
  • Examples of the whitening agent include hydroquinone ⁇ -D-glucose, hydroquinone ⁇ -D-glucose (arbutin), hydroquinone ⁇ -L-glucose, hydroquinone ⁇ -L-glucose, hydroquinone ⁇ -D-galactose, and hydroquinone ⁇ -D-.
  • Hydroquinone derivatives such as galactose, hydroquinone ⁇ -L-galactose, hydroquinone ⁇ -L-galactose; kodiic acid and its salts or derivatives thereof; for example L-ascorbic acid monophosphate ester, L-ascorbic acid 2-sulfate ester and the like L- Ascorbic acid monoesters, L-ascorbic acid glucosides such as L-ascorbic acid 2-glucoside, or L-ascorbic acid such as salts thereof and salts thereof or derivatives thereof; for example, tranexamic acid, dimers of tranexamic acid ( For example, trans-4- (trans-aminomethylcyclohexanecarbonyl) aminomethylcyclohexanecarboxylic acid), an ester of tranexamic acid and hydroquinone (eg, trans-4-aminomethylcyclohexanecarboxylic acid 4'-hydroxyphenyl ester).
  • Elagic acid and its salts or derivatives thereof for example salicylic acid, 3-methoxysalicylic acid and its salts, 4-methoxysalicylic acid and its salts, 5-methoxysalicylic acid and its salts and the like salicylic acid and its salts or derivatives thereof; phenylethyl resorcinol, Examples thereof include alkyl resorcinols such as resorcin, 4-n-butylresorcinol, and resorcinol derivatives such as salts thereof; niacin and derivatives thereof such as nicotinic acid amide; nucleotides such as adenosine and guanosine or derivatives thereof, and the like.
  • activator examples include royal jelly; photosensitizer; cholesterol derivative and the like.
  • Examples of the blood circulation promoter include nonylate valenylamide; nicotinic acid benzyl ester; nicotinic acid ⁇ -butoxyethyl ester; capsaicin; zingeron; cantalistinki; ictamol; tannic acid; ⁇ -borneol; tocopherol nicotinate; inositol hexanicotinate.
  • Cicrandelate; cinnaridine; trazoline; acetylcholine derivative; verapamil; cepharanthin; ⁇ -orizanol; carbronium chloride and the like are exemplified.
  • anti-inflammatory agent examples include tranexamic acid; thiotaurine; hypotaurine; glycyrrhizinic acid derivative; glycyrrhetinic acid derivative; salicylic acid derivative; hinokitiol; zinc oxide; allantoin and the like.
  • antioxidants examples include thiotaurine; glutathione; catechin; albumin; ferritin; metallothionein and the like.
  • enzymes examples include trypsin; lysozyme chloride; chymotrypsin; semi-alkaline protectase; serrapeptase; lipase; hyaluronidase and the like.
  • vitamins examples include vitamin B6; vitamin B6 derivatives such as vitamin B6 hydrochloride; vitamin B2; vitamin B12; nicotinic acid; nicotinic acid derivatives such as nicotinic acid amide; pantotenil ethyl ether and the like.
  • hormonal agent examples include oxytocin; corticotropin; vasopressin; secretin; gastrin; calcitonin and the like.
  • antibacterial agent examples include resorcin; sulfur; salicylic acid; zinc pyrithione; photosensitive element 101; photosensitive element 102; orthovirox; hinokitiol and the like.
  • antiseborrheic agent examples include sulfur; thiantoll and the like.
  • amino acids and their derivatives include serine; methionine; tryptophan; glycine; trimethylglycine; glycylglycine; 1-piperidine propionic acid.
  • sugar alcohols and their derivatives include erythritol; xylitol; mannitol; sorbitol; inositol and the like.
  • the artificial skin forming agents of the present disclosure can be used, for example, for cosmetic or medical purposes.
  • the method of using the artificial skin forming agent of the present disclosure does not include a method of surgery, treatment or diagnosis of a human being.
  • the second agent is applied onto the first agent layer and crosslinked.
  • Method of forming artificial skin a method of applying the second agent to the body surface to form a second agent layer, then applying the first agent on the second agent layer and cross-linking to form an artificial skin.
  • a method may be mentioned in which a mixture is prepared by mixing the first agent and the second agent, and then the mixture is applied to the body surface and crosslinked to form an artificial skin. From the viewpoint of obtaining uniform artificial skin with less unevenness, such a method of use is to apply the first agent to the body surface to form the first agent layer, and then apply the second agent on the first agent layer.
  • a method of cross-linking to form an artificial skin is preferable.
  • the first agent and the second agent the above-mentioned materials and the like can be used in the same manner.
  • This method may be performed only once, but the method may be performed multiple times on the formed artificial skin.
  • the cosmetic may be applied to the body surface or artificially before the first agent, the second agent, or the mixture containing the first agent and the second agent is applied to the body surface. After forming the skin, the cosmetic may be applied to the artificial skin.
  • cosmetics for example, skin care cosmetics such as beauty essence, lotion, milky lotion, sunscreen cosmetics (sunscreen cosmetics), or makeup cosmetics such as foundation, gloss, lipstick, eye shadow, and manicure. Can be used.
  • the method of using the artificial skin forming agent of the present disclosure can also be used as a cosmetic method.
  • the "cosmetological method” is to apply the artificial skin forming agent of the present disclosure to the body surface to form artificial skin, and to beautify the condition of the body surface beautifully or to beautify the condition of the body surface. It means a method of surgery, which is different from the method of surgery, treatment or diagnosis of a human being.
  • the method of applying the first agent or the second agent to the body surface, the cosmetic application layer, or the first agent layer or the second agent layer there is no particular limitation on the method of applying the first agent or the second agent to the body surface, the cosmetic application layer, or the first agent layer or the second agent layer, and for example, a means for spreading with a finger or the like, spray application. , Transfer, etc. can be adopted.
  • the artificial skin-forming agent of the present disclosure can be applied to any part of the body on the surface of the skin, that is, on the surface of the body.
  • it can be appropriately applied to the skin surface such as face (lips, eyes, nose, cheeks, forehead, etc.), neck, ears, hands, arms, legs, legs, chest, abdomen, back and the like.
  • the skin also includes nails and the like in which the keratin of the epidermis of the skin is changed and hardened.
  • the thickness of the artificial skin prepared by using the above-mentioned artificial skin forming agent of the present disclosure is not particularly limited, and is appropriately adjusted in consideration of, for example, breathability, invisibility, compressibility, obstruction to the skin, and the like. Can be done.
  • the thickness of the artificial skin can be, for example, 0.5 ⁇ m or more, 1 ⁇ m or more, 10 ⁇ m or more, 30 ⁇ m or more, or 40 ⁇ m or more.
  • the upper limit of the thickness is not particularly limited, but may be, for example, 150 ⁇ m or less, 100 ⁇ m or less, 90 ⁇ m or less, 80 ⁇ m or less, 70 ⁇ m or less, 60 ⁇ m or less, or 50 ⁇ m or less.
  • the thickness shall be defined as an average value calculated by measuring the thickness of any part of the artificial skin 5 times using a high-precision digital micrometer (MDH-25MB, manufactured by Mitutoyo Co., Ltd.). Can be done.
  • the resulting artificial skin can exhibit good adhesion to the body surface.
  • Such adhesive strength can be evaluated by substituting the adhesive strength of artificial skin applied on the polypropylene substrate.
  • the adhesive strength of the artificial skin on the polypropylene substrate can be 2 N / m or more, 5 N / m or more, 8 N / m or more, 10 N / m or more, or 15 N / m or more.
  • the upper limit of the adhesive strength is not particularly limited, but for example, from the viewpoint of peelability from the skin, 200 N / m or less, 100 N / m or less, 80 N / m or less, 50 N / m or less, or 30 N / m. It can be as follows.
  • the adhesive strength complies with the stripping adhesion test of ASTM C794 and can be measured using an Instron device.
  • the resulting artificial skin can exhibit good tensile strength.
  • the tensile strength of the artificial skin can be 0.05 MPa or more, 0.10 MPa or more, 0.20 MPa or more, or 0.50 MPa or more.
  • the upper limit of the tensile strength is not particularly limited, but may be, for example, 5.0 MPa or less, 3.0 MPa or less, 2.0 MPa or less, or 1.0 MPa or less.
  • the tensile strength is based on the tensile tensile test of ASTM D5083 and can be measured using an Instron device.
  • the resulting artificial skin is capable of exhibiting good breaking elongation.
  • the breaking elongation of the artificial skin can be 25% or more, 50% or more, 100% or more, 200% or more, or 400% or more.
  • the upper limit of the elongation at break is not particularly limited, but may be, for example, 1,500% or less, 1,200% or less, 1,000% or less, 800% or less, or 600% or less.
  • the elongation at break is based on the tensile tensile test of ASTM D5083 and can be measured using an Instron device.
  • the resulting artificial skin can exhibit good oxygen permeability.
  • the oxygen permeability of the artificial skin is 5 ⁇ 10 -9 cm 3 / (cm 2 ⁇ s) or more, or 5 ⁇ 10 -7 cm 3 / (cm 2 ⁇ s) or more, or in the artificial skin with a thickness of 300 ⁇ m. It is possible to achieve 5 ⁇ 10-5 cm 3 / (cm 2 ⁇ s) or more.
  • the upper limit of the oxygen permeability is not particularly limited, but for example, 5 cm 3 / (cm 2 ⁇ s) or less, 0.5 cm 3 / (cm 2 ⁇ s) or less, 5 ⁇ 10 ⁇ 2 cm 3 / (cm).
  • the oxygen permeability can be measured using a Mocon device in accordance with the oxygen gas permeability test of the plastic film and sheet of ASTM F2622.
  • the resulting artificial skin can exhibit good water vapor permeability.
  • the water vapor permeability of the artificial skin is 1 ⁇ 10 -9 cm 3 / (cm 2 ⁇ s) or more, 1 ⁇ 10 -8 cm 3 / (cm 2 ⁇ s) or more, or 1 ⁇ 10 -9 cm 3 / (cm 2 ⁇ s) or more in the artificial skin having a thickness of 300 ⁇ m. It is possible to achieve 1 ⁇ 10-7 cm 3 / (cm 2 ⁇ s) or more.
  • the upper limit of the water vapor permeability is not particularly limited, but for example, 1.5 ⁇ 10 -1 cm 3 / (cm 2 ⁇ s) or less, 1.5 ⁇ 10 ⁇ 2 cm 3 / (cm 2 ⁇ s). Below, 1 ⁇ 10 -4 cm 3 / (cm 2 ⁇ s) or less, 1 ⁇ 10 -5 cm 3 / (cm 2 ⁇ s) or less, or 1 ⁇ 10 -6 cm 3 / (cm 2 ⁇ s) or less. Can be.
  • the water vapor permeability can be measured using a Mocon device in accordance with the water vapor permeability test of the plastic film and sheet of ASTM F1249.
  • kits with artificial skin forming agent can be provided as a kit having the first agent and the second agent constituting such a composition.
  • the kit may include, for example, a member for facilitating the application of the first agent or the like to the body surface, or any member such as the above-mentioned various cosmetics.
  • Examples of such an arbitrary member include an instruction manual, a brush, a cotton swab, a cutter, scissors, the above-mentioned various cosmetics, a cleanser for removing artificial skin from the body surface, a mirror, and the like.
  • the "instruction manual” is, for example, a packaging container for accommodating the kit, a tube for injecting the first agent, etc., in addition to the general instruction manual attached in the form of a document in the kit. It is also possible to include the one in which the instruction manual is printed on the packaging container of.
  • the kit may include, for example, these agents in separate containers to prevent contact of the first and second agents, or a container having two or more compartments. It may be contained separately in each section of. In addition, these contained agents may be configured to be applied one at a time, or may be configured to be mixed together before or during use.
  • Oil-in-water emulsified composition >> The oil-in-water emulsified composition obtained by the formulation shown in Table 1 and the production method shown below was evaluated as follows, and the results are shown in Table 1.
  • A No change in color occurred as compared with the composition immediately after preparation.
  • B There was a slight change in color as a whole as compared with the composition immediately after preparation.
  • C Compared with the composition immediately after preparation, the color was changed as a whole, or the region of less than 1/4 of the bottle was changed to black.
  • D The color did not change to black as a whole, but the color changed as a whole compared to the C evaluation, or the area of 1/4 or more and less than 1/2 of the bottle changed to black. Was there.
  • E It turned black overall, or more than half of the area of the bottle turned black.
  • Example 1 ⁇ Manufacturing method of oil-in-water emulsified composition> (Example 1) Using the formulations shown in Table 1, an oil-in-water emulsified composition was produced by the following method. Here, the numbers shown below correspond to the numbers indicating the ingredients on the left side of the formulation in Table 1.
  • the oil phase part was added to the aqueous phase part 1 and mixed uniformly to prepare a preliminary emulsion.
  • a preliminary emulsion No.
  • the aqueous phase part 2 prepared by mixing the materials of 19 was added and uniformly mixed to prepare an oil-in-water emulsified composition of Example 1.
  • Examples 2 to 12 and Comparative Examples 1 to 3 The oil-in-water emulsified compositions of Examples 2 to 12 and Comparative Examples 1 to 3 were prepared in the same manner as in Example 1 except that the formulations were changed to those shown in Table 1.
  • Example 2 When Example 1 and Example 2 were compared, the composition of Example 2 was superior in storage stability. It is considered that this is because the viscosity of the composition increased with the addition of the emollient agent. That is, it is considered that other agents capable of increasing the viscosity of the composition, for example, thickeners, can exert the same effect.
  • Example 1 When Example 1 and Example 4 were compared, the composition of Example 1 was superior in storage stability. From this result, it was found that when the silicone emulsifier is blended, it is preferable to blend the silicone emulsifier in the oil phase part instead of the aqueous phase part.
  • Example 3 When Example 1 and Example 3 were compared, the composition of Example 3 was superior in storage stability. From this result, in the emulsification composition containing a platinum catalyst, it is preferable to add an emulsifier having an emulsifying ability higher than that of the polymer emulsifier (for example, a silicone-based emulsifier) in an amount of less than 1% by mass, or not to add it. It turned out.
  • an emulsifier having an emulsifying ability higher than that of the polymer emulsifier for example, a silicone-based emulsifier
  • Example 8 When Example 1 and Example 8 were compared, the composition of Example 8 was superior in storage stability. From this result, it was found that increasing the mass ratio of the first unsaturated organopolysiloxane to the total amount of platinum further improved the storage stability. Further, when an emulsifier having an emulsifying ability higher than that of a polymer emulsifier (for example, a silicone-based emulsifier) is blended in an amount of 1% by mass or more, the mass ratio of the first unsaturated organopolysiloxane to the total amount of platinum is increased. It was also found that the storage stability could be improved.
  • a polymer emulsifier for example, a silicone-based emulsifier
  • Example 13 Artificial skin forming agent and artificial skin >> 40.5 parts by mass of divinyldimethicone of 165,000 cst as the second unsaturated organopolysiloxane, 7.9 parts by mass of hydrogen dimethicone as the hydride-functionalized polysiloxane, 6.6 parts by mass of silylated silica as the filler, 6 cst as the oil content. 45.0 parts by mass of dimethicone was uniformly mixed to prepare the first agent.
  • An artificial skin forming agent was obtained using the obtained first agent and the composition of Example 3 described above as the second agent.
  • Example of prescription of oil-in-water emulsified composition >> The following are examples of formulations of the oil-in-water emulsified composition of the present disclosure, but the present invention is not limited to these examples. Each of these was prepared by a conventional method. All of these were excellent in storage stability of the platinum catalyst at high temperatures.
  • Emulsion 1 (Component) (% by mass) Ion-exchanged water 20 1,3-butylene glycol 7 Glycerin 3 Carboxyvinyl polymer (1% sol) 10 Acrylate / Alkyl Acrylate (C10-30) Cross Polymer (1% Sol) 20 Potassium hydroxide 0.1 Niacinamide 5 Dipotassium glycyrrhizinate 0.05 Sodium metabisulfite 0.01 Sodium metaphosphate 0.01 Platinum complex dispersion 1 Divinyl Dimethicone (10cst) 5 Silica 2 Mica 2 Ethanol 12 Phenoxyethanol 0.5 Ion-exchanged water residue
  • Emulsion 2 (Component) (% by mass) Ion-exchanged water 20 1,3-butylene glycol 7 Glycerin 8 (Dimethylacrylamide / Acryloyldimethyltaurine Na) Cross Polymer 0.2 Niacinamide 5 Dipotassium glycyrrhizinate 0.2 0.2 Sodium metabisulfite 0.01 Sodium metaphosphate 0.01 Platinum complex dispersion 1 Divinyl Dimethicone (10cst) 5 Ethanol 10 Phenoxyethanol 0.5 Ion-exchanged water residue

Landscapes

  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Public Health (AREA)
  • General Health & Medical Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Epidemiology (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Transplantation (AREA)
  • Medicinal Chemistry (AREA)
  • Dermatology (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Birds (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Cosmetics (AREA)

Abstract

Provided is an oil-in-water type emulsion composition containing a platinum catalyst, said composition showing high storage stability of the platinum catalyst under high temperatures.　The oil-in-water type emulsion composition according to the present disclosure comprises a dispersion medium containing water and oil droplets dispersed in the dispersion medium, wherein: the oil droplets comprise an oily component, an emulsifier and a catalyst; the oily component comprises a first unsaturated organopolysiloxane; the catalyst comprises a platinum complex coordinated with 1,3-divinyltetramethyldisiloxane; and the ratio by mass of the first unsaturated organopolysiloxane to the total amount of platinum in the platinum complex is 200 or more.

