WO2017130257A1 - シロキサン骨格を有する吸水性樹脂およびこれを含む化粧料 - Google Patents
シロキサン骨格を有する吸水性樹脂およびこれを含む化粧料 Download PDFInfo
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- WO2017130257A1 WO2017130257A1 PCT/JP2016/005112 JP2016005112W WO2017130257A1 WO 2017130257 A1 WO2017130257 A1 WO 2017130257A1 JP 2016005112 W JP2016005112 W JP 2016005112W WO 2017130257 A1 WO2017130257 A1 WO 2017130257A1
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- 0 C1C2=C1CC=*2 Chemical compound C1C2=C1CC=*2 0.000 description 2
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/08—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polysiloxanes
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/89—Polysiloxanes
- A61K8/895—Polysiloxanes containing silicon bound to unsaturated aliphatic groups, e.g. vinyl dimethicone
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
- A61K8/06—Emulsions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
- A61K8/06—Emulsions
- A61K8/062—Oil-in-water emulsions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
- A61Q1/02—Preparations containing skin colorants, e.g. pigments
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q15/00—Anti-perspirants or body deodorants
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/02—Preparations for cleaning the hair
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/12—Preparations containing hair conditioners
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
Definitions
- the present invention relates to a water-absorbent resin having a siloxane skeleton and a cosmetic containing the same.
- Water-soluble or water-swellable polymer compounds such as acrylic polymers, guar gum, and cellulose are used to increase the viscosity of aqueous compositions such as aqueous solutions and oil-in-water (O / W) emulsions.
- the product obtained by neutralizing the carboxy group of the acrylic polymer thickens the aqueous solution or O / W emulsion, but gives them a sticky feeling.
- An acrylic polymer having a long-chain alkyl group introduced has not only thickening properties but also O / W emulsifying performance of silicone oil, but gives a sticky feeling.
- a polymer in which a tris (trimethylsiloxy) structure is introduced into an acrylic polymer (Patent Document 1) is not sufficiently thickened. Guar gum and cellulose are less sticky than acrylic polymers, but their viscosity is not sufficient and there is room for improvement.
- the present invention has been made in view of the above circumstances, and provides a water absorbent resin having a siloxane skeleton capable of thickening an aqueous composition while suppressing stickiness, and a cosmetic containing the same. Objective.
- a structural unit derived from the following polymerizable vinyl monomer (A), a structural unit derived from the following polymerizable vinyl monomer (B), and the following organopolysiloxane (C) Provided is a water-absorbent resin having a siloxane skeleton, wherein the water-absorbent resin has a siloxane skeleton.
- R 1 is a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms
- R 2 is a hydrocarbon group having 1 to 6 carbon atoms
- a combination of different R 2 polymerizable vinyl monomers may also be used.
- A is an integer of 1 to 4, 0 ⁇ b ⁇ 30 and 0 ⁇ c ⁇ 30, 0 ⁇ b + c ⁇ 40
- R 3 is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.
- Such a water-absorbent resin having a siloxane skeleton can increase the viscosity of an aqueous composition while suppressing stickiness.
- the water-absorbent resin having a siloxane skeleton contains 50% to 90% by mass of the structural unit derived from the polymerizable vinyl monomer (A) and the polymerizable vinyl monomer (B) based on the mass of the water-absorbent resin. It is preferable that the copolymer contains 10 to 50% by mass of the structural unit derived from the above and 2 to 30% by mass of the structural unit derived from the organopolysiloxane (C).
- the water-absorbent resin having the siloxane skeleton further includes a structural unit derived from the following polymerizable vinyl monomer (D).
- D A polymerizable vinyl monomer having an organopolysiloxane group represented by the following general formula (5) (In the above formula (5), a, R 1 and R 4 are as described above, g is an integer of 1 to 3, and h is an integer of 0 to 500 on average.)
- aqueous composition can be further thickened, and a cosmetic material When used as, it is possible to obtain a smooth feel that spreads lightly while suppressing stickiness during application.
- the structural unit derived from the polymerizable vinyl monomer (B) in the water-absorbent resin having a siloxane skeleton is a combination of X and a sodium ion / hydrogen atom ⁇ 0.2 (molar ratio). ) Is preferable.
- Any water-absorbing resin having such a siloxane skeleton can be particularly preferably used as a cosmetic material.
- the present invention provides a cosmetic characterized by containing 0.1 to 10% by mass of the water-absorbing resin having a siloxane skeleton.
- the cosmetic of the present invention can suppress stickiness at the time of application, and can impart excellent usability such as a smooth feel that spreads lightly.
- the cosmetic preferably further contains an oil (E) selected from silicone oil, hydrocarbon oil, ester oil, and glyceride oil.
- oil (E) selected from silicone oil, hydrocarbon oil, ester oil, and glyceride oil.
- the cosmetic preferably further contains an alcohol (F) having 2 to 12 carbon atoms.
- an oil agent (E) selected from silicone oil, hydrocarbon oil, ester oil, and glyceride oil, and alcohol (F) having 2 to 12 carbon atoms If it contains, it will become still more preferable as cosmetics.
- the cosmetic preferably further contains a water-soluble or water-swellable polymer (G).
- the film property is sufficient, stickiness and the like are further suppressed, and the cosmetic is more preferable.
- the cosmetic material further contains a powder and / or a colorant as the component (H).
- the cosmetic of the present invention can contain the component (H) according to the dosage form and application of the cosmetic.
- the component (H) is polyethylene powder, polypropylene powder, silicone elastomer spherical powder, spherical polymethylsilsesquioxane powder, silicone elastomer spherical powder whose surface is coated with polymethylsilsesquioxane, or polyurethane powder. It is preferable that it contains.
- Such a component (H) is preferable because it improves the daily stability and feel of the cosmetic (product).
- the cosmetic further contains a surfactant (I).
- the surfactant (I) is a polyoxyalkylene-modified linear or branched organopolysiloxane, a polyglycerin-modified linear or branched organopolysiloxane, or an alkyl co-modified organopolysiloxane thereof. Is preferred.
- the surfactant (I) can be included according to the intended cosmetic.
- the cosmetic preferably further comprises a composition (J) comprising a cross-linked organopolysiloxane polymer other than the water-absorbing resin having the siloxane skeleton and a liquid oil agent.
- the cosmetic further comprises a composition (K) comprising a crosslinked organopolysiloxane polymer having a polyether group and / or a polyglycerin group and a liquid oil other than the water-absorbing resin having the siloxane skeleton. It is preferable that it is included.
- the crosslinked organopolysiloxane polymer having a polyether group and / or a polyglycerin group is a methyl hydrogen polysiloxane grafted with a polyoxyethylene chain and / or a methyl grafted with a polyglycerin chain.
- a cross-linked organopolysiloxane polymer prepared from hydrogen polysiloxane is preferred.
- a cosmetic containing such a composition (K) is preferable because it provides an excellent feel as a cosmetic.
- the cosmetic further comprises a silicone network compound containing SiO 2 units and / or RSiO 3/2 (R is an alkyl group), and a group consisting of a linear acrylic / silicone graft or block copolymer. It is preferable to include the selected silicone resin (L).
- the silicone network compound is a resin composed of R 3 SiO 1/2 units and SiO 2 units, a resin composed of R 3 SiO 1/2 units, R 2 SiO units and SiO 2 units, R Resin composed of 3 SiO 1/2 units and RSiO 3/2 units, resin composed of R 3 SiO 1/2 units, R 2 SiO units and RSiO 3/2 units, R 3 SiO 1/2 units, It is preferably at least one selected from the group consisting of resins composed of R 2 SiO units, RSiO 3/2 units and SiO 2 units.
- the silicone network compound preferably contains at least one selected from a pyrrolidone moiety, a long-chain alkyl moiety, a polyoxyalkylene moiety, a fluoroalkyl moiety, and an amino moiety.
- the linear acrylic / silicone graft or block copolymer is selected from at least one of an anionic group of a pyrrolidone group, a long-chain alkyl group, a polyoxyalkylene group, a fluoroalkyl group, and a carboxy group. It is preferable that it contains an organic group.
- the film property is sufficient and gloss is imparted, which is more preferable as a cosmetic.
- the cosmetic further contains an ultraviolet protection component (M).
- M ultraviolet protection component
- Such a UV protection component (M) can be suitably used as a raw material for skin care cosmetics, makeup cosmetics, UV protection cosmetics, and the like.
- the cosmetic is any one of water-based skin care cosmetics, hair cosmetics, antiperspirants, makeup cosmetics, and UV protection cosmetics.
- the water-absorbent resin having a siloxane skeleton of the present invention can thicken an aqueous composition while suppressing stickiness, so that it is water-based, skin care cosmetic, hair cosmetic, antiperspirant, makeup cosmetic. Or as a raw material for UV protection cosmetics.
- the cosmetic is in the form of liquid, emulsion, cream, solid, paste, gel, or mousse.
- the water-absorbing resin having a siloxane skeleton of the present invention is particularly suitable as a raw material for the cosmetic material of the above form.
- the cosmetic is preferably an O / W cream, foundation, shampoo, or rinse.
- Such a cosmetic is preferable because the thickening effect by the water-absorbing resin having a siloxane skeleton of the present invention can be remarkably obtained.
- the water-absorbing resin having a siloxane skeleton of the present invention can thicken an aqueous composition while suppressing stickiness. Moreover, if it is the cosmetics of this invention, the stickiness at the time of application
- coating is suppressed and the outstanding usability, such as a smooth touch with a light spreading spread, can be provided.
- the present inventors have obtained from several types (two or more) of specific polymerizable monomers and organopolysiloxanes having polymerizable groups at both ends.
- the present inventors have found that the copolymer is an excellent water-absorbing resin and completed the present invention.
- the present invention includes a structural unit derived from the following polymerizable vinyl monomer (A), a structural unit derived from the following polymerizable vinyl monomer (B), and a structural unit derived from the following organopolysiloxane (C).
- the polymerizable vinyl monomer (A) is a monomer represented by the following general formula (1).
