WO2014054686A1 - 新規な共変性オルガノポリシロキサン、それを含有してなる粉体処理剤および粉体組成物 - Google Patents
新規な共変性オルガノポリシロキサン、それを含有してなる粉体処理剤および粉体組成物 Download PDFInfo
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- WO2014054686A1 WO2014054686A1 PCT/JP2013/076811 JP2013076811W WO2014054686A1 WO 2014054686 A1 WO2014054686 A1 WO 2014054686A1 JP 2013076811 W JP2013076811 W JP 2013076811W WO 2014054686 A1 WO2014054686 A1 WO 2014054686A1
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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
- A61K8/896—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate
- A61K8/898—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate containing nitrogen, e.g. amodimethicone, trimethyl silyl amodimethicone or dimethicone propyl PG-betaine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H23/00—Compounds containing boron, silicon, or a metal, e.g. chelates, vitamin B12
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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
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/0216—Solid or semisolid forms
- A61K8/022—Powders; Compacted Powders
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- 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
- A61Q1/08—Preparations containing skin colorants, e.g. pigments for cheeks, e.g. rouge
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- 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
- A61Q1/10—Preparations containing skin colorants, e.g. pigments for eyes, e.g. eyeliner, mascara
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- 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
- A61Q1/12—Face or body powders for grooming, adorning or absorbing
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/14—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/10—General cosmetic use
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/42—Colour properties
- A61K2800/43—Pigments; Dyes
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/54—Polymers characterized by specific structures/properties
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/60—Particulates further characterized by their structure or composition
- A61K2800/65—Characterized by the composition of the particulate/core
- A61K2800/651—The particulate/core comprising inorganic material
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/60—Particulates further characterized by their structure or composition
- A61K2800/65—Characterized by the composition of the particulate/core
- A61K2800/652—The particulate/core comprising organic material
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/60—Particulates further characterized by their structure or composition
- A61K2800/65—Characterized by the composition of the particulate/core
- A61K2800/654—The particulate/core comprising macromolecular material
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- 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
- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
- A61Q1/02—Preparations containing skin colorants, e.g. pigments
- A61Q1/04—Preparations containing skin colorants, e.g. pigments for lips
- A61Q1/06—Lipsticks
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/50—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages
Definitions
- the present invention is a novel co-modified organopolysiloxane copolymer that can be produced at a relatively low cost and easily, and has a group having a carbosilendendron structure in the molecule and a group having a saccharide component as a hydrophilic group. , And a surface treatment agent containing the same, particularly a powder treatment agent. Further, the present invention provides a powder surface-treated with the powder treatment agent, a powder composition containing the co-modified organopolysiloxane copolymer, and a powder dispersion in oil containing an oil agent, The present invention also relates to external preparations containing these, particularly makeup cosmetics.
- surface treatment lipophilic treatment with oil agent, metal soap, etc., hydrophilic treatment with surfactant, water-soluble polymer, etc., hydrophobic treatment with silicone compound, silica treatment, alumina treatment, etc. are known. Yes. Particularly in recent years, surface treatment is often performed with a silicone compound having a reactive site in the molecule. Since the reactive site forms a chemical bond with the powder surface, the surface treatment with the silicone compound is effective in terms of modifying the surface of the powder and simultaneously blocking the surface activity of the powder. In addition, since the surface treatment is performed reliably, the surface treatment agent does not leave the powder surface even when blended with a cosmetic containing a solvent. Moreover, the change in the characteristics of the powder due to the surface treatment can be minimized.
- Patent Document 1 a method of surface-treating powder with methyl hydrogen polysiloxane can be mentioned (Patent Document 1).
- Patent Document 1 a method of surface-treating powder with methyl hydrogen polysiloxane can be mentioned.
- unreacted Si—H groups remain in the powder even after the surface treatment. Therefore, when the powder is blended in cosmetics, hydrogen gas is generated depending on the components in the cosmetics. There was a problem.
- the applicant of the present invention uses a method using a co-modified organopolysiloxane copolymer having a group having a carboxidendron structure in the molecule and a hydrophilic group such as a glycerol derivative or a polyhydric alcohol.
- a co-modified organopolysiloxane copolymer having a group having a carboxidendron structure in the molecule and a hydrophilic group such as a glycerol derivative or a polyhydric alcohol.
- Patent Documents 4, 5, 6, and 7 These co-modified organopolysiloxanes do not generate hydrogen, are safe, can be suitably used for surface treatment of powders, and have excellent compatibility with other raw materials for cosmetics. The dispersibility and stability of the powder in the cosmetic composition containing can be improved.
- organopolysiloxanes having a modifying group in the molecule containing a saccharide component composed of saccharides (saccharides) and sugar derivatives reactions for obtaining the organopolysiloxanes and use in cosmetics have been known for a long time.
- the modified groups containing these saccharide components can be synthesized by a simple method using a simple amino-modified silicone and an inexpensive sugar lactone, so the cost is low, and various sugar lactones can be used to produce a wide variety of sugars. It is also possible to derive to a modified silicone. However, its use is still limited, and it has only been used as some surfactants such as surface treatment agents and gelling agents.
- Patent Document 14 an organopolysiloxane having a sugar residue at the end of a siloxane dendron structure.
- Patent Document 14 do not disclose any co-modified organopolysiloxane having a functional group independent of the siloxane dendron structure and a modified group containing a saccharide component in the molecule, and as a surface treatment agent. There is no description or suggestion about performance.
- siloxane dendron structure which is an organopolysiloxane hydrophobic functional group disclosed in the same document, with a hydrophilic group, it is necessary to introduce a sugar residue into the raw material intermediate through a multi-step reaction (paragraph 0014). This is a completely different invention from the present invention in that it cannot be manufactured at low cost.
- Japanese Patent Laid-Open No. 07-53326 Japanese Patent No. 2719303
- JP-A-10-167946 JP 2002-38013 A International Patent Publication WO2011 / 049246 International Patent Publication WO2011 / 049248 International Patent Publication WO2011-136394 Japanese Patent Application No. 2011-286773 (unpublished at the time of filing) JP-A-62-068820 JP 63-139106
- a modified group containing a saccharide component can be synthesized by a simple method using a simple amino-modified silicone and an inexpensive sugar lactone.
- the amino group is highly reactive, it has different hydrophobic properties. It cannot be easily co-modified with functional groups. For this reason, it has been difficult to synthesize a co-modified organopolysiloxane having a desired hydrophobic functional group in addition to a modified group containing a saccharide component, particularly on an industrial scale, by a conventional production method.
- An object of the present invention is to provide a novel co-modified organopolysiloxane that solves the above problems. More specifically, compared to conventional co-modified silicones, the production cost is low, the synthesis on an industrial scale is easy, the dispersibility of the powder is high, and the compatibility with a wide range of cosmetic raw materials is achieved. An object is to provide a co-modified organopolysiloxane that is excellent and can be suitably used as a cosmetic raw material.
- the present invention also includes a powder treatment agent containing the organopolysiloxane, a powder surface-treated with the powder treatment agent, a powder composition containing the co-modified organopolysiloxane copolymer, Furthermore, it aims at providing the powder dispersion
- the object of the present invention is achieved by a novel co-modified organopolysiloxane having in its molecule a group having a carbosilendendron structure and a hydrophilic group such as a sugar or a sugar derivative.
- this is preferably achieved by a novel co-modified organopolysiloxane having a group having a carbosiloxydendron structure and a sugar lactone amidoalkyl group in the molecule.
- the object of the present invention is to cohydrosilylate a compound having a siloxane dendron structure, a compound having a functional group capable of reacting with a compound having a saccharide component after deprotection reaction, and an organohydrogenpolysiloxane, After obtaining an organopolysiloxane intermediate, the intermediate is deprotected and then reacted with a compound having a saccharide component. Achieved.
- the object of the present invention is also achieved by a surface treatment agent containing a novel co-modified organopolysiloxane, particularly a powder treatment agent. Furthermore, an object of the present invention is to provide a powder surface-treated with the powder treating agent, a powder composition containing the co-modified organopolysiloxane, and a powder dispersion in oil containing an oil agent, It is also achieved by an external preparation containing these, particularly a makeup cosmetic.
- R 1 a R 2 b L 1 c Q d SiO (4-a-b-c-d) / 2
- R 1 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms or a hydrogen atom.
- R 2 represents a substituted or unsubstituted, linear or branched monovalent hydrocarbon group having 6 to 30 carbon atoms, or the following general formula (2-1); (Wherein R 11 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms, a hydroxyl group or a hydrogen atom, and at least one of R 11 is the monovalent hydrocarbon group.
- T I a number in the range of 2 to 10
- r is a number in the range of 1 to 500
- Z is a divalent organic radical
- i is represented of a silylalkyl group represented by L i, 1 ⁇ k when the generation number is the number of repetitions of the silylalkyl group is k
- the number of layers k is an integer of 1 to 10
- L i + 1 is the silylalkyl group when i is less than k
- R 4 when i k
- h i is 0 to Is
- a silylalkyl group having a siloxane dendron structure represented by Q is a group containing a saccharide component and has the formula X- (G 1 ) n- (G 2 ) m , where G 1 is a saccharide component having 5 to 12 carbon atoms, and n + m is 1 -10, n or m can be 0, and G 2 is a saccharide component of 5 to 12 carbon atoms, optionally substituted with an organic or organosilicon
- a, b, c, and d are numbers in a range where 1.0 ⁇ a + b ⁇ 2.5, 0.001 ⁇ c ⁇ 1.5, and 0.001 ⁇ d ⁇ 1.5.
- Q is a group containing a saccharide component obtained by a reaction between an amino group and a hydroxy-functional saccharide.
- Q is bonded to a silicon atom, -R 12 - (N (R 13 ) -R 14) w -NR 15 R 16 (Wherein R 12 is an alkylene group having 2 to 8 carbon atoms, R 13 , R 15 and R 16 are a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, but at least one of all R 13 , R 15 and R 16 is a hydrogen atom, R 14 is an alkylene group having 1 to 4 carbon atoms, and w is a number in the range of 0 ⁇ w ⁇ 6.