Description

白金触媒を含む水中油型乳化組成物、及びその使用方法An oil-in-water emulsified composition containing a platinum catalyst and how to use it.
　本開示は、白金触媒を含む水中油型乳化組成物、及びその使用方法に関する。 The present disclosure relates to an oil-in-water emulsified composition containing a platinum catalyst and a method for using the same.
　従来より、白金触媒は、ポリマー重合などの種々の用途で使用されている。 Conventionally, platinum catalysts have been used in various applications such as polymer polymerization.
　特許文献１には、皮膚に塗布するための配合物であって、ａ）（ｉ）２５℃にて１００，０００～５００，０００ｃｓｔ又はｃＰの粘度を有する高粘度のビニル末端化されたオルガノポリシロキサンの少なくとも１種、２５℃にて５００～５０，０００ｃｓｔ又はｃＰの粘度を有する低粘度のビニル末端化されたオルガノポリシロキサンの少なくとも１種、及び少なくとも１種のヒドリド官能化ポリシロキサンを含む反応性要素；並びに（ｉｉ）補強要素を含む反応性補強成分；及びｂ）白金触媒を含む架橋成分；を含み、架橋成分は、ｉｎ　ｓｉｔｕで反応性補強成分の架橋を促進し、その結果、皮膜が皮膚に形成される、配合物が開示されている。 Patent Document 1 describes a formulation for application to the skin, a) (i) a highly viscous vinyl-terminated organopoly having a viscosity of 100,000-500,000 cst or cP at 25 ° C. Reactions comprising at least one siloxane, at least one low-viscosity vinyl-terminated organopolysiloxane having a viscosity of 500-50,000 cst or cP at 25 ° C., and at least one hydride-functionalized polysiloxane. It contains a sex element; and (ii) a reactive reinforcing component containing a reinforcing element; and b) a cross-linking component containing a platinum catalyst; the cross-linking component promotes cross-linking of the reactive reinforcing component in situ, resulting in a film. Disclosed are formulations that form on the skin.
特許第６１０５４６８号公報Japanese Patent No. 6105468
　白金触媒は、典型的には、保存安定性に劣る不安定な触媒であるため、一般的には、オイル中に分散させ、かつ、窒素パージした状態で冷暗所において保管されている。 Since the platinum catalyst is typically an unstable catalyst with poor storage stability, it is generally stored in a cool and dark place in a state of being dispersed in oil and purged with nitrogen.
　白金触媒の使用形態のバリエーションを増やすには、例えば、白金触媒及び油相に加えて、水相を併用することが考えられる。しかしながら、白金触媒は水分に敏感であり、白金触媒を、水を含む系で安定化させることは困難であった。ましてや、水を含む系において、高温環境下での保存安定性を向上させることはより一層困難であった。 In order to increase the variation of the usage pattern of the platinum catalyst, for example, it is conceivable to use an aqueous phase in combination with the platinum catalyst and the oil phase. However, the platinum catalyst is sensitive to water, and it has been difficult to stabilize the platinum catalyst in a system containing water. Furthermore, in a system containing water, it was even more difficult to improve the storage stability in a high temperature environment.
　したがって、本開示の主題は、高温下での白金触媒の保存安定性に優れる、白金触媒を含む水中油型乳化組成物を提供することである。 Therefore, the subject of the present disclosure is to provide an oil-in-water emulsified composition containing a platinum catalyst, which is excellent in storage stability of the platinum catalyst at high temperatures.
〈態様１〉
　水を含む分散媒、及び
　前記分散媒中に分散している油滴
を含む、水中油型乳化組成物であって、
　前記油滴は、油分、乳化剤、及び触媒を含み、
　前記油分が、第１の不飽和オルガノポリシロキサンを含み、
　前記触媒が、１，３－ジビニルテトラメチルジシロキサンが配位した白金錯体を含み、かつ、
　前記白金錯体における白金の全量に対する前記第１の不飽和オルガノポリシロキサンの質量比が、２００以上である、
水中油型乳化組成物。
〈態様２〉
　前記乳化剤が、高分子乳化剤を含む、態様１に記載の組成物。
〈態様３〉
　前記高分子乳化剤が、（アクリレーツ／アクリル酸アルキル（Ｃ１０－３０））クロスポリマー、（アクリロイルジメチルタウリンアンモニウム／メタクリル酸ベヘネス－２５）クロスポリマー、（アクリル酸ヒドロキシエチル／アクリロイルジメチルタウリンＮａ）コポリマー、ＰＥＧ変性クロスポリマー／コポリマーシロキサン、ポリエーテル変性クロスポリマー／コポリマーシロキサン、及びポリオキシエチレンから選択される少なくとも一種である、態様２に記載の組成物。
〈態様４〉
　シリコーン系乳化剤の配合量が、組成物の全体量に対し、１質量％未満である、態様１～３のいずれかに記載の組成物。
〈態様５〉
　前記第１の不飽和オルガノポリシロキサンの２５℃における粘度が、１，０００ｃｓｔ未満である、態様１～４のいずれかに記載の組成物。
〈態様６〉
　前記第１の不飽和オルガノポリシロキサンが、ビニル基を有するオルガノポリシロキサン、ビニル末端化されたオルガノポリシロキサン、及びビニル化された分岐鎖を有するオルガノポリシロキサンから選択される少なくとも一種である、態様１～５のいずれかに記載の組成物。
〈態様７〉
　前記第１の不飽和オルガノポリシロキサンが、ビニル末端ポリジメチルシロキサンである、態様６に記載の組成物。
〈態様８〉
　２５℃における粘度が、５，０００ｃｓｔ以上である、態様１～７のいずれかに記載の組成物。
〈態様９〉
　第１剤及び第２剤を含む、人工皮膚形成剤であって、
　前記第１剤が、第２の不飽和オルガノポリシロキサン、及びヒドリド官能化ポリシロキサンを含み、
　前記第２剤が、態様１～８のいずれかに記載の水中油型乳化組成物である、
人工皮膚形成剤。
〈態様１０〉
　前記第２の不飽和オルガノポリシロキサンが、ビニル基を有するオルガノポリシロキサン、ビニル末端化されたオルガノポリシロキサン、及びビニル化された分岐鎖を有するオルガノポリシロキサンから選択される少なくとも一種である、態様９に記載の人工皮膚形成剤。
〈態様１１〉
　前記第２の不飽和オルガノポリシロキサンが、ビニル末端ポリジメチルシロキサン、ビニル末端ジフェニルシロキサン－ジメチルシロキサンコポリマー、ビニル末端ポリフェニルメチルシロキサン、ビニルフェニルメチル末端ビニルフェニルシロキサン－フェニルメチルシロキサンコポリマー、ビニル末端トリフルオロプロピルメチルシロキサン－ジメチルシロキサンコポリマー、ビニル末端ジエチルシロキサン－ジメチルシロキサンコポリマー、ビニルメチルシロキサン－ジメチルシロキサンコポリマー、トリメチルシロキシ末端ビニルメチルシロキサン－ジメチルシロキサンコポリマー、シラノール末端ビニルメチルシロキサン－ジメチルシロキサンコポリマー、ビニルメチルシロキサンホモポリマー、ビニルＴ－構造ポリマー、モノビニル末端ポリジメチルシロキサン、ビニルメチルシロキサンターポリマー、及びビニルメトキシシランホモポリマーから選択される少なくとも一種である、態様１０に記載の人工皮膚形成剤。
〈態様１２〉
　前記ヒドリド官能化ポリシロキサンが、非末端及び／又は末端で水酸化されたオルガノポリシロキサンである、態様９～１１のいずれかに記載の人工皮膚形成剤。
〈態様１３〉
　前記ヒドリド官能化ポリシロキサンが、ヒドリド末端ポリジメチルシロキサン、ヒドリド末端ポリフェニル－（ジメチルヒドロシロキシ）シロキサン、ヒドリド末端メチルヒドロシロキサン－フェニルメチルシロキサンコポリマー、トリメチルシロキシ末端メチルヒドロシロキサン－ジメチルシロキサンコポリマー、ポリメチルヒドロシロキサン、トリメチルシロキシ末端ポリエチルヒドロシロキサン、トリエチルシロキサン、メチルヒドロシロキサン－フェニルオクチルメチルシロキサンコポリマー、及びメチルヒドロシロキサン－フェニルオクチルメチルシロキサンターポリマーから選択される少なくとも一種である、態様１２に記載の人工皮膚形成剤。
〈態様１４〉
　前記第１剤、前記第２剤、又はこれらの両方が、繊維、顔料、染料、増粘剤、保護コロイド剤、及び充填剤から選択される少なくとも一種を含む、態様９～１３のいずれかに記載の人工皮膚形成剤。
〈態様１５〉
　態様９～１４のいずれかに記載の前記第１剤及び前記第２剤が、別々の容器に内包されている、又は２つ以上の区画を有する容器の各区画内に別々に内包されている、キット。
〈態様１６〉
　態様９～１４のいずれかに記載の人工皮膚形成剤の使用方法であって、
　前記第１剤を体表に適用して第１剤層を形成した後に、該第１剤層上に前記第２剤を適用し、架橋させて人工皮膚を形成する、
　前記第２剤を体表に適用して第２剤層を形成した後に、該第２剤層上に前記第１剤を適用し、架橋させて人工皮膚を形成する、又は、
　前記第１剤及び前記第２剤を混合して混合物を調製した後に、該混合物を体表に適用し、架橋させて人工皮膚を形成する、
使用方法。
〈態様１７〉
　前記第１剤、前記第２剤、又は前記混合物を体表に適用する前に、化粧料を体表に適用する、又は、
　人工皮膚を形成した後に、化粧料を人工皮膚に適用する、
態様１６に記載の使用方法。
〈態様１８〉
　前記化粧料が、スキンケア化粧料、サンスクリーン化粧料、又はメーキャップ化粧料である、態様１７に記載の使用方法。 <Aspect 1>
An oil-in-water emulsified composition comprising a dispersion medium containing water and oil droplets dispersed in the dispersion medium.
The oil droplets contain an oil, an emulsifier, and a catalyst.
The oil contains the first unsaturated organopolysiloxane and contains
The catalyst contains a platinum complex coordinated with 1,3-divinyltetramethyldisiloxane, and
The mass ratio of the first unsaturated organopolysiloxane to the total amount of platinum in the platinum complex is 200 or more.
Oil-in-water emulsified composition.
<Aspect 2>
The composition according to aspect 1, wherein the emulsifier contains a polymer emulsifier.
<Aspect 3>
The polymer emulsifiers are (Acrylate / alkyl acrylate (C10-30)) cross-polymer, (acryloyldimethyltaurinammonium ammonium methacrylate / behenes-25 methacrylate) cross-polymer, (hydroxyethyl acrylate / acryloyldimethyltaurine Na) copolymer, PEG. The composition according to aspect 2, which is at least one selected from modified crosspolymer / copolymer siloxane, polyether modified crosspolymer / copolymer siloxane, and polyoxyethylene.
<Aspect 4>
The composition according to any one of aspects 1 to 3, wherein the blending amount of the silicone-based emulsifier is less than 1% by mass with respect to the total amount of the composition.
<Aspect 5>
The composition according to any one of aspects 1 to 4, wherein the first unsaturated organopolysiloxane has a viscosity of less than 1,000 cst at 25 ° C.
<Aspect 6>
The first unsaturated organopolysiloxane is at least one selected from an organopolysiloxane having a vinyl group, a vinyl-terminated organopolysiloxane, and an organopolysiloxane having a vinylized branched chain. The composition according to any one of 1-5.
<Aspect 7>
The composition according to embodiment 6, wherein the first unsaturated organopolysiloxane is a vinyl-terminated polydimethylsiloxane.
<Aspect 8>
The composition according to any one of aspects 1 to 7, wherein the viscosity at 25 ° C. is 5,000 cst or more.
<Aspect 9>
An artificial skin-forming agent containing the first agent and the second agent.
The first agent comprises a second unsaturated organopolysiloxane and a hydride-functionalized polysiloxane.
The second agent is the oil-in-water emulsified composition according to any one of aspects 1 to 8.
Artificial skin forming agent.
<Aspect 10>
Aspect in which the second unsaturated organopolysiloxane is at least one selected from an organopolysiloxane having a vinyl group, a vinyl-terminated organopolysiloxane, and an organopolysiloxane having a vinylized branched chain. 9. The artificial skin forming agent according to 9.
<Aspect 11>
The second unsaturated organopolysiloxane is vinyl-terminated polydimethylsiloxane, vinyl-terminated diphenylsiloxane-dimethylsiloxane copolymer, vinyl-terminated polyphenylmethylsiloxane, vinylphenylmethyl-terminated vinylphenylsiloxane-phenylmethylsiloxane copolymer, vinyl-terminated trifluoro. Propylmethylsiloxane-dimethylsiloxane copolymer, vinyl-terminated diethylsiloxane-dimethylsiloxane copolymer, vinylmethylsiloxane-dimethylsiloxane copolymer, trimethylsiloxy-terminated vinylmethylsiloxane-dimethylsiloxane copolymer, silanol-terminated vinylmethylsiloxane-dimethylsiloxane copolymer, vinylmethylsiloxane homo The artificial skin-forming agent according to aspect 10, which is at least one selected from a polymer, a vinyl T-structure polymer, a monovinyl-terminated polydimethylsiloxane, a vinylmethylsiloxane tarpolymer, and a vinylmethoxysilane homopolymer.
<Aspect 12>
The artificial skin-forming agent according to any one of aspects 9 to 11, wherein the hydride-functionalized polysiloxane is an organopolysiloxane hydroxylated at the non-terminal and / or the terminal.
<Aspect 13>
The hydride-functionalized polysiloxanes are hydride-terminated polydimethylsiloxane, hydride-terminated polyphenyl- (dimethylhydrosiloxy) siloxane, hydride-terminated methylhydrosiloxane-phenylmethylsiloxane copolymer, trimethylsiloxy-terminated methylhydrosiloxane-dimethylsiloxane copolymer, and polymethyl. The artificial according to aspect 12, wherein it is at least one selected from hydrosiloxane, trimethylsiloxy-terminated polyethylhydrosiloxane, triethylsiloxane, methylhydrosiloxane-phenyloctylmethylsiloxane copolymer, and methylhydrosiloxane-phenyloctylmethylsiloxane tarpolymer. Skin forming agent.
<Aspect 14>
One of embodiments 9-13, wherein the first agent, the second agent, or both of them comprises at least one selected from fibers, pigments, dyes, thickeners, protective colloid agents, and fillers. The artificial skin-forming agent described.
<Aspect 15>
The first agent and the second agent according to any one of embodiments 9 to 14 are encapsulated in separate containers, or separately encapsulated in each compartment of a container having two or more compartments. ,kit.
<Aspect 16>
A method of using the artificial skin forming agent according to any one of aspects 9 to 14.
After the first agent is applied to the body surface to form the first agent layer, the second agent is applied onto the first agent layer and crosslinked to form an artificial skin.
After the second agent is applied to the body surface to form the second agent layer, the first agent is applied onto the second agent layer and crosslinked to form an artificial skin, or
After preparing a mixture by mixing the first agent and the second agent, the mixture is applied to the body surface and crosslinked to form an artificial skin.
how to use.
<Aspect 17>
Before applying the first agent, the second agent, or the mixture to the body surface, the cosmetic is applied to the body surface, or
After forming the artificial skin, apply the cosmetics to the artificial skin,
The usage method according to aspect 16.
<Aspect 18>
The method of use according to aspect 17, wherein the cosmetic is a skin care cosmetic, a sunscreen cosmetic, or a make-up cosmetic.
　本開示によれば、高温下での白金触媒の保存安定性に優れる、白金触媒を含む水中油型乳化組成物を提供することができる。 According to the present disclosure, it is possible to provide an oil-in-water emulsified composition containing a platinum catalyst, which is excellent in storage stability of the platinum catalyst at high temperatures.
　以下、本開示の実施の形態について詳述する。本開示は、以下の実施の形態に限定されるものではなく、発明の本旨の範囲内で種々変形して実施できる。 Hereinafter, embodiments of the present disclosure will be described in detail. The present disclosure is not limited to the following embodiments, and can be variously modified and implemented within the scope of the spirit of the invention.
　本開示の水中油型乳化組成物は、水を含む分散媒、及びこの分散媒中に分散している油滴を含む、水中油型乳化組成物であって、油滴は、油分、乳化剤、及び触媒を含み、油分が、第１の不飽和オルガノポリシロキサンを含み、触媒が、１，３－ジビニルテトラメチルジシロキサンが配位した白金錯体を含み、かつ、白金錯体における白金の全量に対する第１の不飽和オルガノポリシロキサンの質量比が、２００以上である。 The oil-in-water emulsifying composition of the present disclosure is an oil-in-water emulsifying composition containing a dispersion medium containing water and oil droplets dispersed in the dispersion medium, wherein the oil droplets are an oil component, an emulsifier, and the like. And a catalyst, the oil content contains the first unsaturated organopolysiloxane, the catalyst contains a platinum complex coordinated with 1,3-divinyltetramethyldisiloxane, and the first relative to the total amount of platinum in the platinum complex. The mass ratio of the unsaturated organopolysiloxane of 1 is 200 or more.
　原理によって限定されるものではないが、本開示の水中油型乳化組成物が、高温下での白金触媒の保存安定性に優れ、白金触媒の凝集に伴う、黒化、触媒活性の低下等の不具合を低減又は防止し得る作用原理は以下のとおりであると考える。 Although not limited by the principle, the oil-in-water emulsified composition of the present disclosure has excellent storage stability of the platinum catalyst at high temperatures, and blackening, reduction of catalytic activity, etc. due to aggregation of the platinum catalyst, etc. The principle of action that can reduce or prevent defects is considered to be as follows.
　本開示の白金触媒とは、１，３－ジビニルテトラメチルジシロキサンが白金に対して配位した、下記式１で示される白金錯体を意図する：
Figure JPOXMLDOC01-appb-C000001
 The platinum catalyst of the present disclosure is intended to be a platinum complex represented by the following formula 1 in which 1,3-divinyltetramethyldisiloxane is coordinated with respect to platinum:
Figure JPOXMLDOC01-appb-C000001
　かかる白金触媒は、白金に対して１，３－ジビニルテトラメチルジシロキサンが配位しているため、それが立体障害となり、配位子を有さない白金に比べれば、白金触媒の凝集を抑制することができる。しかしながら、このような配位子を有する白金触媒を、例えば、高粘度のシリコーン油に配合したとしても、窒素パージをした状態で冷暗所において保管しなければ、白金触媒の凝集は進行し、黒く変色してしまう。白金触媒の凝集は、白金触媒の粒子径の増大、すなわち、表面積の低下につながるため、触媒活性の低下を生じさせる原因にもなり得る。 In such a platinum catalyst, 1,3-divinyltetramethyldisiloxane is coordinated with respect to platinum, which causes steric hindrance and suppresses aggregation of the platinum catalyst as compared with platinum having no ligand. can do. However, even if a platinum catalyst having such a ligand is mixed with a high-viscosity silicone oil, for example, if it is not stored in a cool and dark place with nitrogen purge, the platinum catalyst will aggregate and turn black. Resulting in. Aggregation of the platinum catalyst leads to an increase in the particle size of the platinum catalyst, that is, a decrease in the surface area, which may cause a decrease in the catalytic activity.
　配位子である１，３－ジビニルテトラメチルジシロキサンは、温度の上昇に伴い、その熱運動が活発になるため、白金から着脱しやすくなると考えられる。その結果、白金の表面は一時的にむき出し状態になりやすく、隣接する白金と接触したときに凝集しやすくなるため、特に高温下では黒化が進行すると考えられる。 It is considered that 1,3-divinyltetramethyldisiloxane, which is a ligand, becomes easy to be attached to and detached from platinum because its thermal motion becomes active as the temperature rises. As a result, the surface of platinum tends to be temporarily exposed, and when it comes into contact with adjacent platinum, it tends to aggregate, so it is considered that blackening progresses especially at high temperatures.
　本発明者は、保存安定性が一般的により悪くなるといわれている、水を含む系である水中油型乳化組成物の場合であっても、白金触媒を所定量の第１の不飽和オルガノポリシロキサンとともに油相中に配合すると、意外にも、高温下での白金触媒の保存安定性が向上することを見出した。 The present inventor has added a predetermined amount of a platinum catalyst to the first unsaturated organopoly, even in the case of an oil-in-water emulsified composition which is a water-containing system, which is generally said to have worse storage stability. Surprisingly, it was found that the storage stability of the platinum catalyst at high temperatures was improved when it was added to the oil phase together with siloxane.
　油相中に同時に配合する第１の不飽和オルガノポリシロキサンも、白金に対して配位する性能を有している。したがって、温度上昇に伴って、１，３－ジビニルテトラメチルジシロキサンが白金から外れたとしても、第１の不飽和オルガノポリシロキサンがその部位を補完するため、白金触媒の凝集の進行を抑制することができると考えられる。 The first unsaturated organopolysiloxane, which is simultaneously blended in the oil phase, also has the ability to coordinate with platinum. Therefore, even if 1,3-divinyltetramethyldisiloxane deviates from platinum as the temperature rises, the first unsaturated organopolysiloxane complements the site and suppresses the progress of aggregation of the platinum catalyst. It is thought that it can be done.
　加えて、水中油型乳化組成物は、油相が、微小な乳化粒子（油滴）の形態で分散していることも、白金触媒の凝集の進行を抑制する要因の一つであると考えている。つまり、第１の不飽和オルガノポリシロキサンによる補完作用が生じたとしても、新たに配位した第１の不飽和オルガノポリシロキサンも熱運動によって白金触媒から着脱するため、白金の表面がむき出し状態になり得る。油相のみの単一相の場合、白金触媒が存在する油相は連続相であるため、表面がむき出し状態の白金同士が接触する可能性は比較的に高いと考えられる。一方、水中油型乳化組成物の場合は、油相が乳化粒子の形態で分散し、他の乳化粒子中の白金触媒とは水相を介して隔離されたような状態を呈している。その結果、油相のみの単一相の場合に比べて、表面がむき出し状態の白金同士が接触する可能性は低くなると考えられる。 In addition, in the oil-in-water emulsified composition, the fact that the oil phase is dispersed in the form of fine emulsified particles (oil droplets) is considered to be one of the factors that suppress the progress of aggregation of the platinum catalyst. ing. That is, even if the complementary action of the first unsaturated organopolysiloxane occurs, the newly coordinated first unsaturated organopolysiloxane is also detached from the platinum catalyst by thermal motion, so that the surface of platinum is exposed. Can be. In the case of a single phase containing only an oil phase, since the oil phase in which the platinum catalyst is present is a continuous phase, it is considered that there is a relatively high possibility that platinum having a bare surface comes into contact with each other. On the other hand, in the case of the oil-in-water emulsified composition, the oil phase is dispersed in the form of emulsified particles, and is separated from the platinum catalyst in other emulsified particles via the aqueous phase. As a result, it is considered that the possibility of platinum having bare surfaces coming into contact with each other is lower than in the case of a single phase containing only an oil phase.
　したがって、本開示の水中油型乳化組成物によれば、油相中に配合する所定量の第１の不飽和オルガノポリシロキサンによる補完作用と、乳化粒子による白金触媒の隔離作用とが、相乗的に作用するため、白金触媒の高温下での保存安定性が向上し得ると考えている。なお、高温下での保存安定性が優れていれば、それよりも低温での保存安定性がより優れることは言うまでもない。 Therefore, according to the oil-in-water emulsified composition of the present disclosure, the complementary action of the predetermined amount of the first unsaturated organopolysiloxane blended in the oil phase and the separating action of the platinum catalyst by the emulsified particles are synergistic. Therefore, it is thought that the storage stability of the platinum catalyst at high temperatures can be improved. Needless to say, if the storage stability at a high temperature is excellent, the storage stability at a low temperature is more excellent than that.
　本開示における用語の定義は以下のとおりである。 The definitions of terms in this disclosure are as follows.
　本開示において「高温」とは、５０℃以上、６０℃以上、又は７０℃以上を意図することができ、また、９０℃以下、８５℃以下、又は８０℃以下を意図することができる。 In the present disclosure, "high temperature" can be intended to be 50 ° C. or higher, 60 ° C. or higher, or 70 ° C. or higher, and 90 ° C. or lower, 85 ° C. or lower, or 80 ° C. or lower.
　本開示において「粘度」とは、剪断応力又は引張応力のいずれかによって変形させられている流体の抵抗の尺度を指す。例えば、人工皮膚形成剤における第１剤及び第２剤の粘度は、基板の上に形成される層の厚さ、展延性、並びに均一性及び／又は一様性に影響を与える。粘度は、動的粘度（別名、絶対粘度、代表的な単位はＰａ・ｓ、ポアズ、Ｐ、ｃＰである。）又は運動学的粘度（代表的な単位はｃｍ２／ｓ、ストーク、Ｓｔ、ｃｓｔである。）のいずれかとして報告することができ、この運動学的粘度は、動的粘度を測定された流体の密度で割ったものである。本明細書に開示される成分の粘度範囲は、一般に、各成分の供給業者によって、レオメーター又はキャノン・フェンスケ（Ｃａｎｎｏｎ－Ｆｅｎｓｋｅ）チューブ粘度計を用いて測定される運動学的粘度の単位（例えば、ｃｓｔ）として提供されるが、流体の粘度は、例えば、レオメーター（例えば、線形剪断レオメーター若しくは動的剪断レオメーター）又は粘度計（粘度測定計、例えば、毛細管粘度計もしくは回転粘度計とも呼ばれる）を用いて測定することもできる。 In the present disclosure, "viscosity" refers to a measure of the resistance of a fluid being deformed by either shear stress or tensile stress. For example, the viscosities of the first and second agents in an artificial skin forming agent affect the thickness, spreadability, and uniformity and / or uniformity of the layers formed on the substrate. Viscosity is dynamic viscosity (also known as absolute viscosity, typical units are Pa · s, Poise, P, cP) or kinematic viscosity (typical units are cm 2 / s, Stoke, St, It can be reported as any of cst), and this kinematic viscosity is the dynamic viscosity divided by the density of the measured fluid. The viscosity range of the components disclosed herein is generally a unit of kinematic viscosity (eg,) as measured by the supplier of each component using a leometer or a Canon-Fenske tube viscometer. , Cst), but the viscosity of the fluid may be, for example, a leometer (eg, a linear shear leometer or a dynamic shear leometer) or a viscometer (viscosity meter, eg, a capillary viscometer or a rotational viscometer). It can also be measured using (called).
　本開示における「架橋」には、一般に「硬化」と称する概念も包含される。 The term "crosslinking" in the present disclosure also includes the concept generally referred to as "curing".
　本開示において「体表」とは、体の皮膚表面を意味する。 In this disclosure, "body surface" means the skin surface of the body.
《水中油型乳化組成物》
　本開示の白金触媒を含む水中油型乳化組成物（単に「組成物」と称する場合がある。）は、白金触媒の高温下での保存安定性に優れている。 << Oil-in-water emulsification composition >>
The oil-in-water emulsified composition containing the platinum catalyst of the present disclosure (sometimes referred to simply as "composition") is excellent in storage stability of the platinum catalyst at high temperatures.
　いくつかの実施態様において、本開示の組成物は、５０℃、６０℃、及び７０℃から選択される少なくとも一種の温度下、並びに８時間後、１日後、７日後、及び１４日後から選択される少なくとも一種の期間における後述する保存安定性試験で、Ｄ評価、Ｃ評価、Ｂ評価、又はＡ評価を得ることができる。 In some embodiments, the compositions of the present disclosure are selected from at least one temperature selected from 50 ° C, 60 ° C, and 70 ° C, and from 8 hours, 1 day, 7 days, and 14 days. A D rating, a C rating, a B rating, or an A rating can be obtained in a storage stability test described later for at least one period.
　いくつかの実施態様において、本開示の水中油型乳化組成物は、例えば、使用性、乳化安定性、白金触媒の保存安定性等の観点から、組成物の作製直後において、５，０００ｃｓｔ以上、６，０００ｃｓｔ以上、７，０００ｃｓｔ以上、又は８，０００ｃｓｔ以上とすることができる。粘度の上限値については特に制限はなく、例えば、２０，０００ｃｓｔ以下、１８，０００ｃｓｔ以下、又は１５，０００ｃｓｔ以下とすることができる。かかる粘度は、Ｂ型粘度計（芝浦システム株式会社製、ビスメトロン）を、２５℃、１２回転／分（ローターＮｏ．３又はＮｏ．４）の条件で、６０秒間測定したときの値である。 In some embodiments, the oil-in-water emulsified composition of the present disclosure is 5,000 cst or more immediately after preparation of the composition, for example, from the viewpoint of usability, emulsification stability, storage stability of platinum catalyst, and the like. It can be 6,000 cst or more, 7,000 cst or more, or 8,000 cst or more. The upper limit of the viscosity is not particularly limited and may be, for example, 20,000 cst or less, 18,000 cst or less, or 15,000 cst or less. The viscosity is a value measured with a B-type viscometer (Bismetron manufactured by Shibaura System Co., Ltd.) at 25 ° C. and 12 rotations / minute (rotor No. 3 or No. 4) for 60 seconds.
〈分散媒〉
　本開示の水中油型乳化組成物における分散媒は、水を含んでいる。 <Dispersion medium>
The dispersion medium in the oil-in-water emulsified composition of the present disclosure contains water.
（水）
　水の配合量としては特に制限はなく、例えば、使用性、乳化安定性、白金触媒の保存安定性等の観点から、組成物の全量に対し、１５質量％以上、２０質量％以上、３０質量％以上、４０質量％以上、５０質量％以上、６０質量％以上、７０質量％以上、又は８０質量％以上とすることができ、また、９０質量％以下、８０質量％以下、７０質量％以下、６０質量％以下、又は５０質量％以下とすることができる。 (water)
The amount of water to be blended is not particularly limited. For example, from the viewpoint of usability, emulsion stability, storage stability of platinum catalyst, etc., 15% by mass or more, 20% by mass or more, and 30% by mass with respect to the total amount of the composition. % Or more, 40% by mass or more, 50% by mass or more, 60% by mass or more, 70% by mass or more, or 80% by mass or more, and 90% by mass or less, 80% by mass or less, 70% by mass or less. , 60% by mass or less, or 50% by mass or less.
　本開示の水中油型乳化組成物で使用し得る水としては、特に限定されるものではないが、化粧料、医薬部外品等に使用される水を使用することができる。例えば、イオン交換水、蒸留水、超純水、水道水等を使用することができる。 The water that can be used in the oil-in-water emulsified composition of the present disclosure is not particularly limited, but water used for cosmetics, quasi-drugs, etc. can be used. For example, ion-exchanged water, distilled water, ultrapure water, tap water and the like can be used.
〈油滴〉
　水中油型乳化組成物における油相又は分散相としての油滴は、油分、乳化剤、及び触媒を含んでいる。 <Oil drops>
The oil droplets as an oil phase or a dispersed phase in an oil-in-water emulsified composition contain an oil component, an emulsifier, and a catalyst.
（油分）
　油分の配合量としては特に制限はなく、例えば、使用性、乳化安定性、白金触媒の保存安定性等の観点から、組成物の全量に対し、１質量％以上、３質量％以上、５質量％以上、１０質量％以上、１５質量％以上、又は２０質量％以上とすることができ、また、５０質量％以下、４０質量％以下、３０質量％以下、２０質量％以下、１５質量％以下、又は１０質量％以下とすることができる。 (Oil)
The blending amount of the oil is not particularly limited, and for example, from the viewpoint of usability, emulsion stability, storage stability of the platinum catalyst, etc., 1% by mass or more, 3% by mass or more, and 5% by mass with respect to the total amount of the composition. % Or more, 10% by mass or more, 15% by mass or more, or 20% by mass or more, and 50% by mass or less, 40% by mass or less, 30% by mass or less, 20% by mass or less, 15% by mass or less. , Or 10% by mass or less.