- R 1 is a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms
- R 2 is a hydrocarbon group having 1 to 6 carbon atoms, or a group represented by the following general formula (2)
- a combination of different R 2 polymerizable vinyl monomers may also be used.
- A is an integer of 1 to 4, 0 ⁇ b ⁇ 30 and 0 ⁇ c ⁇ 30, 0 ⁇ b + c ⁇ 40
- R 3 is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. .)
- Examples of the hydrocarbon group having 1 to 3 carbon atoms of R 1 include a methyl group, an ethyl group, and a propyl group, and a methyl group is preferable.
- Examples of the hydrocarbon group having 1 to 6 carbon atoms of R 2 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an n-hexyl group. It is a group.
- polymerizable vinyl monomer represented by the general formula (1) when R 2 is a hydrocarbon group having 1 to 6 carbon atoms include methyl methacrylate, isopropyl methacrylate, n-butyl acrylate, and n-hexyl acrylate.
- (Meth) acrylic acid esters such as
- Examples of the (poly) oxyalkylene group represented by the general formula (2) for R 2 include polyoxyethylene, polyoxypropylene, and a block copolymer system of polyethylene oxide and polypropylene oxide.
- a in the general formula (2) is an integer of 1 to 4, and 2 or 3 is preferable.
- B and c are numbers satisfying 0 ⁇ b ⁇ 30 and 0 ⁇ c ⁇ 30, satisfying 0 ⁇ b + c ⁇ 40, and preferably satisfying 0 ⁇ b ⁇ 20 and 0 ⁇ c ⁇ 20.
- Specific examples of the polymerizable vinyl monomer represented by the general formula (1) when R 2 is a group represented by the general formula (2) include, for example, ethylene glycol methyl ether acrylate, ethylene glycol-n-butyl ether acrylate, Examples include diethylene glycol methyl ether methacrylate, triethylene glycol methyl ether acrylate, tetraethylene glycol methyl ether methacrylate, polyethylene glycol (polymerization degree of about 9), methyl ether methacrylate, dipropylene glycol methyl ether acrylate, and the like. ⁇ 10) The use of methyl ether methacrylate is preferred.
- Such component (A) examples include Blemmer PME-100, Blemmer PME-200, Blemmer PME-400, Blemmer PP-1000, Blemmer PP500, Blemmer PP-800 [more, manufactured by NOF Corporation]; Trade names such as NK ester M-20G, NK ester M-40G, NK ester M-90G [above, Shin-Nakamura Chemical Co., Ltd.]; CBA Biscoat 190 [Osaka Organic Chemical Co., Ltd.] are listed.
- Polymerizable vinyl monomer (B) The polymerizable vinyl monomer (B) is a monomer represented by the following general formula (3). (In the above formula (3), R 1 is as described above. X is a hydrogen atom, an alkali metal ion, an ammonium ion, or an organic ammonium ion, and may be a combination of different X polymerizable vinyl monomers.)
- Examples of X are hydrogen atom, sodium ion, potassium ion, ammonium ion, and alkanol ammonium ion, and sodium ion is particularly preferable.
- the component (B) where X is a hydrogen atom may be neutralized with a basic substance.
- the basic substance include water
- alkali metal hydroxides such as sodium oxide, potassium hydroxide and lithium hydroxide
- ammonium such as ammonium, primary alkyl ammonium, secondary alkyl ammonium and tertiary alkyl ammonium.
- sodium hydroxide is the most common and preferred.
- the preferred temperature for carrying out the neutralization reaction is 10 to 80 ° C., more preferably 20 to 50 ° C.
- the salt formation by the neutralization reaction may be neutralized in multiple stages before radical polymerization, after radical polymerization.
- X is a combination of a hydrogen atom and a sodium ion, and a sodium ion / hydrogen atom ⁇ 0.2 (molar ratio). ) Is preferable. That is, the degree of neutralization of the water absorbent resin of the present invention is determined based on the number of moles of acid groups (—COOH) in the water absorbent resin, the number of moles of base (—COOX) / the number of moles of acid groups (—COOH). The ratio is preferably 0.2 or more, particularly 1.0 to 0.2, more preferably 1.0 to 0.4, and still more preferably 0.8 to 0.5.
- Organopolysiloxane (C) is an organopolysiloxane having a polymerizable group at both ends of the following general formula (4).
- k is an integer of 1 to 4
- R 1 is as described above
- R 4 is a hydrocarbon group having 1 to 8 carbon atoms
- R 5 is R 4 or the general formula (2)
- And is an integer of 0 ⁇ m ⁇ 100, 0 ⁇ n ⁇ 20, and 0 ⁇ m + n ⁇ 100.
- R 4 examples include alkyl groups such as methyl, ethyl and butyl groups, cycloalkyl groups such as cyclopentyl and cyclohexyl groups, aryl groups such as phenyl and tolyl groups, and aralkyl groups such as benzyl and phenethyl groups. Is done. An alkyl group having 1 to 4 carbon atoms or a phenyl group is preferable, and a methyl group is more preferable.
- Examples of the (poly) oxyalkylene group represented by the general formula (2) for R 5 include polyoxyethylene, polyoxypropylene, and a block copolymer system of polyethylene oxide and polypropylene oxide.
- m and n are integers satisfying 0 ⁇ m ⁇ 100 and 0 ⁇ n ⁇ 20 and satisfying 0 ⁇ m + n ⁇ 100, and preferably 60 ⁇ m ⁇ 95 and 0 ⁇ n. It is an integer of ⁇ 10.
- the water-absorbing resin having a siloxane skeleton that is a polymer can increase the viscosity of the aqueous composition while suppressing stickiness.
- the water-absorbent resin having a siloxane skeleton of the present invention comprises 50% to 90% by mass of the structural unit derived from the polymerizable vinyl monomer (A) based on the mass of the water-absorbent resin, and the polymerizable vinyl monomer ( It is preferable that the structural unit derived from B) is contained in an amount of 10 to 50% by mass and the structural unit derived from the organopolysiloxane (C) in an amount of 2 to 30% by mass.
- the water-absorbent resin having the siloxane skeleton further includes a structural unit derived from the following polymerizable vinyl monomer (D).
- D A polymerizable vinyl monomer having an organopolysiloxane group represented by the following general formula (5) (In the above formula (5), a, R 1 and R 4 are as described above, g is an integer of 1 to 3, and h is an integer of 0 to 500 on average.)
- R 4 in the above formula (5) is an alkyl group such as a methyl group, an ethyl group or a butyl group, a cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, an aryl group such as a phenyl group or a tolyl group, a benzyl group or a phenethyl group.
- aralkyl groups such as An alkyl group having 1 to 4 carbon atoms or a phenyl group is preferable, and a methyl group is more preferable.
- H is an integer having an average of 0 to 500, preferably an integer of 0 to 300, and more preferably an integer of 0 to 250.
- a copolymer having h of 500 or less is preferable because it does not become difficult to prepare.
- g is an integer of 1 to 3, particularly preferably g is 1 and h is an integer of 10 to 250 on average.
- the proportion of the structural unit derived from the polymerizable vinyl monomer (D) having the organopolysiloxane group is preferably 5 to 30% by mass with respect to the mass of the water absorbent resin having the siloxane skeleton. More preferably, it is mass%. If the water-absorbing resin having the siloxane skeleton contains a structural unit derived from the polymerizable vinyl monomer (D), the aqueous composition can be further thickened and used as a cosmetic material. In this case, it is possible to obtain a smooth feeling that spreads lightly while suppressing stickiness during application.
- the water-absorbent resin having a siloxane skeleton of the present invention can be produced by a general radical polymerization reaction, and is not particularly limited, but usually (A), (B), (C), and (D) as necessary.
- the monomer is diluted with a solvent and polymerized with a radical initiator.
- Examples of the solvent for polymerization include water, ethanol, isopropanol, acetone, toluene, and preferably isopropanol.
- the radical polymerization method is not particularly limited, and bulk polymerization, precipitation polymerization, reverse phase suspension polymerization, spray polymerization, drop polymerization, solution polymerization, and the like are possible. From the viewpoint of performance and ease of polymerization control, reverse phase suspension polymerization, spray or drop polymerization, and aqueous solution polymerization are preferred.
- a dispersing agent can be used during the polymerization.
- the dispersant include cationic and amphoteric surfactants such as sorbitan fatty acid ester and carboxymethyldimethylcetylammonium, anionic surfactants such as polyoxyethylene dodecyl ether sulfate sodium salt, cellulose ester, and maleic acid.
- examples thereof include polymerized dispersants such as modified polybutadiene and isopropyl methacrylate-dimethylaminoethyl methacrylate quaternary salt.
- the amount of the dispersant used is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the monomer.
- an ionic surfactant as a monomer dispersant in terms of preventing aggregation of the superabsorbent resin particles.
- the polymerization initiator that can be used in the synthesis of the water-absorbing resin having a siloxane skeleton of the present invention is appropriately selected depending on the polymerization form.
- examples of such polymerization initiators include photodecomposition polymerization initiators, thermal decomposition polymerization initiators, and redox polymerization initiators.
- the polymerization initiator is used in an amount of 0.001 to 10 mol%, preferably 0.001 to 5 mol%, based on the monomer. If the amount of the polymerization initiator used is 10 mol% or less, there is no fear of causing coloring or off-flavor, and if it is 0.001 mol or more, the residual monomer is not likely to increase, which is preferable.
- photodegradable polymerization initiators include benzoin derivatives, benzyl derivatives, acetophenone derivatives, benzophenone derivatives, and azo compounds.
- thermal decomposition type polymerization initiator include persulfates (sodium persulfate, potassium persulfate, ammonium persulfate, etc.), peroxides (hydrogen peroxide, t-butyl peroxide, methyl ethyl ketone peroxide, etc.), Azo compounds (2,2′-azobis (isobutyric acid) dimethyl, 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydro Chloride) and perchlorates (potassium perchlorate, sodium perchlorate, etc.).
- redox polymerization initiator examples include a system in which a reducing compound such as sulfite, L-ascorbic acid or ferrous salt is used in combination with the persulfate or peroxide.
- a photodegradable initiator and a thermal decomposable polymerization initiator can be used in combination.