- (n1 + n2 + n3 + n4) is a number in the range of 2-50, n1 is 0-45, n2 is 0-30, n3 is 1 to 20 and n4 are numbers in the range of 0.1 to 2.
- L 1 is a functional group represented by the following General Formula (2-1) or General Formula (2-2); Formula (2-1): Formula (2-2): (Wherein R 1 , R 2 and Z are the same groups as described above, and a 1 and a 2 are each independently a number ranging from 0 to 3) Q is bonded to a silicon atom, -R 12 - (N (R 13 ) -R 14) w -NR 15 R 16 (Wherein R 12 is an alkylene group having 2 to 8 carbon atoms, R 13 , R 15 and R 16 are a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, but at least one of all R 13 , R 15 and R 16 is a hydrogen atom, R 14 is an alkylene group having 1 to 4 carbon atoms, and w is a number in the range of 0 ⁇ w ⁇ 6.
- N1 + n2 + n3 + n4 is a number ranging from 2 to 50
- n1 is a number ranging from 0 to 45
- n2 is a number ranging from 0 to 30
- n3 is a number ranging from 1 to 20
- n4 is a number ranging from 0.1 to 2.
- Process for producing an organopolysiloxane intermediate Step (III): a co-modified organopolysiloxane intermediate obtained in Step (I) or Step (II); Reacting a compound having a saccharide component.
- the step (II) is an essential step, The production of the co-modified organopolysiloxane according to [8], wherein the compound having a functional group capable of reacting with the compound having a saccharide component after the deprotection reaction is an allylamine protected by an organosilyl group.
- Method. [10] The method for producing a co-modified organopolysiloxane according to [9], wherein the organosilyl group is a bisdimethylsilylethylene group.
- the method for producing a co-modified organopolysiloxane comprising the following steps (I) to (III): Step (IA): Compound having a siloxane dendron structure, Allylamine protected by bisdimethylsilylethylene groups, and organohydrogenpolysiloxane, A step of producing a co-modified organopolysiloxane intermediate having a functional group capable of reacting with a compound having a saccharide component after the deprotection reaction by cohydrosilylation.
- a powder composition comprising (A) the co-modified organopolysiloxane according to any one of [1] to [7] and (B) a powder or a colorant.
- the component (B) is one or more selected from the group consisting of inorganic pigment powders, organic pigment powders, and resin powders having an average particle diameter in the range of 1 nm to 20 ⁇ m. 13].
- the external preparation composition according to [16] which is a cosmetic or a medicine.
- a cosmetic comprising the powder composition according to [13] or [14].
- a makeup cosmetic comprising (B) a powder or a colorant and (C) a silicone oil which is liquid at 5 to 100 ° C., a nonpolar organic compound or a low polar organic compound. Is achieved.
- the production efficiency of the powder dispersion in the mixed oil system and the production efficiency of the powder are lower than that of the polyglycerin or xylitol-modified organopolysiloxane and compared with the conventional polyether-modified organopolysiloxane.
- a novel co-modified organopolysiloxane having excellent dispersibility, excellent compatibility with a wide range of cosmetic raw materials, and suitable for use as a cosmetic raw material can be suitably provided especially on an industrial scale. Thereby, in particular, it is possible to provide a material characterized in that the adjustment of the powder dispersion in oil is facilitated and the powder dispersibility and stability are excellent.
- the novel co-modified organopolysiloxane of the present invention can provide various cosmetics containing the same, and in particular, cosmetics using the above-mentioned powder dispersion in oil, especially makeup cosmetics. It can provide suitably.
- novel co-modified organopolysiloxane of the present invention its use as various treatment agents, particularly its use as a powder treatment agent and its use as a cosmetic raw material will be described in detail. Further, a powder dispersion in oil, an external preparation, preferably a cosmetic, particularly preferably a makeup cosmetic, using the novel co-modified organopolysiloxane of the present invention will be described in detail.
- novel co-modified organopolysiloxane according to the present invention can be applied to the same use as the co-modified organopolysiloxane described in Patent Document 5 (International Patent Publication No. WO2011 / 049248).
- various treatment agents especially as powder treatment agents and as cosmetic raw materials, in combination with optional cosmetic raw material components, for external preparations, especially cosmetic dosage forms, types and formulation examples can be used in the same manner as the co-modified organopolysiloxane disclosed in Patent Document 5, and can be blended into various cosmetics.
- the co-modified organopolysiloxane according to the present invention is a co-modified organopolysiloxane having a group having a siloxane dendron structure and a sugar or sugar derivative residue as a hydrophilic group, and specifically represented by the following general formula (1).
- R 1 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms or a hydrogen atom.
- R 2 represents a substituted or unsubstituted, linear or branched monovalent hydrocarbon group having 6 to 30 carbon atoms, or the following general formula (2-1); (Wherein R 11 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms, a hydroxyl group or a hydrogen atom, and at least one of R 11 is the monovalent hydrocarbon group.
- R 3 represents a substituted or unsubstituted, linear or branched monovalent hydrocarbon group having 1 to 30 carbon atoms, and R 4 each independently represents an alkyl group having 1 to 6 carbon atoms or phenyl represents a group
- Z is a divalent organic radical
- i is represented of a silylalkyl group represented by L i
- the number of layers is a number of repetitions of the silylalkyl group is an integer of 1 ⁇ k when k
- the number of layers k is an integer of 1 to 10
- L i + 1 is the silylalkyl group when i is less than k
- R 4 when i k
- h i is
- R 1 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms or a hydrogen atom.
- the monovalent organic group represented by R 1 does not include the group corresponding to the above L 1 or Q, and is preferably independently an alkyl group or aryl group having 1 to 10 carbon atoms, methyl, Linear, branched or cyclic alkyl groups such as ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, pentyl, neopentyl, cyclopentyl, hexyl; phenyl group.
- R 1 is a methyl group or a phenyl group.
- R 1 includes a hydrogen atom bonded to a carbon atom of these groups at least partially containing a halogen atom such as fluorine, or an epoxy group, acyl group, carboxyl group, amino group, methacryl group, mercapto group, or the like. It may be substituted with an organic group.
- R 2 is a functional group optionally contained in the co-modified organopolysiloxane according to the present invention, and is a substituted or unsubstituted, straight-chain or branched monovalent hydrocarbon group having 6 to 30 carbon atoms. is there.
- R 1 are all alkyl groups having 5 or less carbon atoms (particularly methyl group) or phenyl groups, in order to improve the affinity with hydrocarbon oils (cosmetic raw materials) in particular, R 2 It is preferable that the long chain hydrocarbon group is included.
- R 2 is preferably an alkyl group having 6 or more carbon atoms such as hexyl group, heptyl group, octyl group, decyl group, dodecyl group; cycloalkyl group such as cyclohexyl group; aryl such as tolyl group, xylyl group, naphthyl group, etc. Groups, and organic groups in which the hydrogen atoms bonded to the carbon atoms of these groups are at least partially halogen atoms such as fluorine, or epoxy groups, acyl groups, carboxyl groups, amino groups, methacryl groups, mercapto groups, etc. And an alkyl group having 8 to 20 carbon atoms is preferable.
- the chain organosiloxane group represented by the general formula (2-1) or (2-2) has a linear polysiloxane chain structure.
- each R 11 is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms, a hydroxyl group, or a hydrogen atom.
- the substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms includes an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 6 to 30 carbon atoms, carbon A cycloalkyl group having 6 to 30 atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a decyl group; a cyclopentyl group, a cyclohexyl group, etc.
- Cycloalkyl groups aryl groups such as phenyl and tolyl groups are exemplified, and the hydrogen atoms bonded to the carbon atoms of these groups are at least partially halogen atoms such as fluorine, or epoxy groups, acyl groups, carboxyl groups, It may be substituted with an organic group containing an amino group, a methacryl group, a mercapto group, or the like.
- R 11 is particularly preferably a methyl group, a phenyl group or a hydroxyl group, a form in which a part of R 11 is a methyl group and a part is a long-chain alkyl group having 8 to 30 carbon atoms. Is preferred.
- t is a number in the range of 2 to 10
- r is a number in the range of 1 to 500
- r is a number in the range of 2 to 500. It is preferable.
- Such a linear organosiloxane group is hydrophobic, and from the viewpoint of compatibility with various oils, r is preferably a number in the range of 1 to 100, and a number in the range of 2 to 30. Particularly preferred.
- Examples of the substituted or unsubstituted, linear or branched monovalent hydrocarbon group represented by R 3 in the general formula (3) include, for example, a methyl group, an ethyl group, Alkyl groups such as propyl, butyl, pentyl, hexyl, heptyl and octyl; cycloalkyl such as cyclopentyl and cyclohexyl; alkenyl such as vinyl, allyl and butenyl; phenyl and tolyl Aryl groups such as aralkyl groups; aralkyl groups such as benzyl groups; and hydrogen atoms bonded to carbon atoms of these groups are at least partially halogen atoms such as fluorine, or epoxy groups, glycidyl groups, acyl groups, carboxyl groups , Groups substituted with an organic group including an amino group, a methacryl group, a mercapto group and the like (provided that the total number
- the co-modified organopolysiloxane according to the present invention is a modified group other than a group having a siloxane dendron structure (-L 1 ) and a group containing a saccharide component (-Q) for the purpose of imparting further functionality, particularly a short group.
- Chain or medium chain hydrocarbon based groups can be introduced or designed as R 1 . That is, when R 1 is a substituted monovalent hydrocarbon group, the substituent can be appropriately selected according to the characteristics to be imparted and the application.
- an amino group, an aminoethylaminopropyl group, a carboxyl group, or the like is introduced as a substituent for a monovalent hydrocarbon group for the purpose of improving the feeling of use, feel or sustainability. Can do.