　油分としては特に制限はなく、例えば、液体油脂、固体油脂、ロウ類、炭化水素油、シリコーン油、極性油等を挙げることができる。油分は単独で又は二種以上組み合わせて使用することができる。なかでも、油滴中に配合される触媒に配位している１，３－ジビニルテトラメチルジシロキサンとの相溶性の観点から、シリコーン油が好ましい。油分中のシリコーン油の割合としては特に制限はなく、例えば、油分の全量に対し、５０質量％以上、６０質量％以上、７０質量％以上、８０質量％以上、又は９０質量％以上であることが好ましい。かかる割合の上限値としては特に制限はないが、例えば、１００質量％以下、１００質量％未満、９８質量％以下、又は９５質量％以下とすることができる。 The oil content is not particularly limited, and examples thereof include liquid fats and oils, solid fats and oils, waxes, hydrocarbon oils, silicone oils, and polar oils. The oil content can be used alone or in combination of two or more. Of these, silicone oil is preferable from the viewpoint of compatibility with 1,3-divinyltetramethyldisiloxane, which is coordinated with the catalyst blended in the oil droplets. The ratio of silicone oil in the oil content is not particularly limited, and is, for example, 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, or 90% by mass or more with respect to the total amount of oil content. Is preferable. The upper limit of such a ratio is not particularly limited, but may be, for example, 100% by mass or less, less than 100% by mass, 98% by mass or less, or 95% by mass or less.
ａ．第１の不飽和オルガノポリシロキサン
　本開示の組成物は、油分として、シリコーン油の一種である第１の不飽和オルガノポリシロキサンを含む。第１の不飽和オルガノポリシロキサンは、白金触媒に対する分散剤としての機能も有している。 a. First Unsaturated Organopolysiloxane The composition of the present disclosure contains, as an oil component, a first unsaturated organopolysiloxane which is a kind of silicone oil. The first unsaturated organopolysiloxane also has a function as a dispersant for a platinum catalyst.
　第１の不飽和オルガノポリシロキサンとしては、触媒の保存安定性を向上させる性能を奏する限り特に制限はなく、例えば、ビニル基を有するオルガノポリシロキサン、ビニル末端化されたオルガノポリシロキサン、及びビニル化された分岐鎖を有するオルガノポリシロキサンから選択される少なくとも一種の不飽和オルガノポリシロキサンを使用することができる。 The first unsaturated organopolysiloxane is not particularly limited as long as it has the ability to improve the storage stability of the catalyst. For example, an organopolysiloxane having a vinyl group, a vinyl-terminated organopolysiloxane, and a vinylized organopolysiloxane. At least one unsaturated organopolysiloxane selected from organopolysiloxanes having a branched chain can be used.
　具体的には、例えば、ビニル末端ポリジメチルシロキサン、ビニル末端ジフェニルシロキサン－ジメチルシロキサンコポリマー、ビニル末端ポリフェニルメチルシロキサン、ビニルフェニルメチル末端ビニルフェニルシロキサン－フェニルメチルシロキサンコポリマー、ビニル末端トリフルオロプロピルメチルシロキサン－ジメチルシロキサンコポリマー、ビニル末端ジエチルシロキサン－ジメチルシロキサンコポリマー、ビニルメチルシロキサン－ジメチルシロキサンコポリマー、トリメチルシロキシ末端ビニルメチルシロキサン－ジメチルシロキサンコポリマー、シラノール末端ビニルメチルシロキサン－ジメチルシロキサンコポリマー、ビニルメチルシロキサンホモポリマー、ビニルＴ－構造ポリマー、ビニルＱ－構造ポリマー、モノビニル末端ポリジメチルシロキサン、ビニルメチルシロキサンターポリマー、及びビニルメトキシシランホモポリマーを挙げることができる。第１の不飽和オルガノポリシロキサンは、単独で又は二種以上組み合わせて使用することができる。なかでも、触媒に対する配位子の補完性能、それに伴う触媒の保存安定性等の観点から、ビニル末端ポリジメチルシロキサンが好ましく、ジビニルジメチコン、１，３－ジビニルテトラメチルジシロキサンがより好ましい。本開示において「末端」とは、片末端及び両末端のいずれかを意図している。これらを区別する場合には、例えば、「ビニル片末端」、「ビニル両末端」と表記することができる。 Specifically, for example, vinyl-terminated polydimethylsiloxane, vinyl-terminated diphenylsiloxane-dimethylsiloxane copolymer, vinyl-terminated polyphenylmethylsiloxane, vinylphenylmethyl-terminated vinylphenylsiloxane-phenylmethylsiloxane copolymer, vinyl-terminated trifluoropropylmethylsiloxane-. Dimethylsiloxane Polymer, Vinyl-Terminated diethylsiloxane-Dimethylsiloxane Polymeric, Vinylmethylsiloxane-Dimethylsiloxane Polymeri, trimethylsiloxy-Terminated Vinylmethylsiloxane-Dimethylsiloxane Polymeric, Cyranol-Terminated Vinylmethylsiloxane-Dimethylsiloxane Polymericator, Vinylmethylsiloxane Homopolymer, Vinyl T -Structural polymers, vinyl Q-structural polymers, monovinyl-terminated polydimethylsiloxanes, vinylmethylsiloxane terpolymers, and vinylmethoxysilane homopolymers can be mentioned. The first unsaturated organopolysiloxane can be used alone or in combination of two or more. Of these, vinyl-terminated polydimethylsiloxane is preferable, and divinyldimethicone and 1,3-divinyltetramethyldisiloxane are more preferable, from the viewpoint of the complementing performance of the ligand to the catalyst and the storage stability of the catalyst. In the present disclosure, the term "end" is intended to be either one end or both ends. When distinguishing these, for example, it can be expressed as "vinyl single end" or "vinyl both ends".
　本開示の乳化組成物において、第１の不飽和オルガノポリシロキサンは、後述する白金錯体における白金の全量に対する第１の不飽和オルガノポリシロキサンの質量比が、２００以上となるように含まれている。かかる質量比は、２３０以上、２５０以上、２７０以上、３００以上、３５０以上、４００以上、４５０以上、又は５００以上であることが好ましい。かかる質量比の上限値としては特に制限はないが、例えば、２，０００以下、１，５００以下、１，０００以下、９００以下、８００以下、７００以下、６００以下、又は５００以下とすることができる。このような割合で第１の不飽和オルガノポリシロキサンを配合すると、配位子である１，３－ジビニルテトラメチルジシロキサンが白金から外れた場合に、その箇所を第１の不飽和オルガノポリシロキサンで優位に補完することができる。その結果、触媒の高温下での保存安定性を向上させることができる。 In the emulsified composition of the present disclosure, the first unsaturated organopolysiloxane is contained so that the mass ratio of the first unsaturated organopolysiloxane to the total amount of platinum in the platinum complex described later is 200 or more. .. The mass ratio is preferably 230 or more, 250 or more, 270 or more, 300 or more, 350 or more, 400 or more, 450 or more, or 500 or more. The upper limit of the mass ratio is not particularly limited, but may be, for example, 2,000 or less, 1,500 or less, 1,000 or less, 900 or less, 800 or less, 700 or less, 600 or less, or 500 or less. can. When the first unsaturated organopolysiloxane is blended in such a ratio, when the ligand 1,3-divinyltetramethyldisiloxane is removed from platinum, the portion thereof is designated as the first unsaturated organopolysiloxane. Can be complemented with. As a result, the storage stability of the catalyst under high temperature can be improved.
　油分中の第１の不飽和オルガノポリシロキサンの配合割合としては、触媒に対する配位子の補完性能、それに伴う触媒の保存安定性等の観点から、例えば、油分の全量に対し、５０質量％以上、６０質量％以上、７０質量％以上、８０質量％以上、又は９０質量％以上であることが好ましい。かかる割合の上限値としては特に制限はないが、例えば、１００質量％以下、１００質量％未満、９８質量％以下、又は９５質量％以下とすることができる。 The mixing ratio of the first unsaturated organopolysiloxane in the oil is, for example, 50% by mass or more with respect to the total amount of the oil from the viewpoint of the complementing performance of the ligand to the catalyst and the storage stability of the catalyst. , 60% by mass or more, 70% by mass or more, 80% by mass or more, or 90% by mass or more. The upper limit of such a ratio is not particularly limited, but may be, for example, 100% by mass or less, less than 100% by mass, 98% by mass or less, or 95% by mass or less.
　第１の不飽和オルガノポリシロキサンは、その大きさを粘度で間接的に特定することができる。すなわち、粘度が小さければ、その大きさも小さく、粘度が大きければ、その大きさも大きいといえる。触媒に対する配位子の補完性能、それに伴う触媒の保存安定性等の観点から、第１の不飽和オルガノポリシロキサンの２５℃における粘度は、１，０００ｃｓｔ未満、７００ｃｓｔ以下、５００ｃｓｔ以下、又は３００ｃｓｔ以下であることが好ましく、５０ｃｓｔ以上、１００ｃｓｔ以上、又は１５０ｃｓｔ以上であることが好ましい。かかる粘度は、Ｂ型粘度計（芝浦システム株式会社製、ビスメトロン）を、２５℃、１２回転／分（ローターＮｏ．３又はＮｏ．４）の条件で、６０秒間測定したときの値である。 The size of the first unsaturated organopolysiloxane can be indirectly specified by the viscosity. That is, it can be said that if the viscosity is small, the size is also small, and if the viscosity is large, the size is also large. The viscosity of the first unsaturated organopolysiloxane at 25 ° C. is less than 1,000 cst, 700 cst or less, 500 cst or less, or 300 cst or less from the viewpoint of the complementing performance of the ligand to the catalyst and the storage stability of the catalyst. It is preferably 50 cst or more, 100 cst or more, or 150 cst or more. The viscosity is a value measured with a B-type viscometer (Bismetron manufactured by Shibaura System Co., Ltd.) at 25 ° C. and 12 rotations / minute (rotor No. 3 or No. 4) for 60 seconds.
　このような１，０００ｃｓｔ未満の低粘度の第１の不飽和オルガノポリシロキサンを使用する場合には、白金錯体における白金の全量に対する１，０００ｃｓｔ未満の低粘度の第１の不飽和オルガノポリシロキサンの質量比は、１５０超、１５５以上、１６０以上、１８０以上、２００以上、２３０以上、２５０以上、２７０以上、３００以上、３５０以上、４００以上、４５０以上、又は５００以上であることが好ましい。かかる質量比の上限値としては特に制限はないが、例えば、２，０００以下、１，５００以下、１，０００以下、９００以下、８００以下、７００以下、６００以下、又は５００以下とすることができる。 When such a first unsaturated organopolysiloxane having a viscosity of less than 1,000 cst is used, the first unsaturated organopolysiloxane having a viscosity of less than 1,000 cst with respect to the total amount of platinum in the platinum complex is used. The mass ratio is preferably more than 150, 155 or more, 160 or more, 180 or more, 200 or more, 230 or more, 250 or more, 270 or more, 300 or more, 350 or more, 400 or more, 450 or more, or 500 or more. The upper limit of the mass ratio is not particularly limited, but may be, for example, 2,000 or less, 1,500 or less, 1,000 or less, 900 or less, 800 or less, 700 or less, 600 or less, or 500 or less. can.
　第１の不飽和オルガノポリシロキサンとしては、２５℃における粘度が、５０ｃｓｔ以上、１，０００ｃｓｔ未満の不飽和オルガノポリシロキサンを使用することが好ましいが、例えば、２５℃における粘度が、５０ｃｓｔ未満の不飽和オルガノポリシロキサン、及び／又は１，０００ｃｓｔ以上の不飽和オルガノポリシロキサンを、使用してもよく或いは併用してもよい。併用する場合、第１の不飽和オルガノポリシロキサン中における、５０ｃｓｔ以上、１，０００ｃｓｔ未満の不飽和オルガノポリシロキサンの配合割合としては、例えば、第１の不飽和オルガノポリシロキサンの全量に対し、３０質量％以上、４０質量％以上、５０質量％以上、６０質量％以上、７０質量％以上、又は８０質量％以上とすることができ、また、１００質量％未満、９８質量％以下、又は９５質量％以下とすることができる。 As the first unsaturated organopolysiloxane, it is preferable to use an unsaturated organopolysiloxane having a viscosity at 25 ° C. of 50 cst or more and less than 1,000 cst. For example, an unsaturated organopolysiloxane having a viscosity at 25 ° C. of less than 50 cst is used. Saturated organopolysiloxane and / or unsaturated organopolysiloxane of 1,000 cst or more may be used or used in combination. When used in combination, the blending ratio of the unsaturated organopolysiloxane of 50 cst or more and less than 1,000 cst in the first unsaturated organopolysiloxane is, for example, 30 with respect to the total amount of the first unsaturated organopolysiloxane. It can be mass% or more, 40% by mass or more, 50% by mass or more, 60% by mass or more, 70% by mass or more, or 80% by mass or more, and less than 100% by mass, 98% by mass or less, or 95% by mass. It can be less than or equal to%.
ｂ．その他のシリコーン油
　第１の不飽和オルガノポリシロキサン以外のその他のシリコーン油としては特に制限はなく、例えば、ジメチルポリシロキサン（ジメチコン）、メチルフェニルポリシロキサン、メチルハイドロジェンポリシロキサン等の鎖状シリコーン；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の環状シリコーンなどを使用することができる。その他のシリコーン油は単独で又は二種以上組み合わせて使用することができる。 b. Other Silicone Oils The silicone oils other than the first unsaturated organopolysiloxane are not particularly limited, and for example, chain silicones such as dimethylpolysiloxane (dimethicone), methylphenylpolysiloxane, and methylhydrogenpolysiloxane; Cyclic silicones such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane can be used. Other silicone oils can be used alone or in combination of two or more.
（乳化剤）
　本開示における乳化剤とは、乳化機能（界面活性能）を有する剤を意図し、一般に界面活性剤と称する剤も包含することができる。 (emulsifier)
The emulsifier in the present disclosure is intended to be an agent having an emulsifying function (surfactant ability), and may also include an agent generally referred to as a surfactant.
　乳化剤の配合量としては特に制限はなく、例えば、乳化安定性、白金触媒の保存安定性等の観点から、組成物の全量に対し、０．０１質量％以上、０．０５質量％以上、０．１質量％以上、又は０．２質量％以上とすることができ、また、５質量％以下、４質量％以下、３質量％以下、２質量％以下、又は１質量％以下とすることができる。 The amount of the emulsifier to be blended is not particularly limited. For example, from the viewpoint of emulsion stability, storage stability of the platinum catalyst, etc., 0.01% by mass or more, 0.05% by mass or more, and 0 with respect to the total amount of the composition. It can be 1% by mass or more, 0.2% by mass or more, and 5% by mass or less, 4% by mass or less, 3% by mass or less, 2% by mass or less, or 1% by mass or less. can.
　乳化剤としては、例えば、アニオン性、カチオン性、両性、又は非イオン性の乳化剤を使用することができる。乳化剤は単独で又は二種以上組み合わせて使用することができる。 As the emulsifier, for example, anionic, cationic, amphoteric, or nonionic emulsifiers can be used. The emulsifier can be used alone or in combination of two or more.
　乳化剤のなかでも、白金触媒の保存安定性等の観点から、高分子乳化剤が好ましい。高分子乳化剤は、一般的な乳化剤（界面活性剤）に比べ、典型的には、分子量が大きく、乳化能力の低い乳化剤（界面活性剤）を意図することができる。乳化安定性の向上を図る場合、一般的には、乳化能力の高い乳化剤が使用される。本発明者は、特定の白金触媒を含む乳化組成物の場合には、意外にも、乳化能力の比較的低い高分子乳化剤を使用した方が、白金触媒の保存安定性等がより一層優れることを見出した。原理は定かではないが、高分子乳化剤の使用による、白金触媒の保存安定性のより一層の向上効果は、次のように考えている。 Among the emulsifiers, polymer emulsifiers are preferable from the viewpoint of storage stability of the platinum catalyst. The polymer emulsifier can typically be intended as an emulsifier (surfactant) having a large molecular weight and a low emulsifying ability as compared with a general emulsifier (surfactant). When improving the emulsification stability, an emulsifier having a high emulsifying ability is generally used. Surprisingly, in the case of an emulsified composition containing a specific platinum catalyst, the present inventor finds that the use of a polymer emulsifier having a relatively low emulsifying ability is even more excellent in the storage stability of the platinum catalyst. I found. Although the principle is not clear, the effect of further improving the storage stability of the platinum catalyst by using the polymer emulsifier is considered as follows.
　高分子乳化剤以外の一般的な乳化能力の高い乳化剤（界面活性剤）を使用すると、乳化粒子が細かくなるため、通常であれば、乳化組成物は安定化する。しかしながら、本開示で使用する白金触媒は、１，３－ジビニルテトラメチルジシロキサンが、触媒の表面に配位している。その結果、乳化能力の高い乳化剤が、かかる白金触媒を油相から水相へ引き抜くように作用するため、水相側へ移動した白金触媒は、不安定となって凝集が進み、黒化しやすくなると考えている。一方、乳化能力の低い高分子乳化剤は、このような白金触媒の水相への引き抜き作用が弱いため、白金触媒を油相中で安定的に保存し得ると考えている。 If a general emulsifier (surfactant) having a high emulsifying ability other than a polymer emulsifier is used, the emulsified particles become finer, so that the emulsified composition is usually stabilized. However, in the platinum catalyst used in the present disclosure, 1,3-divinyltetramethyldisiloxane is coordinated on the surface of the catalyst. As a result, the emulsifier having a high emulsifying ability acts to pull out the platinum catalyst from the oil phase to the aqueous phase, so that the platinum catalyst moved to the aqueous phase side becomes unstable, aggregates, and becomes easy to blacken. thinking. On the other hand, it is considered that the polymer emulsifier having a low emulsifying ability can stably store the platinum catalyst in the oil phase because the pulling action of the platinum catalyst into the aqueous phase is weak.
　高分子乳化剤の重量平均分子量は、乳化安定性、白金触媒の保存安定性等の観点から、５００以上、７００以上、１，０００以上、１，５００以上、又は２，０００以上とすることができる。高分子乳化剤の重量平均分子量の上限値については特に制限はなく、例えば、１，０００，０００以下、１００，０００以下、１０，０００以下、又は５，０００以下とすることができる。なお、乳化剤の重量平均分子量は、乳化剤をＮ，Ｎ－ジメチルホルムアミド(ＤＭＦ)に溶解させて０．５％溶液を作製し、これを用いて以下の条件でＧＰＣ（ゲルパーミエーションクロマトグラフィー）により測定して求めたポリスチレン換算値である：
　カラム：α－Ｍ（昭和電工株式会社製）を２本直列に連結して使用した。
　溶離液：６０ｍｍｏｌ／ＬのＨ３ＰＯ４と５０ｍｍｏｌ／ＬのＬｉＢｒのＤＭＦ溶液
　流速　：１．０ｍＬ／分
　カラム温度：４０℃
　検出器：ＲＩ
　検量線：ポリスチレンを用いて作成した。 The weight average molecular weight of the polymer emulsifier can be 500 or more, 700 or more, 1,000 or more, 1,500 or more, or 2,000 or more from the viewpoint of emulsion stability, storage stability of the platinum catalyst, and the like. .. The upper limit of the weight average molecular weight of the polymer emulsifier is not particularly limited, and may be, for example, 1,000,000 or less, 100,000 or less, 10,000 or less, or 5,000 or less. For the weight average molecular weight of the emulsifier, dissolve the emulsifier in N, N-dimethylformamide (DMF) to prepare a 0.5% solution, and use this to prepare a 0.5% solution by GPC (gel permeation chromatography) under the following conditions. It is a polystyrene conversion value obtained by measurement:
Column: Two α-M (manufactured by Showa Denko KK) were connected in series and used.
Eluent: 60 mmol / L H 3 PO 4 and 50 mmol / L LiBr DMF solution Flow rate: 1.0 mL / min Column temperature: 40 ° C.
Detector: RI
Calibration curve: Prepared using polystyrene.
　高分子乳化剤としては特に制限はなく、例えば、（アクリレーツ／アクリル酸アルキル（Ｃ１０－３０））クロスポリマー、（アクリロイルジメチルタウリンアンモニウム／メタクリル酸ベヘネス－２５）クロスポリマー、（アクリル酸ヒドロキシエチル／アクリロイルジメチルタウリンＮａ）コポリマー、ＰＥＧ変性クロスポリマー／コポリマーシロキサン、ポリエーテル変性クロスポリマー／コポリマーシロキサン、及びポリオキシエチレンから選択される少なくとも一種を挙げることができる。なかでも、乳化安定性、白金触媒の保存安定性等の観点から、（アクリレーツ／アクリル酸アルキル（Ｃ１０－３０））クロスポリマーが好ましい。 The polymer emulsifier is not particularly limited, and is, for example, (Acrylate / alkyl acrylate (C10-30)) crosspolymer, (acryloyldimethyltaurineammonium / behenes-25 methacrylate) crosspolymer, (hydroxyethyl acrylate / acryloyldimethyl). At least one selected from taurine Na) copolymer, PEG-modified crosspolymer / copolymer siloxane, polyether-modified crosspolymer / copolymer siloxane, and polyoxyethylene can be mentioned. Among them, (Acrylate / alkyl acrylate (C10-30)) crosspolymer is preferable from the viewpoint of emulsion stability, storage stability of platinum catalyst and the like.
　乳化剤は、白金触媒の保存安定性等の観点から、高分子乳化剤以外の一般的な乳化剤（界面活性剤）、なかでもシリコーン系乳化剤の使用量が少ないことが好ましい。このような乳化剤の配合量としては、例えば、組成物の全体量に対し、１質量％未満、０．７質量％以下、０．５質量％以下、０．３質量％以下、又は０．１質量％以下であることが好ましく、また、このような乳化剤は、組成物中に含まれないことがより好ましい。 As the emulsifier, it is preferable that the amount of general emulsifiers (surfactants) other than polymer emulsifiers (surfactants), especially silicone emulsifiers, is small from the viewpoint of storage stability of the platinum catalyst. The blending amount of such an emulsifier is, for example, less than 1% by mass, 0.7% by mass or less, 0.5% by mass or less, 0.3% by mass or less, or 0.1 by mass with respect to the total amount of the composition. It is preferably not more than% by mass, and it is more preferable that such an emulsifier is not contained in the composition.
　高分子乳化剤以外の一般的な乳化剤（界面活性剤）の重量平均分子量としては、５００未満、４５０以下、又は４００以下とすることができ、また、１００以上、１５０以上、又は２００以上とすることができる。 The weight average molecular weight of general emulsifiers (surfactants) other than polymer emulsifiers can be less than 500, 450 or less, or 400 or less, and 100 or more, 150 or more, or 200 or more. Can be done.
　高分子乳化剤以外の一般的な乳化剤（界面活性剤）のＨＬＢとしては、２．０以上、３．０以上、又は４．０以上とすることができ、また、１０．０以下、９．０以下、又は８．０以下とすることができる。 The HLB of a general emulsifier (surfactant) other than a polymer emulsifier can be 2.0 or more, 3.0 or more, or 4.0 or more, and 10.0 or less, 9.0. It can be less than or equal to or less than 8.0.
（触媒）
　本開示の乳化組成物は、触媒として、少なくとも、下記式１で示される１，３－ジビニルテトラメチルジシロキサンが配位した白金錯体を含む：
Figure JPOXMLDOC01-appb-C000002
 (catalyst)
The emulsified composition of the present disclosure contains, as a catalyst, at least a platinum complex coordinated with 1,3-divinyltetramethyldisiloxane represented by the following formula 1.
Figure JPOXMLDOC01-appb-C000002
　かかる白金錯体の含有量としては特に制限はなく、組成物の全体量に対し、０．０１質量％以上、０．０５質量％以上、０．１０質量％以上、０．１５質量％以上、又は０．２０質量％以上とすることができる。含有量の上限値としては特に制限はなく、３．０質量％以下、２．５質量％以下、２．０質量％以下、１．５質量％以下、１．０質量％以下、０．７０質量％以下、０．５０質量％以下、又は０．３０質量％以下とすることができる。 The content of the platinum complex is not particularly limited, and is 0.01% by mass or more, 0.05% by mass or more, 0.10% by mass or more, 0.15% by mass or more, or 0.15% by mass or more, based on the total amount of the composition. It can be 0.20% by mass or more. The upper limit of the content is not particularly limited, and is 3.0% by mass or less, 2.5% by mass or less, 2.0% by mass or less, 1.5% by mass or less, 1.0% by mass or less, 0.70. It can be mass% or less, 0.50 mass% or less, or 0.30 mass% or less.
　白金錯体中の白金自体の含有量としては特に制限はなく、組成物の全体量に対し、０．００１質量％以上、０．００５質量％以上、０．０１０質量％以上、０．０１５質量％以上、又は０．０２０質量％以上とすることができる。含有量の上限値としては特に制限はなく、１．０質量％以下、０．５０質量％以下、０．１０質量％以下、又は０．０５０質量％以下とすることができる。 The content of platinum itself in the platinum complex is not particularly limited, and is 0.001% by mass or more, 0.005% by mass or more, 0.010% by mass or more, and 0.015% by mass with respect to the total amount of the composition. The above, or 0.020% by mass or more can be used. The upper limit of the content is not particularly limited and may be 1.0% by mass or less, 0.50% by mass or less, 0.10% by mass or less, or 0.050% by mass or less.
　本開示の乳化組成物は、上記の白金錯体の他に、本開示の効果に影響を及ぼさない範囲で、他の触媒を含んでもよい。 The emulsified composition of the present disclosure may contain other catalysts in addition to the above-mentioned platinum complex as long as the effects of the present disclosure are not affected.
　他の触媒としては、例えば、第ＶＩＩＩ族の金属触媒、例えば、上記白金錯体以外の白金触媒、ロジウム触媒、パラジウム触媒、コバルト触媒、ニッケル触媒、ルテニウム触媒、オスミウム触媒、及びイリジウム触媒、並びに第ＩＶＡ族の金属触媒、例えば、ゲルマニウム触媒及びスズ触媒を挙げることができる。他の触媒は、単独で又は二種以上組み合わせて使用することができる。 Examples of other catalysts include Group VIII metal catalysts, such as platinum catalysts other than the platinum complex, rhodium catalysts, palladium catalysts, cobalt catalysts, nickel catalysts, ruthenium catalysts, osmium catalysts, and iridium catalysts, and IVA. Group metal catalysts such as germanium catalysts and tin catalysts can be mentioned. Other catalysts can be used alone or in combination of two or more.
　上記白金錯体以外の白金触媒としては、例えば、白金カルボニルシクロビニルメチルシロキサン錯体、白金シクロビニルメチルシロキサン錯体、白金オクタンアルデヒド／オクタノール錯体、及び他のＰｔ（０）触媒、例えば、カールシュテット触媒、白金－アルコール錯体、白金－アルコキシド錯体、白金－エーテル錯体、白金－アルデヒド錯体、白金－ケトン錯体、白金－ハロゲン錯体、白金－硫黄錯体、白金－窒素錯体、白金－リン錯体、白金－炭素二重結合錯体、白金炭素三重結合錯体、白金－イミド錯体、白金－アミド錯体、白金－エステル錯体、白金－リン酸エステル錯体、白金－チオールエステル錯体、白金孤立電子対錯体、白金－芳香族錯体、白金π－電子錯体、及びこれらの組合せが挙げられる。 Examples of platinum catalysts other than the platinum complex include platinum carbonylcyclovinylmethylsiloxane complex, platinumcyclovinylmethylsiloxane complex, platinum octanealdehyde / octanol complex, and other Pt (0) catalysts, such as Karlstead catalyst. Platinum-alcohol complex, platinum-alkoxide complex, platinum-ether complex, platinum-aldehyde complex, platinum-ketone complex, platinum-halogen complex, platinum-sulfur complex, platinum-nitrogen complex, platinum-phosphorus complex, platinum-carbon double Bonded complex, platinum carbon triple bond complex, platinum-imide complex, platinum-amide complex, platinum-ester complex, platinum-phosphate ester complex, platinum-thiol ester complex, platinum isolated electron pair complex, platinum-aromatic complex, platinum π-Electronic complexes and combinations thereof can be mentioned.
　ロジウム触媒としては、例えば、三塩化トリス（ジブチルスルフィド）ロジウム及び三塩化ロジウム水和物が挙げられる。 Examples of the rhodium catalyst include tris trichloride (dibutyl sulfide) rhodium and rhodium trichloride hydrate.
　スズ触媒としては、例えば、オクタン酸スズ（ＩＩ）、ネオデカン酸スズ（ＩＩ）、ジブチルスズジイソオクチルマレエート、ジ－ｎ－ブチルビス（２，４－ペンタンジオネート）スズ、ジ－ｎ－ブチルブトキシクロロスズ、ジブチルスズジラウレート、ジメチルスズジネオデカノエート、ジメチルヒドロキシ（オレエート）スズ、及びオレイン酸スズ（ＩＩ）が挙げられる。 Examples of the tin catalyst include tin octanoate (II), tin neodecanoate (II), dibutyltin diisooctylmaleate, di-n-butylbis (2,4-pentandionate) tin, and di-n-butylbutoxy. Included are chlorotin, dibutyltin dilaurate, dimethyltin dineodecanoate, dimethylhydroxy (oleate) tin, and tin oleate (II).
　上記白金錯体以外の他の触媒の配合量としては、触媒の全量に対し、５０質量％未満、３０質量％以下、１０質量％以下、５質量％以下、又は１質量％以下とすることができる。乳化安定性、白金触媒の保存安定性等の観点から、他の触媒は乳化組成物中に含まれないことが好ましい。 The blending amount of the catalyst other than the platinum complex may be less than 50% by mass, 30% by mass or less, 10% by mass or less, 5% by mass or less, or 1% by mass or less with respect to the total amount of the catalyst. .. From the viewpoint of emulsion stability, storage stability of the platinum catalyst, etc., it is preferable that other catalysts are not contained in the emulsified composition.
〈任意成分〉
　本開示の水中油型乳化組成物は、本開示の効果に影響を及ぼさない範囲で、各種成分を適宜配合することができる。このような任意成分として、例えば、保湿剤、エモリエント剤、増粘剤、水溶性高分子、油溶性高分子、シリコーン化多糖類等の皮膜形成剤、イソステアリン酸等の高級脂肪酸、金属イオン封鎖剤、エタノール等の低級アルコール、ステアリルアルコール等の高級アルコール、１，３－ブチレングリコール等の多価アルコール、各種抽出液、糖、アミノ酸、有機アミン、キレート剤、紫外線吸収剤、ｐＨ調整剤、皮膚栄養剤、ビタミン、医薬品、医薬部外品、化粧品等に適用可能な水溶性薬剤、緩衝剤、退色防止剤、防腐剤、噴射剤、有機系粉末、顔料、染料、色素、香料等を挙げることができる。任意成分は、単独で又は二種以上組み合わせて使用することができる。 <Arbitrary ingredient>
The oil-in-water emulsified composition of the present disclosure may appropriately contain various components as long as it does not affect the effects of the present disclosure. Such optional components include, for example, moisturizing agents, emollients, thickeners, water-soluble polymers, oil-soluble polymers, film-forming agents such as siliconeized polysaccharides, higher fatty acids such as isostearic acid, and metal ion sequestering agents. , Lower alcohols such as ethanol, higher alcohols such as stearyl alcohol, polyhydric alcohols such as 1,3-butylene glycol, various extracts, sugars, amino acids, organic amines, chelating agents, ultraviolet absorbers, pH adjusters, skin nutrition Water-soluble agents applicable to agents, vitamins, pharmaceuticals, non-pharmaceutical products, cosmetics, etc., buffers, anti-fading agents, preservatives, propellants, organic powders, pigments, dyes, pigments, fragrances, etc. can. The optional ingredients can be used alone or in combination of two or more.
《人工皮膚形成剤》
　上述した本開示の水中油型乳化組成物は、種々の用途に使用することができる。次の用途に限定されないが、本開示の水中油型乳化組成物は、白金触媒の保存安定性に優れ、変色等の不具合を低減又は抑制することができることから、色調の変化を防止することが望まれている用途、例えば、第１剤及び第２剤を含む人工皮膚形成剤の第２剤として好適に使用することができる。かかる人工皮膚形成剤は、例えば、第１剤を体表に塗布して第１剤層を形成した後、第２剤を第１剤層に塗布して第１剤層を架橋させることによって、人工皮膚を形成することができる。 《Artificial skin forming agent》
The oil-in-water emulsified composition of the present disclosure described above can be used for various purposes. Although not limited to the following uses, the oil-in-water emulsified composition of the present disclosure has excellent storage stability of the platinum catalyst, and can reduce or suppress defects such as discoloration, so that it is possible to prevent changes in color tone. It can be suitably used as a second agent of an artificial skin forming agent containing a first agent and a second agent, for example, in a desired application. Such an artificial skin forming agent is obtained, for example, by applying the first agent to the body surface to form the first agent layer and then applying the second agent to the first agent layer to crosslink the first agent layer. Artificial skin can be formed.