- a peroxide salt is preferable for achieving the object of the present invention.
- the polymerization initiator may be added all at once or dissolved in a solvent and dropped. Moreover, you may add suitably in the middle of reaction.
- the water-containing gel-like water-absorbing polymer obtained by polymerization is subjected to post-treatment as necessary, for example, washing and drying for the purpose of removing the residual monomer and residual initiator after polymerization, thereby obtaining a desired water-absorbing resin. be able to.
- the solvent is not particularly limited, and examples thereof include water, acetone, alcohols, isoparaffin, volatile silicone and the like. These may be used alone, or may be washed in combination or stepwise.
- the drying step is not particularly limited as long as it is a normal method, but heat drying, hot air drying, vacuum drying, infrared drying, microwave drying, freeze drying, dehydration by azeotropy with a hydrophobic organic solvent, and high-temperature steam are used. It is preferable to perform drying by a drying method such as high-humidity drying. More preferred is hot air drying.
- the drying temperature and time are not particularly limited, but a temperature of less than 150 ° C. or a drying time of less than 5 hours is preferable because there is no possibility of causing deterioration of the resin, a decrease in water absorption ratio, or coloring problems.
- the particle size may be adjusted as necessary after the drying step, or the particle size may be uniformed by surface crosslinking.
- the particle size can be appropriately adjusted by polymerization, pulverization, classification, granulation, fine powder recovery and the like.
- organic cross-linking agents As the surface cross-linking agent used for surface cross-linking, various organic or inorganic cross-linking agents can be used, but organic surface cross-linking agents are preferred. Examples include polyhydric alcohols, epoxy compounds, polyvalent amine compounds or their condensates with haloepoxy compounds, dehydrated ester reactive crosslinking agents consisting of oxazoline compounds, (mono, di, or poly) oxazolidinone compounds.
- the shape of the water-absorbent resin having a siloxane skeleton of the present invention may be any of a spherical shape, a block shape, a scale shape, a plate shape, an egg shape, a fiber shape, an indefinite shape, and a granulated shape in which particles are solidified.
- the average particle size of the water-absorbent resin having a siloxane skeleton described in the present application is not particularly limited, but the average particle size in an unabsorbed state (less than 5% loss of heating after 150 ° C./3 hours) is preferably 100 nm or more and 1 mm or less. More preferably, it is 300 nm or more and 500 ⁇ m or less.
- the average particle size is measured by appropriately selecting from a microscope method, a light scattering method, a laser diffraction method, a liquid phase precipitation method, an electric resistance method, etc. according to each shape.
- the water-absorbent resin having a siloxane skeleton of the present invention has a cross-linking part, has an action of gelling an aqueous solvent, and exhibits a thickening effect on an aqueous composition.
- the gelation described here is a state in which a low-viscosity liquid exhibits little or no fluidity due to the water-absorbent resin having the siloxane skeleton.
- the aqueous solvent may be water alone or a mixture of water and another organic solvent.
- the organic solvent to be mixed is not particularly limited, but an amphiphilic solvent is preferable. Examples of the amphiphilic solvent include alcohols such as methanol, ethanol, propanol, and 2-propanol, ketones such as acetone, and ethers such as tetrahydrofuran and dioxane.
- the antioxidant has a function of suppressing the oxidative degradation of the polyether, and the addition of the antioxidant to the water-absorbent resin having a siloxane skeleton of the present invention can suppress a decrease in swellability over time.
- antioxidants include phenolic, amine-based, sulfur-based, phosphorus-based, waxes, and metal complexes thereof, vitamin C (L-ascorbic acid), vitamin E ( ⁇ -tocopherol), kojic acid, and the like. Natural product-derived compounds and derivatives thereof. Most of these are commercially available, and usually commercially available antioxidants may be used.
- the cosmetic of the present invention varies depending on the target cosmetic dosage form, but the water-absorbent resin having the siloxane skeleton as a solid, that is, as a copolymer containing water that cannot be removed by ordinary methods. 0.1 to 10% by mass, preferably 0.5 to 5.0% by mass.
- the content of the water-absorbing resin (copolymer) having the siloxane skeleton is within the above range, a smooth feel with a light spread can be obtained while reliably suppressing stickiness during coating.
- the water-absorbent resin having a siloxane skeleton of the present invention is suitable as a thickener for cosmetic materials containing water. Further, the water-absorbent resin having a siloxane skeleton of the present invention can also act as an emulsifier for a silicone oil agent in an aqueous cosmetic containing a silicone oil agent to give a fine-grained emulsion. In particular, it is suitable for forming an oil-in-water emulsion and can provide a cosmetic with a refreshing feeling without oiliness. Further, the cosmetic to which the water-absorbing resin having a siloxane skeleton of the present invention is added does not leave a sticky feeling even after the water has volatilized.
- the water-absorbent resin having a siloxane skeleton of the present invention is preferably used as an oil-in-water emulsion of 10 to 50% by mass. Diluted. Moreover, it is also possible to remove the water from the aqueous composition to which the water-absorbing resin having a siloxane skeleton of the present invention has been added and make it into a powder form, and blend it into a cosmetic as a thickener or an emulsifier.
- the cosmetics according to the present invention are externally applied cosmetics externally applied to the skin and hair, and are water-based, ie containing water, such as skin care cosmetics, hair cosmetics, antiperspirants, makeup cosmetics, ultraviolet rays Protective cosmetics are included.
- Skin care cosmetics include emulsions, creams, lotions, calamine lotions, cleansings, packs, oil liquids, massages, serums, cleaning agents, deodorants, hand creams, lip balms, after shave lotions, pre-shave lotions and the like.
- hair cosmetics include shampoos, rinses, conditioners, treatments, hair colors, hair tonics, and set agents.
- UV protective cosmetics include sunscreen agents and suntan agents.
- makeup cosmetics such as makeup base, liquid foundation, eye shadow, mascara, eyeliner, eyebrow, lipstick and the like can be mentioned.
- O / W type creams As the cosmetic of the present invention, particularly preferred are O / W type creams, foundations, shampoos, rinses and the like.
- the form of the cosmetic according to the present invention can be liquid, emulsion, cream, solid, paste, gel, mousse or the like.
- the cosmetic of the present invention has various components used in the cosmetic, for example, an oil agent (E) selected from silicone oil, hydrocarbon oil, ester oil, and glyceride oil, and has a carbon number.
- an oil agent (E) selected from silicone oil, hydrocarbon oil, ester oil, and glyceride oil, and has a carbon number.
- Each component such as 2 to 12 alcohols (F) can be included.
- each component will be described.
- an oil agent (E) selected from silicone oil, hydrocarbon oil, ester oil, and glyceride oil any solid, semi-solid, or liquid at room temperature should be used as long as it is used for ordinary cosmetics. Can do.
- the oil agent is silicone oil, hydrocarbon oil, ester oil, or glyceride oil that is liquid at room temperature.
- the cosmetic of the present invention contains silicone oil.
- silicone oils include dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, dimethylsiloxane / methylphenylsiloxane copolymer, etc., which are liquid at room temperature with a viscosity of 0.65 to 1 million mm 2 / s.
- Organopolysiloxane octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), tetramethyltetrahydrogencyclotetrasiloxane (H4), tetramethyltetraphenylcyclotetrasiloxane Cyclic siloxane such as tristrimethylsiloxysilane (M3T), tetrakistrimethylsiloxysilane (M4Q), tristrimethylsiloxypropylsilane, tristrimethylsiloxybuty Silane, tris trimethylsiloxy-hexyl silane, branched siloxanes such as tris trimethylsiloxy phenyl silane, higher alkoxy-modified silicones such as stearoxysilicone silicones, alkyl-modified silicones, amino-modified silicones, fluorine-mod
- dimethylpolysiloxane decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, tristrimethylsiloxysilane, tetrakistrimethylsiloxysilane, and methylphenylpolysiloxane having a viscosity of 1 to 500,000 mm 2 / s.
- the dimethylpolysiloxane having a viscosity of 1 to 500,000 mm 2 / s may be a solution composed of low-viscosity silicone oil and gum-like dimethylpolysiloxane.
- Hydrocarbon oils include ozokerite, ⁇ -olefin oligomer, light isoparaffin, light liquid isoparaffin, squalane, synthetic squalane, vegetable squalane, squalene, ceresin, paraffin, paraffin wax, liquid paraffin, liquid isoparaffin, pristane, polyisobutylene, micro Crystalline wax, petrolatum, etc .; higher fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, undecylenic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA), isostearic acid, 12-hydroxystearic acid and the like.
- higher fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, undecylenic
- Ester oils include diisobutyl adipate, 2-hexyldecyl adipate, di-2-heptylundecyl adipate, N-alkyl glycol monoisostearate, isocetyl isostearate, trimethylolpropane triisostearate, di-2-ethyl Ethylene glycol hexanoate, cetyl 2-ethylhexanoate, trimethylolpropane tri-2-ethylhexanoate, pentaerythritol tetra-2-ethylhexanoate, cetyl octanoate, octyldodecyl gum ester, oleyl oleate, octyldodecyl oleate Decyl oleate, neopentyl glycol dicaprate, triethyl citrate, 2-ethylhexyl succinate,
- glyceride oils include acetoglyceryl, glyceryl triisooctanoate, glyceryl triisostearate, glyceryl triisopalmitate, glyceryl monostearate, glyceryl di-2-heptylundecanoate, glyceryl trimyristate, and diglyceryl myristate. Is mentioned.
- the cosmetic of the present invention may contain an oil agent (hereinafter referred to as other oil agent) other than the oil agent (E) selected from the silicone oil, hydrocarbon oil, ester oil, and glyceride oil.
- oil agent selected from the silicone oil, hydrocarbon oil, ester oil, and glyceride oil.
- Any solid, semi-solid, or liquid at room temperature can be used as long as it is used for the material.
- Preferable examples include natural animal and vegetable oils and fats, semi-synthetic oils, higher fatty acids, higher alcohols having 11 or more carbon atoms, and fluorine-based oils, in which part or all of the oils are liquid at room temperature.