- R 1 is preferably a monovalent hydrocarbon group or monovalent fluorinated hydrocarbon group having 1 to 8 carbon atoms that does not have an aliphatic unsaturated bond.
- the monovalent hydrocarbon group having no aliphatic unsaturated bond belonging to R 3 include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group; phenyl group, tolyl group, xylyl group Aryl groups such as benzyl groups, etc., and monovalent fluorinated hydrocarbon groups include perfluoroalkyl groups such as trifluoropropyl groups and pentafluoroethyl groups.
- R 3 is preferably a methyl group, an ethyl group, or a phenyl group. Particularly, 90 mol to 100% of all R 1 are selected from a methyl group, an ethyl group, or a phenyl group. It is preferred that
- the silylalkyl group having a siloxane dendron structure includes a structure in which carbosiloxane units spread in a dendrimer shape, and is a functional group exhibiting high water repellency compared to a linear or simple branched polysiloxane unit.
- the co-modified organopolysiloxane of the present invention can obtain high compatibility with various oils such as hydrocarbon oil and ester oil as well as silicone oil due to the presence of the siloxane dendron structure.
- the co-modified organopolysiloxane of the present invention can obtain a unique and excellent feeling of use due to the presence of the siloxane dendron structure. Moreover, from the good balance of the combination with the hydrophilic group, the co-modified organopolysiloxane of the present invention can be provided with an excellent oil thickening effect and gelling ability. Furthermore, the silylalkyl group having a siloxane dendron structure is a functional group imparting advantageous properties that it can be used in combination with a wide range of cosmetic ingredients because it is chemically stable.
- R 4 is an alkyl group having 1 to 6 carbon atoms or a phenyl group.
- alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n- Examples include linear, branched or cyclic alkyl groups such as butyl, i-butyl, s-butyl, pentyl, neopentyl, cyclopentyl and hexyl.
- i specifies the generation of a silylalkyl group represented by L i
- the number of layers is a number of repetitions of the silylalkyl group is an integer of 1 ⁇ k when k
- the number of layers k is 1
- L i + 1 is a silylalkyl group when i is less than k
- is a methyl group or a phenyl group when i k.
- h i is a number in the range of 0 to 3.
- the number k of layers is industrially preferably an integer of 1 to 3, more preferably 1 or 2.
- the group represented by L 1 is represented as follows.
- R 2 and Z are the same groups as described above.
- L 1 is represented by the following general formula (3-2): It is represented by
- L 1 is represented by the following general formula (3-3): It is represented by
- h i each independently represents a number in the range of 0 to 3, and in the structure represented by the general formulas (3-1) to (3-3) when the number of layers is 1 to 3.
- H 1 , h 2 and h 3 are each independently a number in the range of 0-3.
- h i are particularly preferably numbers in the range of 0 to 1, and h i is particularly preferably 0.
- each Z is independently a divalent organic group, specifically, a silicon-bonded hydrogen atom, an alkenyl group, an acryloxy group
- examples include divalent organic groups formed by addition reaction of a functional group having an unsaturated hydrocarbon group such as a methacryloxy group at the end.
- the functional group is not limited to this, and can be selected as appropriate.
- each Z independently represents the following general formula: Is a group selected from divalent organic groups represented by the formula:
- each R 7 independently represents a substituted or unsubstituted, linear or branched alkylene group or alkenylene group having 2 to 22 carbon atoms, or 6 to 22 carbon atoms.
- R 5 represents a linear alkylene group such as ethylene group, propylene group, butylene group, hexylene group; methylmethylene group, methylethylene group, 1-methylpentylene group, 1,4-dimethylbutylene group.
- a branched alkylene group such as R 5 is preferably selected from an ethylene group, a propylene group, a methylethylene group, or a hexylene group.
- R 8 represents the following formula: Is a group selected from divalent organic groups represented by
- Z in L 1 is preferably a divalent organic group represented by the general formula: —R 7 — introduced by the reaction of a silicon-bonded hydrogen atom and an alkenyl group.
- Z is preferably a divalent organic group represented by the general formula: —R 7 —COO—R 8 — introduced by reaction of a silicon-bonded hydrogen atom with an unsaturated carboxylic ester group.
- the silylalkyl group represented by L is a 2 ⁇ L k L i
- Z is preferably an alkylene group having 2 to 10 carbon atoms, an ethylene group, a propylene group
- a group selected from a methylethylene group and a hexylene group is particularly preferable, and an ethylene group is most preferable.
- Saccharide-functional silicones and methods of making them are known in the art.
- US Pat. No. 4,591,652 describes a method for producing polyhydroxysilanes by reacting a silane having an amine-terminated substituent with an aldonic acid lactone.
- Japanese Patent 62-68820 discloses organopolysiloxanes containing saccharide residues made from aminosiloxanes and saccharide lactones.
- International Publication No. WO 94/29324 describes siloxanyl-modified compounds comprising a surfactant or surface modifier formed from an epoxy trisiloxane reaction product and a saccharide lactone, and methods for their preparation.
- International Publication No. WO 02/088456 describes amide-functional aminopolydiorganosiloxanes formed from aminosiloxanes and saccharide lactones.
- Synthetic methods for linking saccharides and siloxanes are also known in the art.
- US Pat. No. 5,831,080 describes organosilicone compounds containing glycoside groups made by hydrosilylation of allyl functional saccharide groups.
- US Pat. No. 6,517,933 B1 describes a hybrid polymer material comprising a set of natural building blocks containing saccharides and a synthetic set of building blocks containing polysiloxanes.
- a number of possible linking chemistries have been described. The entire disclosures of the above referenced patent technical documents are incorporated herein by reference.
- saccharide siloxanes can be modified by reaction of anionic or cationic monomers to functional sites on the sugar siloxane.
- Q is a group containing a saccharide component and has the formula X- (G 1 ) n- (G 2 ) m .
- Q is a sugar lactone amide alkyl group formed by amide bonding of a sugar lactone compound and an aminoalkyl group, but is not limited thereto.
- G 1 is a saccharide component having 5 to 12 carbon atoms
- b + c is 1 to 10
- b or c can be 0, and
- G 2 is additionally an organic or organosilicon group It is a saccharide component having 5 to 12 carbon atoms which may be substituted.
- the saccharide component is preferably a sugar residue structure derived from a hydroxy-functional saccharide, and is a structure derived from aldonic acid, oligoaldonic acid, uronic acid, oligouronic acid or a sugar residue derived therefrom. More preferably.
- a structure derived from a sugar residue derived from a sugar lactone compound (a sugar acid obtained by dehydrating cyclization in a molecule) is particularly preferable.
- the group containing a saccharide component represented by Q can impart hydrophilicity to the co-modified organopolysiloxane according to the present invention.
- sugar lactone compound obtained by intramolecular cyclization of a sugar acid examples include lactones derived from aldonic acid, uronic acid, or lactobionic acid. More specifically, aldonic acid lactones derived from reducing monosaccharides such as D-glucose, D-galactose, D-allose, D-aldose, D-mannose, D-gulose, D-idose, D-talose, etc.
- Lactones of aldonic acids derived from reducing disaccharides such as maltose, cellobiose, lactose, xylobiose, isomaltose, nigerose and cordobiose; aldonic acids derived from reducing trisaccharides such as maltotriose, vanose and isomaltotriose Lactones of aldonic acids derived from reducing oligosaccharides of tetrasaccharides or higher; lactones of uronic acids such as D-glucuronic acid, L-iduronic acid and mannuronic acid; lactones of lactobionic acid. These can be used alone or as a mixture.
- aldonolactone such as gluconolactone (GL) derived from D-glucose and lactobionolactone (LBL) derived from lactobionic acid are suitable.
- X is a linking group, and the following: —R 5 —NHC (O) —R 6 —; —R 5 —NHC (O) O—R 6 —; —R 5 —NH—C (O) —NH—R 6 —; —R 5 —O—R 6 —; —R 5 —CH (OH) —CH 2 —O—R 6 —; —R 5 —S—R 6 —; —R 5 —CH (OH) —CH 2 —NH—R 6 —; and —R 5 —N (R 1 ) —R 6 — Independently selected from the group consisting of: R 5 and R 6 are divalent spacer groups comprising (R a ) u (R b ) v (R c ) x , wherein u, v and x At least one must be 1, and R a and R c are either an alkylene group having 1 to 12 carbon atoms or a
- X is specifically a divalent functional group containing an amide, amino, urethane, urea, ester, ether, thioether, or acetal functional linking group, and is an amide obtained by the reaction of an amino group and a hydroxy functional saccharide.
- a linking group containing a bond is preferred.
- X is preferably an amide functional linking group obtained by reaction of an aminoalkyl group bonded to a silicon atom and a sugar lactone compound. That is, the co-modified organopolysiloxane of the present invention has a sugar lactone amide alkyl group obtained by the reaction of an aminoalkyl group bonded to a silicon atom and a sugar lactone compound as the group (Q) containing a saccharide component. Particularly preferred.
- Q is bonded to a silicon atom, -R 12 - (N (R 13 ) -R 14) w -NR 15 R 16 (Wherein R 12 is an alkylene group having 2 to 8 carbon atoms, R 13 , R 15 and R 16 are a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, but at least one of all R 13 , R 15 and R 16 is a hydrogen atom, R 14 is an alkylene group having 1 to 4 carbon atoms, and w is a number in the range of 0 ⁇ w ⁇ 6.
- an amino group represented by Particularly preferred is a sugar lactone amide alkyl group (Q 1 ) obtained by the reaction of a sugar lactone compound.
- the amino group is preferably an aminoalkyl group having 2 to 20 carbon atoms, particularly preferably an aminopropyl group or an aminoethylaminoisobutyl group.
- the sugar lactone compound is preferably aldonolactone or the like, and gluconolactone (GL) or lactobionolactone (LBL) is particularly preferable.