　いくつかの実施態様において、人工皮膚形成剤の塗布性能は、Ｂ型粘度計（芝浦システム株式会社製、ビスメトロン）を用いた粘度で評価することができる。２５℃、６０回転／分（ローターＮｏ．３又はＮｏ．４）の条件で測定した本開示の人工皮膚形成剤における第１剤及び第２剤の作製直後の粘度は、例えば、１００ｍＰａ・ｓ以上、５００ｍＰａ・ｓ以上、１，０００ｍＰａ・ｓ以上、２，０００ｍＰａ・ｓ以上、５，０００ｍＰａ・ｓ以上、７，５００ｍＰａ・ｓ以上、１０，０００ｍＰａ・ｓ以上、又は１５，０００ｍＰａ・ｓ以上にすることができ、１，０００，０００ｍＰａ・ｓ以下、７５０，０００ｍＰａ・ｓ以下、５００，０００ｍＰａ・ｓ以下、２５０，０００ｍＰａ・ｓ以下、２００，０００ｍＰａ・ｓ以下、１７５，０００ｍＰａ・ｓ以下、１５０，０００ｍＰａ・ｓ以下、１２５，０００ｍＰａ・ｓ以下、１００，０００ｍＰａ・ｓ以下、又は８０，０００ｍＰａ・ｓ以下にすることができる。なかでも、滑らかな塗布性能及び皮膚からの液だれ抑制等の観点から、人工皮膚形成剤は、２０，０００ｍＰａ・ｓ以下、１５，０００ｍＰａ・ｓ以下、又は１０，０００ｍＰａ・ｓ以下の粘度を有することが好ましく、３，０００ｍＰａ・ｓ以上、５，０００ｍＰａ・ｓ以上、又は７，０００ｍＰａ・ｓ以上の粘度を有することが好ましい。 In some embodiments, the application performance of the artificial skin forming agent can be evaluated by the viscosity using a B-type viscometer (Shibaura System Co., Ltd., Bismetron). The viscosities of the first and second agents of the artificial skin forming agent of the present disclosure measured under the conditions of 25 ° C. and 60 rotations / minute (rotor No. 3 or No. 4) immediately after preparation are, for example, 100 mPa · s or more. , 500 mPa · s or more, 1,000 mPa · s or more, 2,000 mPa · s or more, 5,000 mPa · s or more, 7,500 mPa · s or more, 10,000 mPa · s or more, or 15,000 mPa · s or more Can be 1,000,000 mPa · s or less, 750,000 mPa · s or less, 500,000 mPa · s or less, 250,000 mPa · s or less, 200,000 mPa · s or less, 175,000 mPa · s or less, 150, It can be 000 mPa · s or less, 125,000 mPa · s or less, 100,000 mPa · s or less, or 80,000 mPa · s or less. Among them, the artificial skin forming agent has a viscosity of 20,000 mPa · s or less, 15,000 mPa · s or less, or 10,000 mPa · s or less from the viewpoint of smooth application performance and suppression of dripping from the skin. It is preferable to have a viscosity of 3,000 mPa · s or more, 5,000 mPa · s or more, or 7,000 mPa · s or more.
　また、いくつかの実施態様において、２５℃、６０回転／分（ローターＮｏ．３）の条件で測定した本開示の人工皮膚形成剤における第１剤及び第２剤の２週間後の粘度は、滑らかな塗布性能及び皮膚からの液だれ抑制等の観点から、５０，０００ｍＰａ・ｓ以下、３０，０００ｍＰａ・ｓ以下、又は１５，０００ｍＰａ・ｓ以下であることが好ましく、５，０００ｍＰａ・ｓ以上、７，０００ｍＰａ・ｓ以上、又は１０，０００ｍＰａ・ｓ以上であることが好ましい。 Further, in some embodiments, the viscosities of the first agent and the second agent in the artificial skin forming agent of the present disclosure measured under the conditions of 25 ° C. and 60 rpm (rotor No. 3) after 2 weeks are determined. From the viewpoint of smooth application performance and suppression of dripping from the skin, it is preferably 50,000 mPa · s or less, 30,000 mPa · s or less, or 15,000 mPa · s or less, preferably 5,000 mPa · s or more. It is preferably 7,000 mPa · s or more, or 10,000 mPa · s or more.
　いくつかの実施態様において、人工皮膚の被膜性能は、例えば、皮膚からの引き剥がし時の人工皮膚の破れの有無で評価することができる。例えば、適用した人工皮膚の破れが、全体の、１５％以下、１０％以下、又は５％以下であると、被膜性能に優れているといえる。破れの下限値については特に制限はないが、例えば０％以上又は０％超とすることができる。この他、後述する引張強度、破断伸びなどによって被膜性能を評価することもできる。 In some embodiments, the film performance of the artificial skin can be evaluated, for example, by the presence or absence of tearing of the artificial skin when peeled from the skin. For example, when the tearing of the applied artificial skin is 15% or less, 10% or less, or 5% or less of the whole, it can be said that the film performance is excellent. The lower limit of tearing is not particularly limited, but may be, for example, 0% or more or more than 0%. In addition, the film performance can be evaluated based on the tensile strength and elongation at break, which will be described later.
〈第１剤〉
　本開示の人工皮膚形成剤を構成する第１剤は、第２の不飽和オルガノポリシロキサン、及びヒドリド官能化ポリシロキサンを含んでいる。 <First agent>
The first agent constituting the artificial skin forming agent of the present disclosure contains a second unsaturated organopolysiloxane and a hydride-functionalized polysiloxane.
　第１剤は、例えば、無水の形態であってもよく、或いは、水中油型又は油中水型のエマルジョンの形態であってもよいが、第１剤を体表へ適用した後の乾燥性及び架橋性等の観点から、第１剤は、無水の形態であることが有利である。 The first agent may be, for example, in the form of an anhydrous form, or may be in the form of an oil-in-water type or a water-in-oil type emulsion, but the drying property after the first agent is applied to the body surface. From the viewpoint of crosslinkability and the like, it is advantageous that the first agent is in an anhydrous form.
　無水の形態は、通常、細菌又はカビに対する保存料を必要としないので、類似の成分を有するエマルジョンよりも長期間保存することができる。ここで、本開示において「無水」とは、組成物中に水が含まれていないことを意図することに加え、水の含有量が低量、即ち、１０質量％以下、５質量％以下、２質量％以下、１質量％以下、又は０．１質量％以下であることも意図する。 The anhydrous form usually does not require a preservative against bacteria or mold, so it can be stored for a longer period of time than an emulsion with similar components. Here, in the present disclosure, "anhydrous" means that the composition does not contain water, and the content of water is low, that is, 10% by mass or less, 5% by mass or less. It is also intended to be 2% by mass or less, 1% by mass or less, or 0.1% by mass or less.
　第１剤は、体表に塗布等によって適用されるため、塗布性能の観点から、体温以下のガラス転移温度を有することが好ましい。例えば、ガラス転移温度は、３７℃以下、２５℃以下、１０℃以下、又は０℃以下にすることができる。ガラス転移温度の下限値については特に制限はないが、例えば、－３０℃以上、－２０℃以上、又は－１０℃以上とすることができる。ここで、「ガラス転移温度」とは、固体状態から液体状態への転移が起こる温度を指し、例えば、ＡＳＴＭ　Ｄ３４１８－０３に準拠した示差走査熱量計（ＤＳＣ）を用いて測定することができる。 Since the first agent is applied to the body surface by coating or the like, it is preferable to have a glass transition temperature equal to or lower than the body temperature from the viewpoint of coating performance. For example, the glass transition temperature can be 37 ° C. or lower, 25 ° C. or lower, 10 ° C. or lower, or 0 ° C. or lower. The lower limit of the glass transition temperature is not particularly limited, but may be, for example, −30 ° C. or higher, −20 ° C. or higher, or −10 ° C. or higher. Here, the "glass transition temperature" refers to the temperature at which the transition from the solid state to the liquid state occurs, and can be measured using, for example, a differential scanning calorimeter (DSC) compliant with ASTM D3418-03.
（第２の不飽和オルガノポリシロキサン）
　第２の不飽和オルガノポリシロキサンとしては特に制限はなく、例えば、少なくとも２つの炭素－炭素二重結合又は少なくとも１つの炭素－炭素三重結合を分子内に有する一種以上のオルガノポリシロキサンを挙げることができる。第２の不飽和オルガノポリシロキサンとして好ましくは、平均して少なくとも２つのアルケニル官能基を有し、かつ２５℃で１０，０００～２，０００，０００ｃｓｔの粘度を有する一種以上のオルガノポリシロキサンを挙げることができる。ここで、本開示では、「炭素－炭素二重結合」及び「炭素－炭素三重結合」を、単に「二重結合」及び「三重結合」と称する場合がある。第２の不飽和オルガノポリシロキサンは単独で又は二種以上組み合わせて使用することができる。 (Second unsaturated organopolysiloxane)
The second unsaturated organopolysiloxane is not particularly limited, and examples thereof include one or more organopolysiloxanes having at least two carbon-carbon double bonds or at least one carbon-carbon triple bond in the molecule. can. The second unsaturated organopolysiloxane is preferably one or more organopolysiloxanes having at least two alkenyl functional groups on average and a viscosity of 10,000-2,000,000 cst at 25 ° C. be able to. Here, in the present disclosure, "carbon-carbon double bond" and "carbon-carbon triple bond" may be simply referred to as "double bond" and "triple bond". The second unsaturated organopolysiloxane can be used alone or in combination of two or more.
　このようなオルガノポリシロキサンは、二重結合又は三重結合を、ポリマーの末端単位に、ポリマーの非末端モノマー単位に、又はこれらの組合せにおいて含んでもよく、なかでも、ポリマーの非末端モノマー単位に含むことが好ましい。 Such organopolysiloxanes may contain double or triple bonds in the terminal units of the polymer, in the non-terminal monomer units of the polymer, or in combinations thereof, among others, in the non-terminal monomer units of the polymer. Is preferable.
　ある実施態様では、オルガノポリシロキサン中の二重結合含有モノマー単位は、平均して、４０モノマー単位以上、２００モノマー単位以上、４００モノマー単位以上、１，０００モノマー単位以上、又は２，０００モノマー単位以上離れていてもよい。 In one embodiment, the double bond-containing monomer units in the organopolysiloxane averaged 40 monomer units or more, 200 monomer units or more, 400 monomer units or more, 1,000 monomer units or more, or 2,000 monomer units. It may be separated by more than that.
　ある実施態様では、二重結合又は三重結合を有するオルガノポリシロキサンの二重結合又は三重結合含有モノマー単位の量は、例えば、０．０１質量％以上又は０．０３質量％以上にすることができ、２質量％以下又は０．６質量％以下にすることができる。 In certain embodiments, the amount of double or triple bond containing monomer units of an organopolysiloxane having a double or triple bond can be, for example, 0.01% by weight or more or 0.03% by weight or more. , 2% by mass or less or 0.6% by mass or less.
　ある実施態様では、二重結合又は三重結合を有するオルガノポリシロキサンのビニル当量は、例えば、１キログラム当たり、０．００５以上又は０．０１以上にすることができ、０．５以下又は０．２５以下にすることができる。オルガノポリシロキサン中の二重結合又は三重結合の近似モル量は、オルガノポリシロキサンの平均分子量に基づいて計算することができる。ここで、本明細書に開示される人工皮膚形成剤における各成分の平均分子量又は分子質量は、一般に、各成分の供給業者によって提供され、ダルトン（Ｄａ）又はそれと等価のｇ／ｍｏｌの単位で表すことができる。 In certain embodiments, the vinyl equivalent of the organopolysiloxane having a double or triple bond can be, for example, 0.005 or more or 0.01 or more per kilogram, 0.5 or less or 0.25. It can be: The approximate molar amount of double or triple bonds in an organopolysiloxane can be calculated based on the average molecular weight of the organopolysiloxane. Here, the average molecular weight or molecular mass of each component in the artificial skin-forming agent disclosed herein is generally provided by the supplier of each component and is in units of dalton (Da) or equivalent g / mol. Can be represented.
　ある実施態様では、第２の不飽和オルガノポリシロキサンは、２５℃で、１０，０００～２，０００，０００ｃｓｔの粘度を有することができる。かかる粘度の下限値としては、２０，０００ｃｓｔ以上、４０，０００ｃｓｔ以上、６０，０００ｃｓｔ以上、８０，０００ｃｓｔ以上、又は１００，０００ｃｓｔ以上であることが好ましく、１２５，０００ｃｓｔ以上又は１５０，０００ｃｓｔ以上であることがより好ましい。粘度の上限値としては、１，０００，０００ｃｓｔ以下、５００，０００ｃｓｔ以下、４５０，０００ｃｓｔ以下、４００，０００ｃｓｔ以下、３５０，０００ｃｓｔ以下、３００，０００ｃｓｔ以下、又は２５０，０００ｃｓｔ以下であることが好ましく、２００，０００ｃｓｔ以下又は１８０，０００ｃｓｔ以下であることがより好ましく、１６５，０００ｃｓｔ以下であることがさらに好ましい。 In one embodiment, the second unsaturated organopolysiloxane can have a viscosity of 10,000-2,000,000 cst at 25 ° C. The lower limit of the viscosity is preferably 20,000 cst or more, 40,000 cst or more, 60,000 cst or more, 80,000 cst or more, or 100,000 cst or more, and 125,000 cst or more or 150,000 cst or more. Is more preferable. The upper limit of the viscosity is preferably 1,000,000 cst or less, 500,000 cst or less, 450,000 cst or less, 400,000 cst or less, 350,000 cst or less, 300,000 cst or less, or 250,000 cst or less. It is more preferably 200,000 cst or less or 180,000 cst or less, and further preferably 165,000 cst or less.
　ある実施態様では、第２の不飽和オルガノポリシロキサンは、６０，０００Ｄａ～５００，０００Ｄａの平均分子量を有することができる。かかる平均分子量の下限値としては、７２，０００Ｄａ以上、８４，０００Ｄａ以上、９６，０００Ｄａ以上、又は１００，０００Ｄａ以上であることが好ましく、１４０，０００Ｄａ以上又は１５０，０００Ｄａ以上であることがより好ましい。平均分子量の上限値としては、２００，０００Ｄａ以下、１９０，０００Ｄａ以下、１８０，０００Ｄａ、又は１７０，０００Ｄａ以下であることが好ましく、１６０，０００Ｄａ以下であることがより好ましく、１５５，０００Ｄａ以下がさらに好ましい。 In some embodiments, the second unsaturated organopolysiloxane can have an average molecular weight of 60,000 Da to 500,000 Da. The lower limit of the average molecular weight is preferably 72,000 Da or more, 84,000 Da or more, 96,000 Da or more, or 100,000 Da or more, and more preferably 140,000 Da or more or 150,000 Da or more. .. The upper limit of the average molecular weight is preferably 200,000 Da or less, 190,000 Da or less, 180,000 Da, or 170,000 Da or less, more preferably 160,000 Da or less, and further preferably 155,000 Da or less. preferable.
　第２の不飽和オルガノポリシロキサンとして、例えば、ビニル基を有するオルガノポリシロキサン、ビニル末端化されたオルガノポリシロキサン、及びビニル化された分岐鎖を有するオルガノポリシロキサンから選択される少なくとも一種を挙げることができる。 As the second unsaturated organopolysiloxane, for example, at least one selected from an organopolysiloxane having a vinyl group, a vinyl-terminated organopolysiloxane, and an organopolysiloxane having a vinylized branched chain is mentioned. Can be done.
　このような第２の不飽和オルガノポリシロキサンとしては、具体的には、例えば、ビニル末端ポリジメチルシロキサン、ビニル末端ジフェニルシロキサン－ジメチルシロキサンコポリマー、ビニル末端ポリフェニルメチルシロキサン、ビニルフェニルメチル末端ビニルフェニルシロキサン－フェニルメチルシロキサンコポリマー、ビニル末端トリフルオロプロピルメチルシロキサン－ジメチルシロキサンコポリマー、ビニル末端ジエチルシロキサン－ジメチルシロキサンコポリマー、ビニルメチルシロキサン－ジメチルシロキサンコポリマー、トリメチルシロキシ末端ビニルメチルシロキサン－ジメチルシロキサンコポリマー、シラノール末端ビニルメチルシロキサン－ジメチルシロキサンコポリマー、ビニルメチルシロキサンホモポリマー、ビニルＴ－構造ポリマー、モノビニル末端ポリジメチルシロキサン、ビニルメチルシロキサンターポリマー、及びビニルメトキシシランホモポリマーから選択される少なくとも一種を採用することができる。なかでも、ビニル末端ポリジメチルシロキサンが好ましく、ジビニルジメチコン、１，３－ジビニルテトラメチルジシロキサンがより好ましい。 Specific examples of such a second unsaturated organopolysiloxane include vinyl-terminated polydimethylsiloxane, vinyl-terminated diphenylsiloxane-dimethylsiloxane copolymer, vinyl-terminated polyphenylmethylsiloxane, and vinylphenylmethyl-terminated vinylphenylsiloxane. -Phenylmethylsiloxane copolymer, vinyl-terminated trifluoropropylmethylsiloxane-dimethylsiloxane copolymer, vinyl-terminated diethylsiloxane-dimethylsiloxane copolymer, vinylmethylsiloxane-dimethylsiloxane copolymer, trimethylsiloxy-terminated vinylmethylsiloxane-dimethylsiloxane copolymer, silanol-terminated vinylmethyl At least one selected from a siloxane-dimethylsiloxane copolymer, a vinylmethylsiloxane homopolymer, a vinyl T-structure polymer, a monovinyl-terminated polydimethylsiloxane, a vinylmethylsiloxane tarpolymer, and a vinylmethoxysilane homopolymer can be employed. Of these, vinyl-terminated polydimethylsiloxane is preferable, and divinyldimethicone and 1,3-divinyltetramethyldisiloxane are more preferable.
　第１剤中における第２の不飽和オルガノポリシロキサンの配合量については、要する被膜性能等に応じて適宜調整すればよく、特に制限はない。例えば、第２の不飽和オルガノポリシロキサンの配合量としては、第１剤全体に対し、５質量％以上、１０質量％以上、２０質量％以上、３０質量％以上、３５質量％以上、又は４０質量％以上とすることができ、９０質量％以下、８０質量％以下、７０質量％以下、６０質量％以下、５０質量％以下、又は４５質量％以下とすることができる。 The blending amount of the second unsaturated organopolysiloxane in the first agent may be appropriately adjusted according to the required coating performance and the like, and is not particularly limited. For example, the blending amount of the second unsaturated organopolysiloxane is 5% by mass or more, 10% by mass or more, 20% by mass or more, 30% by mass or more, 35% by mass or more, or 40 with respect to the entire first agent. It can be 90% by mass or less, 80% by mass or less, 70% by mass or less, 60% by mass or less, 50% by mass or less, or 45% by mass or less.
（ヒドリド官能化ポリシロキサン）
　ヒドリド官能化ポリシロキサンとしては特に制限はなく、例えば、以下の式２の化合物を挙げることができる。ヒドリド官能化ポリシロキサンは単独で又は二種以上組み合わせて使用することができる：
Figure JPOXMLDOC01-appb-C000003
 (Hydride functionalized polysiloxane)
The hydride-functionalized polysiloxane is not particularly limited, and examples thereof include compounds of the following formula 2. Hydride-functionalized polysiloxanes can be used alone or in combination of two or more:
Figure JPOXMLDOC01-appb-C000003
　式２中、Ｒ１ｂ、Ｒ２ｂ、Ｒ３ｂ、Ｒ４ｂ、Ｒ５ｂ、Ｒ６ｂ、Ｒ７ｂ、Ｒ８ｂ、Ｒ９ｂ及びＲ１０ｂは、それぞれ独立して、水素、Ｃ１－２０アルキル、Ｃ２－２０アルケニル、Ｃ５－１０アリール、ヒドロキシル、又はＣ１－２０アルコキシから選択され、ｍ及びｎは、それぞれ独立して、１０～６０００の整数である。但し、Ｒ１ｂ、Ｒ２ｂ、Ｒ３ｂ、Ｒ４ｂ、Ｒ５ｂ、Ｒ６ｂ、Ｒ７ｂ、Ｒ８ｂ、Ｒ９ｂ及びＲ１０ｂの少なくとも１つは水素である。 In Equation 2, R 1b , R 2b , R 3b , R 4b , R 5b , R 6b , R 7b , R 8b , R 9b and R 10b are independently hydrogen, C 1-20 alkyl and C 2 respectively. Selected from -20 alkenyl, C 5-10 aryl, hydroxyl, or C 1-20 alkoxy, m and n are independently integers from 10 to 6000. However, at least one of R 1b , R 2b , R 3b , R 4b , R 5b , R 6b , R 7b , R 8b , R 9b and R 10b is hydrogen.
　いくつかの実施態様において、Ｒ１ｂ、Ｒ２ｂ、Ｒ３ｂ、Ｒ４ｂ、Ｒ５ｂ、Ｒ６ｂ、Ｒ７ｂ、Ｒ８ｂ、Ｒ９ｂ及びＲ１０ｂの少なくとも１つは水素であり、残りはＣ１－２０アルキルである。 In some embodiments, at least one of R 1b , R 2b , R 3b , R 4b , R 5b , R 6b , R 7b , R 8b , R 9b and R 10b is hydrogen and the rest is C 1- . It is 20 alkyl.
　いくつかの実施形態において、Ｒ１ｂ、Ｒ２ｂ、Ｒ３ｂ、Ｒ４ｂ、Ｒ５ｂ、Ｒ６ｂ、Ｒ７ｂ、Ｒ８ｂ、Ｒ９ｂ及びＲ１０ｂの少なくとも２つは水素である（例えば、官能化ヒドリドポリシロキサン分子当たり２個のＳｉ－Ｈ単位）。 In some embodiments, at least two of R 1b , R 2b , R 3b , R 4b , R 5b , R 6b , R 7b , R 8b , R 9b and R 10b are hydrogen (eg, functionalized hydrides). 2 Si—H units per polysiloxane molecule).
　他の実施形態において、Ｒ１ｂ、Ｒ２ｂ、Ｒ３ｂ、Ｒ４ｂ、Ｒ５ｂ、Ｒ６ｂ、Ｒ７ｂ、Ｒ８ｂ、Ｒ９ｂ及びＲ１０ｂの少なくとも３つは水素（例えば、官能化ヒドリドポリシロキサン分子当たり３個のＳｉ－Ｈ単位）である。 In other embodiments, at least three of R 1b , R 2b , R 3b , R 4b , R 5b , R 6b , R 7b , R 8b , R 9b and R 10b are hydrogen (eg, a functionalized hydride polysiloxane molecule). 3 Si—H units per unit).
　いくつかの実施形態において、Ｒ１ｂ、Ｒ２ｂ、Ｒ３ｂ、Ｒ４ｂ、Ｒ５ｂ、Ｒ６ｂ、Ｒ７ｂ、Ｒ８ｂ、Ｒ９ｂ及びＲ１０ｂの少なくとも２つは水素（例えば、官能化ヒドリドポリシロキサン分子当たり２個のＳｉ－Ｈ単位）であり、残りはＣ１－２０アルキルである。 In some embodiments, at least two of R 1b , R 2b , R 3b , R 4b , R 5b , R 6b , R 7b , R 8b , R 9b and R 10b are hydrogen (eg, functionalized hydride polysiloxane). 2 Si—H units per molecule), with the rest being C 1-20 alkyl.
　他の実施形態において、Ｒ１ｂ、Ｒ２ｂ、Ｒ３ｂ、Ｒ４ｂ、Ｒ５ｂ、Ｒ６ｂ、Ｒ７ｂ、Ｒ８ｂ、Ｒ９ｂ及びＲ１０ｂの少なくとも３つは水素（例えば、官能化ヒドリドポリシロキサン分子当たり３個のＳｉ－Ｈ単位）であり、残りはＣ１－２０アルキルである。 In other embodiments, at least three of R 1b , R 2b , R 3b , R 4b , R 5b , R 6b , R 7b , R 8b , R 9b and R 10b are hydrogen (eg, a functionalized hydride polysiloxane molecule). 3 per Si—H unit), the rest are C 1-20 alkyl.
　いくつかの実施形態において、Ｒ４ｂ、Ｒ５ｂ、Ｒ９ｂ及びＲ１０ｂの少なくとも２つは水素（例えば、官能化ヒドリドポリシロキサン分子当たり２個のＳｉ－Ｈ単位）であり、残りはＣ１－２０アルキルである。 In some embodiments, at least two of R 4b , R 5b , R 9b and R 10b are hydrogen (eg, two Si—H units per functionalized hydride polysiloxane molecule) and the rest are C 1- . It is 20 alkyl.
　他の実施形態において、Ｒ４ｂ、Ｒ５ｂ、Ｒ９ｂ及びＲ１０ｂの少なくとも３つは水素（例えば、官能化ヒドリドポリシロキサン分子当たり３個のＳｉ－Ｈ単位）であり、残りはＣ１－２０アルキルである。 In other embodiments, at least three of R 4b , R 5b , R 9b and R 10b are hydrogen (eg, 3 Si—H units per functionalized hydride polysiloxane molecule) and the rest are C 1-20 . It is alkyl.
　いくつかの実施態様において、ｍ及びｎの合計は、１０～１，３００、１０～１，１００、１０～６００、１５～５００、１５～４００、２０～３００、２０～２００、２５～１００、２５～７５、３０～５０、又は４０～４５の整数である。 In some embodiments, the sum of m and n is 10-1,300, 10-1,100, 10-600, 15-500, 15-400, 20-300, 20-200, 25-100, It is an integer of 25 to 75, 30 to 50, or 40 to 45.
　いくつかの実施態様において、ヒドリド官能化ポリシロキサンとして、非末端及び／又は末端で水酸化されたオルガノポリシロキサンを挙げることができ、また、少なくとも２つのＳｉ－Ｈ単位を分子内に有する一種以上のオルガノポリシロキサンから構成され、好ましくは、平均して少なくとも２つのＳｉ－Ｈ単位を有し、かつ２５℃で２～１００，０００ｃｓｔの粘度を有する一種以上のオルガノポリシロキサンを挙げることができる。 In some embodiments, the hydride-functionalized polysiloxane can include a non-terminal and / or terminally hydroxylated organopolysiloxane, and one or more having at least two Si—H units in the molecule. Can be mentioned, preferably, one or more organopolysiloxanes composed of the organopolysiloxanes of the above, preferably having at least two Si—H units on average and having a viscosity of 2 to 100,000 cst at 25 ° C.
　ある実施態様では、Ｓｉ－Ｈ単位を有するオルガノポリシロキサンは、このようなＳｉ－Ｈ単位を、ポリマーの末端単位に、ポリマーの非末端モノマー単位に、又はこれらの組合せにおいて含んでもよい。なかでも、Ｓｉ－Ｈ単位は、ポリマーの非末端モノマー単位に含むことが好ましい。この場合のヒドリド官能化ポリシロキサンは、アルキル末端化されていてもよい。例えば、式２中、Ｒ２ｂ及びＲ７ｂの１つ又は両方が、Ｃ１－２０アルキルであってもよい。 In certain embodiments, the organopolysiloxane having Si—H units may contain such Si—H units in the terminal units of the polymer, in the non-terminal monomer units of the polymer, or in combinations thereof. Among them, the Si—H unit is preferably contained in the non-terminal monomer unit of the polymer. The hydride-functionalized polysiloxane in this case may be alkyl-terminated. For example, in Formula 2, one or both of R 2b and R 7b may be C 1-20 alkyl.
　一実施態様において、式２中、Ｒ１ｂ、Ｒ２ｂ、Ｒ３ｂ、Ｒ６ｂ、Ｒ７ｂ及びＲ８ｂの１つ、２つ、３つ、４つ、５つ又は６つが、Ｃ１－２０アルキルであってもよい。 In one embodiment, in Formula 2, one, two, three, four, five or six of R 1b , R 2b , R 3b , R 6b , R 7b and R 8b are C 1-20 alkyl. May be.
　一実施態様において、Ｒ１ｂ、Ｒ２ｂ、Ｒ３ｂ、Ｒ４ｂ、Ｒ５ｂ、Ｒ６ｂ、Ｒ７ｂ、Ｒ８ｂ及びＲ１０ｂは、それぞれＣ１－２０アルキル、例えば、Ｃ１アルキル（例えば、メチル）であり、Ｒ９ｂは水素であってもよい。 In one embodiment, R 1b , R 2b , R 3b , R 4b , R 5b , R 6b , R 7b , R 8b and R 10b are C 1-20 alkyl, eg, C 1 alkyl (eg, methyl), respectively. And R 9b may be hydrogen.
　一実施態様において、Ｒ１ｂ、Ｒ２ｂ、Ｒ３ｂ、Ｒ４ｂ、Ｒ５ｂ、Ｒ６ｂ、Ｒ７ｂ、Ｒ８ｂ及びＲ９ｂは、それぞれＣ１－２０アルキル、例えば、Ｃ１アルキル（例えば、メチル）であり、Ｒ１０ｂは水素であってもよい。 In one embodiment, R 1b , R 2b , R 3b , R 4b , R 5b , R 6b , R 7b , R 8b and R 9b are C 1-20 alkyl, eg, C 1 alkyl (eg, methyl), respectively. And R 10b may be hydrogen.
　ある実施態様では、オルガノポリシロキサン中のＳｉ－Ｈ含有モノマー単位は、平均して、１モノマー単位以上、２モノマー単位以上、５モノマー単位以上、１０モノマー単位以上、２０モノマー単位以上、４０モノマー単位以上、２００モノマー単位以上、４００モノマー単位以上、１，０００モノマー単位以上、又は２，０００モノマー単位以上離れていてもよい。 In one embodiment, the Si—H-containing monomer unit in the organopolysiloxane averages 1 monomer unit or more, 2 monomer units or more, 5 monomer units or more, 10 monomer units or more, 20 monomer units or more, and 40 monomer units. As mentioned above, it may be separated by 200 monomer units or more, 400 monomer units or more, 1,000 monomer units or more, or 2,000 monomer units or more.
　ある実施態様では、Ｓｉ－Ｈ単位を有するオルガノポリシロキサンのＳｉ－Ｈ含有モノマー単位量は、０．００３質量％以上、０．０１質量％以上、０．１質量％以上、１質量％以上、３質量％以上、５質量％以上、１０質量％以上、２０質量％以上、又は２６質量％以上にすることができ、また、５０質量％以下、４５質量％以下、４０質量％以下、３５質量％以下、３０質量％以下、又は２７質量％以下にすることができる。 In one embodiment, the Si—H-containing monomer unit amount of the organopolysiloxane having Si—H units is 0.003% by mass or more, 0.01% by mass or more, 0.1% by mass or more, and 1% by mass or more. It can be 3% by mass or more, 5% by mass or more, 10% by mass or more, 20% by mass or more, or 26% by mass or more, and 50% by mass or less, 45% by mass or less, 40% by mass or less, 35% by mass. % Or less, 30% by mass or less, or 27% by mass or less.
　ある実施態様では、Ｓｉ－Ｈ単位を有するオルガノポリシロキサンのＳｉ－Ｈ含有量は、０．１ｍｍｏｌ／ｇ以上、０．５ｍｍｏｌ／ｇ以上、１ｍｍｏｌ／ｇ以上、２ｍｍｏｌ／ｇ以上、３ｍｍｏｌ／ｇ以上、又は４ｍｍｏｌ／ｇ以上にすることができ、２０ｍｍｏｌ／ｇ以下、１０ｍｍｏｌ／ｇ以下、９ｍｍｏｌ／ｇ以下、８ｍｍｏｌ／ｇ以下、７ｍｍｏｌ／ｇ以下、６ｍｍｏｌ／ｇ以下、又は５ｍｍｏｌ／ｇ以下にすることができる。オルガノポリシロキサン中のＳｉ－Ｈ単位の近似モル量は、オルガノポリシロキサンの平均分子量に基づいて計算することができる。 In one embodiment, the Si—H content of the organopolysiloxane having the Si—H unit is 0.1 mmol / g or more, 0.5 mmol / g or more, 1 mmol / g or more, 2 mmol / g or more, 3 mmol / g or more. , Or 4 mmol / g or more, 20 mmol / g or less, 10 mmol / g or less, 9 mmol / g or less, 8 mmol / g or less, 7 mmol / g or less, 6 mmol / g or less, or 5 mmol / g or less. Can be done. The approximate molar amount of Si—H units in the organopolysiloxane can be calculated based on the average molecular weight of the organopolysiloxane.
　ある実施態様では、ヒドリド官能化ポリシロキサンは、２５℃で、２～５００，０００ｃｓｔの粘度を有することができる。かかる粘度の下限値としては、３ｃｓｔ以上、４ｃｓｔ以上、５ｃｓｔ以上、１０ｃｓｔ以上、１２ｃｓｔ以上、１５ｃｓｔ以上、２０ｃｓｔ以上、２５ｃｓｔ以上、又は３０ｃｓｔ以上であることが好ましく、４０ｃｓｔ以上であることがより好ましい。粘度の上限値としては、２００，０００ｃｓｔ以下、１００，０００ｃｓｔ以下、５０，０００ｃｓｔ以下、２０，０００ｃｓｔ以下、１０，０００ｃｓｔ以下、５，０００ｃｓｔ以下、２，０００ｃｓｔ以下、又は１，０００ｃｓｔ以下であることが好ましく、５００ｃｓｔ以下であることがより好ましい。ヒドリド官能化ポリシロキサンの粘度としては、２５℃で、４５～１００ｃｓｔ、又は４５～５０ｃｓｔの範囲が特に好ましい。 In one embodiment, the hydride functionalized polysiloxane can have a viscosity of 2 to 500,000 cst at 25 ° C. The lower limit of the viscosity is preferably 3 cst or more, 4 cst or more, 5 cst or more, 10 cst or more, 12 cst or more, 15 cst or more, 20 cst or more, 25 cst or more, or 30 cst or more, and more preferably 40 cst or more. The upper limit of the viscosity shall be 200,000 cst or less, 100,000 cst or less, 50,000 cst or less, 20,000 cst or less, 10,000 cst or less, 5,000 cst or less, 2,000 cst or less, or 1,000 cst or less. Is preferable, and 500 cst or less is more preferable. The viscosity of the hydride-functionalized polysiloxane is particularly preferably in the range of 45 to 100 cst or 45 to 50 cst at 25 ° C.
　ある実施態様では、ヒドリド官能化ポリシロキサンは、４００～５００，０００Ｄａの平均分子量を有することができる。かかる平均分子量の下限値としては、５００Ｄａ以上、８００Ｄａ以上、９００Ｄａ以上、１，０００Ｄａ以上、１，２００Ｄａ以上、１，４００Ｄａ以上、１，６００Ｄａ以上、１，８００Ｄａ以上、２，０００Ｄａ以上、又は２，２００Ｄａ以上であることが好ましく、２，３００Ｄａ以上であることがより好ましい。平均分子量の上限値としては、２５０，０００Ｄａ以下、１４０，０００Ｄａ以下、１００，０００Ｄａ以下、７２，０００Ｄａ以下、６２，７００Ｄａ以下、６０，０００Ｄａ以下、５０，０００Ｄａ以下、４９，５００Ｄａ以下、３６，０００Ｄａ以下、２８，０００Ｄａ以下、２５，０００Ｄａ以下、２０，０００Ｄａ以下、１５，０００Ｄａ以下、１０，０００Ｄａ以下、５，０００Ｄａ以下、又は４，０００Ｄａ以下であることが好ましく、２，５００Ｄａ以下であることがより好ましい。 In some embodiments, the hydride functionalized polysiloxane can have an average molecular weight of 400-500,000 Da. The lower limit of the average molecular weight is 500 Da or more, 800 Da or more, 900 Da or more, 1,000 Da or more, 1,200 Da or more, 1,400 Da or more, 1,600 Da or more, 1,800 Da or more, 2,000 Da or more, or 2 , 200 Da or more, more preferably 2,300 Da or more. The upper limit of the average molecular weight is 250,000 Da or less, 140,000 Da or less, 100,000 Da or less, 72,000 Da or less, 62,700 Da or less, 60,000 Da or less, 50,000 Da or less, 49,500 Da or less, 36, It is preferably 000 Da or less, 28,000 Da or less, 25,000 Da or less, 20,000 Da or less, 15,000 Da or less, 10,000 Da or less, 5,000 Da or less, or 4,000 Da or less, preferably 2,500 Da or less. Is more preferable.
　ヒドリド官能化ポリシロキサンは、次のものに限定されないが、例えば、ヒドリド末端ポリジメチルシロキサン、ヒドリド末端ポリフェニル－（ジメチルヒドロシロキシ）シロキサン、ヒドリド末端メチルヒドロシロキサン－フェニルメチルシロキサンコポリマー、トリメチルシロキシ末端メチルヒドロシロキサン－ジメチルシロキサンコポリマー、ポリメチルヒドロシロキサン、トリメチルシロキシ末端ポリエチルヒドロシロキサン、トリエチルシロキサン、メチルヒドロシロキサン－フェニルオクチルメチルシロキサンコポリマー、及びメチルヒドロシロキサン－フェニルオクチルメチルシロキサンターポリマーから選択される少なくとも一種を採用することができる。なかでも、ヒドリド末端ポリジメチルシロキサンが好ましく、ハイドロゲンジメチコンがより好ましい。 Hydride-functionalized polysiloxanes are, but are not limited to, for example, hydride-terminated polydimethylsiloxanes, hydride-terminated polyphenyl- (dimethylhydrosiloxy) siloxanes, hydride-terminated methylhydrosiloxane-phenylmethylsiloxane copolymers, trimethylsiloxy-terminated methyls. At least one selected from hydrosiloxane-dimethylsiloxane copolymer, polymethylhydrosiloxane, trimethylsiloxy-terminated polyethylhydrosiloxane, triethylsiloxane, methylhydrosiloxane-phenyloctylmethylsiloxane copolymer, and methylhydrosiloxane-phenyloctylmethylsiloxane tarpolymer. Can be adopted. Of these, hydride-terminated polydimethylsiloxane is preferable, and hydrogendimethicone is more preferable.
　第１剤中におけるヒドリド官能化ポリシロキサンの配合量については、要する被膜性能等に応じて適宜調整すればよく、特に制限はない。例えば、ヒドリド官能化ポリシロキサンの配合量としては、第１剤全体に対し、１質量％以上、３質量％以上、又は５質量％以上とすることができ、７５質量％以下、６０質量％以下、５０質量％以下、４０質量％以下、３０質量％以下、２０質量％以下、又は１０質量％以下とすることができる。 The blending amount of the hydride-functionalized polysiloxane in the first agent may be appropriately adjusted according to the required film performance and the like, and is not particularly limited. For example, the blending amount of the hydride-functionalized polysiloxane can be 1% by mass or more, 3% by mass or more, or 5% by mass or more, and 75% by mass or less, 60% by mass or less, based on the entire first agent. , 50% by mass or less, 40% by mass or less, 30% by mass or less, 20% by mass or less, or 10% by mass or less.