- natural animal and vegetable oils and semi-synthetic oils include avocado oil, linseed oil, almond oil, ibotarou, eno oil, olive oil, cacao butter, kapok wax, kaya oil, carnauba wax, liver oil, candelilla wax, beef tallow, beef leg fat , Beef bone fat, hydrogenated beef tallow, kyounin oil, whale wax, hydrogenated oil, wheat germ oil, sesame oil, rice germ oil, rice bran oil, sugarcane wax, sasanqua oil, safflower oil, shea butter, cinnamon oil, cinnamon oil, jojo Barrow, shellac wax, turtle oil, soybean oil, tea seed oil, camellia oil, evening primrose oil, corn oil, lard, rapeseed oil, Japanese kiri oil, nukarou, germ oil, horse fat, persic oil, palm oil, palm kernel oil , Castor oil, hydrogenated castor oil, castor oil fatty acid methyl ester, sunflower oil, grape oil,
- Examples include cholesterol, phytosterol, POE cholesterol ether, monostearyl glycerin ether (batyl alcohol), monooleyl glyceryl ether (ceracyl alcohol), and the like.
- fluorinated oil examples include perfluoropolyether, perfluorodecalin, perfluorooctane, fluorinated pitch, and fluoroalcohol. These may be used alone or in combination of two or more as required.
- the blending amount of the oil agent (E) and the other oil agents in the cosmetic is appropriately adjusted depending on the cosmetic dosage form, but is preferably 1.0 to 80.0% by mass, particularly preferably based on the total mass of the cosmetic. Is 1.0 to 50.0% by mass. If it is 1.0 mass% or more, the effect of an oil agent (E) can fully be exhibited, and if it is 80.0 mass% or less, stickiness etc. are further suppressed and it will become still more preferable as cosmetics.
- the cosmetic of the present invention may further contain an alcohol (F) having 2 to 12 carbon atoms.
- the component (F) is preferably a water-soluble mono- or polyhydric alcohol.
- the amount of component (F) is appropriately adjusted depending on the cosmetic dosage form, but is preferably 0.1 to 50.0% by mass of the total cosmetic mass. If it is 0.1% by mass or more, the effect of imparting moisture retention, antibacterial or antibacterial properties is sufficient, and if it is 50.0% by mass or less, stickiness and the like are further suppressed, and the cosmetic is further improved. This is preferable.
- component (F) examples include lower monohydric alcohols such as ethanol, propanol and isopropanol, ethylene glycol, propylene glycol, 1,3-butylene glycol, diethylene glycol, dipropylene glycol, polyethylene glycol, isoprenol, glycerin, diglycerin, Examples thereof include polyhydric alcohols such as triglycerin and sugar alcohols such as sorbitol and maltose.
- the cosmetic of the present invention may further contain one or more water-soluble or water-swellable polymers (G).
- G water-soluble or water-swellable polymers
- examples of these include gum arabic, tragacanth, arabinogalactan, locust bean gum (carob gum), guar gum, caraya gum, carrageenan, pectin, agar, quince seed (quince), starch (rice, corn, potato, wheat), algae Collagen, Tran gum, locust bean gum and other plant polymers, xanthan gum, dextran, succinoglucan, pullulan and other microbial polymers, collagen, casein, albumin, gelatin and other animal polymers, carboxymethyl starch, methyl hydroxy Starch polymers such as propyl starch, methylcellulose, ethylcellulose, methylhydroxypropylcellulose, carboxymethylcellulose, hydroxymethylcellulose, hydroxypro Cellulose polymers such as cellulose cellulose, nitrocellulose, sodium cellulose sulfate
- the blending amount of the component (G) is preferably 0.01 to 25.0% by mass of the total mass of the cosmetic. If it is 0.01 mass% or more, these film properties will be sufficient, and if it is 25.0 mass% or less, stickiness etc. will be suppressed and it will become still more preferable as cosmetics.
- the cosmetic composition of the present invention may further comprise components conventionally used in cosmetics, for example, powders and / or colorants (H), surfactants (I), cross-linked organopolyesters as described below, if necessary.
- Siloxane (J, K), silicone resin (L), UV protection component (M) and the like can be included.
- the powder and / or colorant as the component (H) are those used in normal cosmetics, the shape (spherical, rod-like, needle-like, plate-like, irregular shape, scale-like, spindle-like, etc.) ), Particle diameter (smoke, fine particles, pigment grade, etc.) and particle structure (porous, nonporous, etc.) can be used.
- examples thereof include inorganic powders, organic powders, surfactant metal salt powders, colored pigments, pearl pigments, metal powder pigments, tar dyes and natural dyes as colorants.
- inorganic powders include titanium oxide, zirconium oxide, zinc oxide, cerium oxide, magnesium oxide, barium sulfate, calcium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, talc, mica, kaolin, sericite, muscovite, Synthetic mica, phlogopite, saucite, biotite, lithia mica, silicic acid, anhydrous silicic acid, aluminum silicate, magnesium silicate, magnesium aluminum silicate, calcium silicate, barium silicate, strontium silicate, metal tungstate Salt, hydroxyapatite, vermiculite, hydrite, bentonite, montmorillonite, hectorite, zeolite, ceramic powder, dicalcium phosphate, alumina, aluminum hydroxide, boron nitride, boron nitride, silica, etc. That.
- organic powders examples include polyamide powder, polyester powder, polyethylene powder, polypropylene powder, polystyrene powder, polyurethane powder, benzoguanamine powder, polymethylbenzoguanamine powder, tetrafluoroethylene powder, polymethylmethacrylate powder, cellulose, silk powder, nylon Silicone elastomer spherical powder having a structure in which powder, 12 nylon, 6 nylon, and dimethyl silicone are cross-linked (see JP-A-3-93934), spherical polymethylsilsesquioxane powder (see JP-A-3-47848), Silicone elastomer spherical powder whose surface is coated with polymethylsilsesquioxane (see JP-A-7-196815), styrene Crylic acid copolymer, divinylbenzene / styrene copolymer, vinyl resin, urea resin, phenol resin, fluorine resin, acrylic resin, melamine resin, epoxy resin, polycarbon
- Surfactant metal salt powder includes zinc stearate, aluminum stearate, calcium stearate, magnesium stearate, zinc myristate, magnesium myristate, zinc cetyl phosphate, calcium cetyl phosphate, zinc sodium cetyl phosphate, etc. Illustrated.
- colored pigments include inorganic red pigments such as iron oxide, iron hydroxide and iron titanate, inorganic brown pigments such as ⁇ -iron oxide, inorganic yellow pigments such as yellow iron oxide and loess, black iron oxide, carbon Inorganic black pigments such as black, inorganic purple pigments such as manganese violet and cobalt violet, inorganic green pigments such as chromium hydroxide, chromium oxide, cobalt oxide and cobalt titanate, inorganic blue pigments such as bitumen and ultramarine blue, tar dyes And a synthetic resin powder obtained by combining these powders.
- inorganic red pigments such as iron oxide, iron hydroxide and iron titanate
- inorganic brown pigments such as ⁇ -iron oxide
- inorganic yellow pigments such as yellow iron oxide and loess
- black iron oxide carbon Inorganic black pigments such as black
- inorganic purple pigments such as manganese violet and cobalt violet
- inorganic green pigments such as
- pearl pigments include titanium oxide-coated mica, titanium oxide-coated mica, bismuth oxychloride, titanium oxide-coated bismuth oxychloride, titanium oxide-coated talc, fish scale foil, and titanium oxide-coated colored mica.
- examples thereof include powder, copper powder, and stainless steel powder.
- Red No. 3 Red No. 104, Red No. 106, Red No. 201, Red No. 202, Red No. 204, Red No. 205, Red No. 220, Red No. 226, Red No. 227, Red No. 228, Red 230, Red 401, Red 505, Yellow 4, Yellow 5, Yellow 202, Yellow 203, Yellow 204, Yellow 401, Blue 1, Blue 2, Blue 201, Blue 404 , Green No. 3, Green No. 201, Green No. 204, Green No. 205, Orange No. 201, Orange No. 203, Orange No. 204, Orange No. 206, Orange No. 207 and the like.
- natural pigments include carminic acid, laccaic acid, calsamine, bradylin, and crocin.
- These powders may be powder composites or those treated with general oils, silicone oils, fluorine compounds, surfactants, and the like.
- fluorine compound treatment silicone resin treatment, pendant treatment, silane coupling agent treatment, titanium coupling agent treatment, oil agent treatment, N-acylated lysine treatment, polyacrylic acid treatment, metal soap treatment, amino acid treatment, inorganic compound treatment
- the surface treatment may be performed in advance by plasma treatment, mechanochemical treatment, or the like. One or two or more can be used as necessary.
- silicone elastomer spherical powder polyethylene powder, polypropylene powder, polytetrafluoroethylene powder, spherical polymethylsilsesquioxane powder, silicone elastomer spherical powder coated with polymethylsilsesquioxane, polyurethane powder It is used to improve the stability and feel over time.
- the blending amount of the powder and / or colorant (H) varies greatly depending on the cosmetic dosage form, but is generally from 0.1 to 50% by mass, preferably 0.5%, based on the total mass of the cosmetic. ⁇ 30% by mass.
- Surfactant (I) includes nonionic, anionic, cationic and amphoteric active agents, which are selected according to the intended cosmetic.
- nonionic surfactants are preferably used for skin creams, anionic surfactants, betaine (amphoteric) surfactants for shampoos, and cationic surfactants for rinses.
- nonionic surfactants include sorbitan fatty acid ester, glycerin fatty acid ester, polyglycerin fatty acid ester, propylene glycol fatty acid ester, polyethylene glycol fatty acid ester, sucrose fatty acid ester, polyoxyethylene alkyl ether, polyoxypropylene alkyl ether , Polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene propylene glycol fatty acid ester, polyoxyethylene castor oil, poly Oxyethylene hydrogenated castor oil, polyoxyethylene phytostanol ether, polyoxy Ethylene phytosterol ether, polyoxyethylene cholestanol ether, polyoxyethylene cholesteryl ether, polyoxyalkylene-modified organopolysiloxane (see Japanese Patent No.