- the reaction between the aminoalkyl group and the sugar lactone compound is preferably carried out by using the sugar lactone compound in an amount of 1.0 to 1.3 times mol of the intermediate of the co-modified organopolysiloxane having an aminoalkyl group. It can be achieved by mixing in the solution and stirring at a solution concentration of 5 to 30% by weight under heating and reflux for 3 to 20 hours.
- the solvent used in this case lower alcohols such as methanol, ethanol, 1-propanol and 2-propanol are suitable.
- a linear co-modified organopolysiloxane represented by the following structural formula (1-1) is preferably exemplified.
- (n1 + n2 + n3 + n4) is a number in the range of 0 to 50, preferably 5 to 45, particularly preferably. Is 10-40.
- n1 is a number in the range of 0 to 45, preferably 5 to 45, and more preferably 10 to 45.
- n2 is a number in the range of 0 to 30, preferably 0 to 25, and more preferably 0 to 20.
- n3 is a number in the range of 0 to 20, preferably 1 to 15, and more preferably 1 to 10.
- n4 is a number in the range of 0 to 2, preferably 0.1 to 1.8, and more preferably 0.2 to 1.5.
- the co-modified organopolysiloxane according to the present application has a relatively low degree of polymerization, and can be oriented on various powder surfaces to impart appropriate water repellency. It can be used very suitably as a powder surface treatment agent used for surface treatment and dispersion of powders for use in foods.
- a linear co-modified organopolysiloxane represented by the following structural formula (1-1-1).
- R 1 , R 2 , L 1 and Q are the same groups as described above, and n1 to n4 are the same numbers as described above.
- the co-modified organopolysiloxane according to the present application is preferably exemplified by a co-modified organopolysiloxane represented by the following structural formula (1-1-A) or (1-1-B).
- Z, R 1 , R 2 , and Q 1 are the same groups as those described above, and R is the above-described R 1 , R 2 , L 1 , Q 1 is a group selected from. N1 to n4 are the same numbers as described above.
- the co-modified organopolysiloxane according to the present application has one carbon-carbon double at one end of the molecular chain compared to the organohydrogenpolysiloxane having a reactive functional group such as Si—H.
- a reactive organopolysiloxane intermediate is produced by addition reaction of the compound with the compound, optionally followed by a deprotection reaction.
- the reactive organopolysiloxane intermediate and the saccharide component It can be obtained by reacting a compound having The type of addition reaction in the first step is not particularly limited, but it is preferable to carry out the addition reaction in the presence of a hydrosilylation reaction catalyst from the viewpoint of reaction control, purity and yield. Further, the crude product of the co-modified organopolysiloxane obtained by this two-stage reaction may be a mixture with a compound having a saccharide component.
- the compound having a functional group capable of reacting with the compound having the saccharide component described above has a molecular chain.
- a compound having a reactive functional group such as an alkenyl group at one end and an amino group protected by an organic group at the other end is preferable.
- Such a compound having a protected amino group can be selected as desired, but industrially it is an allylamine whose amino group is protected by an organic group such as an organosilyl group, an amide group or an imide group. Is particularly preferred.
- Examples of the protective group for allylamine include 1,2-bisdimethylsilylethylene, 1,2-bisdimethylsilylbenzene, trimethylsilyl group, succinic anhydride, phthalic anhydride, dialkylmaleic anhydride, and benzoyl chloride. From the viewpoint of workability and ease of deprotection, 1,2-bisdimethylsilylethylene is particularly effective.
- the co-modified organopolysiloxane according to the present application is most preferably
- the amino group of the co-modified organopolysiloxane intermediate is deprotected
- it can be obtained by reacting the reactive organopolysiloxane intermediate after the deprotection reaction with a compound having a saccharide component (particularly a sugar lactone compound).
- component (A) is hydrophobic and comprises a silylalkyl group having a siloxane dendron structure exhibiting high water repellency and a hydrophilic saccharide component. Since it has a group to be contained in the same molecule and is excellent in lipophilic raw material and blending stability, it is useful as various treatment agents and cosmetic raw material components, especially surface treatment agents used in cosmetics, especially powders. It is extremely useful as a powder treatment agent used for surface treatment and powder dispersion.
- the degree of polymerization of the co-modified organopolysiloxane is relatively low, and the modification rate by the group containing a silylalkyl group having a siloxane dendron structure and a saccharide component is within a certain range.
- a co-modified organopolysiloxane having a chain structure represented by the structural formulas (1-1), (1-1-1), (1-1-A) and (1-1-B) is used. It can be particularly preferably exemplified.
- the co-modified organopolysiloxane according to the present invention has an accumulated hydrophilic group, it can be oriented strongly on the surface of various powders and impart appropriate water repellency. And can be suitably used as a powder surface treatment agent.
- the co-modified organopolysiloxane according to the present invention has better dispersion stability in a mixed oil system when used as a powder treatment agent, compared to known co-modified organopolysiloxanes. Even when a powder composition obtained by treating the body surface with a treatment agent is prepared and then dispersed in an oil agent as a dispersion medium, stable dispersion is difficult with conventional powder treatment agents.
- the obtained powder is also characterized by giving a powder dispersion in oil excellent in stability without causing aggregation and sedimentation.
- the co-modified organopolysiloxane of the present invention is well-familiar with various other hydrophilic and hydrophobic components in cosmetics and improves the dispersibility and stability of the powders in cosmetics including powders. can do. Therefore, the powder treatment agent of the present invention and the powder surface treatment agent of the present invention can improve the stability of cosmetics containing powder and the uniform dispersibility of the powder. And the cosmetic containing the powder surface-treated with the powder surface treatment agent has high stability, and the powder is uniformly dispersed in the cosmetic.
- the blending amount of the co-modified organopolysiloxane in the powder treatment agent of the present invention is not particularly limited as long as the powder treatment effect is exhibited, but it should be, for example, 50 to 100% by weight (mass)%. 70 to 100% by mass is preferable, and 90 to 100% by mass is more preferable.
- the powder treatment agent of the present invention may be a surface treatment of a powder in combination with the co-modified organopolysiloxane according to the present invention and another known surface treatment agent.
- other known surface treatment agents include, for example, methyl hydrogen polysiloxane, silicone resin, metal soap, silane coupling agent, silica, alumina, titanium oxide and other inorganic oxides, perfluoroalkyl silane, perfluoroalkyl
- a surface treatment agent using a fluorine compound such as a phosphoric ester salt can be used. Therefore, the powder surface treatment agent of the present invention may contain, for example, another surface treatment agent of 0.1 to 50% by mass, preferably 1 to 30% by mass, more preferably 5 to 10% by mass.
- the amount of the co-modified organopolysiloxane and the powder or colorant is 0 with respect to 100 parts by mass of the powder or colorant.
- the amount is preferably from 1 to 50 parts by weight, and particularly preferably from 0.5 to 40 parts by weight. If the amount is less than the lower limit, the effect of the surface treatment may not be sufficient, and if the treatment amount exceeds the upper limit, no significant change in texture occurs, and there is a tendency to form a uniform mixture of the powder and the co-modified organopolysiloxane. Increase.
- the co-modified organopolysiloxane according to the present invention can be used for the treatment of the powder surface using a known method. These methods are not particularly limited, but can be appropriately selected from the following methods, for example. 1. A method in which a target powder is surface-treated by dispersing it in a medium selected from organic solvents mixed with a treatment agent. 2. A method in which powder and a powder treatment agent are mixed and then surface treatment is performed using a pulverizer such as a ball mill or a jet mill. 3. A treatment method in which a treatment agent is mixed in a solvent, powder is dispersed and adsorbed on the surface, and then dried and sintered.
- the present invention also relates to (A) a powder composition comprising the co-modified organopolysiloxane according to the present invention and (B) a powder or a colorant.
- the powder composition can be obtained by mixing (B) powder or colorant and (A) the co-modified organopolysiloxane according to the present invention by the above method, etc. It does not matter the purpose such as improvement of dispersibility of body, premix for cosmetic raw materials.
- the powder dispersion in oil referred to in the present invention is a dispersion of the powder composition obtained as described above in an oil agent, or a co-modified organopolysiloxane dissolved or dispersed in an oil agent.
- the powder is added and mixed and dispersed, and its form is a liquid dispersion.
- Such a liquid dispersion may be referred to as a “slurry”.
- the oil agent is not particularly limited as long as a liquid dispersion can be prepared, and is generally used as a component of cosmetics. Usually, it is a liquid at room temperature, but is a solid such as wax. It may be a high-viscosity and viscous gum or paste that will be described later.
- the oil agent is preferably (C) one or more oil agents selected from silicone oil, a nonpolar organic compound or a low polarity organic compound that is liquid at 5 to 100 ° C.
- the dispersion in oil of the present invention can be appropriately prepared by a known method such as the following method. 1. A method in which the powder composition obtained as described above is added and dispersed in an oil agent such as ester oil or silicone oil. 2. A method in which a co-modified organopolysiloxane is dissolved or dispersed in the above-mentioned oil agent, a powder is added thereto, and the mixture is mixed with a dispersing device such as a ball mill, a bead mill, or a sand mill. And the obtained powder dispersion in oil can be mix
- an external preparation composition especially cosmetics
- the powder composition and the in-oil powder dispersion containing the co-modified organopolysiloxane according to the present invention can be suitably used as an external preparation composition, particularly a cosmetic or a cosmetic raw material.
- the powder or colorant (B) used in the powder composition and the powder dispersion in oil according to the present invention is generally used as a component of cosmetics, white and colored pigments, and constitution Contains pigments.
- White and colored pigments are used for coloring cosmetics, while extender pigments are used for improving the feel of cosmetics.
- the “powder” in the present invention white and colored pigments usually used in cosmetics, and extender pigments can be used without particular limitation. In this invention, it is preferable to mix
- Powder shape (spherical, rod-like, needle-like, plate-like, irregular shape, spindle-like, bowl-like, etc.), particle size (fog-like, fine particles, pigment grade, etc.), and particle structure (porous, nonporous) Etc.) is not limited at all, but the average primary particle diameter is preferably in the range of 1 nm to 100 ⁇ m.