（他のポリマー）
　第１剤は、任意に、他のポリマーを含むことができる。他のポリマーは単独で又は二種以上組み合わせて使用することができる。 (Other polymers)
The first agent can optionally include other polymers. Other polymers can be used alone or in combination of two or more.
　ある実施態様では、他のポリマーは、２５℃で、０．７ｃｓｔ～５０，０００ｃｓｔの粘度を有することができる。かかる粘度の下限値としては、１ｃｓｔ以上、６ｃｓｔ以上、１０ｃｓｔ以上、２０ｃｓｔ以上、５０ｃｓｔ以上、１００ｃｓｔ以上、２００ｃｓｔ以上、３００ｃｓｔ以上、４００ｃｓｔ以上、７５０ｃｓｔ以上、１，０００ｃｓｔ以上、１，５００ｃｓｔ以上、２，０００ｃｓｔ以上、２，５００ｃｓｔ以上、３，０００ｃｓｔ以上、３，５００ｃｓｔ以上、又は４０００ｃｓｔ以上とすることができる。粘度の上限値としては、４５，０００ｃｓｔ以下、４０，０００ｃｓｔ以下、３５，０００ｃｓｔ以下、３０，０００ｃｓｔ以下、２５，０００ｃｓｔ以下、２０，０００ｃｓｔ以下、１５，０００ｃｓｔ以下、１２，０００ｃｓｔ以下、１０，０００ｃｓｔ以下、５，０００ｃｓｔ以下、４，０００ｃｓｔ以下、２，０００ｃｓｔ以下、１，５００ｃｓｔ以下、又は１，０００ｃｓｔ以下とすることができる。 In one embodiment, the other polymer can have a viscosity of 0.7 cst to 50,000 cst at 25 ° C. The lower limit of the viscosity is 1 cst or more, 6 cst or more, 10 cst or more, 20 cst or more, 50 cst or more, 100 cst or more, 200 cst or more, 300 cst or more, 400 cst or more, 750 cst or more, 1,000 cst or more, 1,500 cst or more, 2, It can be 000 cst or more, 2,500 cst or more, 3,000 cst or more, 3,500 cst or more, or 4000 cst or more. The upper limit of the viscosity is 45,000 cst or less, 40,000 cst or less, 35,000 cst or less, 30,000 cst or less, 25,000 cst or less, 20,000 cst or less, 15,000 cst or less, 12,000 cst or less, 10,000 cst or less. Hereinafter, it can be 5,000 cst or less, 4,000 cst or less, 2,000 cst or less, 1,500 cst or less, or 1,000 cst or less.
　ある実施態様において、他のポリマーは、１８０Ｄａ～８０，０００Ｄａの平均分子量を有することができる。かかる平均分子量の下限値としては、５００Ｄａ以上、８００Ｄａ以上、１，５００Ｄａ以上、３，０００Ｄａ以上、６，０００Ｄａ以上、９，４００Ｄａ以上、１０，０００Ｄａ以上、１５，０００Ｄａ以上、２０，０００Ｄａ以上、３０，０００Ｄａ以上、４０，０００Ｄａ以上、５０，０００Ｄａ以上、５５，０００Ｄａ以上、６０，０００Ｄａ以上、又は６２，０００Ｄａ以上とすることができる。平均分子量の上限値としては、７５，０００Ｄａ以下、７０，０００Ｄａ以下、６５，０００Ｄａ以下、又は６３，０００Ｄａ以下とすることができる。 In one embodiment, the other polymer can have an average molecular weight of 180Da-80,000Da. The lower limit of the average molecular weight is 500 Da or more, 800 Da or more, 1,500 Da or more, 3,000 Da or more, 6,000 Da or more, 9,400 Da or more, 10,000 Da or more, 15,000 Da or more, 20,000 Da or more, It can be 30,000 Da or more, 40,000 Da or more, 50,000 Da or more, 55,000 Da or more, 60,000 Da or more, or 62,000 Da or more. The upper limit of the average molecular weight can be 75,000 Da or less, 70,000 Da or less, 65,000 Da or less, or 63,000 Da or less.
　他のポリマーとして、好ましくは、平均して少なくとも１つのアルケニル官能基を有し、かつ２５℃で０．７～５０，０００ｃｓｔの粘度を有する一種以上のオルガノポリシロキサンを挙げることができる。 As the other polymer, preferably, one or more organopolysiloxanes having at least one alkenyl functional group on average and having a viscosity of 0.7 to 50,000 cst at 25 ° C. can be mentioned.
　具体的には、他のポリマーとして、例えば、ビニル末端ポリジメチルシロキサン、ビニル末端ジフェニルシロキサン－ジメチルシロキサンコポリマー、ビニル末端ポリフェニルメチルシロキサン、ビニルフェニルメチル末端ビニルフェニルシロキサン－フェニルメチルシロキサンコポリマー、ビニル末端トリフルオロプロピルメチルシロキサン－ジメチルシロキサンコポリマー、ビニル末端ジエチルシロキサン－ジメチルシロキサンコポリマー、ビニルメチルシロキサン－ジメチルシロキサンコポリマー、トリメチルシロキシ末端ビニルメチルシロキサン－ジメチルシロキサンコポリマー、シラノール末端ビニルメチルシロキサン－ジメチルシロキサンコポリマー、ビニル末端ビニルゴム、ビニルメチルシロキサンホモポリマー、ビニルＴ－構造ポリマー、ビニルＱ－構造ポリマー、不飽和有機ポリマー（例えば、不飽和脂肪アルコール、不飽和脂肪酸、不飽和脂肪エステル、不飽和脂肪アミド、不飽和脂肪ウレタン、不飽和脂肪ウレア、セラミド、クロセチン、レシチン、及びスフィンゴシンが挙げられる。）、モノビニル末端ポリジメチルシロキサン、ビニルメチルシロキサンターポリマー、ビニルメトキシシランホモポリマー、ビニル末端ポリアルキルシロキサンポリマー、及びビニル末端ポリアルコキシシロキサンポリマーから選択される少なくとも一種を採用することができる。なかでも、ビニル末端ポリジメチルシロキサンが好ましく、ジビニルジメチコン、１，３－ジビニルテトラメチルジシロキサンがより好ましい。 Specifically, as other polymers, for example, vinyl-terminated polydimethylsiloxane, vinyl-terminated diphenylsiloxane-dimethylsiloxane copolymer, vinyl-terminated polyphenylmethylsiloxane, vinylphenylmethyl-terminated vinylphenylsiloxane-phenylmethylsiloxane copolymer, vinyl-terminated tori. Fluoropropylmethylsiloxane-dimethylsiloxane polymer, vinyl-terminated diethylsiloxane-dimethylsiloxane copolymer, vinylmethylsiloxane-dimethylsiloxane copolymer, trimethylsiloxy-terminated vinylmethylsiloxane-dimethylsiloxane copolymer, silanol-terminated vinylmethylsiloxane-dimethylsiloxane copolymer, vinyl-terminated vinyl rubber , Vinyl Methylsiloxane Homopolymer, Vinyl T-Structural Polymer, Vinyl Q-Structural Polymer, Unsaturated Organic Polymer (eg, Unsaturated Fat Alcohol, Unsaturated Fatty Acid, Unsaturated Fat Ester, Unsaturated Fat Amid, Unsaturated Fat Urethane, Unsaturated fatty ureas, ceramides, crosetins, lecithins, and sphingosine), monovinyl-terminated polydimethylsiloxanes, vinylmethylsiloxane terpolymers, vinylmethoxysilane homopolymers, vinyl-terminated polyalkylsiloxane polymers, and vinyl-terminated polyalkoxysiloxanes. At least one selected from polymers can be adopted. Of these, vinyl-terminated polydimethylsiloxane is preferable, and divinyldimethicone and 1,3-divinyltetramethyldisiloxane are more preferable.
　第１剤中における他のポリマーの配合量については、要する被膜性能等に応じて適宜調整すればよく、特に制限はない。例えば、他のポリマーの配合量としては、第１剤全体に対し、０．０１質量％以上、０．１質量％以上、０．３質量％以上、又は０．５質量％以上とすることができ、２０質量％以下、１５質量％以下、又は１０質量％以下にすることができる。 The blending amount of the other polymer in the first agent may be appropriately adjusted according to the required coating performance and the like, and is not particularly limited. For example, the blending amount of the other polymer may be 0.01% by mass or more, 0.1% by mass or more, 0.3% by mass or more, or 0.5% by mass or more with respect to the entire first agent. It can be 20% by mass or less, 15% by mass or less, or 10% by mass or less.
〈第２の不飽和オルガノポリシロキサン、ヒドリド官能化ポリシロキサン、他のポリマーにおける官能基比率〉
　ある実施態様では、ヒドリド官能化ポリシロキサン由来のＳｉ－Ｈ官能基と、第２の不飽和オルガノポリシロキサン由来のアルケニル官能基とのモル比は、６０：１～１：５であることが好ましく、４５：１～１５：１であることがより好ましい。 <Functional group ratio in second unsaturated organopolysiloxane, hydride-functionalized polysiloxane, and other polymers>
In one embodiment, the molar ratio of the Si—H functional group derived from the hydride-functionalized polysiloxane to the alkenyl functional group derived from the second unsaturated organopolysiloxane is preferably 60: 1 to 1: 5. , 45: 1 to 15: 1, more preferably.
　ある実施態様では、ヒドリド官能化ポリシロキサン由来のＳｉ－Ｈ官能基と、他のポリマー由来のアルケニル官能基とのモル比は、６０：１～１：５であることが好ましく、４５：１～１５：１であることがより好ましい。 In one embodiment, the molar ratio of Si—H functional groups derived from hydride-functionalized polysiloxane to alkenyl functional groups derived from other polymers is preferably 60: 1 to 1: 5, preferably 45: 1 to 45. It is more preferably 15: 1.
　ある実施態様では、第２の不飽和オルガノポリシロキサン由来のアルケニル官能基と、他のポリマー由来のアルケニル官能基とのモル比は、１００：１～１：１００であることが好ましく、１０：１～１：１０であることがより好ましい。 In one embodiment, the molar ratio of the alkenyl functional group derived from the second unsaturated organopolysiloxane to the alkenyl functional group derived from the other polymer is preferably 100: 1 to 1: 100, 10: 1. It is more preferably ~ 1:10.
〈第２剤〉
　上述した本開示の水中油型乳化組成物を、人工皮膚形成剤の第２剤として使用することができる。かかる組成物中に含まれる触媒が、上述した第２の不飽和オルガノポリシロキサン及びヒドリド官能化ポリシロキサンの架橋を促進することができる。 <Second agent>
The oil-in-water emulsified composition of the present disclosure described above can be used as a second agent of an artificial skin forming agent. The catalyst contained in such a composition can promote the cross-linking of the above-mentioned second unsaturated organopolysiloxane and hydride-functionalized polysiloxane.
〈任意成分〉
　本開示の人工皮膚形成剤は、第１剤及び／又は第２剤に対し、本開示の効果に影響を及ぼさない範囲で、任意成分を１種以上配合することができる。 <Arbitrary ingredient>
The artificial skin forming agent of the present disclosure may contain one or more arbitrary components with respect to the first agent and / or the second agent as long as the effects of the present disclosure are not affected.
　任意成分としては特に制限はないが、例えば、感触改質剤、粘着改質剤、展延性促進剤、希釈剤、接着改質剤、乳化剤、エモリエント剤、界面活性剤、溶媒、成膜剤、ヒューメクタント、保存料、繊維、顔料、染料、増粘剤、保護コロイド剤、充填剤、皮膚透過促進剤、光学改質剤、散乱剤、吸着剤、磁気材料、気体輸送改質剤、液体輸送改質剤、ｐＨ改質剤、増感改質剤、審美的改質剤を挙げることができる。 The optional component is not particularly limited, but for example, a feel modifier, a tackifier modifier, a spread accelerator, a diluent, an adhesion modifier, an emulsifier, an emollient agent, a surfactant, a solvent, a film forming agent, etc. Emulsifiers, preservatives, fibers, pigments, dyes, thickeners, protective colloids, fillers, skin permeation enhancers, optical modifiers, scatterers, adsorbents, magnetic materials, gas transport modifiers, liquids Examples include transport modifiers, pH modifiers, sensitizer modifiers, and aesthetic modifiers.
　充填剤としては、例えば、炭素、銀、マイカ、硫化亜鉛、酸化亜鉛、二酸化チタン、酸化アルミニウム、粘土、チョーク、タルク、方解石（例えば、ＣａＣＯ３）、硫酸バリウム、二酸化ジルコニウム、ポリマービーズ、シリカ（例えば、フュームドシリカ、ケイ酸、又は無水シリカ）、アルミン酸シリカ、及びケイ酸カルシウムから選択される少なくとも一種を挙げることができ、これらは表面処理が施されていてもよい。このような充填剤は、被膜（人工皮膚）の物理的特性（例えば強度）を向上させることができ、また、粘度調整剤としての役割を果たすこともできる。なかでも、充填剤として、表面処理されたシリカ、例えば、ヘキサメチルジシラザン、ポリジメチルシロキサン、ヘキサデシルシラン、又はメタクリルシラン等の表面処理剤で処理されたシリカが好ましい。また、フュームドシリカも好ましく、例えば、ヘキサメチルジシラザン等で表面処理されたフュームドシリカも好適に使用することができる。 Fillers include, for example, carbon, silver, mica, zinc sulfide, zinc oxide, titanium dioxide, aluminum oxide, clay, chalk, talc, calculus (eg CaCO 3 ), barium sulfate, zirconium dioxide, polymer beads, silica (eg, CaCO 3). For example, at least one selected from fumed silica, silicic acid, or anhydrous silica), silica aluminate, and calcium silicate can be mentioned, which may be surface treated. Such a filler can improve the physical properties (eg strength) of the coating (artificial skin) and can also serve as a viscosity modifier. Among them, as the filler, surface-treated silica, for example, silica treated with a surface-treating agent such as hexamethyldisilazane, polydimethylsiloxane, hexadecylsilane, or methacrylsilane is preferable. Further, fumed silica is also preferable, and for example, fumed silica surface-treated with hexamethyldisilazane or the like can also be preferably used.
　ある実施態様では、充填剤は、５０～５００ｍ２／ｇの比表面積を有することができる。充填剤の比表面積としては、１００～３５０ｍ２／ｇであることが好ましく、１３５～２５０ｍ２／ｇであることがより好ましい。ここで、充填剤の比表面積は、ＢＥＴ法を用いて算出することができる。 In certain embodiments, the filler can have a specific surface area of 50-500 m 2 / g. The specific surface area of the filler is preferably 100 to 350 m 2 / g, more preferably 135 to 250 m 2 / g. Here, the specific surface area of the filler can be calculated using the BET method.
　ある実施態様では、充填剤は、１ｎｍ～２０μｍの面積円相当粒子径を有することができる。充填剤の面積円相当粒子径としては、２ｎｍ～１μｍであることが好ましく、５ｎｍ～５０ｎｍであることがより好ましい。ここで、充填剤の面積円相当粒子径とは、例えば、透過型電子顕微鏡で観察した充填剤粒子の投影面積と同じ面積を有する円形状の粒子に換算した場合の粒子径を意図することができる。かかる面積円相当粒子径は、１０個以上の粒子の平均値と規定することができる。 In some embodiments, the filler can have a particle size equivalent to an area circle of 1 nm to 20 μm. The particle size corresponding to the area circle of the filler is preferably 2 nm to 1 μm, and more preferably 5 nm to 50 nm. Here, the particle size equivalent to the area circle of the filler is intended to be, for example, the particle size when converted into circular particles having the same area as the projected area of the filler particles observed with a transmission electron microscope. can. The particle size corresponding to the area circle can be defined as an average value of 10 or more particles.
　第１剤に充填剤を配合する場合、その配合量としては、第１剤全体に対し、例えば、１質量％以上、３質量％以上、又は５質量％以上とすることができ、２５質量％以下、１５質量％以下、又は１０質量％以下とすることができる。 When the filler is blended with the first agent, the blending amount may be, for example, 1% by mass or more, 3% by mass or more, or 5% by mass or more, and 25% by mass, based on the entire first agent. Hereinafter, it can be 15% by mass or less, or 10% by mass or less.
　人工皮膚の補強性等の観点から、第２の不飽和オルガノポリシロキサン、ヒドリド官能化ポリシロキサン及び他のポリマーの合計量と、充填剤との質量比は、１００：１～１：１とすることができ、好ましくは、５０：１～２：１であり、より好ましくは、１５：１～３：１であり、さらに好ましくは、１０：１～４：１であり、特に好ましくは、５：１～９：１である。 From the viewpoint of reinforcing the artificial skin, the mass ratio of the total amount of the second unsaturated organopolysiloxane, hydride-functionalized polysiloxane and other polymers to the filler is 100: 1 to 1: 1. It can be preferably 50: 1 to 2: 1, more preferably 15: 1 to 3: 1, still more preferably 10: 1 to 4: 1, and particularly preferably 5. 1 to 9: 1.
　任意成分のうち顔料、染料及び充填剤から選択される少なくとも一種は、第１剤に配合することが好ましい。特に、顔料及び染料に関しては、これらを第２剤の方に配合した場合、この第２剤を第１剤の適用面に対して塗っていると、その途中で固まってしまい、顔料又は染料が局在化しやすくなるため、色むらが発生する場合がある。色むらを抑制する観点から、顔料及び染料は、第１剤に配合することが有利である。また、第２剤には、色むらが発生しない範囲で、顔料、染料及び充填剤を配合してもよいが、これらは第２剤に含まれないことが有利である。 Of the optional components, at least one selected from pigments, dyes and fillers is preferably added to the first agent. In particular, with regard to pigments and dyes, when these are blended in the second agent, if this second agent is applied to the application surface of the first agent, it will harden in the middle and the pigment or dye will be formed. Color unevenness may occur because it is easy to localize. From the viewpoint of suppressing color unevenness, it is advantageous to add the pigment and the dye to the first agent. Further, the second agent may contain a pigment, a dye and a filler as long as color unevenness does not occur, but it is advantageous that these are not included in the second agent.
　ある実施態様では、本開示の組成物は、第１剤及び／又は第２剤に対し、一種以上の薬剤をさらに配合することができる。このような薬剤としては、例えば、化粧剤、治療剤、刺激応答剤、薬物送達剤を挙げることができる。 In certain embodiments, the compositions of the present disclosure may further comprise one or more agents with respect to the first and / or second agent. Examples of such agents include cosmetics, therapeutic agents, stimulant responsive agents, and drug delivery agents.
　好適な化粧剤としては、例えば、保湿剤、紫外線吸収剤、皮膚保護剤、皮膚鎮静剤、皮膚美白剤、皮膚光沢剤、皮膚軟化剤、皮膚平滑化剤、皮膚漂白剤、皮膚角質除去剤、皮膚引き締め剤、美容剤、ビタミン、抗酸化剤、細胞シグナル伝達剤、細胞調節剤、細胞相互作用剤、皮膚日焼け剤、老化防止剤、しわ防止剤、スポットリデューサー、α－ヒドロキシ酸、β－ヒドロキシ酸、セラミドを挙げることができる。 Suitable cosmetic agents include, for example, moisturizers, UV absorbers, skin protectants, skin soothing agents, skin whitening agents, skin brighteners, skin softening agents, skin smoothing agents, skin bleaching agents, skin keratin removers, etc. Skin tightening agents, beauty agents, vitamins, antioxidants, cell signaling agents, cell regulators, cell interacting agents, skin tanning agents, anti-aging agents, anti-wrinkle agents, spot reducers, α-hydroxy acid, β-hydroxy Examples include acid and ceramide.
　好適な治療剤としては、例えば、疼痛緩和剤、鎮痛薬、抗掻痒剤、抗座瘡剤（例えば、β－ヒドロキシ酸、サリチル酸、過酸化ベンゾイル）、抗炎症剤、抗ヒスタミン薬、コルチコステロイド、ＮＳＡＩＤ（非ステロイド性抗炎症薬）、防腐剤、抗生物質、抗細菌剤、抗真菌剤、抗ウイルス剤、抗アレルギー剤、抗刺激物質、虫除け剤、光線療法剤、血液凝固剤、抗新生物薬、免疫系増進剤、免疫系抑制剤、コールタール、アントラリン、フルオシノニド、メトトレキセート、シクロスポリン、ピメクロリムス、タクロリムス、アザチオプリン、フルオロウラシル、セラミド、反対刺激剤、皮膚冷却化合物を挙げることができる。 Suitable therapeutic agents include, for example, pain relievers, analgesics, antipruritic agents, anti-sciatic agents (eg, β-hydroxy acid, salicylic acid, benzoyl peroxide), anti-inflammatory agents, anti-histamine agents, corticosteroids. , NSAID (non-steroidal anti-inflammatory drug), preservatives, antibiotics, antibacterial agents, antifungal agents, antiviral agents, antiallergic agents, antistimulants, insect repellents, phototherapy agents, blood coagulants, anti-new Examples thereof include biopharmaceuticals, immune system enhancers, immune system suppressants, coaltal, anthraline, fluorinide, methotrexate, cyclosporin, pimechlorimus, tachlorimus, azathiopurine, fluorouracil, ceramide, anti-inflammatory agents, and skin cooling compounds.
　好適な薬剤としては、例えば、美白剤、賦活剤、血行促進剤、抗炎症剤、抗酸化剤、酵素、ビタミン類、ホルモン剤、抗菌剤、抗脂漏剤、アミノ酸及びその誘導体、糖アルコール及びその誘導体、脂溶性薬剤、脂溶性処理された薬剤、並びに育毛用薬剤を挙げることができる。これらは単独で又は複数組み合わせて使用することができる。 Suitable agents include, for example, whitening agents, activators, blood circulation promoters, anti-inflammatory agents, antioxidants, enzymes, vitamins, hormones, antibacterial agents, anti-fat leak agents, amino acids and their derivatives, sugar alcohols and Examples thereof include derivatives thereof, fat-soluble agents, fat-soluble treated agents, and hair-growth agents. These can be used alone or in combination.
　美白剤としては、例えば、ハイドロキノンα－Ｄ－グルコース、ハイドロキノンβ－Ｄ－グルコース（アルブチン）、ハイドロキノンα－Ｌ－グルコース、ハイドロキノンβ－Ｌ－グルコース、ハイドロキノンα－Ｄ－ガラクトース、ハイドロキノンβ－Ｄ－ガラクトース、ハイドロキノンα－Ｌ－ガラクトース、ハイドロキノンβ－Ｌ－ガラクトース等のハイドロキノン誘導体；コウジ酸及びその塩若しくはその誘導体；例えばＬ－アスコルビン酸モノリン酸エステル、Ｌ－アスコルビン酸２－硫酸エステルなどのＬ－アスコルビン酸モノエステル類、Ｌ－アスコルビン酸２－グルコシドなどのＬ－アスコルビン酸グルコシド類、又はこれらの塩などのＬ－アスコルビン酸及びその塩若しくはその誘導体；例えばトラネキサム酸、トラネキサム酸の二量体（例えば、塩酸トランス－４－（トランス－アミノメチルシクロヘキサンカルボニル）アミノメチルシクロヘキサンカルボン酸）、トラネキサム酸とハイドロキノンのエステル体（例えば、トランス－４－アミノメチルシクロへキサンカルボン酸４’－ヒドロキシフェニルエステル）、トラネキサム酸とゲンチシン酸のエステル体（例えば、２－（トランス－４－アミノメチルシクロヘキシルカルボニルオキシ）－５－ヒドロキシ安息香酸およびその塩）、トラネキサム酸のアミド体（例えば、トランス－４－アミノメチルシクロヘキサンカルボン酸メチルアミドおよびその塩、トランス－４－（ｐ－メトキシベンゾイル）アミノメチルシクロヘキサンカルボン酸およびその塩、トランス－４－グアニジノメチルシクロヘキサンカルボン酸およびその塩）等のトラネキサム酸及びその塩若しくはその誘導体；エラグ酸及びその塩若しくはその誘導体；例えばサリチル酸、３－メトキシサリチル酸およびその塩、４－メトキシサリチル酸およびその塩、５－メトキシサリチル酸およびその塩等のサリチル酸およびその塩若しくはその誘導体；フェニルエチルレゾルシノール、レゾルシン、４－ｎ－ブチルレゾルシノールなどのアルキルレゾルシノール、およびこれらの塩等のレゾルシノール誘導体；ニコチン酸アミドなどのナイアシン及びその誘導体；アデノシン、グアノシン等のヌクレオチド若しくはその誘導体等、が例示される。 Examples of the whitening agent include hydroquinone α-D-glucose, hydroquinone β-D-glucose (arbutin), hydroquinone α-L-glucose, hydroquinone β-L-glucose, hydroquinone α-D-galactose, and hydroquinone β-D-. Hydroquinone derivatives such as galactose, hydroquinone α-L-galactose, hydroquinone β-L-galactose; kodiic acid and its salts or derivatives thereof; for example L-ascorbic acid monophosphate ester, L-ascorbic acid 2-sulfate ester and the like L- Ascorbic acid monoesters, L-ascorbic acid glucosides such as L-ascorbic acid 2-glucoside, or L-ascorbic acid such as salts thereof and salts thereof or derivatives thereof; for example, tranexamic acid, dimers of tranexamic acid ( For example, trans-4- (trans-aminomethylcyclohexanecarbonyl) aminomethylcyclohexanecarboxylic acid), an ester of tranexamic acid and hydroquinone (eg, trans-4-aminomethylcyclohexanecarboxylic acid 4'-hydroxyphenyl ester). , 2- (Trans-4-aminomethylcyclohexylcarbonyloxy) -5-hydroxybenzoic acid and its salts), an amide form of tranexamic acid (eg, trans-4-aminomethyl) Cyclohexanecarboxylic acid methylamide and its salts, trans-4- (p-methoxybenzoyl) aminomethylcyclohexanecarboxylic acid and its salts, trans-4-guanidinomethylcyclohexanecarboxylic acid and its salts) and other tranexamic acids and their salts or derivatives thereof. Elagic acid and its salts or derivatives thereof; for example salicylic acid, 3-methoxysalicylic acid and its salts, 4-methoxysalicylic acid and its salts, 5-methoxysalicylic acid and its salts and the like salicylic acid and its salts or derivatives thereof; phenylethyl resorcinol, Examples thereof include alkyl resorcinols such as resorcin, 4-n-butylresorcinol, and resorcinol derivatives such as salts thereof; niacin and derivatives thereof such as nicotinic acid amide; nucleotides such as adenosine and guanosine or derivatives thereof, and the like.
　賦活剤としては、例えば、ローヤルゼリー；感光素；コレステロール誘導体等、が例示される。 Examples of the activator include royal jelly; photosensitizer; cholesterol derivative and the like.
　血行促進剤としては、例えば、ノニル酸ワレニルアミド；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；アセチルコリン誘導体；ベラパミル；セファランチン；γ－オリザノール；塩化カルブロニウム等、が例示される。 Examples of the blood circulation promoter include nonylate valenylamide; nicotinic acid benzyl ester; nicotinic acid β-butoxyethyl ester; capsaicin; zingeron; cantalistinki; ictamol; tannic acid; α-borneol; tocopherol nicotinate; inositol hexanicotinate. Cicrandelate; cinnaridine; trazoline; acetylcholine derivative; verapamil; cepharanthin; γ-orizanol; carbronium chloride and the like are exemplified.
　抗炎症剤としては、例えば、トラネキサム酸；チオタウリン；ヒポタウリン；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、が例示される。 Examples of the anti-inflammatory agent include tranexamic acid; thiotaurine; hypotaurine; glycyrrhizinic acid derivative; glycyrrhetinic acid derivative; salicylic acid derivative; hinokitiol; zinc oxide; allantoin and the like.
　抗酸化剤としては、例えば、チオタウリン；グルタチオン；カテキン；アルブミン；フェリチン；メタロチオネイン等、が例示される。 Examples of the antioxidant include thiotaurine; glutathione; catechin; albumin; ferritin; metallothionein and the like.
　酵素としては、例えば、トリプシン；塩化リゾチーム；キモトリプシン；セミアルカリプロテナーゼ；セラペプターゼ；リパーゼ；ヒアルロニダーゼ等、が例示される。 Examples of the enzyme include trypsin; lysozyme chloride; chymotrypsin; semi-alkaline protectase; serrapeptase; lipase; hyaluronidase and the like.
　ビタミン類としては、例えば、ビタミンＢ６；ビタミンＢ６塩酸塩などのビタミンＢ６誘導体；ビタミンＢ２；ビタミンＢ１２；ニコチン酸；ニコチン酸アミドなどのニコチン酸誘導体；パントテニールエチルエーテル等、が例示される。 Examples of vitamins include vitamin B6; vitamin B6 derivatives such as vitamin B6 hydrochloride; vitamin B2; vitamin B12; nicotinic acid; nicotinic acid derivatives such as nicotinic acid amide; pantotenil ethyl ether and the like.
　ホルモン剤としては、例えば、オキシトシン；コルチコトロピン；バソプレッシン；セクレチン；ガストリン；カルシトニン等、が例示される。 Examples of the hormonal agent include oxytocin; corticotropin; vasopressin; secretin; gastrin; calcitonin and the like.
　抗菌剤としては、例えば、レゾルシン；イオウ；サリチル酸；ジンクピリチオン；感光素１０１号；感光素１０２号；オルトビロックス；ヒノキチオール等、が例示される。 Examples of the antibacterial agent include resorcin; sulfur; salicylic acid; zinc pyrithione; photosensitive element 101; photosensitive element 102; orthovirox; hinokitiol and the like.
　抗脂漏剤としては、例えば、硫黄；チアントール等、が例示される。 Examples of the antiseborrheic agent include sulfur; thiantoll and the like.
　アミノ酸及びその誘導体としては、例えば、セリン；メチオニン；トリプトファン；グリシン；トリメチルグリシン；グリシルグリシン；1-ピペリジンプロピオン酸 等、が例示される。 Examples of amino acids and their derivatives include serine; methionine; tryptophan; glycine; trimethylglycine; glycylglycine; 1-piperidine propionic acid.
　糖アルコール及びその誘導体としては、例えば、エリスリトール;キシリトール;マンニトール;ソルビトール;イノシトール等、が例示される。 Examples of sugar alcohols and their derivatives include erythritol; xylitol; mannitol; sorbitol; inositol and the like.
《人工皮膚形成剤の使用方法》
　本開示の人工皮膚形成剤は、例えば、化粧用又は医療用として使用することができる。ここで、本開示の人工皮膚形成剤の使用方法には、人間を手術、治療又は診断する方法は包含しない。 << How to use artificial skin forming agent >>
The artificial skin forming agents of the present disclosure can be used, for example, for cosmetic or medical purposes. Here, the method of using the artificial skin forming agent of the present disclosure does not include a method of surgery, treatment or diagnosis of a human being.
　本開示の人工皮膚形成剤の使用方法としては、例えば、第１剤を体表に適用して第１剤層を形成した後に、この第１剤層上に第２剤を適用し、架橋させて人工皮膚を形成する方法；第２剤を体表に適用して第２剤層を形成した後に、この第２剤層上に第１剤を適用し、架橋させて人工皮膚を形成する方法；或いは、第１剤及び第２剤を混合して混合物を調製した後に、該混合物を体表に適用し、架橋させて人工皮膚を形成する方法を挙げることができる。むらの少ない均一な人工皮膚を得る観点から、かかる使用方法としては、第１剤を体表に適用して第１剤層を形成した後に、この第１剤層上に第２剤を適用し、架橋させて人工皮膚を形成する方法が好ましい。ここで、第１剤及び第２剤については、上述した材料などを同様に使用することができる。 As a method of using the artificial skin forming agent of the present disclosure, for example, after applying the first agent to the body surface to form the first agent layer, the second agent is applied onto the first agent layer and crosslinked. Method of forming artificial skin; a method of applying the second agent to the body surface to form a second agent layer, then applying the first agent on the second agent layer and cross-linking to form an artificial skin. Alternatively, a method may be mentioned in which a mixture is prepared by mixing the first agent and the second agent, and then the mixture is applied to the body surface and crosslinked to form an artificial skin. From the viewpoint of obtaining uniform artificial skin with less unevenness, such a method of use is to apply the first agent to the body surface to form the first agent layer, and then apply the second agent on the first agent layer. , A method of cross-linking to form an artificial skin is preferable. Here, as the first agent and the second agent, the above-mentioned materials and the like can be used in the same manner.
　この方法は、１回で済ませてもよいが、形成した人工皮膚に対して、かかる方法を複数回実施してもよい。 This method may be performed only once, but the method may be performed multiple times on the formed artificial skin.
　いくつかの実施態様では、第１剤、第２剤、又は第１剤及び第２剤を含む混合物を体表に適用する前に、化粧料を体表に適用してもよく、或いは、人工皮膚を形成した後に、化粧料を人工皮膚に適用してもよい。 In some embodiments, the cosmetic may be applied to the body surface or artificially before the first agent, the second agent, or the mixture containing the first agent and the second agent is applied to the body surface. After forming the skin, the cosmetic may be applied to the artificial skin.
　化粧料として特に制限はなく、例えば、美容液、化粧水、乳液等のスキンケア化粧料、サンスクリーン化粧料（日焼け止め化粧料）、又はファンデーション、グロス、口紅、アイシャドー、マニキュア等のメーキャップ化粧料を使用することができる。 There are no particular restrictions on the cosmetics, for example, skin care cosmetics such as beauty essence, lotion, milky lotion, sunscreen cosmetics (sunscreen cosmetics), or makeup cosmetics such as foundation, gloss, lipstick, eye shadow, and manicure. Can be used.
　また、いくつかの実施態様において、本開示の人工皮膚形成剤の使用方法は、美容方法として利用することもできる。なお、「美容方法」とは、本開示の人工皮膚形成剤を体表に適用して人工皮膚を形成し、体表の状態を美しく整えて美化すること又は体表の状態を美しく整えて美化する方法を意味し、人間を手術、治療又は診断する方法とは相違する。 Further, in some embodiments, the method of using the artificial skin forming agent of the present disclosure can also be used as a cosmetic method. The "cosmetological method" is to apply the artificial skin forming agent of the present disclosure to the body surface to form artificial skin, and to beautify the condition of the body surface beautifully or to beautify the condition of the body surface. It means a method of surgery, which is different from the method of surgery, treatment or diagnosis of a human being.