- polyoxyalkylene-modified linear or branched organopolysiloxane Preferably, polyglycerin-modified linear or branched organopolysiloxane, or their alkyl co-modified organopolysiloxane is used.
- anionic surfactants include fatty acid soaps such as sodium stearate and triethanolamine palmitate, alkyl ether carboxylic acids and salts thereof, carboxylates such as condensation of amino acids and fatty acids, alkyl sulfonic acids, alkene sulfonic acids Sulfonates of fatty acid esters, sulfonates of fatty acid amides, sulfonates of alkyl sulfonates and their formalin condensates, alkyl sulfate esters, secondary higher alcohol sulfates, alkyl and allyl ether sulfates Salt, sulfate ester of fatty acid ester, sulfate ester salt of fatty acid alkylolamide, sulfate ester salt such as funnel oil, alkyl phosphate, ether phosphate, alkyl allyl ether phosphate, amide phosphate, N-acyl Amino acid based activator, etc. And
- cationic surfactants include alkylamine salts, amine salts such as polyamines and amino alcohol fatty acid derivatives, alkyl quaternary ammonium salts, aromatic quaternary ammonium salts, pyridium salts, imidazolium salts and the like.
- amphoteric surfactants examples include betaines, aminocarboxylates, imidazoline derivatives, and the like.
- the blending amount of the surfactant (I) is preferably from 0.1 to 20% by mass, more preferably from 0.5 to 10% by mass, based on the total mass of the cosmetic.
- the cosmetic of the present invention may further contain a composition (J) comprising a cross-linked organopolysiloxane polymer other than the water-absorbent resin having a siloxane skeleton and a liquid oil.
- the crosslinked organopolysiloxane polymer can be obtained by reacting an alkyl hydrogen polysiloxane with a crosslinking agent having a reactive vinyl unsaturated group at the molecular chain terminal.
- the alkyl hydrogen polysiloxane include methyl hydrogen polysiloxane having a linear or partially branched unit, and methyl hydrogen polysiloxane grafted with an alkyl chain having 6 to 20 carbon atoms.
- crosslinking agent examples include those having two or more vinyl reactive sites in the molecule, such as methyl vinyl polysiloxane and ⁇ , ⁇ -alkenyl diene. Examples thereof include the compositions described in Japanese Patent Nos. 1925781, 1932769, and International Publication Nos. WO03-24413.
- the cross-linked methylpolysiloxane may be used as a liquid oil, for example, a low viscosity silicone of 0.65 to 100.0 mm 2 / sec (25 ° C.) higher than its own weight, a hydrocarbon oil such as liquid paraffin, squalane, isododecane, trioctanoin, etc. Swell with glyceride oil or ester oil.
- a liquid oil for example, a low viscosity silicone of 0.65 to 100.0 mm 2 / sec (25 ° C.) higher than its own weight, a hydrocarbon oil such as liquid paraffin, squalane, isododecane, trioctanoin, etc. Swell with glyceride oil or ester oil.
- the blending amount of the crosslinked organopolysiloxane (J) swollen with the oil agent depends on the kind and amount of the oil agent, but is preferably 0.5 to 60% by mass, more preferably based on the total mass of the cosmetic. It is 2 to 50% by mass, more preferably 3 to 40% by mass.
- the cosmetic of the present invention may further include a composition (K) comprising a crosslinked organopolysiloxane polymer having a polyether group and / or a polyglycerin group and a liquid oil agent.
- the crosslinked organopolysiloxane polymer having a polyether group and / or a polyglycerin group can be obtained by reacting an alkyl hydrogen polysiloxane with a crosslinking agent having a reactive vinyl unsaturated group at the molecular chain terminal.
- the alkyl hydrogen polysiloxane include methyl hydrogen polysiloxane grafted with a polyoxyethylene chain, methyl hydrogen polysiloxane grafted with a polyglycerin chain, and the like.
- Cross-linked organopolysiloxane polymer is made from low-viscosity silicone, liquid paraffin, squalane, isododecane and other glyceride oils such as trioctanoin, with a viscosity of 0.65 mm to 100.0 mm 2 / sec (25 ° C). Swell to ester oil.
- Cross-linking agents such as methyl vinyl polysiloxane, ⁇ , ⁇ -alkenyl dienes, glyceryl triallyl ether, polyoxyalkynylated glyceryl triallyl ether, trimethylolpropane triallyl ether, polyoxyalkynylated trimethylolpropane triallyl ether, etc.
- cross-linked product obtained by reacting them has at least one hydrophilic group.
- the composition (K) those described in Japanese Patent Nos. 2631772, 9-136913, 2001-342255, and International Publication WO03 / 20828 are preferable.
- the blending amount of the cross-linked organopolysiloxane (K) swollen with the oil agent depends on the type and amount of the oil agent, but is preferably 0.5 to 60% by mass, more preferably based on the total mass of the cosmetic. It is 2 to 50% by mass, more preferably 3 to 40% by mass.
- the cosmetic of the present invention is a silicone resin selected from the group consisting of a silicone network compound containing SiO 2 units and / or RSiO 3/2 (R is an alkyl group) and a linear acrylic / silicone graft or block copolymer. (L) may be further included.
- the silicone resin (L) is preferably a gum or solid at normal temperature.
- the silicone network compound may contain in the molecule at least one selected from a pyrrolidone moiety, a long-chain alkyl moiety, a polyoxyalkylene moiety and a fluoroalkyl moiety, and an amino moiety.
- the silicone graft or block copolymer may have at least one organic group selected from an anionic group of a pyrrolidone group, a long-chain alkyl group, a polyoxyalkylene group, a fluoroalkyl group, and a carboxy group. .
- the silicone network compound is a silicone network compound represented by MQ, MDQ, MT, MDT, and MDTQ (where M, D, T, and Q are R 3 SiO 1/2 unit, R 2 SiO unit, RSiO 3 / 2 units and SiO 2 units) are preferred.
- the silicone network compound includes a resin composed of R 3 SiO 1/2 units and SiO 2 units, a resin composed of R 3 SiO 1/2 units, R 2 SiO units, and SiO 2 units, R 3 SiO 1 / 2 unit and resin composed of RSiO 3/2 unit, R 3 SiO 1/2 unit, resin composed of R 2 SiO unit and RSiO 3/2 unit, R 3 SiO 1/2 unit, R 2 SiO It is preferably at least one selected from the group consisting of a resin composed of units, RSiO 3/2 units and SiO 2 units.
- Silicone resins such as acrylic silicone resins and silicone network compounds may be dissolved in low-viscosity silicone oils, volatile silicone oils, and other solvents, all of which are blended when this silicone resin (L) is used.
- the amount of the resin (L) is preferably 0.1 to 20% by mass, more preferably 1 to 10% by mass, based on the total mass of the cosmetic.
- the cosmetic of the present invention may further contain an ultraviolet protection component (M).
- the ultraviolet protective component (M) include organic ultraviolet absorbers in addition to those having the above-described inorganic pigments and metal powders having ultraviolet scattering ability.
- an inorganic ultraviolet scattering agent it is particularly preferred to blend it as a dispersion in an oil.
- SPD-T1, T2, T1S, T1V, T3V, and T5 are examples of dispersions using titanium oxide as a pigment having ultraviolet scattering ability and D5 as an oil agent.
- Examples of dispersions using zinc oxide as a pigment having ultraviolet scattering ability and D5 as an oil agent include SPD-Z1, Z2, Z3, Z1S, Z3S, and Z5 (all trade names manufactured by Shin-Etsu Chemical Co., Ltd.).
- a non-volatile oil agent such as M3T, M4Q, volatile hydrocarbon oil or the like may be used instead of D5.
- organic ultraviolet absorbers examples include paraaminobenzoic acid, ethyl paraaminobenzoate, glyceryl paraaminobenzoate, amyl paradimethylaminobenzoate, octyl paradimethylaminobenzoate, 4- [N, N-di (2-hydroxy) Propyl) amino] benzoic acid ester UV absorbers such as ethyl benzoate, salicylic acid UV absorbers such as methyl salicylate, ethylene glycol salicylate, phenyl salicylate, octyl salicylate, benzyl salicylate, p-tert-butylphenyl salicylate, homomentyl salicylate Cinnamate UV absorbers such as benzyl cinnamate, 2-ethoxyethyl paramethoxycinnamate, octyl paramethoxycinnamate, di-2-methoxycinnamate mono-2-ethylhexanoate,
- the blending amount of the ultraviolet protection component (M) is preferably 0.1 to 20% by mass, more preferably 1 to 10% by mass, based on the total mass of the cosmetic.
- organic purple ultraviolet protection components 2-methoxyhexyl paramethoxycinnamate and 4-t-butyl-4'-methoxy-dibenzoylmethane are particularly preferably used.
- the ultraviolet protection component (M) it is also possible to use a material in which an organic ultraviolet absorber is sealed in a polymer powder.
- the polymer powder may or may not be hollow, and the average primary particle size of the polymer powder is preferably in the range of 0.1 to 50 ⁇ m, and the particle size distribution may be broad or sharp. Absent.
- the polymer include acrylic resin, methacrylic resin, styrene resin, urethane resin, polyethylene resin, polypropylene resin, polyethylene terephthalate resin, silicone resin, nylon resin, and acrylamide resin.
- These polymer powders are preferably powders in which an organic ultraviolet absorber is incorporated in the range of 0.1 to 30% by mass of the powder mass, and in particular, 4-tert-butyl-4′-methoxy-di, which is a UVA absorber. It is preferable to blend benzoylmethane.
- the cosmetics of the present invention include other components used in normal cosmetics, such as oil-soluble gelling agents (including organically modified clay minerals), resins, moisturizers, antibacterial and antiseptics, antibacterial agents, and perfumes. , Salts, antioxidants, pH adjusters, chelating agents, refreshing agents, anti-inflammatory agents, skin beautifying agents (whitening agents, cell activators, rough skin improving agents, blood circulation promoters, skin astringents, antiseborrheic agents, etc.) Vitamins, amino acids, nucleic acids, hormones, inclusion compounds and the like can be added.