- these powders or colorants are blended as pigments, one or more kinds selected from inorganic pigment powders, organic pigment powders, and resin powders having an average particle diameter in the range of 1 nm to 20 ⁇ m. Is preferably blended.
- the powder examples include inorganic powders, organic powders, surfactant metal salt powders (metal soaps), colored pigments, pearl pigments, metal powder pigments, and the like, which are combined. be able to. Furthermore, what gave the water repellency process to these surfaces can be mentioned.
- the powder or colorant is preferably treated with another powder dispersant or surface treatment agent.
- the inventors of the present application have disclosed International Publication No. WO2009 / 022621 and JP2011. -148784, JP2011-149017, JP2011-246704, JP2011-246705, JP2011-246706, International Publication WO2009 / 022621, International Publication WO2011 No. 049246, International Publication No. WO2011 / 049248, Japanese Patent Application No. 2011-286773 and the like, and the dispersion or surface treatment is carried out by the novel powder treatment agent and treatment method, or these novel powder treatments
- _Ka may be. Since these new treatment agents are further excellent in performance such as inherent feeling improvement effect, dispersion stability, etc., when used in combination with the new cosmetic raw material of the present invention, further cosmetic functions, feel, storage stability, etc. The improvement effect is expected.
- the silicone elastomer powder is a crosslinked product of a linear diorganopolysiloxane mainly composed of diorganosiloxy units (D units), and an organohydrogenpolysiloxane having a silicon-bonded hydrogen atom at the side chain or terminal and a side chain or
- a diorganopolysiloxane having an unsaturated hydrocarbon group such as an alkenyl group at the terminal can be suitably obtained by a crosslinking reaction under a hydrosilylation reaction catalyst.
- Silicone elastomer powder is softer and more resilient than silicone resin powder consisting of T units and Q units, and also has excellent oil absorption, so that it absorbs fats and oils on the skin and prevents breakup of makeup. it can.
- a moist feel can be imparted without reducing the suede feel of the silicone elastomer powder.
- the co-modified organopolysiloxane is blended in the cosmetic together with the silicone elastomer powder, the dispersion stability of the powder in the entire cosmetic is improved, and a cosmetic that is stable over time can be obtained.
- the silicone elastomer powder can take various shapes such as a spherical shape, a flat shape, and an indefinite shape.
- the silicone elastomer powder may be in the form of an oil dispersion.
- the cosmetic of the present invention is a silicone elastomer powder having a particle shape, and has an average primary particle diameter measured by observation using an electron microscope and / or laser diffraction / scattering method of 0.1. Silicone elastomer powder that falls within a range of ⁇ 50 ⁇ m and has a spherical primary particle shape can be suitably blended.
- the silicone elastomer constituting the silicone elastomer powder preferably has a hardness of 80 or less, more preferably 65 or less according to the type A durometer of JIS K 6253 “Testing method for hardness of vulcanized rubber and thermoplastic rubber”. .
- silicone elastomer powders in particular, specific examples of silicone elastomer spherical powder are the same as those disclosed by the applicants in paragraph 0168 of the above-mentioned Patent Document 5 (International Patent Publication No. WO2011 / 049248), As illustrated in the paragraphs 0150 to 0152, silicone elastomer powders subjected to various water repellency treatments may be used.
- the mixture of the co-modified organopolysiloxane and (B) powder or colorant is a form in which the powder is dispersed in the co-modified organopolysiloxane, and the amount of the powder in the mixture is particularly limited. Although not intended, the range of 50 to 99% by mass of the total mixture is preferable, and 80 to 90% by mass is more preferable.
- the oil agent used for the powder-in-oil dispersion according to the present invention is preferably (C) one or more selected from silicone oil, nonpolar organic compound, or low polar organic compound that is liquid at 5 to 100 ° C.
- the nonpolar organic compound and the low polarity organic compound are preferably hydrocarbon oil and fatty acid ester oil. These are components that are widely used as base materials for makeup cosmetics in particular.
- These oil agents include known vegetable oils, animal fats, higher alcohols, liquid fatty acid triglycerides, artificial sebum.
- One type or two or more types selected from fluorine-based oils may be used in combination.
- the co-modified organopolysiloxane exhibits excellent dispersibility even for these non-silicone oils, so that hydrocarbon oils and fatty acid ester oils can be stably blended into cosmetics, and the moisture retention characteristics of these non-silicone oils Can be maintained. Therefore, the co-modified organopolysiloxane can improve the temporal stability of these non-silicone oils in cosmetics.
- hydrocarbon oil and / or fatty acid ester oil together with silicone oil, in addition to the refreshing feel unique to silicone oil, it retains moisture on the skin and moisturizes skin and hair in cosmetics.
- a moisturizing feeling also referred to as “moist feeling”
- a smooth feel can be imparted, and there is an advantage that the temporal stability of the cosmetic is not impaired.
- cosmetics containing hydrocarbon oils and / or fatty acid ester oils and silicone oils apply these moisturizing ingredients (hydrocarbon oils and / or fatty acid ester oils) on the skin or hair in a more stable and uniform state. Therefore, the moisturizing effect of the moisturizing component on the skin is improved.
- cosmetics containing silicone oil together with non-silicone oils can give a smoother and moist feel. There is an advantage that you can.
- fluorinated oil examples include perfluoropolyether, perfluorodecalin, and perfluorooctane.
- the blending amount of the oil agent in the powder-in-oil dispersion of the present invention is not particularly limited, but is preferably blended within the range of 0.1 to 50% by mass in the cosmetic raw material. 5 to 25% by mass is more preferable.
- the co-modified organopolysiloxane, a powder composition containing the co-modified organopolysiloxane, or a powder dispersion in oil can be suitably used as an external preparation composition, in particular, as a cosmetic or a cosmetic raw material.
- External preparation compositions in particular, external preparation compositions that are cosmetics or pharmaceuticals are included in the present invention.
- the co-modified organopolysiloxane, the powder composition containing the same, or the powder dispersion in oil is suitable as a makeup cosmetic material, and various makeup cosmetics containing these are: It is included in a particularly preferable form of the present invention.
- the cosmetic of the present invention can further contain (D) water, and the cosmetic of the present invention can take the form of an oil-in-water emulsion or a water-in-oil emulsion.
- the cosmetic of the present invention exhibits excellent emulsion stability and feeling of use.
- the preparation of the water-containing cosmetic and the emulsion cosmetic is the same as that disclosed by the applicants in paragraphs 0128 to 0146 of Patent Document 5 (International Patent Publication No. WO2011 / 049248).
- the co-modified organopolysiloxane is mixed with powder and oil in the presence of an alcohol such as ethanol to form a cosmetic raw material that is a premix of an emulsion that is a uniform solubilized product,
- a uniform oil-in-water emulsion or a water-in-oil emulsion type cosmetic can be produced by mixing the premix with water using the above-described apparatus.
- the cosmetic of the present invention can further contain (E) other surfactant.
- These surfactants are components that function as a skin or hair washing component or an oil emulsifier, and a desired one can be selected according to the type and function of the cosmetic.
- the other surfactant is selected from the group consisting of an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, and a semipolar surfactant.
- the co-modified organopolysiloxane is preferably used in combination with polyoxyalkylene-modified silicone, polyglyceryl-modified silicone, glyceryl-modified silicone, sugar alcohol-modified silicone, and these silicone-based nonionic surfactants are alkyl Those in which branching, linear silicone branching, siloxane dendrimer branching, and the like are applied as needed simultaneously with the hydrophilic group can also be suitably used.
- one or more polyhydric alcohols and / or lower monohydric alcohols can be used as the component (F) according to the purpose.
- These alcohols are the same as those disclosed by the applicants in paragraphs 0159 and 0160 of Patent Document 5 (International Patent Publication No. WO2011 / 049248).
- one or more inorganic salts and / or organic acid salts can be used as the component (G) depending on the purpose.
- These salts are common to those disclosed by the applicants in paragraph 0161 of the above-mentioned Patent Document 5 (International Patent Publication No. WO2011 / 049248).
- component (H) crosslinkable organopolysiloxane, organopolysiloxane elastomer spherical powder, silicone resin, acrylic silicone dendrimer copolymer, silicone raw rubber, polyamide-modified silicone, alkyl-modified At least one selected from the group consisting of silicone wax and alkyl-modified silicone resin wax can be used.
- silicone components are common to those disclosed by the applicants in paragraphs 0161 to 0193 of the above-mentioned Patent Document 5 (International Patent Publication No. WO2011 / 049248).
- (H-1) polyoxypropylene disclosed in International Patent Publication No.
- WO2011 / 028770 PITUITUS SILICONE FLUIDS can be mentioned, and at least one selected from these can be used in the cosmetic of the present invention depending on the purpose. it can.
- liquid and slightly crosslinkable organopolysiloxanes proposed by the present applicants in Japanese Patent Application (Japanese Patent Application No. 2010-289722) and priority claims based thereon can also be used in the present invention.
- one or more water-soluble polymers can be used as the component (J) depending on the purpose.
- These water-soluble polymers are the same as those disclosed by the applicants in paragraph 0201 of the above-mentioned Patent Document 5 (International Patent Publication No. WO2011 / 049248).
- one or more ultraviolet protection components can be used as the component (K) depending on the purpose.
- These UV protection components are common to the organic and inorganic UV protection components disclosed by the applicants in paragraphs 0202 to 0204 of the above-mentioned Patent Document 5 (International Patent Publication No. WO2011 / 049248).