　体表、化粧料適用層、又は第１剤層若しくは第２剤層に対し、第１剤又は第２剤を適用する方法としては特に制限はなく、例えば、指などで塗り広げる手段、スプレー塗布、転写などを採用することができる。 There is no particular limitation on the method of applying the first agent or the second agent to the body surface, the cosmetic application layer, or the first agent layer or the second agent layer, and for example, a means for spreading with a finger or the like, spray application. , Transfer, etc. can be adopted.
〈適用部位〉
　本開示の人工皮膚形成剤は、体のあらゆる部分における皮膚の表面上、即ち、体表上であれば、いかなる箇所に適用することができる。例えば、顔（唇、目元、鼻、頬、額など）、首、耳、手、腕、脚、足、胸、腹、背中等の皮膚表面に対して適宜適用することができる。ここで、皮膚には、皮膚の表皮の角質が変化して硬化した爪なども含まれる。 <Applicable site>
The artificial skin-forming agent of the present disclosure can be applied to any part of the body on the surface of the skin, that is, on the surface of the body. For example, it can be appropriately applied to the skin surface such as face (lips, eyes, nose, cheeks, forehead, etc.), neck, ears, hands, arms, legs, legs, chest, abdomen, back and the like. Here, the skin also includes nails and the like in which the keratin of the epidermis of the skin is changed and hardened.
《人工皮膚》
〈厚さ〉
　上述した本開示の人工皮膚形成剤を用いて調製した人工皮膚の厚さとしては特に制限はなく、例えば、通気性、不可視性、圧縮性、皮膚に対する閉塞性等を考慮して適宜調整することができる。人工皮膚の厚さとしては、例えば、０．５μｍ以上、１μｍ以上、１０μｍ以上、３０μｍ以上、又は４０μｍ以上にすることができる。厚さの上限値については特に制限はないが、例えば、１５０μｍ以下、１００μｍ以下、９０μｍ以下、８０μｍ以下、７０μｍ以下、６０μｍ以下、又は５０μｍ以下にすることができる。ここで、厚さは、高精度デジマチックマイクロメータ（ＭＤＨ－２５ＭＢ、株式会社ミツトヨ製）を使用し、人工皮膚の任意の部分の厚さを５回測定して算出した平均値として定義することができる。 《Artificial skin》
<thickness>
The thickness of the artificial skin prepared by using the above-mentioned artificial skin forming agent of the present disclosure is not particularly limited, and is appropriately adjusted in consideration of, for example, breathability, invisibility, compressibility, obstruction to the skin, and the like. Can be done. The thickness of the artificial skin can be, for example, 0.5 μm or more, 1 μm or more, 10 μm or more, 30 μm or more, or 40 μm or more. The upper limit of the thickness is not particularly limited, but may be, for example, 150 μm or less, 100 μm or less, 90 μm or less, 80 μm or less, 70 μm or less, 60 μm or less, or 50 μm or less. Here, the thickness shall be defined as an average value calculated by measuring the thickness of any part of the artificial skin 5 times using a high-precision digital micrometer (MDH-25MB, manufactured by Mitutoyo Co., Ltd.). Can be done.
〈性能〉
　本開示の人工皮膚形成剤から調製された人工皮膚は、例えば、以下に示すような各種性能に対して優れた結果をもたらすことができる。 <Performance>
Artificial skin prepared from the artificial skin forming agents of the present disclosure can provide excellent results for various performances as shown below, for example.
（接着力）
　いくつかの実施態様において、得られた人工皮膚は、体表に対して良好な接着力を呈することができる。かかる接着力は、ポリプロピレン基板上に適用した人工皮膚の接着力で代替して評価することができる。ポリプロピレン基板上での人工皮膚の接着力としては、２Ｎ／ｍ以上、５Ｎ／ｍ以上、８Ｎ／ｍ以上、１０Ｎ／ｍ以上、又は１５Ｎ／ｍ以上を達成することができる。接着力の上限値については特に制限はないが、例えば、皮膚からの引き剥がし性等の観点から、２００Ｎ／ｍ以下、１００Ｎ／ｍ以下、８０Ｎ／ｍ以下、５０Ｎ／ｍ以下、又は３０Ｎ／ｍ以下とすることができる。ここで、接着力は、ＡＳＴＭ　Ｃ７９４の剥離接着試験に準拠し、インストロン装置を用いて測定することができる。 (Adhesive strength)
In some embodiments, the resulting artificial skin can exhibit good adhesion to the body surface. Such adhesive strength can be evaluated by substituting the adhesive strength of artificial skin applied on the polypropylene substrate. The adhesive strength of the artificial skin on the polypropylene substrate can be 2 N / m or more, 5 N / m or more, 8 N / m or more, 10 N / m or more, or 15 N / m or more. The upper limit of the adhesive strength is not particularly limited, but for example, from the viewpoint of peelability from the skin, 200 N / m or less, 100 N / m or less, 80 N / m or less, 50 N / m or less, or 30 N / m. It can be as follows. Here, the adhesive strength complies with the stripping adhesion test of ASTM C794 and can be measured using an Instron device.
（引張強度）
　いくつかの実施態様において、得られた人工皮膚は、良好な引張強度を呈することができる。人工皮膚の引張強度としては、０．０５ＭＰａ以上、０．１０ＭＰａ以上、０．２０ＭＰａ以上、又は０．５０ＭＰａ以上を達成することができる。引張強度の上限値については特に制限はないが、例えば、５．０ＭＰａ以下、３．０ＭＰａ以下、２．０ＭＰａ以下、又は１．０ＭＰａ以下とすることができる。ここで、引張強度は、ＡＳＴＭ　Ｄ５０８３の伸長引張試験に準拠し、インストロン装置を用いて測定することができる。 (Tensile strength)
In some embodiments, the resulting artificial skin can exhibit good tensile strength. The tensile strength of the artificial skin can be 0.05 MPa or more, 0.10 MPa or more, 0.20 MPa or more, or 0.50 MPa or more. The upper limit of the tensile strength is not particularly limited, but may be, for example, 5.0 MPa or less, 3.0 MPa or less, 2.0 MPa or less, or 1.0 MPa or less. Here, the tensile strength is based on the tensile tensile test of ASTM D5083 and can be measured using an Instron device.
（破断伸び）
　いくつかの実施態様において、得られた人工皮膚は、良好な破断伸びを呈することができる。人工皮膚の破断伸びとしては、２５％以上、５０％以上、１００％以上、２００％以上、又は４００％以上を達成することができる。破断伸びの上限値については特に制限はないが、例えば、１，５００％以下、１，２００％以下、１，０００％以下、８００％以下、又は６００％以下とすることができる。ここで、破断伸びは、ＡＳＴＭ　Ｄ５０８３の伸長引張試験に準拠し、インストロン装置を用いて測定することができる。 (Breaking elongation)
In some embodiments, the resulting artificial skin is capable of exhibiting good breaking elongation. The breaking elongation of the artificial skin can be 25% or more, 50% or more, 100% or more, 200% or more, or 400% or more. The upper limit of the elongation at break is not particularly limited, but may be, for example, 1,500% or less, 1,200% or less, 1,000% or less, 800% or less, or 600% or less. Here, the elongation at break is based on the tensile tensile test of ASTM D5083 and can be measured using an Instron device.
（酸素透過率）
　いくつかの実施態様において、得られた人工皮膚は、良好な酸素透過率を呈することができる。人工皮膚の酸素透過率としては、厚さ３００μｍの人工皮膚において、５×１０－９ｃｍ３／（ｃｍ２・ｓ）以上、５×１０－７ｃｍ３／（ｃｍ２・ｓ）以上、又は５×１０－５ｃｍ３／（ｃｍ２・ｓ）以上を達成することができる。酸素透過率の上限値については特に制限はないが、例えば、５ｃｍ３／（ｃｍ２・ｓ）以下、０．５ｃｍ３／（ｃｍ２・ｓ）以下、５×１０－２ｃｍ３／（ｃｍ２・ｓ）以下、５×１０－３ｃｍ３／（ｃｍ２・ｓ）以下、又は５×１０－４ｃｍ３／（ｃｍ２・ｓ）以下とすることができる。ここで、酸素透過率は、ＡＳＴＭ　Ｆ２６２２のプラスチックフィルム及びシートの酸素ガス透過率試験に準拠し、モコン装置を用いて測定することができる。 (Oxygen permeability)
In some embodiments, the resulting artificial skin can exhibit good oxygen permeability. The oxygen permeability of the artificial skin is 5 × 10 -9 cm 3 / (cm 2 · s) or more, or 5 × 10 -7 cm 3 / (cm 2 · s) or more, or in the artificial skin with a thickness of 300 μm. It is possible to achieve 5 × 10-5 cm 3 / (cm 2 · s) or more. The upper limit of the oxygen permeability is not particularly limited, but for example, 5 cm 3 / (cm 2 · s) or less, 0.5 cm 3 / (cm 2 · s) or less, 5 × 10 − 2 cm 3 / (cm). It can be 2 · s) or less, 5 × 10 -3 cm 3 / (cm 2 · s) or less, or 5 × 10 -4 cm 3 / (cm 2 · s) or less. Here, the oxygen permeability can be measured using a Mocon device in accordance with the oxygen gas permeability test of the plastic film and sheet of ASTM F2622.
（水蒸気透過率）
　いくつかの実施態様において、得られた人工皮膚は、良好な水蒸気透過率を呈することができる。人工皮膚の水蒸気透過率としては、厚さ３００μｍの人工皮膚において、１×１０－９ｃｍ３／（ｃｍ２・ｓ）以上、１×１０－８ｃｍ３／（ｃｍ２・ｓ）以上、又は１×１０－７ｃｍ３／（ｃｍ２・ｓ）以上を達成することができる。水蒸気透過率の上限値については特に制限はないが、例えば、１．５×１０－１ｃｍ３／（ｃｍ２・ｓ）以下、１．５×１０－２ｃｍ３／（ｃｍ２・ｓ）以下、１×１０－４ｃｍ３／（ｃｍ２・ｓ）以下、１×１０－５ｃｍ３／（ｃｍ２・ｓ）以下、又は１×１０－６ｃｍ３／（ｃｍ２・ｓ）以下とすることができる。ここで、水蒸気透過率は、ＡＳＴＭ　Ｆ１２４９のプラスチックフィルム及びシートの水蒸気透過率試験に準拠し、モコン装置を用いて測定することができる。 (Water vapor permeability)
In some embodiments, the resulting artificial skin can exhibit good water vapor permeability. The water vapor permeability of the artificial skin is 1 × 10 -9 cm 3 / (cm 2 · s) or more, 1 × 10 -8 cm 3 / (cm 2 · s) or more, or 1 × 10 -9 cm 3 / (cm 2 · s) or more in the artificial skin having a thickness of 300 μm. It is possible to achieve 1 × 10-7 cm 3 / (cm 2 · s) or more. The upper limit of the water vapor permeability is not particularly limited, but for example, 1.5 × 10 -1 cm 3 / (cm 2 · s) or less, 1.5 × 10 − 2 cm 3 / (cm 2 · s). Below, 1 × 10 -4 cm 3 / (cm 2 · s) or less, 1 × 10 -5 cm 3 / (cm 2 · s) or less, or 1 × 10 -6 cm 3 / (cm 2 · s) or less. Can be. Here, the water vapor permeability can be measured using a Mocon device in accordance with the water vapor permeability test of the plastic film and sheet of ASTM F1249.
《人工皮膚形成剤を備えるキット》
　本開示の人工皮膚形成剤は、かかる組成物を構成する第１剤及び第２剤を有するキットとして提供することができる。キットは、第１剤及び第２剤以外に、例えば、第１剤等を体表へ塗布しやすくするための部材、上述した各種化粧料などの任意の部材を有していてもよい。 << Kit with artificial skin forming agent >>
The artificial skin forming agent of the present disclosure can be provided as a kit having the first agent and the second agent constituting such a composition. In addition to the first agent and the second agent, the kit may include, for example, a member for facilitating the application of the first agent or the like to the body surface, or any member such as the above-mentioned various cosmetics.
　このような任意の部材としては、例えば、使用説明書、刷毛、綿棒、カッター、ハサミ、上述した各種化粧料、体表から人工皮膚を除去するためのクレンザー、鏡等を挙げることができる。ここで、「使用説明書」とは、キット内に書類の形態で添付されている一般的な使用説明書以外に、例えば、キットを収容する包装容器、又は第１剤等を注入するチューブ等の包装容器に対して使用説明文が印字された状態のものも包含することができる。 Examples of such an arbitrary member include an instruction manual, a brush, a cotton swab, a cutter, scissors, the above-mentioned various cosmetics, a cleanser for removing artificial skin from the body surface, a mirror, and the like. Here, the "instruction manual" is, for example, a packaging container for accommodating the kit, a tube for injecting the first agent, etc., in addition to the general instruction manual attached in the form of a document in the kit. It is also possible to include the one in which the instruction manual is printed on the packaging container of.
　ある実施態様では、キットは、第１剤及び第２剤の接触を防止するために、例えば、これらの剤が、別々の容器に内包されていてもよく、又は２つ以上の区画を有する容器の各区画内に別々に内包されていてもよい。また、これらの内包されている剤は、１度に１つずつ適用されるように構成されてもよく、又は使用前若しくは使用時に一緒に混合されるように構成されてもよい。 In certain embodiments, the kit may include, for example, these agents in separate containers to prevent contact of the first and second agents, or a container having two or more compartments. It may be contained separately in each section of. In addition, these contained agents may be configured to be applied one at a time, or may be configured to be mixed together before or during use.
　以下に実施例を挙げて、本発明についてさらに詳しく説明を行うが、本発明はこれらに限定されるものではない。なお、以下、特に断りのない限り、配合量は質量％で示す。 The present invention will be described in more detail with reference to examples below, but the present invention is not limited thereto. Hereinafter, unless otherwise specified, the blending amount is shown in% by mass.
《実施例１～１２及び比較例１～３：水中油型乳化組成物》
　表１に示す処方及び下記に示す製造方法により得た水中油型乳化組成物について、以下の評価を行い、その結果を表１に示す。 << Examples 1 to 12 and Comparative Examples 1 to 3: Oil-in-water emulsified composition >>
The oil-in-water emulsified composition obtained by the formulation shown in Table 1 and the production method shown below was evaluated as follows, and the results are shown in Table 1.
〈評価方法〉
（保存安定性試験）
　調製した水中油型乳化組成物を５０ｍｌのスクリュー管瓶に投入した後、別個に、７０℃の恒温槽中に８時間、及び５０℃の恒温槽中に２週間保管し、下記の評価基準により保存安定性を目視で評価した。ここで、Ａ～Ｄ評価までが合格、Ｅ評価は不合格とみなすことができる。 <Evaluation method>
(Storage stability test)
The prepared oil-in-water emulsified composition was placed in a 50 ml screw tube bottle and then separately stored in a constant temperature bath at 70 ° C. for 8 hours and in a constant temperature bath at 50 ° C. for 2 weeks according to the following evaluation criteria. Storage stability was visually evaluated. Here, the evaluations A to D can be regarded as passing, and the evaluation E can be regarded as failing.
Ａ：作製直後の組成物と比較して、色の変化が生じていなかった。
Ｂ：作製直後の組成物と比較して、全体的にわずかに色の変化が生じていた。
Ｃ：作製直後の組成物と比較して、全体的に色の変化が生じていた、或いは、瓶の１／４未満の領域が黒色に変化していた。
Ｄ：全体的に黒色には変化していないが、Ｃ評価に比べて全体的に色の変化が生じていた、或いは、瓶の１／４以上、１／２未満の領域が黒色に変化していた。
Ｅ：全体的に黒色に変化していた、或いは、瓶の１／２以上の領域が黒色に変化していた。 A: No change in color occurred as compared with the composition immediately after preparation.
B: There was a slight change in color as a whole as compared with the composition immediately after preparation.
C: Compared with the composition immediately after preparation, the color was changed as a whole, or the region of less than 1/4 of the bottle was changed to black.
D: The color did not change to black as a whole, but the color changed as a whole compared to the C evaluation, or the area of 1/4 or more and less than 1/2 of the bottle changed to black. Was there.
E: It turned black overall, or more than half of the area of the bottle turned black.
〈水中油型乳化組成物の製造方法〉
（実施例１）
　表１に示す処方を用い、以下の方法によって水中油型乳化組成物を製造した。ここで、以下に示す番号は、表１の処方の左側の成分を示す番号と一致する。 <Manufacturing method of oil-in-water emulsified composition>
(Example 1)
Using the formulations shown in Table 1, an oil-in-water emulsified composition was produced by the following method. Here, the numbers shown below correspond to the numbers indicating the ingredients on the left side of the formulation in Table 1.
　Ｎｏ．１のイオン交換水の一部に、Ｎｏ．２～Ｎｏ．６の材料を添加し、均一に混合して水相パーツ１を調製した。 No. In a part of the ion-exchanged water of No. 1, No. 2-No. The materials of No. 6 were added and mixed uniformly to prepare an aqueous phase part 1.
　Ｎｏ．１３のジビニルジメチコンに、Ｎｏ．８及び１０の材料を添加し、均一に混合して油相パーツを調製した。 No. No. 13 divinyldimethicone was added to No. Materials 8 and 10 were added and mixed uniformly to prepare oil phase parts.
　水相パーツ１に油相パーツを添加し、均一に混合して予備乳化物を調製した。この予備乳化物に、Ｎｏ．１のイオン交換水の残部とＮｏ．１７～Ｎｏ．１９の材料を混合して調製した水相パーツ２を添加し、均一に混合して、実施例１の水中油型乳化組成物を調製した。 The oil phase part was added to the aqueous phase part 1 and mixed uniformly to prepare a preliminary emulsion. In this preliminary emulsion, No. The rest of the ion-exchanged water of No. 1 and No. 17-No. The aqueous phase part 2 prepared by mixing the materials of 19 was added and uniformly mixed to prepare an oil-in-water emulsified composition of Example 1.
（実施例２～１２及び比較例１～３）
　表１の処方に変更したこと以外は、実施例１と同様にして、実施例２～１２及び比較例１～３の水中油型乳化組成物を調製した。 (Examples 2 to 12 and Comparative Examples 1 to 3)
The oil-in-water emulsified compositions of Examples 2 to 12 and Comparative Examples 1 to 3 were prepared in the same manner as in Example 1 except that the formulations were changed to those shown in Table 1.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
〈結果〉
　表１の比較例１～３の結果から分かるように、白金の全量に対する第１の不飽和オルガノポリシロキサンの質量比が２００未満の場合には、いずれの条件下でも、組成物は黒色に変色してしまい、保存安定性に劣ることが確認できた。一方、白金の全量に対する第１の不飽和オルガノポリシロキサンの質量比が２００以上である、実施例１～１２の組成物は、少なくとも７０℃で８時間の条件下においてＡ～Ｄ評価の結果が得られており、比較例１～３の組成物に比べて、保存安定性に優れることが確認できた。 <result>
As can be seen from the results of Comparative Examples 1 to 3 in Table 1, when the mass ratio of the first unsaturated organopolysiloxane to the total amount of platinum is less than 200, the composition turns black under any condition. It was confirmed that the storage stability was inferior. On the other hand, the compositions of Examples 1 to 12, in which the mass ratio of the first unsaturated organopolysiloxane to the total amount of platinum is 200 or more, are evaluated as A to D under the conditions of at least 70 ° C. for 8 hours. It was obtained, and it was confirmed that the composition was superior in storage stability as compared with the compositions of Comparative Examples 1 to 3.
　実施例１と実施例２とを比較した場合、実施例２の組成物の方が、保存安定性に優れていた。これは、エモリエント剤の配合に伴い、組成物の粘度が増加したためであると考えられる。すなわち、組成物の粘度を上昇させ得る他の剤、例えば増粘剤も同様の効果を奏し得ると考える。 When Example 1 and Example 2 were compared, the composition of Example 2 was superior in storage stability. It is considered that this is because the viscosity of the composition increased with the addition of the emollient agent. That is, it is considered that other agents capable of increasing the viscosity of the composition, for example, thickeners, can exert the same effect.
　実施例１と実施例４とを比較した場合、実施例１の組成物の方が、保存安定性に優れていた。この結果から、シリコーン系乳化剤を配合する場合には、シリコーン系乳化剤は水相パーツではなく、油相パーツ中に配合した方が好ましいことが分かった。 When Example 1 and Example 4 were compared, the composition of Example 1 was superior in storage stability. From this result, it was found that when the silicone emulsifier is blended, it is preferable to blend the silicone emulsifier in the oil phase part instead of the aqueous phase part.
　実施例１と実施例３とを比較した場合、実施例３の組成物の方が、保存安定性に優れていた。この結果から、白金触媒を含む乳化組成物においては、高分子乳化剤よりも乳化能力の高い乳化剤（例えばシリコーン系乳化剤）は、１質量％未満の量で配合するか、或いは、配合しないことが好ましいことが分かった。 When Example 1 and Example 3 were compared, the composition of Example 3 was superior in storage stability. From this result, in the emulsification composition containing a platinum catalyst, it is preferable to add an emulsifier having an emulsifying ability higher than that of the polymer emulsifier (for example, a silicone-based emulsifier) in an amount of less than 1% by mass, or not to add it. It turned out.
　実施例３、６、７を比較すると分かるように、第１の不飽和オルガノポリシロキサンの粘度が低くなると、組成物の保存安定性が向上することが分かった。 As can be seen by comparing Examples 3, 6 and 7, it was found that when the viscosity of the first unsaturated organopolysiloxane is lowered, the storage stability of the composition is improved.
　実施例１と実施例８を比較した場合、実施例８の組成物の方が、保存安定性に優れていた。この結果から、白金の全量に対する第１の不飽和オルガノポリシロキサンの質量比を増加させると、保存安定性がより向上することが分かった。また、高分子乳化剤よりも乳化能力の高い乳化剤（例えばシリコーン系乳化剤）を１質量％以上配合する場合には、白金の全量に対する第１の不飽和オルガノポリシロキサンの質量比を増加させることによって、保存安定性を向上させ得ることも分かった。 When Example 1 and Example 8 were compared, the composition of Example 8 was superior in storage stability. From this result, it was found that increasing the mass ratio of the first unsaturated organopolysiloxane to the total amount of platinum further improved the storage stability. Further, when an emulsifier having an emulsifying ability higher than that of a polymer emulsifier (for example, a silicone-based emulsifier) is blended in an amount of 1% by mass or more, the mass ratio of the first unsaturated organopolysiloxane to the total amount of platinum is increased. It was also found that the storage stability could be improved.
《実施例１３：人工皮膚形成剤及び人工皮膚》
　第２の不飽和オルガノポリシロキサンとして１６５，０００ｃｓｔのジビニルジメチコン４０．５質量部、ヒドリド官能化ポリシロキサンとしてハイドロゲンジメチコン７．９質量部、充填剤としてシリル化シリカ６．６質量部、油分として６ｃｓｔのジメチコン４５．０質量部を均一に混合して第１剤を調製した。 << Example 13: Artificial skin forming agent and artificial skin >>
40.5 parts by mass of divinyldimethicone of 165,000 cst as the second unsaturated organopolysiloxane, 7.9 parts by mass of hydrogen dimethicone as the hydride-functionalized polysiloxane, 6.6 parts by mass of silylated silica as the filler, 6 cst as the oil content. 45.0 parts by mass of dimethicone was uniformly mixed to prepare the first agent.
　得られた第１剤と、第２剤として上述した実施例３の組成物とを用いて人工皮膚形成剤を得た。 An artificial skin forming agent was obtained using the obtained first agent and the composition of Example 3 described above as the second agent.
　第１剤を皮膚に適用して未架橋状態の第１剤層を形成し、その上から第２剤を第１剤層に対してかき混ぜるように適用したところ、変色及び架橋不良などの不具合が生じていない良好な人工皮膚が形成されることが確認できた。 When the first agent was applied to the skin to form an uncrosslinked first agent layer, and then the second agent was applied to the first agent layer by stirring, problems such as discoloration and poor crosslinking occurred. It was confirmed that good artificial skin that did not occur was formed.
《水中油型乳化組成物の処方例》
　以下に、本開示の水中油型乳化組成物の処方例を挙げるが、これらの例示に限定されるものではない。これらは常法により各々調製した。これらはいずれも、高温下での白金触媒の保存安定性に優れていた。 << Example of prescription of oil-in-water emulsified composition >>
The following are examples of formulations of the oil-in-water emulsified composition of the present disclosure, but the present invention is not limited to these examples. Each of these was prepared by a conventional method. All of these were excellent in storage stability of the platinum catalyst at high temperatures.
(処方例1:化粧水)
(成分)　　　　　　　　　　　　　　　　　　　　　　　　　　　 (質量%)
イオン交換水　　　　　　　　　　　　　　　　　　　　　　　　　　 20
1,3-ブチレングリコール　　　　　　　　　　　　　　　　　　　　　　7
グリセリン　　　　　　　　　　　　　　　　　　　　　　　　　　　　3
カルボキシビニルポリマー(1%ゾル)　　　　　　　　　　　　　　　　　5
アクリレーツ/アクリル酸アルキル(C10-30)クロスポリマー(1%ゾル)　　10
水酸化カリウム　　　　　　　　　　　　　　　　　　　　　　　　 0.05
ナイアシンアミド　　　　　　　　　　　　　　　　　　　　　　　　　5
ピロ亜硫酸Na　　　　　　　　　　　　　　　　　　　　　　　　　 0.01
メタリン酸Na　　　　　　　　　　　　　　　　　　　　　　　　　 0.01
白金錯体分散液　　　　　　　　　　　　　　　　　　　　　　　　　　1
ジビニルジメチコン(10cst)　　　　　　　　　　　　　　　　　　　　 5
シリカ　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　5
エタノール　　　　　　　　　　　　　　　　　　　　　　　　　　　 12
フェノキシエタノール　　　　　　　　　　　　　　　　　　　　　　0.5
イオン交換水　　　　　　　　　　　　　　　　　　　　　　　　　　残余 (Prescription example 1: Toner)
(Component) (% by mass)
Ion-exchanged water 20
1,3-butylene glycol 7
Glycerin 3
Carboxyvinyl polymer (1% sol) 5
Acrylate / Alkyl Acrylate (C10-30) Cross Polymer (1% Sol) 10
Potassium hydroxide 0.05
Niacinamide 5
Sodium metabisulfite 0.01
Sodium metaphosphate 0.01
Platinum complex dispersion 1
Divinyl Dimethicone (10cst) 5
Silica 5
Ethanol 12
Phenoxyethanol 0.5
Ion-exchanged water residue
(処方例2:乳液1)
(成分)　　　　　　　　　　　　　　　　　　　　　　　　　　　 (質量%)
イオン交換水　　　　　　　　　　　　　　　　　　　　　　　　　　 20
1,3-ブチレングリコール　　　　　　　　　　　　　　　　　　　　　　7
グリセリン　　　　　　　　　　　　　　　　　　　　　　　　　　　　3
カルボキシビニルポリマー(1%ゾル)　　　　　　　　　　　　　　　　 10
アクリレーツ/アクリル酸アルキル(C10-30)クロスポリマー(1%ゾル)　　20
水酸化カリウム　　　　　　　　　　　　　　　　　　　　　　　　　0.1
ナイアシンアミド　　　　　　　　　　　　　　　　　　　　　　　　　5
グリチルリチン酸ジカリウム　　　　　　　　　　　　　　　　　　 0.05
ピロ亜硫酸Na　　　　　　　　　　　　　　　　　　　　　　　　　 0.01
メタリン酸Na　　　　　　　　　　　　　　　　　　　　　　　　　 0.01
白金錯体分散液　　　　　　　　　　　　　　　　　　　　　　　　　　1
ジビニルジメチコン(10cst)　　　　　　　　　　　　　　　　　　　　 5
シリカ　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　2
マイカ　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　2
エタノール　　　　　　　　　　　　　　　　　　　　　　　　　　　 12
フェノキシエタノール　　　　　　　　　　　　　　　　　　　　　　0.5
イオン交換水　　　　　　　　　　　　　　　　　　　　　　　　　　残余 (Prescription example 2: Emulsion 1)
(Component) (% by mass)
Ion-exchanged water 20
1,3-butylene glycol 7
Glycerin 3
Carboxyvinyl polymer (1% sol) 10
Acrylate / Alkyl Acrylate (C10-30) Cross Polymer (1% Sol) 20
Potassium hydroxide 0.1
Niacinamide 5
Dipotassium glycyrrhizinate 0.05
Sodium metabisulfite 0.01
Sodium metaphosphate 0.01
Platinum complex dispersion 1
Divinyl Dimethicone (10cst) 5
Silica 2
Mica 2
Ethanol 12
Phenoxyethanol 0.5
Ion-exchanged water residue
(処方例3:乳液2)
(成分)　　　　　　　　　　　　　　　　　　　　　　　　　　　 (質量%)
イオン交換水　　　　　　　　　　　　　　　　　　　　　　　　　　 20
1,3-ブチレングリコール　　　　　　　　　　　　　　　　　　　　　　7
グリセリン　　　　　　　　　　　　　　　　　　　　　　　　　　　　8
(ジメチルアクリルアミド/アクリロイルジメチルタウリンNa)クロスポリマー
　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　0.2
ナイアシンアミド　　　　　　　　　　　　　　　　　　　　　　　　　5
グリチルリチン酸ジカリウム　　　　　　　　　　　　　　　　　　　0.2
ピロ亜硫酸Na　　　　　　　　　　　　　　　　　　　　　　　　　 0.01
メタリン酸Na　　　　　　　　　　　　　　　　　　　　　　　　　 0.01
白金錯体分散液　　　　　　　　　　　　　　　　　　　　　　　　　　1
ジビニルジメチコン(10cst)　　　　　　　　　　　　　　　　　　　　 5
エタノール　　　　　　　　　　　　　　　　　　　　　　　　　　　 10
フェノキシエタノール　　　　　　　　　　　　　　　　　　　　　　0.5
イオン交換水　　　　　　　　　　　　　　　　　　　　　　　　　　残余 (Prescription example 3: Emulsion 2)
(Component) (% by mass)
Ion-exchanged water 20
1,3-butylene glycol 7
Glycerin 8
(Dimethylacrylamide / Acryloyldimethyltaurine Na) Cross Polymer 0.2
Niacinamide 5
Dipotassium glycyrrhizinate 0.2 0.2
Sodium metabisulfite 0.01
Sodium metaphosphate 0.01
Platinum complex dispersion 1
Divinyl Dimethicone (10cst) 5
Ethanol 10
Phenoxyethanol 0.5
Ion-exchanged water residue
(処方例4:ファンデーション)
(成分)　　　　　　　　　　　　　　　　　　　　　　　　　　　 (質量%)
イオン交換水　　　　　　　　　　　　　　　　　　　　　　　　　　 20
1,3-ブチレングリコール　　　　　　　　　　　　　　　　　　　　　　7
グリセリン　　　　　　　　　　　　　　　　　　　　　　　　　　　　8
(ジメチルアクリルアミド/アクリロイルジメチルタウリンNa)クロスポリマー
　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　0.2
ナイアシンアミド　　　　　　　　　　　　　　　　　　　　　　　　　5
グリチルリチン酸ジカリウム　　　　　　　　　　　　　　　　　　　0.2
ピロ亜硫酸Na　　　　　　　　　　　　　　　　　　　　　　　　　 0.01
メタリン酸Na　　　　　　　　　　　　　　　　　　　　　　　　　 0.01
白金錯体分散液　　　　　　　　　　　　　　　　　　　　　　　　　　1
ジビニルジメチコン(10cst)　　　　　　　　　　　　　　　　　　　　 5
顔料級酸化チタン　　　　　　　　　　　　　　　　　　　　　　　　　8
赤酸化鉄　　　　　　　　　　　　　　　　　　　　　　　　　　　 0.35
黄色酸化鉄　　　　　　　　　　　　　　　　　　　　　　　　　　　1.5
黒酸化鉄　　　　　　　　　　　　　　　　　　　　　　　　　　　　0.1
シリカ　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　5
マイカ　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　3
エタノール　　　　　　　　　　　　　　　　　　　　　　　　　　　 10
フェノキシエタノール　　　　　　　　　　　　　　　　　　　　　　0.5
イオン交換水　　　　　　　　　　　　　　　　　　　　　　　　　　残余 (Prescription example 4: Foundation)
(Component) (% by mass)
Ion-exchanged water 20
1,3-butylene glycol 7
Glycerin 8
(Dimethylacrylamide / Acryloyldimethyltaurine Na) Cross Polymer 0.2
Niacinamide 5
Dipotassium glycyrrhizinate 0.2 0.2
Sodium metabisulfite 0.01
Sodium metaphosphate 0.01
Platinum complex dispersion 1
Divinyl Dimethicone (10cst) 5
Pigment grade titanium oxide 8
Red iron oxide 0.35
Yellow iron oxide 1.5
Black iron oxide 0.1
Silica 5
Mica 3
Ethanol 10
Phenoxyethanol 0.5
Ion-exchanged water residue
(処方例5:サンスクリーン)
(成分)　　　　　　　　　　　　　　　　　　　　　　　　　　　 (質量%)
イオン交換水　　　　　　　　　　　　　　　　　　　　　　　　　　 20
1,3-ブチレングリコール　　　　　　　　　　　　　　　　　　　　　　7
グリセリン　　　　　　　　　　　　　　　　　　　　　　　　　　　　8
(ジメチルアクリルアミド/アクリロイルジメチルタウリンNa)クロスポリマー
　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　0.2
ナイアシンアミド　　　　　　　　　　　　　　　　　　　　　　　　　5
グリチルリチン酸ジカリウム　　　　　　　　　　　　　　　　　　　0.2
ピロ亜硫酸Na　　　　　　　　　　　　　　　　　　　　　　　　　 0.01
メタリン酸Na　　　　　　　　　　　　　　　　　　　　　　　　　 0.01
白金錯体分散液　　　　　　　　　　　　　　　　　　　　　　　　　　1
ジビニルジメチコン(10cst)　　　　　　　　　　　　　　　　　　　　 5
微粒子酸化チタン　　　　　　　　　　　　　　　　　　　　　　　　　5
微粒子酸化亜鉛　　　　　　　　　　　　　　　　　　　　　　　　　　3
メトキシケイヒ酸エチルへキシル　　　　　　　　　　　　　　　　　　5
オクトクリレン　　　　　　　　　　　　　　　　　　　　　　　　　　2
ビスエチルヘキシルオキシフェノールメトキシフェニルトリアジン　　　1
シリカ　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　5
エタノール　　　　　　　　　　　　　　　　　　　　　　　　　　　　8
フェノキシエタノール　　　　　　　　　　　　　　　　　　　　　　0.5
イオン交換水　　　　　　　　　　　　　　　　　　　　　　　　　　残余 (Prescription example 5: Sunscreen)
(Component) (% by mass)
Ion-exchanged water 20
1,3-butylene glycol 7
Glycerin 8
(Dimethylacrylamide / Acryloyldimethyltaurine Na) Cross Polymer 0.2
Niacinamide 5
Dipotassium glycyrrhizinate 0.2 0.2
Sodium metabisulfite 0.01
Sodium metaphosphate 0.01
Platinum complex dispersion 1
Divinyl Dimethicone (10cst) 5
Fine particle titanium oxide 5
Fine particle zinc oxide 3
Ethylhexyl methoxycinnamate 5
Octocrylene 2
Bisethylhexyloxyphenol methoxyphenyl triazine 1
Silica 5
Ethanol 8
Phenoxyethanol 0.5
Ion-exchanged water residue