- oil-soluble gelling agents include metal soaps such as aluminum stearate, magnesium stearate, zinc myristate, amino acid derivatives such as N-lauroyl-L-glutamic acid, ⁇ , ⁇ -di-n-butylamine, and dextrin palmitate
- dextrin stearates dextrin fatty acid esters such as dextrin 2-ethylhexanoic acid palmitate
- sucrose fatty acid esters such as sucrose palmitate, sucrose stearate, monobenzylidene sorbitol, sorbitol such as dibenzylidene sorbitol Selected from organically modified clay minerals such as benzylidene derivatives, dimethylbenzyl dodecyl ammonium montmorillonite clay, dimethyl dioctadecyl ammonium montmorillonite clay, etc.
- the gelling agent can be used alone or in combination of two or more in the oil phase component.
- glycerin As humectants, glycerin, sorbitol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, glucose, xylitol, maltitol, polyethylene glycol, hyaluronic acid, chondroitin sulfate, pyrrolidone carboxylate, polyoxyethylene methyl glucoside, Examples include polyoxypropylene methyl glucoside.
- Antibacterial and antiseptics include paraoxybenzoic acid alkyl esters, benzoic acid, sodium benzoate, sorbic acid, potassium sorbate, phenoxyethanol, etc.
- antibacterial agents include benzoic acid, salicylic acid, carboxylic acid, sorbic acid, paraoxybenzoic acid alkyl ester , Parachlorometacresol, hexachlorophene, benzalkonium chloride, chlorhexidine chloride, trichlorocarbanilide, triclosan, photosensitizer, phenoxyethanol and the like.
- antioxidant examples include tocopherol, butylhydroxyanisole, dibutylhydroxytoluene, phytic acid and the above-described antioxidants
- pH adjuster examples include lactic acid, citric acid, glycolic acid, succinic acid, tartaric acid, dl -Malic acid, potassium carbonate, sodium hydrogen carbonate, ammonium hydrogen carbonate, etc.
- Chelating agents such as alanine, sodium edetate, sodium polyphosphate, sodium metaphosphate, phosphoric acid, etc.
- Cooling agents include L-menthol, camphor
- anti-inflammatory agents include allantoin, glycyrrhetinic acid, glycyrrhizic acid, tranexamic acid, and azulene.
- whitening agents such as arbutin, glutathione, and yukinoshita extract, royal jelly, photosensitizer, cholesterol derivatives, cell activators such as calf blood extract, rough skin improver, nonyl acid wallenylamide, Nicotinic acid benzyl ester, nicotinic acid ⁇ -butoxyethyl ester, capsaicin, zingerone, cantalis tincture, ictamol, caffeine, tannic acid, ⁇ -borneol, tocopherol nicotinate, inositol hexanicotinate, cyclandrate, cinnarizine, trazoline, Examples thereof include blood circulation promoters such as acetylcholine, verapamil, cephalanthin and ⁇ -oryzanol, skin astringents such as zinc oxide and tannic acid, and antiseborrheic agents such as sulfur and thi
- Vitamins such as vitamin A oil, retinol, retinol acetate, retinol palmitate, etc., vitamin B2 such as riboflavin, riboflavin butyrate, flavin adenine nucleotide, pyridoxine hydrochloride, pyridoxine dioctanoate, pyridoxine tripalmi Vitamin B6 such as tate, vitamin B12 and derivatives thereof, vitamin B such as vitamin B15 and derivatives thereof, L-ascorbic acid, L-ascorbic acid dipalmitate, L-ascorbic acid-2-sodium sulfate, L- Vitamin C such as ascorbic acid phosphate diester dipotassium, vitamin D such as ergocalciferol and cholecalciferol, ⁇ -tocopherol, ⁇ -tocopherol, dl- ⁇ -tocopherol acetate , Vitamin E such as dl- ⁇ -tocopocoprol
- amino acids As amino acids, glycine, valine, leucine, isoleucine, serine, threonine, phenylalanine, arginine, lysine, aspartic acid, glutamic acid, cystine, cysteine, methionine, tryptophan, etc., nucleic acid, deoxyribonucleic acid, etc., hormone, estradiol , Etenyl estradiol and the like.
- Examples 1 to 7, Comparative Example 1 After mixing the white powders obtained in Synthesis Examples 1 to 7 and Synthesis Comparative Example 1 at a ratio of 5:95 (mass ratio) of powder and water and using a spatula or the like, the white powder was made. With a shear mixer, a square hole type high shear screen was used for the head, the number of revolutions was 3300 rpm, the mixture was mixed for 15 minutes, and the mixture was allowed to stand in an atmosphere of 25 ° C. for 1 day, and then the viscosity and pH were measured to confirm the stickiness. (Examples 1 to 7, Comparative Example 1). The results are shown in Table 1 below.
- the degree of stickiness in Table 1 is shown as follows. ⁇ : almost non-sticky ⁇ : slightly sticky ⁇ : sticky
- the water-absorbent resin having a siloxane skeleton of the present invention was able to obtain a thickening effect while suppressing stickiness by mixing with water (Example 1). ⁇ 7).
- a resin other than the water-absorbing resin having a siloxane skeleton of the present invention was used, the stickiness became strong (Comparative Example 1).
- Example 9 O / W type cream (Note 1) Shin-Etsu Chemical Co., Ltd .: KSG-15 (Note 2) Shin-Etsu Chemical Co., Ltd .: KF-6011 (Note 3) Shin-Etsu Chemical Co., Ltd .: Metroles SM-4000 (Note 4) Made by SEPIC: Sepigel 305 (Production method)
- the cream obtained as described above spreads lightly, has no stickiness or oiliness, and gives a fresh and refreshing feeling.
- B Components 1 to 3 were heated and mixed and added to the mixture obtained in A and emulsified with stirring.
- C Component 4 was added to the emulsion obtained in B and emulsified with stirring, and component 11 was added thereto to make it uniform.
- the UV cut cream obtained as described above gave light finish, no stickiness or oily feeling, and a transparent finish.
- B Components 1 to 3 were heated and mixed and added to the mixture obtained in A and emulsified with stirring.