- UV protective components that can be preferably used include fine particle titanium oxide, fine particle zinc oxide, 2-ethylhexyl paramethoxycinnamate, 4-tert-butyl-4′-methoxydibenzoylmethane, hexyl diethylaminohydroxybenzoyl benzoate, benzoate Triazole ultraviolet absorber and 2,4,6-tris [4- (2-ethylhexyloxycarbonyl) anilino] 1,3,5-triazine ” ⁇ INCI: octyltriazone ⁇ , 2,4-bis ⁇ [4- (2-Ethyl-hexyloxy) -2-hydroxy] phenyl ⁇ -6- (4-methoxy Cyphenyl) -1,3,5-triazine is at least one selected from the group consisting of triazine-based ultraviolet absorbers such as ⁇ INCI: bis-ethylhexyloxyphenol methoxyphenyl triazine, trade name
- UV protection components are widely used, are easily available, and have a high UV protection effect, so that they can be suitably used.
- the ultraviolet protective component is added to the cosmetic while improving the overall cosmetic feel and storage stability by using the cosmetic raw material containing the co-modified organopolysiloxane in combination with the ultraviolet protective component. Therefore, it is possible to impart an excellent UV protection function to cosmetics.
- the ultraviolet protection component is preferably blended in a total amount of 0.1 to 40.0% by weight (mass) based on the total cosmetic, and 0.5 to 15. It is more preferable to blend in the range of 0% by weight (mass).
- the cosmetics of the present invention include oil-soluble gelling agents, organically modified clay minerals, antibacterial preservatives, physiologically active ingredients, skin-beautifying ingredients, pH adjusters, antioxidants, solvents, Various components such as a chelating agent, a moisturizing component, and a fragrance can be used as long as the object of the present invention is not impaired.
- These optional ingredients for cosmetics are the same as those disclosed by the applicants in paragraphs 0207, 0208, 0220 to 0228 of the above-mentioned Patent Document 5 (International Patent Publication No. WO2011 / 049248).
- the cosmetics of the present invention include skin care products such as skin cleansing products, skin care products, makeup products, antiperspirant products, UV protection products; hair cleansing products, hair styling products, Hair coloring products, hair nourishing products, hair rinse products, hair conditioner products, hair treatment products, etc .;
- Examples of the medicament of the present invention include, but are not limited to, hair growth agents, hair growth agents, analgesics, bactericides, anti-inflammatory agents, refreshing agents, and skin antiaging agents.
- the type, form, and container of the external preparation composition according to the present invention are the same as those disclosed by the applicants in paragraphs 0230 to 0233 of the above-mentioned Patent Document 5 (International Patent Publication No. WO2011 / 049248).
- the co-modified organopolysiloxane is particularly useful as a raw material for various makeup cosmetics, and the cosmetic according to the present invention comprises (A) the co-modified organopolysiloxane, (B) powder or colorant. And (C) a makeup cosmetic comprising a silicone oil that is liquid at 5 to 100 ° C., a non-polar organic compound or a low-polar organic compound.
- Such makeup cosmetics include foundations, liquid foundations, oily foundations, makeup bases, white powders, face powders, lipsticks, lip balms, creams, lip glosses, eye shadows, eyeliners, eye creams, eyebrows, eyelash cosmetics, Examples include eyebrow pencil, eyebrow brush, mascara, blusher, cheek cosmetics (blush color, cheek rouge), nail polish, pedicure, nail color, nail lacquer, enamel remover, nail polish and the like.
- the viscosity is a measured value at 25 ° C.
- the Me 3 SiO group (or Me 3 Si group) is represented as “M”
- the Me 2 SiO group is represented as “D”
- the MeHSiO group is represented as “D H ”
- the methyl group in D is represented by the units have been modified by any of the substituents denoted as D R.
- Example 1 Synthesis of Co-modified Organopolysiloxane Compound P1> Stepwise, in the presence of 0.1 g of platinum catalyst, 31.3 g of tristrimethylsiloxyvinylsilane and 6.3 g of allylamine A were added to 61.3 g of methylhydrogenpolysiloxane represented by the average composition formula MD 15 DH 3 M in the reactor. The reaction was carried out at 75-90 ° C. for 10 hours with stirring under nitrogen flow.
- Example 2 Synthesis of Co-modified Organopolysiloxane Compound P2>
- 80 g of methylhydrogenpolysiloxane represented by the average composition formula MD 33 DH 3 M was charged stepwise with 18.5 g of tristrimethylsiloxyvinylsilane and 6.3 g of allylamine A in the presence of 0.1 g of a platinum catalyst. The reaction was carried out at 75-90 ° C. for 10 hours with stirring under nitrogen flow.
- R 1 and R A have the structures shown below, and R 2 is a gluconolactone amidopropyl group obtained by a reaction between an aminopropyl group and gluconolactone.
- R 1 —C 2 H 4 —Si (OSiMe 3 ) 3
- R A —C 3 H 6 NH 2
- R 1 , R A and R 3 have the structures shown below, and R 2 is a gluconolactone amidopropyl group obtained by the reaction of an aminopropyl group and gluconolactone.
- R 1 —C 2 H 4 —Si (OSiMe 3 ) 3
- R A —C 3 H 6 NH 2
- R 3 -C 12 H 25
- organopolysiloxane compound R2 used in the comparative experiment is the following product.
- ES5612 Polyether-modified silicone (trade name: ES5612, manufactured by Toray Dow Corning)
- Table 1 summarizes the average composition formulas of “co-modified organopolysiloxane compounds P1” to “P3” according to the present invention synthesized by the above method and “comparative co-modified organopolysiloxane compound R1” according to the comparative example.
- R 1 —C 2 H 4 —Si (OSiMe 3 ) 3
- R 2 Gluconolactone amidopropyl group obtained by reaction of aminopropyl group and gluconolactone
- R 3 -C 12 H 25
- the evaluation criteria are as follows. ⁇ : A low-viscosity slurry can be produced, and there is no thickening over time. ⁇ ⁇ : Low-viscosity slurry can be produced, and gelation occurs with time. ⁇ : High-viscosity slurry can be produced, and the viscosity decreases with time. ⁇ -: Slurry cannot be produced.
- the novel co-modified organopolysiloxanes P1 to P3 according to the present invention were able to produce a slurry that was a fine-particle titanium oxide dispersion in oil, whereas the comparative compounds R1 and R2 were produced at the time of production. Even if it was gelled or manufactured, there was a problem in stability, and a remarkable difference was observed in the performance as a powder treatment agent. This is because the product of the present invention has a siloxane dendron structure as compared with the comparative compound, and therefore exhibits excellent dispersion performance due to a high steric effect.
- the sugar residue which is a hydrophilic group of the product of the present invention has a plurality of hydroxy groups, it is considered to have a high affinity for the powder. That is, in the product of the present invention, the molecular structure is highly controlled as compared with the comparative product, so that it is considered possible to produce a good titanium oxide slurry.
- Decamethylcyclopentasiloxane, dimethicone cross polymer (Note 2) 2 parts 13.1,3-butylene glycol 5 parts 14. Glycerin 3 parts15. Sodium chloride 0.5 part16. Preservative appropriate amount17. Purified water remaining amount 18.
- Step 1 Components 1, 4, 6, 7, and 12 were mixed with stirring.
- Step 2 Components 2, 3, 5, and 8 to 11 were kneaded and mixed using a three-roll.
- Step 3 The mixture of Step 2 was added to the mixture obtained in Step 1 under stirring, and the mixture was further stirred and mixed.
- Step 4 An aqueous phase in which components 13 to 18 were uniformly dissolved was added to the mixture obtained in Step 3 and emulsified, and filled into a container to obtain a product.
- the obtained W / O type liquid foundation was excellent in emulsification stability, excellent in water resistance and makeup sustainability when used, with little noticeable kilos and wrinkles, and was excellent in spreading and sticking.
- Step 1 Components 1, 2, 5, 7, 8, 13, 14, and 15 were mixed with stirring.
- Step 2 Components 3, 4, 6, 9 to 12 were kneaded and mixed using three rolls.
- Step 3 The mixture of Step 2 was added to the mixture obtained in Step 1 under stirring, and the mixture was further stirred and mixed.
- Step 4 An aqueous phase in which components 16 to 21 were uniformly dissolved was added to the mixture obtained in Step 3 and emulsified, and filled into a container to obtain a product.
- the obtained W / O type liquid foundation was excellent in emulsification stability, excellent in water resistance and makeup sustainability, indistinguishable from kilos and wrinkles, had a light touch and excellent adhesion when used.
- Liquid Foundation (O / W type) (component) 1. Carboxydecyltrisiloxane 1 part2. Polysorbate 80 1.2 parts3. Sorbitan sesquioleate 0.2 part4. 4. Glyceryl stearate 1.5 parts Behenyl alcohol 2.5 parts6. Cyclopentasiloxane 8 parts7. Dimethicone (6cs) 3 parts8. Squalane 3 parts 9. Isotridecyl isononanoate 3 parts 10. 10. 3 parts glyceryl tricaprylate caprate Co-modified organopolysiloxane P3 0.2 part 12. Silicone-treated titanium oxide 8.5 parts13. Silicone-treated red iron oxide 0.4 part14. Silicone-treated yellow iron oxide 1 part15. 16. Silicone-treated black iron oxide 0.1 part 16.1.3-butylene glycol 8 parts Sodium hydroxide aqueous solution (1%) 15 parts 18. Carbomer (2%) 10 parts 19. Purified water remaining
- Step 1 1-6 and 8-10 were mixed with stirring.
- Step 2 7 and 11 to 15 were kneaded and mixed using three rolls.
- Step 3 The mixture of Step 2 was added to the mixture obtained in Step 1 under stirring, and the mixture was further stirred and mixed.
- Step 4 An aqueous phase in which components 16 to 19 were uniformly dissolved was added to the mixture obtained in Step 3 and emulsified, and filled into a container to obtain a product.
- the obtained O / W type liquid foundation was excellent in emulsification stability, excellent in water resistance and makeup sustainability, and not easily noticeable in kilos and wrinkles, and excellent in spreading and sticking.
- Step 1 Ingredients 1-9 are mixed.
- Step 2 Components 10 to 13 are mixed.
- Step 3 The aqueous phase obtained in Step 2 was added to the mixture obtained in Step 1 under stirring and emulsified, and then filled into a container to obtain a product.