Claims (18)

  1. 　水を含む分散媒、及び
    　前記分散媒中に分散している油滴
    を含む、水中油型乳化組成物であって、
    　前記油滴は、油分、乳化剤、及び触媒を含み、
    　前記油分が、第１の不飽和オルガノポリシロキサンを含み、
    　前記触媒が、１，３－ジビニルテトラメチルジシロキサンが配位した白金錯体を含み、かつ、
    　前記白金錯体における白金の全量に対する前記第１の不飽和オルガノポリシロキサンの質量比が、２００以上である、
    水中油型乳化組成物。     An oil-in-water emulsified composition comprising a dispersion medium containing water and oil droplets dispersed in the dispersion medium.
    The oil droplets contain an oil, an emulsifier, and a catalyst.
    The oil contains the first unsaturated organopolysiloxane and contains
    The catalyst contains a platinum complex coordinated with 1,3-divinyltetramethyldisiloxane, and
    The mass ratio of the first unsaturated organopolysiloxane to the total amount of platinum in the platinum complex is 200 or more.
    Oil-in-water emulsified composition.
  2. 　前記乳化剤が、高分子乳化剤を含む、請求項１に記載の組成物。 The composition according to claim 1, wherein the emulsifier contains a polymer emulsifier.
  3. 　前記高分子乳化剤が、（アクリレーツ／アクリル酸アルキル（Ｃ１０－３０））クロスポリマー、（アクリロイルジメチルタウリンアンモニウム／メタクリル酸ベヘネス－２５）クロスポリマー、（アクリル酸ヒドロキシエチル／アクリロイルジメチルタウリンＮａ）コポリマー、ＰＥＧ変性クロスポリマー／コポリマーシロキサン、ポリエーテル変性クロスポリマー／コポリマーシロキサン、及びポリオキシエチレンから選択される少なくとも一種である、請求項２に記載の組成物。 The polymer emulsifiers are (Acrylate / alkyl acrylate (C10-30)) cross-polymer, (acryloyldimethyltaurinammonium ammonium methacrylate / behenes-25 methacrylate) cross-polymer, (hydroxyethyl acrylate / acryloyldimethyltaurine Na) copolymer, PEG. The composition according to claim 2, wherein the composition is at least one selected from modified crosspolymer / copolymer siloxane, polyether modified crosspolymer / copolymer siloxane, and polyoxyethylene.
  4. 　シリコーン系乳化剤の配合量が、組成物の全体量に対し、１質量％未満である、請求項１～３のいずれか一項に記載の組成物。 The composition according to any one of claims 1 to 3, wherein the blending amount of the silicone-based emulsifier is less than 1% by mass with respect to the total amount of the composition.
  5. 　前記第１の不飽和オルガノポリシロキサンの２５℃における粘度が、１，０００ｃｓｔ未満である、請求項１～４のいずれか一項に記載の組成物。 The composition according to any one of claims 1 to 4, wherein the first unsaturated organopolysiloxane has a viscosity of less than 1,000 cst at 25 ° C.
  6. 　前記第１の不飽和オルガノポリシロキサンが、ビニル基を有するオルガノポリシロキサン、ビニル末端化されたオルガノポリシロキサン、及びビニル化された分岐鎖を有するオルガノポリシロキサンから選択される少なくとも一種である、請求項１～５のいずれか一項に記載の組成物。 The first unsaturated organopolysiloxane is at least one selected from an organopolysiloxane having a vinyl group, a vinyl-terminated organopolysiloxane, and an organopolysiloxane having a vinylized branched chain. Item 2. The composition according to any one of Items 1 to 5.
  7. 　前記第１の不飽和オルガノポリシロキサンが、ビニル末端ポリジメチルシロキサンである、請求項６に記載の組成物。 The composition according to claim 6, wherein the first unsaturated organopolysiloxane is a vinyl-terminated polydimethylsiloxane.
  8. 　２５℃における粘度が、５，０００ｃｓｔ以上である、請求項１～７のいずれか一項に記載の組成物。 The composition according to any one of claims 1 to 7, wherein the viscosity at 25 ° C. is 5,000 cst or more.
  9. 　第１剤及び第２剤を含む、人工皮膚形成剤であって、
    　前記第１剤が、第２の不飽和オルガノポリシロキサン、及びヒドリド官能化ポリシロキサンを含み、
    　前記第２剤が、請求項１～８のいずれか一項に記載の水中油型乳化組成物である、
    人工皮膚形成剤。     An artificial skin-forming agent containing the first agent and the second agent.
    The first agent comprises a second unsaturated organopolysiloxane and a hydride-functionalized polysiloxane.
    The second agent is the oil-in-water emulsified composition according to any one of claims 1 to 8.
    Artificial skin forming agent.
  10. 　前記第２の不飽和オルガノポリシロキサンが、ビニル基を有するオルガノポリシロキサン、ビニル末端化されたオルガノポリシロキサン、及びビニル化された分岐鎖を有するオルガノポリシロキサンから選択される少なくとも一種である、請求項９に記載の人工皮膚形成剤。 The second unsaturated organopolysiloxane is at least one selected from an organopolysiloxane having a vinyl group, a vinyl-terminated organopolysiloxane, and an organopolysiloxane having a vinylized branched chain. Item 9. The artificial skin forming agent according to Item 9.
  11. 　前記第２の不飽和オルガノポリシロキサンが、ビニル末端ポリジメチルシロキサン、ビニル末端ジフェニルシロキサン－ジメチルシロキサンコポリマー、ビニル末端ポリフェニルメチルシロキサン、ビニルフェニルメチル末端ビニルフェニルシロキサン－フェニルメチルシロキサンコポリマー、ビニル末端トリフルオロプロピルメチルシロキサン－ジメチルシロキサンコポリマー、ビニル末端ジエチルシロキサン－ジメチルシロキサンコポリマー、ビニルメチルシロキサン－ジメチルシロキサンコポリマー、トリメチルシロキシ末端ビニルメチルシロキサン－ジメチルシロキサンコポリマー、シラノール末端ビニルメチルシロキサン－ジメチルシロキサンコポリマー、ビニルメチルシロキサンホモポリマー、ビニルＴ－構造ポリマー、モノビニル末端ポリジメチルシロキサン、ビニルメチルシロキサンターポリマー、及びビニルメトキシシランホモポリマーから選択される少なくとも一種である、請求項１０に記載の人工皮膚形成剤。 The second unsaturated organopolysiloxane is vinyl-terminated polydimethylsiloxane, vinyl-terminated diphenylsiloxane-dimethylsiloxane copolymer, vinyl-terminated polyphenylmethylsiloxane, vinylphenylmethyl-terminated vinylphenylsiloxane-phenylmethylsiloxane copolymer, vinyl-terminated trifluoro. Propylmethylsiloxane-dimethylsiloxane copolymer, vinyl-terminated diethylsiloxane-dimethylsiloxane copolymer, vinylmethylsiloxane-dimethylsiloxane copolymer, trimethylsiloxy-terminated vinylmethylsiloxane-dimethylsiloxane copolymer, silanol-terminated vinylmethylsiloxane-dimethylsiloxane copolymer, vinylmethylsiloxane homo The artificial skin-forming agent according to claim 10, which is at least one selected from a polymer, a vinyl T-structure polymer, a monovinyl-terminated polydimethylsiloxane, a vinylmethylsiloxane tarpolymer, and a vinylmethoxysilane homopolymer.
  12. 　前記ヒドリド官能化ポリシロキサンが、非末端及び／又は末端で水酸化されたオルガノポリシロキサンである、請求項９～１１のいずれか一項に記載の人工皮膚形成剤。 The artificial skin-forming agent according to any one of claims 9 to 11, wherein the hydride-functionalized polysiloxane is an organopolysiloxane hydroxylated at the non-terminal and / or the terminal.
  13. 　前記ヒドリド官能化ポリシロキサンが、ヒドリド末端ポリジメチルシロキサン、ヒドリド末端ポリフェニル－（ジメチルヒドロシロキシ）シロキサン、ヒドリド末端メチルヒドロシロキサン－フェニルメチルシロキサンコポリマー、トリメチルシロキシ末端メチルヒドロシロキサン－ジメチルシロキサンコポリマー、ポリメチルヒドロシロキサン、トリメチルシロキシ末端ポリエチルヒドロシロキサン、トリエチルシロキサン、メチルヒドロシロキサン－フェニルオクチルメチルシロキサンコポリマー、及びメチルヒドロシロキサン－フェニルオクチルメチルシロキサンターポリマーから選択される少なくとも一種である、請求項１２に記載の人工皮膚形成剤。 The hydride-functionalized polysiloxanes are hydride-terminated polydimethylsiloxane, hydride-terminated polyphenyl- (dimethylhydrosiloxy) siloxane, hydride-terminated methylhydrosiloxane-phenylmethylsiloxane copolymer, trimethylsiloxy-terminated methylhydrosiloxane-dimethylsiloxane copolymer, and polymethyl. 12. According to claim 12, it is at least one selected from hydrosiloxane, trimethylsiloxy-terminated polyethylhydrosiloxane, triethylsiloxane, methylhydrosiloxane-phenyloctylmethylsiloxane copolymer, and methylhydrosiloxane-phenyloctylmethylsiloxane tarpolymer. Artificial skin forming agent.
  14. 　前記第１剤、前記第２剤、又はこれらの両方が、繊維、顔料、染料、増粘剤、保護コロイド剤、及び充填剤から選択される少なくとも一種を含む、請求項９～１３のいずれか一項に記載の人工皮膚形成剤。 Any of claims 9-13, wherein the first agent, the second agent, or both of them comprises at least one selected from fibers, pigments, dyes, thickeners, protective colloid agents, and fillers. The artificial skin forming agent according to paragraph 1.
  15. 　請求項９～１４のいずれか一項に記載の前記第１剤及び前記第２剤が、別々の容器に内包されている、又は２つ以上の区画を有する容器の各区画内に別々に内包されている、キット。 The first agent and the second agent according to any one of claims 9 to 14 are encapsulated in separate containers, or separately encapsulated in each compartment of a container having two or more compartments. It has been a kit.
  16. 　請求項９～１４のいずれか一項に記載の人工皮膚形成剤の使用方法であって、
    　前記第１剤を体表に適用して第１剤層を形成した後に、該第１剤層上に前記第２剤を適用し、架橋させて人工皮膚を形成する、
    　前記第２剤を体表に適用して第２剤層を形成した後に、該第２剤層上に前記第１剤を適用し、架橋させて人工皮膚を形成する、又は、
    　前記第１剤及び前記第２剤を混合して混合物を調製した後に、該混合物を体表に適用し、架橋させて人工皮膚を形成する、
    使用方法。     The method for using the artificial skin forming agent according to any one of claims 9 to 14.
    After the first agent is applied to the body surface to form the first agent layer, the second agent is applied onto the first agent layer and crosslinked to form an artificial skin.
    After the second agent is applied to the body surface to form the second agent layer, the first agent is applied onto the second agent layer and crosslinked to form an artificial skin, or
    After preparing a mixture by mixing the first agent and the second agent, the mixture is applied to the body surface and crosslinked to form an artificial skin.
    how to use.
  17. 　前記第１剤、前記第２剤、又は前記混合物を体表に適用する前に、化粧料を体表に適用する、又は、
    　人工皮膚を形成した後に、化粧料を人工皮膚に適用する、
    請求項１６に記載の使用方法。     Before applying the first agent, the second agent, or the mixture to the body surface, the cosmetic is applied to the body surface, or
    After forming the artificial skin, apply the cosmetics to the artificial skin,
    The method of use according to claim 16.
  18. 　前記化粧料が、スキンケア化粧料、サンスクリーン化粧料、又はメーキャップ化粧料である、請求項１７に記載の使用方法。 The method of use according to claim 17, wherein the cosmetic is a skin care cosmetic, a sunscreen cosmetic, or a makeup cosmetic.
PCT/JP2021/043041 2020-12-07 2021-11-24 Oil-in-water type emulsion composition containing platinum catalyst and method of using same WO2022124079A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2022568170A JPWO2022124079A1 (en) 2020-12-07 2021-11-24
CN202180074880.5A CN116437972A (en) 2020-12-07 2021-11-24 Oil-in-water emulsion compositions comprising platinum catalysts and methods of use thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2020-202760 2020-12-07
JP2020202760 2020-12-07