- C Component 4 was added to the emulsion obtained in B and emulsified with stirring, and component 11 was added thereto to make it uniform.
- the UV cut cream obtained as described above gave light finish, no stickiness or oily feeling, and a transparent finish.
- Antiperspirant (roll-on) composition (Note 1) Shin-Etsu Chemical Co., Ltd .: KF-6011 (Production method)
- the antiperspirant composition obtained as described above had no stickiness at the time of application, gave a smooth and smooth feel after drying, and was excellent in usability.
- Example 18 Shampoo (Production method) Ingredients 1-6 were mixed in a mixer. The obtained shampoo had no stickiness during application, had a smooth feel, and had excellent usability.
- the cosmetics of the present invention have an excellent feeling of use, such as being free of stickiness and weight when applied, lightly spreading, and having a smooth and smooth feel on the back skin. It is possible to have.
- the present invention is not limited to the above embodiment.
- the above-described embodiment is an exemplification, and the present invention has any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits the same effects. It is contained in the technical range.
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Abstract
Description
(A)下記一般式(1)の重合性ビニルモノマー
(B)下記一般式(3)の重合性ビニルモノマー
(C)下記一般式(4)の両末端に重合性基を有するオルガノポリシロキサン
(D)下記一般式(5)で表わされるオルガノポリシロキサン基を有する重合性ビニルモノマー
上記重合性ビニルモノマー(A)は、下記一般式(1)で表されるモノマーである。
上記重合性ビニルモノマー(B)は、下記一般式(3)で表されるモノマーである。
オルガノポリシロキサン(C)は、下記一般式(4)の両末端に重合性基を有するオルガノポリシロキサンである。
(D)下記一般式(5)で表わされるオルガノポリシロキサン基を有する重合性ビニルモノマー
1リットル攪拌棒付きセパラフラスコに、メタクリル酸ポリオキシプロピル(ブレンマーPP-1000、日本油脂株式会社製:下記平均構造式(6))50g、メタクリル酸12g、下記平均構造式(7)で表わされる両末端メタクリル側鎖ポリエーテル変性シリコーン6g、イソプロピルアルコール100g、2,2’-アゾビス(イソ酪酸)ジメチル0.034g(全モノマー量に対して0.054モル%)を入れ、攪拌して均一な溶液にした後、窒素を流しながら80℃まで加温し8時間反応させた。冷却後、25%NaOH11gを添加し、部分中和を行った後、得られたゲルを過剰のイソプロピルアルコールで洗浄し、ろ過で得た粉末を減圧乾燥機で10時間乾燥し、その後粉砕機で粉砕することにより目的とする白色粉末状の吸水性ポリマー粒子1を得た(中和度(メタクリル酸をアルカリで中和した割合)=0.5(モル比))。
1リットル攪拌棒付きセパラフラスコに、メタクリル酸ポリオキシエチル(ブレンマーPME-400、日本油脂株式会社製:下記平均構造式(8))50g、メタクリル酸12g、上記平均構造式(7)で表わされる両末端メタクリル側鎖ポリエーテル変性シリコーン6g、イソプロピルアルコール100g、2,2’-アゾビス(イソ酪酸)ジメチル0.034g(全モノマー量に対して0.062モル%)を入れ、攪拌して均一な溶液にした後、窒素を流しながら80℃まで加温し8時間反応させた。冷却後、25%NaOH11gを添加し、部分中和を行った後、得られたゲルを過剰のイソプロピルアルコールで洗浄し、ろ過で得た粉末を減圧乾燥機で10時間乾燥し、その後粉砕機で粉砕することにより目的とする白色粉末状の吸水性ポリマー粒子2を得た(中和度(メタクリル酸をアルカリで中和した割合)=0.5(モル比))。
1リットル攪拌棒付きセパラフラスコに、メタクリル酸ポリオキシプロピル(ブレンマーPP-1000、日本油脂株式会社製:上記平均構造式(6))50g、メタクリル酸12g、下記平均構造式(9)で表わされる両末端メタクリル側鎖ポリエーテル変性シリコーン6g、イソプロピルアルコール100g、2,2’-アゾビス(イソ酪酸)ジメチル0.034g(全モノマー量に対して0.054モル%)を入れ、攪拌して均一な溶液にした後、窒素を流しながら80℃まで加温し8時間反応させた。冷却後、25%NaOH11gを添加し、部分中和を行った後、得られたゲルを過剰のイソプロピルアルコールで洗浄し、ろ過で得た粉末を減圧乾燥機で10時間乾燥し、その後粉砕機で粉砕することにより目的とする白色粉末状の吸水性ポリマー粒子3を得た(中和度(メタクリル酸をアルカリで中和した割合)=0.5(モル比))。
1リットル攪拌棒付きセパラフラスコに、メタクリル酸ヘキシル50g、メタクリル酸12g、上記平均構造式(7)で表わされる両末端メタクリル側鎖ポリエーテル変性シリコーン6g、イソプロピルアルコール100g、2,2’-アゾビス(イソ酪酸)ジメチル0.034g(全モノマー量に対して0.034モル%)を入れ、攪拌して均一な溶液にした後、窒素を流しながら80℃まで加温し8時間反応させた。冷却後、25%NaOH11gを添加し、部分中和を行った後、得られたゲルを過剰のイソプロピルアルコールで洗浄し、ろ過で得た粉末を減圧乾燥機で10時間乾燥し、その後粉砕機で粉砕することにより目的とする白色粉末状の吸水性ポリマー粒子4を得た(中和度(メタクリル酸をアルカリで中和した割合)=0.5(モル比))。
1リットル攪拌棒付きセパラフラスコに、メタクリル酸ポリオキシプロピル(ブレンマーPP-1000、日本油脂株式会社製:上記平均構造式(6))50g、メタクリル酸12g、上記平均構造式(7)で表わされる両末端メタクリル側鎖ポリエーテル変性シリコーン6g、下記平均構造式(10)で表わされる片末端メタクリルシリコーン8g、イソプロピルアルコール100g、2,2’-アゾビス(イソ酪酸)ジメチル0.034g(全モノマー量に対して0.054モル%)を入れ、攪拌して均一な溶液にした後、窒素を流しながら80℃まで加温し8時間反応させた。冷却後、25%NaOH11gを添加し、部分中和を行った後、得られたゲルを過剰のイソプロピルアルコールで洗浄し、ろ過で得た粉末を減圧乾燥機で10時間乾燥し、その後粉砕機で粉砕することにより目的とする白色粉末状の吸水性ポリマー粒子5を得た(中和度(メタクリル酸をアルカリで中和した割合)=0.5(モル比))。
1リットル攪拌棒付きセパラフラスコに、メタクリル酸ポリオキシプロピル(ブレンマーPP-1000、日本油脂株式会社製:上記平均構造式(6))50g、メタクリル酸6g、メタクリル酸ナトリウム6g、上記平均構造式(7)で表わされる両末端メタクリル側鎖ポリエーテル変性シリコーン6g、イソプロピルアルコール100g、2,2’-アゾビス(イソ酪酸)ジメチル0.034g(全モノマー量に対して0.057モル%)を入れ、窒素を流しながら80℃まで加温し8時間反応させた。冷却後、得られたゲルを過剰のイソプロピルアルコールで洗浄し、ろ過で得た粉末を減圧乾燥機で10時間乾燥し、その後粉砕機で粉砕することにより目的とする白色粉末状の吸水性ポリマー粒子6を得た。(中和度(メタクリル酸をアルカリで中和した割合)=0.44(モル比))。
1リットル攪拌棒付きセパラフラスコに、メタクリル酸ポリオキシプロピル(ブレンマーPP-1000、日本油脂株式会社製:上記平均構造式(6))20g、メタクリル酸ポリオキシエチル(ブレンマーPME-400、日本油脂株式会社製:上記平均構造式(8))10g、メタクリル酸18g、上記平均構造式(7)で表わされる両末端メタクリル側鎖ポリエーテル変性シリコーン6g、イソプロピルアルコール100g、2,2’-アゾビス(イソ酪酸)ジメチル0.027g(全モノマー量に対して0.042モル%)を入れ、窒素を流しながら80℃まで加温し8時間反応させた。冷却後、25%NaOH20gを添加し、部分中和を行った後、得られたゲルを過剰のイソプロピルアルコールで洗浄し、ろ過で得た粉末を減圧乾燥機で10時間乾燥し、その後粉砕機で粉砕することにより目的とする白色粉末状の吸水性ポリマー粒子7を得た。(中和度(メタクリル酸をアルカリで中和した割合)=0.60(モル比))。
1リットル攪拌棒付きセパラフラスコに、メタクリル酸ポリオキシプロピル(ブレンマーPP-1000、日本油脂株式会社製:平均構造式(6))50g、メタクリル酸12g、ポリエチレングリコールジメタクリレート(ブレンマーPDE-600、日本油脂株式会社製:下記平均構造式(11))2g、イソプロピルアルコール100g、2,2’-アゾビス(イソ酪酸)ジメチル0.034g(全モノマー量に対して0.054モル%)を入れ、攪拌して均一な溶液にした後、窒素を流しながら80℃まで加温し8時間反応させた。冷却後、25%NaOH11gを添加し、部分中和を行った後、得られたゲルを過剰のイソプロピルアルコールで洗浄し、ろ過で得た粉末を減圧乾燥機で10時間乾燥し、その後粉砕機で粉砕することにより目的とする白色粉末状の吸水性ポリマー粒子8を得た(中和度(メタクリル酸をアルカリで中和した割合)=0.5(モル比))。
上記合成実施例1~7、合成比較例1で得られた白色粉末を、粉末と水を5:95(質量比)の割合で混ぜ、ヘラなどを使い良く馴染ませた後、SILVERSON社製ハイシアミキサーで、ヘッドに角穴型ハイシアースクリーンを使用し、回転数3300rpm、15分間混合し、25℃の雰囲気下に1日静置した後、粘度、pHを測定し、べたつき具合を確認した(実施例1~7、比較例1)。結果を下記表1に示す。
○:ほぼべたつきなし
△:少しべたつく
×:べたつく
本発明のシロキサン骨格を有する吸水性樹脂は、水と混ぜることで、べたつき感を抑制しつつ、増粘効果を得ることができた(実施例1~7)。一方で、本発明のシロキサン骨格を有する吸水性樹脂以外の樹脂を用いた場合には、べたつきが強くなった(比較例1)。
(注2)信越化学工業(株)製:KF-6011
(注3)信越化学工業(株)製:メトローズSM-4000
(注4)SEPIC製:セピゲル305
(製造方法)
A:成分5~12を混合した。
B:成分1~4を混合溶解し、Aで得られた混合物に加えて攪拌乳化した。
以上のようにして得られたクリームは、のび広がりが軽くて、べたつきや油っぽさがなく、みずみずしく、さっぱりとした使用感を与えた。
(注2)信越化学工業(株)製:KF-6011
(注3)信越化学工業(株)製:メトローズSM-4000
(注4)SEPIC製:セピゲル305
(製造方法)
A:成分5~12を混合した。
B:成分1~4を混合溶解し、Aで得られた混合物に加えて攪拌乳化した。
以上のようにして得られたクリームは、のび広がりが軽くて、べたつきや油っぽさがなく、みずみずしく、さっぱりとした使用感を与えた。
(注2)信越化学工業(株)製:KF-6011
(注3)信越化学工業(株)製:メトローズSM-4000
(注4)SEPIC製:セピゲル305
(製造方法)
A:成分5~12を混合した。
B:成分1~4を混合溶解し、Aで得られた混合物に加えて攪拌乳化した。
以上のようにして得られたクリームは、のび広がりが軽くて、べたつきや油っぽさがなく、みずみずしく、さっぱりとした使用感を与えた。
(注2)信越化学工業(株)製:KF-6011
(注3)信越化学工業(株)製:メトローズSM-4000
(注4)SEPIC製:セピゲル305
(製造方法)
A:成分5~12を混合した。
B:成分1~4を混合溶解し、Aで得られた混合物に加えて攪拌乳化した。