- This Formulation Example 4 is a sunscreen cream comprising a dispersion of inorganic ultraviolet protection components treated with the co-modified polyorganosiloxane P3 according to the present invention.
- This sunscreen cream contains a large amount of water phase component and inorganic UV protection component, but does not cause separation of oily components and powder, and can be stocked for a long time at around 40 ° C (summer temperature), Excellent stability over time. Furthermore, when used, it has an excellent feeling of use with good spread and reduced stickiness, no irritation, and a durable UV protection effect. Such good usability was not changed even before and after storage at around 40 ° C.
- Step 1 Ingredients 1-9 are mixed.
- Step 2 Add the mixture of components 10 to 12 to the mixture of Step 1 and emulsify.
- the obtained sunscreen had a reduced stickiness when applied on the skin, had an excellent feeling of use, and provided a durable UV protection effect.
- Base cream (component) 1. Dimethylpolysiloxane (2 mm 2 / s) 2 parts Decamethylcyclopentasiloxane 10 parts3. Polyether-modified silicone (Note 1) 2 parts 4. Cetyl isooctanoate 5 parts5. Co-modified organopolysiloxane P2 0.5 part6. 6. 2-ethylhexyl paramethoxycinnamate 2 parts Silicone elastomer (Note 2) 4 parts8. Silicone-treated titanium oxide 6 parts9. Silicone-treated red iron oxide 0.3 part10. Silicone-treated yellow iron oxide 0.7 parts11. Silicone-treated black iron oxide 0.07 parts 12. Organically modified bentonite 0.5 part13.
- Step 1 Components 1 to 15 are mixed and dispersed.
- Step 2 Components 16-19 are mixed.
- Step 3 The mixture obtained in Step 1 was added to the mixture obtained in Step 1, emulsified at room temperature, and filled into a container to obtain a product.
- This foundation cream had good elongation spread, and was excellent in the uniformity of the decorative film and the adhesion to the skin. Also, there were few noticeable textures, wrinkles and pores. And it had a stable emulsified state.
- Step 1 Components 1 to 18 are dissolved by heating.
- Step 2 Components 19 to 21 are mixed.
- Step 3 Add the mixture of Step 2 to the mixture of Step 1 and further stir and mix.
- Process 4 The component 22 was added to the mixture of the process 3, and it filled with the airtight container, and obtained the product.
- This lipstick had a high-class feeling, good spread, uniformly applied to the lips, and gave a finish with excellent gloss and transparency. Furthermore, after application, the stickiness on the lips was not felt, and the storage stability when the product was stocked was also good.
- Liquid lipstick (component) 1. Phenylmethyl silicone 10 parts2. Isopropyl myristate 10 parts3. 3. Cyclopentasiloxane / (acrylates / polytrimethylsiloxy methacrylate) copolymer (Note 1) 5 parts 4. Part of fumed silicic acid 0.1 parts Spherical urethane powder 5 parts6. 6. Cyclopentasiloxane / trimethylsiloxysilicic acid (Note 2) 5 parts Co-modified organopolysiloxane P2 1 part8. Polyether-modified silicone (Note 3) 1.5 parts9. Octyl methoxycinnamate 1 part10. Red 202 No. 0.5 part11. Titanium oxide 0.5 part12.
- Lipstick (ingredient) 1. Polyethylene-polypropylene copolymer 5 parts2. Candelilla wax 5 parts3. Carnauba wax 5 parts4. Vaseline 10 parts 5.2 cetyl 2-ethylhexanoate 10 parts 6. Diglycerin diisostearate 14.5 parts7. Macadamia nut oil 7 parts8. 8. Inulin stearate (Leopard ISK2 manufactured by Chiba Flour Mills) 23 parts9. Co-modified organopolysiloxane P3 2 parts10. Red No. 201 1 part11. Red No. 202 3 parts 12. Yellow No. 4 aluminum lake 3 parts13. Titanium oxide 1 part14. Black iron oxide 0.5 part15. Iron oxide mica titanium 10 parts16. Preservative appropriate amount17. Perfume
- the obtained eye shadow stretched smoothly during use and was excellent in color development.
- the obtained mascara had a deep black appearance when used and was excellent in gloss.
- the adhesion to the heel was good, the curl / volume effect of the heel was excellent, and the durability was excellent.
- Patent Document 5 describes emulsions, lip glosses, oily foundations, water-in-oil emulsion transparent antiperspirant compositions, non-water as compositions that can be replaced by the co-modified organopolysiloxane according to the present invention.
- paragraphs 0559 to 0501 disclose the following formulation examples.
- Example 1 Emulsification foundation [Example 2 Liquid foundation] [Example 3 Foundation] [Example 4: Water-in-oil cream] [Example 5] Water-in-oil emulsion composition [Example 6] Water-in-oil emulsified lipstick (liquid) [Example 7 Liquid lipstick] [Example 8 Lipstick] [Example 9 Sunscreen emulsion] [Example 10 Emulsion] [Example 11: Sun cut cream] [Example 12: UV cut water-in-oil emulsion] [Example 13: Sunscreen agent] [Example 14] Water-in-oil emulsified sunscreen [Example 15 O / W cream] [Example 16 Eye shadow] [Example 17 mascara] [Example 18: mascara] [Example 19: Solid powder eye shadow] [Example 20: Pressed powder cosmetic] [Example 21: Powder foundation] [Example 22: Pressed foundation] [Example 19
- the co-modified organopolysiloxane according to the present invention can be supplied at a relatively low cost, especially on an industrial scale, and has excellent surface treatment performance and surface activity. It can be used for various purposes. For example, varnishes and paint additives with excellent heat resistance, weather resistance, and electrical properties, polyol main agents, foam stabilizers and modifiers for various urethanes and foams, mold release agents, release agents, antifoaming agents, greases and oils Compound, insulation / polish / water repellent / heat medium / refrigerant / lubricating oil, rubber and resin modifiers and additives, surface treatments, silane coupling agents and blends and modifiers Examples include precursors, coating / sealing materials for construction / lining, protective agents for optical fibers / electric wires, lubricants, buffering agents, and the like, but are not limited thereto.