Publications (1)

Publication Number Publication Date
WO2022124079A1 true WO2022124079A1 (en) 2022-06-16

Family

ID=81974444

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2021/043041 WO2022124079A1 (en) 2020-12-07 2021-11-24 Oil-in-water type emulsion composition containing platinum catalyst and method of using same

Country Status (3)

Country Link
JP (1) JPWO2022124079A1 (en)
CN (1) CN116437972A (en)
WO (1) WO2022124079A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115558298A (en) * 2022-09-30 2023-01-03 浙江佳华精化股份有限公司 Efficient platinum catalyst master batch and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3715334A (en) * 1970-11-27 1973-02-06 Gen Electric Platinum-vinylsiloxanes
JPS4889960A (en) * 1972-02-16 1973-11-24
JP2013536861A (en) * 2010-08-31 2013-09-26 リビング プルーフ，インコーポレーテッド Dermal composition and method of use thereof
JP2017523283A (en) * 2014-07-23 2017-08-17 ダウ コーニング コーポレーションＤｏｗ Ｃｏｒｎｉｎｇ Ｃｏｒｐｏｒａｔｉｏｎ Silicone elastomer composition

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3715334A (en) * 1970-11-27 1973-02-06 Gen Electric Platinum-vinylsiloxanes
JPS4889960A (en) * 1972-02-16 1973-11-24
JP2013536861A (en) * 2010-08-31 2013-09-26 リビング プルーフ，インコーポレーテッド Dermal composition and method of use thereof
JP2017523283A (en) * 2014-07-23 2017-08-17 ダウ コーニング コーポレーションＤｏｗ Ｃｏｒｎｉｎｇ Ｃｏｒｐｏｒａｔｉｏｎ Silicone elastomer composition

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115558298A (en) * 2022-09-30 2023-01-03 浙江佳华精化股份有限公司 Efficient platinum catalyst master batch and preparation method thereof
CN115558298B (en) * 2022-09-30 2023-06-30 浙江佳华精化股份有限公司 High-efficiency platinum catalyst master batch and preparation method thereof

Also Published As

Publication number Publication date
JPWO2022124079A1 (en) 2022-06-16
CN116437972A (en) 2023-07-14

Similar Documents

Publication Publication Date Title
US10441527B2 (en) Fluid compositions and personal care
KR101005468B1 (en) Oil Type Oil Painting Hair Cosmetic
JP5667332B2 (en) Composition for cosmetic production, cosmetic and method for producing water-containing cosmetic
JP5383035B2 (en) Process for producing amino acid-modified organopolysiloxane emulsion
JP2013010934A (en) Novel organopolysiloxane elastomer and use therefor
JP4160165B2 (en) Polyorganosiloxane emulsion and cosmetics using the same
US20180064630A1 (en) Pituitous silicone fluid composition
WO2014104258A1 (en) Method for producing transparent or semi-transparent liquid glycerin-derivative-modified silicone composition
JP2019529670A (en) Silicone resin-linear copolymers and related methods
WO2022124079A1 (en) Oil-in-water type emulsion composition containing platinum catalyst and method of using same
WO2017188309A1 (en) Novel organopolysiloxane or acid neutralization salt thereof, and uses of these
CN115243733A (en) Composition for forming artificial skin and method of using the same
US20240156692A1 (en) Oil-in-water composition for second agent for coating-type body corrective film formation agent
WO2022215533A1 (en) Second agent of coating-type body corrective film-forming agent comprising first and second agents, and lubricant layer-forming agent to be applied to body corrective film
EP3448528B1 (en) Crosslinked polyorganosiloxane and personal care composition containing same
JP2017178806A (en) Emulsifying moisture retention cosmetics and method of use thereof
WO2022030284A1 (en) Base coat agent for coating-type body corrective film and method for using same
US20230172817A1 (en) O/w emulsion and w/o emulsion inverted therefrom, and personal care composition containing same
JP4136963B2 (en) Hair cosmetics
JP2021165263A (en) Makeup application method
JP2000178141A (en) Hair cosmetic
WO2023037983A1 (en) Method for enhancing skin permeation of water-soluble drug
WO2024142934A1 (en) Application-type coating formation agent and kit that includes said formation agent
WO2023037984A1 (en) Application type body-correcting-film forming agent
WO2024154597A1 (en) Oil-in-water composition for second agent of coating-type film-forming agent

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21903183

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2022568170

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21903183

Country of ref document: EP

Kind code of ref document: A1