以上のようにして得られたクリームは、のび広がりが軽くて、べたつきや油っぽさがなく、みずみずしく、さっぱりとした使用感を与えた。
(注2)信越化学工業(株)製:KF-6011
(注3)信越化学工業(株)製:メトローズSM-4000
(注4)SEPIC製:セピゲル305
(製造方法)
A:成分5~12を混合した。
B:成分1~4を混合溶解し、Aで得られた混合物に加えて攪拌乳化した。
以上のようにして得られたクリームは、のび広がりが軽くて、べたつきや油っぽさがなく、みずみずしく、さっぱりとした使用感を与えた。
(注2)信越化学工業(株)製:KF-6011
(注3)信越化学工業(株)製:メトローズSM-4000
(注4)SEPIC製:セピゲル305
(製造方法)
A:成分5~12を混合した。
B:成分1~4を混合溶解し、Aで得られた混合物に加えて攪拌乳化した。
以上のようにして得られたクリームは、のび広がりが軽くて、べたつきや油っぽさがなく、みずみずしく、さっぱりとした使用感を与えた。
(注2)信越化学工業(株)製:KF-6011
(注3)信越化学工業(株)製:メトローズSM-4000
(注4)SEPIC製:セピゲル305
(製造方法)
A:成分5~12を混合した。
B:成分1~4を混合溶解し、Aで得られた混合物に加えて攪拌乳化した。
以上のようにして得られたクリームは、のび広がりが重く、べたつきのある使用感を与えた。
(注1)信越化学工業(株)製:KSG-15(商品名)
(注2)信越化学工業(株)製:SPD-T5(商品名)
(注3)信越化学工業(株)製:KF-6013(商品名)
(注4)信越化学工業(株)製:KF-6011(商品名)
(注5)セピック製:セピゲル 305(商品名)
(注6)信越化学工業(株)製:メトローズSM-4000(商品名)
(製造方法)
A:成分5~9及び10、12、13を混合した。
B:成分1~3を加熱混合し、Aで得た混合物に加えて攪拌乳化した。
C:成分4をBで得た乳化物に加えて攪拌乳化し、そこに成分11を加えて均一にした。
以上のようにして得られたUVカットクリームは、のびが軽く、べたつきや油感がなく、透明感がある仕上がりを与えた。
(注2)信越化学工業(株)製:SPD-T5(商品名)
(注3)信越化学工業(株)製:KF-6013(商品名)
(注4)信越化学工業(株)製:KF-6011(商品名)
(注5)セピック製:セピゲル 305(商品名)
(注6)信越化学工業(株)製:メトローズSM-4000(商品名)
(製造方法)
A:成分5~9及び10、12、13を混合した。
B:成分1~3を加熱混合し、Aで得た混合物に加えて攪拌乳化した。
C:成分4をBで得た乳化物に加えて攪拌乳化し、そこに成分11を加えて均一にした。
以上のようにして得られたUVカットクリームは、のびが軽く、べたつきや油感がなく、透明感がある仕上がりを与えた。
(注2)信越化学工業(株)製:KSG-15(商品名)
(注3)信越化学工業(株)製:KF-6017(商品名)
(製造方法)
A:成分1~7を混合した。
B:成分8~11を混合した後、Aで得た混合物に加えて乳化した。
以上のようにして得られた乳液は、べたつきがなく、のび広がりも軽く、しかも、密着感に優れ、使用感の良いW/O型乳液であった。
(製造方法)
A:成分1~7を混合した。
B:Aで得られた混合物をロールオン容器に充填した。
以上の様にして得られた制汗剤組成物は、塗布時のベタつきも無く、乾燥後さらっとしたなめらかな感触を与え、使用性に優れた。
Claims (23)
- 下記重合性ビニルモノマー(A)に由来する構造単位、下記重合性ビニルモノマー(B)に由来する構造単位、及び下記オルガノポリシロキサン(C)に由来する構造単位を含む共重合体であることを特徴とする、シロキサン骨格を有する吸水性樹脂。
(A)下記一般式(1)の重合性ビニルモノマー
(B)下記一般式(3)の重合性ビニルモノマー
(C)下記一般式(4)の両末端に重合性基を有するオルガノポリシロキサン
- 前記シロキサン骨格を有する吸水性樹脂は、該吸水性樹脂の質量に対し、前記重合性ビニルモノマー(A)に由来する構造単位を50%~90質量%、前記重合性ビニルモノマー(B)に由来する構造単位を10~50質量%、前記オルガノポリシロキサン(C)に由来する構造単位を2~30質量%の割合で含む共重合体であることを特徴とする請求項1に記載のシロキサン骨格を有する吸水性樹脂。
- シロキサン骨格を有する吸水性樹脂における前記重合性ビニルモノマー(B)に由来する構造単位は、Xが水素原子とナトリウムイオンの組み合わせであり、ナトリウムイオン/水素原子≧0.2(モル比)であることを特徴とする請求項1から請求項3のいずれか一項に記載のシロキサン骨格を有する吸水性樹脂。
- 請求項1から4のいずれか一項に記載のシロキサン骨格を有する吸水性樹脂を、0.1~10質量%含有するものであることを特徴とする化粧料。
- 前記化粧料は、更に、シリコーン油、炭化水素油、エステル油、及びグリセライド油から選ばれる油剤(E)を含むものであることを特徴とする請求項5に記載の化粧料。
- 前記化粧料は、更に、炭素数2~12のアルコール(F)を含むものであることを特徴とする請求項5又は請求項6に記載の化粧料。
- 前記化粧料は、更に、水溶性又は水膨潤性高分子(G)を含むものであることを特徴とする請求項5から請求項7のいずれか1項に記載の化粧料。
- 前記化粧料は、更に、(H)成分として、粉体及び/又は着色剤を含むものであること特徴とする請求項5から請求項8のいずれか1項に記載の化粧料。
- 前記(H)成分が、ポリエチレンパウダー、ポリプロピレンパウダー、シリコーンエラストマー球状パウダー、球状ポリメチルシルセスキオキサンパウダー、ポリメチルシルセスキオキサンで表面を被覆したシリコーンエラストマー球状パウダー、又はポリウレタンパウダーを含むものであることを特徴とする請求項9に記載の化粧料。
- 前記化粧料は、更に、界面活性剤(I)を含むものであることを特徴とする請求項5から請求項10のいずれか1項に記載の化粧料。
- 前記界面活性剤(I)が、ポリオキシアルキレン変性直鎖又は分岐状オルガノポリシロキサン、ポリグリセリン変性直鎖又は分岐状オルガノポリシロキサン、あるいはそれらのアルキル共変性オルガノポリシロキサンであることを特徴とする請求項11に記載の化粧料。
- 前記化粧料は、更に、前記シロキサン骨格を有する吸水性樹脂以外の架橋型オルガノポリシロキサン重合物と、液状油剤とからなる組成物(J)を含むものであることを特徴とする請求項5から請求項12のいずれか1項に記載の化粧料。
- 前記化粧料は、更に、前記シロキサン骨格を有する吸水性樹脂以外の、ポリエーテル基及び/又はポリグリセリン基を有する架橋型オルガノポリシロキサン重合物と液状油剤とからなる組成物(K)を含むものであることを特徴とする請求項5から請求項12のいずれか一項に記載の化粧料。
- 前記ポリエーテル基及び/又はポリグリセリン基を有する架橋型オルガノポリシロキサン重合物が、ポリオキシエチレン鎖がグラフトされたメチルハイドロジェンポリシロキサン、及び/又はポリグリセリン鎖がグラフトされたメチルハイドロジェンポリシロキサンから調製された架橋型オルガノポリシロキサン重合物であることを特徴とする請求項14に記載の化粧料。
- 前記化粧料は、更に、SiO2単位及び/又はRSiO3/2(Rはアルキル基)を含むシリコーン網状化合物、及び、直鎖状のアクリル/シリコーングラフトもしくはブロック共重合体からなる群より選ばれるシリコーン樹脂(L)を含むものであることを特徴とする請求項5から請求項15のいずれか1項に記載の化粧料。
- 前記シリコーン網状化合物が、R3SiO1/2単位及びSiO2単位から構成される樹脂、R3SiO1/2単位、R2SiO単位及びSiO2単位から構成される樹脂、R3SiO1/2単位及びRSiO3/2単位から構成される樹脂、R3SiO1/2単位、R2SiO単位及びRSiO3/2単位から構成される樹脂、R3SiO1/2単位、R2SiO単位、RSiO3/2単位及びSiO2単位から構成される樹脂から成る群から選択される少なくとも1種であることを特徴とする請求項16に記載の化粧料。
- 前記シリコーン網状化合物が、ピロリドン部分、長鎖アルキル部分、ポリオキシアルキレン部分、フルオロアルキル部分、及びアミノ部分の中から選択される少なくとも1種を含有するものであることを特徴とする請求項17に記載の化粧料。
- 前記直鎖状のアクリル/シリコーングラフトもしくはブロック共重合体が、ピロリドン基、長鎖アルキル基、ポリオキシアルキレン基、フルオロアルキル基、カルボキシ基のアニオン性基の中から少なくとも一つ選択された有機基を含有するものであることを特徴とする請求項16から請求項18のいずれか一項に記載の化粧料。
- 前記化粧料は、更に、紫外線防御成分(M)を含むものであることを特徴とする請求項5から請求項19のいずれか1項に記載の化粧料。
- 前記化粧料が、水系の、スキンケア化粧料、頭髪化粧料、制汗剤、メイクアップ化粧料、又は紫外線防御用化粧料のいずれかであることを特徴とする請求項5~20のいずれか1項に記載の化粧料。
- 前記化粧料の形態が、液状、乳液状、クリーム状、固形状、ペースト状、ゲル状、又はムース状であることを特徴とする請求項21に記載の化粧料。
- 前記化粧料が、O/W型のクリーム、ファンデーション、シャンプー、又はリンスであることを特徴とする請求項22に記載の化粧料。
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US16/070,589 US10786440B2 (en) | 2016-01-29 | 2016-12-13 | Water absorbing resin having siloxane skeleton and cosmetic containing the same |
CN201680080307.4A CN108602930B (zh) | 2016-01-29 | 2016-12-13 | 具有硅氧烷骨架的吸水性树脂及包含所述吸水性树脂的化妆材料 |
EP16887846.0A EP3409703B1 (en) | 2016-01-29 | 2016-12-13 | Water absorbent resin having siloxane skeleton, and cosmetic including same |
KR1020187021725A KR102649137B1 (ko) | 2016-01-29 | 2016-12-13 | 실록산 골격을 갖는 흡수성 수지 및 이를 포함하는 화장료 |
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WO2024135815A1 (ja) * | 2022-12-23 | 2024-06-27 | ダウ・東レ株式会社 | ラジカル重合性ポリカーボネート変性シリコーン化合物、それを用いる新規シリコーン-ポリカーボネート共重合体粒子および化粧料組成物その他の用途 |
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US20220289888A1 (en) * | 2019-08-21 | 2022-09-15 | Shin-Etsu Chemical Co., Ltd. | Silicone and a method for preparing the same |
US11840608B2 (en) * | 2019-08-21 | 2023-12-12 | Shin-Etsu Chemical Co., Ltd. | Silicone and a method for preparing the same |
WO2024135815A1 (ja) * | 2022-12-23 | 2024-06-27 | ダウ・東レ株式会社 | ラジカル重合性ポリカーボネート変性シリコーン化合物、それを用いる新規シリコーン-ポリカーボネート共重合体粒子および化粧料組成物その他の用途 |
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CN108602930A (zh) | 2018-09-28 |
JP6510435B2 (ja) | 2019-05-08 |
US10786440B2 (en) | 2020-09-29 |
CN108602930B (zh) | 2020-11-17 |
JP2017132947A (ja) | 2017-08-03 |
EP3409703A4 (en) | 2019-07-31 |
EP3409703B1 (en) | 2021-11-10 |
EP3409703A1 (en) | 2018-12-05 |
KR102649137B1 (ko) | 2024-03-20 |
US20190021982A1 (en) | 2019-01-24 |
KR20180104300A (ko) | 2018-09-20 |
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