Abstract
Description
「[1] 下記一般式(1)
R1 aR2 bL1 cQdSiO(4―a―b―c―d)/2 (1)
で表される、シロキサンデンドロン構造を有する基(L1)およびサッカリド成分を含有する基(Q)を有する共変性オルガノポリシロキサン。
{一般式(1)中、
R1は置換もしくは非置換の炭素原子数1~30の一価炭化水素基または水素原子である。
R2は、炭素原子数6~30の、置換もしくは非置換の、直鎖状もしくは分岐状の一価炭化水素基、または、下記一般式(2-1);
表し、L1はi=1のときの下記一般式(3)で示される、シロキサンデンドロン構造を有するシリルアルキル基であり、
一般式(3):
Qはサッカリド成分を含有する基であり、式X-(G1)n-(G2)mを有し、式中G1は、炭素原子数5~12のサッカリド成分であり、n+mは1~10であり、nまたはmは0であることができ、G2は、有機または有機ケイ素基で追加的に置換されていてもよい、炭素原子数5~12のサッカリド成分であり、
Xは連結基であって、以下の:
-R5-NHC(O)-R6-;
-R5-NHC(O)O-R6-;
-R5-NH-C(O)-NH-R6-;
-R5-O-R6-;
-R5-CH(OH)-CH2-O-R6-;
-R5-S-R6-;
-R5-CH(OH)-CH2-NH-R6-;および
-R5-N(R1)-R6-
からなる群から独立して選択され、R5およびR6は、(Ra)u(Rb)v(Rc)xを含む二価のスペーサー基であり、ここでu、vおよびxの少なくとも1つは1でなければならず、RaおよびRcは、炭素原子数1~12のアルキレン基または(RdO)pで表されるポリオキシアルキレン基のいずれかであり、ここでRdはHまたは炭素原子数1~12であり、pは1~50の任意の整数であり、各(RdO)は、同じであっても異なっていてもよく、Rbは-N(Re)-であり、ここでReはHまたは炭素原子数1~12のアルキル基であり、またはX-Yであり、ここでXは以前に定義した通りかR5であり、Yはカルボン酸、ホスフェート、サルフェート、スルホネート、または第四級アンモニウム基である。)
a、b、c及びdは、1.0≦a+b≦2.5、 0.001≦c≦1.5、及び0.001≦d≦1.5となる範囲の数である。}
[2] 前記のQが、アミノ基とヒドロキシ官能サッカリドの反応により得られるサッカリド成分を含有する基である、[1] に記載の共変性オルガノポリシロキサン。
[3] 前記のQが、ケイ素原子に結合し、
-R12-(N(R13)-R14)w-NR15R16
(式中、R12は炭素数2~8のアルキレン基であり、
R13、R15、R16は水素原子又は炭素数1~10の一価有機基であるが、全てのR13、R15およびR16のうち少なくとも一つは水素原子であり、
R14は炭素数1~4のアルキレン基であり、wは0≦w≦6の範囲の数である。)
で示されるアミノ基と、
糖ラクトン化合物の反応により得られる糖ラクトンアミドアルキル基である、[1]または[2]に記載の共変性オルガノポリシロキサン。
[4] 下記構造式(1-1)で表される、[1]~[3]のいずれかに記載の共変性オルガノポリシロキサン。
[5] 下記構造式(1-1-1)で表される、[1]~[4]のいずれかに記載の共変性オルガノポリシロキサン。
[6] 構造式(1-1)または構造式(1-1-1)において、L1が下記一般式(2-1)または一般式(2-2)で表される官能基であり、
一般式(2-1):
Qがケイ素原子に結合し、
-R12-(N(R13)-R14)w-NR15R16
(式中、R12は炭素数2~8のアルキレン基であり、
R13、R15、R16は水素原子又は炭素数1~10の一価有機基であるが、全てのR13、R15およびR16のうち少なくとも一つは水素原子であり、
R14は炭素数1~4のアルキレン基であり、wは0≦w≦6の範囲の数である。)
で示されるアミノ基と、
糖ラクトン化合物の反応により得られる糖ラクトンアミドアルキル基(Q1)である、[4]または[5]に記載の共変性オルガノポリシロキサン。
[7] 下記構造式(1-1-A)または(1-1-B)で表される、[6]に記載の共変性オルガノポリシロキサン。
[8] 以下の工程(I)~工程(III)を含む、[1]~[7]のいずれかに記載の共変性オルガノポリシロキサンの製造方法。
工程(I):シロキサンデンドロン構造を有する化合物、
直接または脱保護反応後に、サッカリド成分を有する化合物と反応可能な官能基を有する化合物、および
オルガノハイドロジェンポリシロキサンを、
共ヒドロシリル化させることにより、直接または脱保護反応後にサッカリド成分を有する化合物と反応可能な官能基を持った共変性オルガノポリシロキサン中間体を製造する工程。
工程(II):工程(I)で得られた共変性オルガノポリシロキサン中間体を、その必要に応じ、脱保護反応することにより、サッカリド成分を有する化合物と反応可能な官能基を持った共変性オルガノポリシロキサン中間体を製造する工程
工程(III): 工程(I)または工程(II)で得られた共変性オルガノポリシロキサン中間体と、
サッカリド成分を有する化合物を反応させる工程。
[9] 前記の工程(II)が必須の工程であり、
脱保護反応後に、サッカリド成分を有する化合物と反応可能な官能基を有する化合物が、オルガノシリル基によって保護されたアリルアミンであることを特徴とする、[8]に記載の共変性オルガノポリシロキサンの製造方法。
[10] 前記のオルガノシリル基が、ビスジメチルシリルエチレン基であることを特徴とする、[9]に記載の共変性オルガノポリシロキサンの製造法。
[10-1] 最も好適には、以下の工程(I)~工程(III)を含む、前記の[8]~[10]のいずれかに記載の共変性オルガノポリシロキサンの製造方法。
工程(I-A):シロキサンデンドロン構造を有する化合物、
ビスジメチルシリルエチレン基によって保護されたアリルアミン、および
オルガノハイドロジェンポリシロキサンを、
共ヒドロシリル化させることにより、脱保護反応後にサッカリド成分を有する化合物と反応可能な官能基を持った共変性オルガノポリシロキサン中間体を製造する工程。
工程(II-B):工程(I)で得られた共変性オルガノポリシロキサン中間体を、脱保護反応することにより、サッカリド成分を有する化合物と反応可能な官能基を持った共変性オルガノポリシロキサン中間体を製造する工程
工程(III): 工程(I)または工程(II)で得られた共変性オルガノポリシロキサン中間体と、
サッカリド成分を有する化合物を反応させる工程。
[11] [1]~[7]のいずれかに記載の共変性オルガノポリシロキサンを含有する表面処理剤。
[12] [1]~[7]のいずれかに記載の共変性オルガノポリシロキサンを含有する粉体処理剤。
[13] (A)[1]~[7]のいずれかに記載の共変性オルガノポリシロキサン
および(B)粉体又は着色剤
を含有してなる粉体組成物。
[14] 前記の(B)成分が、平均粒子径が1nm~20μmの範囲にある無機顔料粉体、有機顔料粉体、樹脂粉体よりなる群より選ばれる1種又は2種類以上である[13]に記載の粉体組成物。
[15] (A)[1]~[7]のいずれかに記載の共変性オルガノポリシロキサン、(B)粉体又は着色剤および(C)5~100℃で液状であるシリコーンオイル、非極性有機化合物または低極性有機化合物から選択される1以上の油剤を含有してなる油中粉体分散物。
[16] [1]~[7]のいずれかに記載の共変性オルガノポリシロキサンを含有する外用剤組成物。
[17] 化粧料または医薬である[16]に記載の外用剤組成物。
[18] [13]または[14]に記載の粉体組成物を含有する化粧料。
[19] [15]に記載の油中粉体分散物を含有する化粧料。
[20] (A)[1]~[7]のいずれかに記載の共変性オルガノポリシロキサン、
(B)粉体又は着色剤 および
(C)5~100℃で液状であるシリコーンオイル、非極性有機化合物または低極性有機化合物 を含有してなる、メークアップ化粧料。」により達成される。
一般式(1):
R1 aR2 bL1 cQdSiO(4―a―b―c―d)/2 (1)
R1は置換もしくは非置換の炭素原子数1~30の一価炭化水素基または水素原子である。
R2は、炭素原子数6~30の、置換もしくは非置換の、直鎖状もしくは分岐状の一価炭化水素基、または、下記一般式(2-1);
は水素原子であり、R11のうち少なくとも1つは前記一価炭化水素基である。tは2~
10の範囲の数であり、rは1~500の範囲の数である)若しくは下記一般式(2-2
);
表し、
L1はi=1のときの下記一般式(3);
R3は炭素原子数1~30の、置換若しくは非置換の、直鎖状若しくは分岐状の一価炭化水素基を表し、R4はそれぞれ独立して炭素原子数1~6のアルキル基又はフェニル基を表し、Zは二価有機基を表し、iはLiで示されるシリルアルキル基の階層を表し、該シリルアルキル基の繰り返し数である階層数がkのとき1~kの整数であり、階層数kは1~10の整数であり、Li+1はiがk未満のときは該シリルアルキル基であり、i=kのときはR4であり、hiは0~3の範囲の数である)で表される、シロキサンデンドロン構造を有するシリルアルキル基を表し、
Qはサッカリド成分を含有する基であり、式X-(G1)n-(G2)mを有し、式中G1は、炭素原子数5~12のサッカリド成分であり、n+mは1~10であり、nまたはmは0であることができ、G2は、有機または有機ケイ素基で追加的に置換されていてもよい、炭素原子数5~12のサッカリド成分であり、
Xは連結基であって、以下の:
-R5-NHC(O)-R6-;
-R5-NHC(O)O-R6-;
-R5-NH-C(O)-NH-R6-;
-R5-O-R6-;
-R5-CH(OH)-CH2-O-R6-;
-R5-S-R6-;
-R5-CH(OH)-CH2-NH-R6-;および
-R5-N(R1)-R6-
からなる群から独立して選択され、R5およびR6は、(Ra)u(Rb)v(Rc)xを含む二価のスペーサー基であり、ここでu、vおよびxの少なくとも1つは1でなければならず、R7およびR9は、炭素原子数1~12のアルキレン基または(RdO)pで表されるポリオキシアルキレン基のいずれかであり、ここでRdはHまたは炭素原子数1~12であり、pは1~50の任意の整数であり、各(RdO)は、同じであっても異なっていてもよく、Rbは-N(Re)-であり、ここでReはHまたは炭素原子数1~12のアルキル基であり、またはX-Yであり、ここでXは以前に定義した通りかR5であり、Yはカルボン酸、ホスフェート、サルフェート、スルホネート、または第四級アンモニウム基である。)
a 、b、c及びdは、1.0≦a+b≦2.5、 0.001≦c≦1.5、及び0.001≦d≦1.5となる範囲の数である。
-R5-NHC(O)-R6-;
-R5-NHC(O)O-R6-;
-R5-NH-C(O)-NH-R6-;
-R5-O-R6-;
-R5-CH(OH)-CH2-O-R6-;
-R5-S-R6-;
-R5-CH(OH)-CH2-NH-R6-;および
-R5-N(R1)-R6-
からなる群から独立して選択され、R5およびR6は、(Ra)u(Rb)v(Rc)xを含む二価のスペーサー基であり、ここでu、vおよびxの少なくとも1つは1でなければならず、RaおよびRcは、炭素原子数1~12のアルキレン基または(RdO)pで表されるポリオキシアルキレン基のいずれかであり、ここでRdはHまたは炭素原子数1~12であり、pは1~50の任意の整数であり、各(RdO)は、同じであっても異なっていてもよく、Rbは-N(Re)-であり、ここでReはHまたは炭素原子数1~12のアルキル基であり、またはX-Yであり、ここでXは以前に定義した通りかR5であり、Yはカルボン酸、ホスフェート、サルフェート、スルホネート、または第四級アンモニウム基である。
-R12-(N(R13)-R14)w-NR15R16
(式中、R12は炭素数2~8のアルキレン基であり、
R13、R15、R16は水素原子又は炭素数1~10の一価有機基であるが、全てのR13、R15およびR16のうち少なくとも一つは水素原子であり、
R14は炭素数1~4のアルキレン基であり、wは0≦w≦6の範囲の数である。)
で示されるアミノ基と、
糖ラクトン化合物の反応により得られる糖ラクトンアミドアルキル基(Q1)であるであることが特に好ましい。この時、上記のアミノ基は、炭素原子数が2~20のアミノアルキル基であることが好ましく、アミノプロピル基またはアミノエチルアミノイソブチル基であることが特に好ましい。また、糖ラクトン化合物は、アルドノルラクトン等であることが好ましく、グルコノラクトン(GL)またはラクトビオノラクトン(LBL)が特に好ましい。ここで、アミノアルキル基と糖ラクトン化合物との反応は、好適には糖ラクトン化合物をアミノアルキル基を有する共変性オルガノポリシロキサンの中間体に対して1.0~1.3倍モル用いて溶媒中で混合し、溶液濃度5~30重量%で加熱還流下に3~20時間攪拌することによって達成できる。この際用いる溶媒としてはメタノール、エタノール、1-プロパノール、2-プロパノールなどの低級アルコールが適している。
n1は0~45の範囲の数であり、好適には5~45であり、より好適には10~45である。
n2は0~30の範囲の数であり、好適には0~25であり、より好適には0~20である。
n3は0~20の範囲の数であり、好適には1~15であり、より好適には1~10である。
n4は0~2の範囲の数であり、好適には0.1~1.8であり、より好適には0.2~1.5である。n1~n4は前記の範囲にある場合、本願に係る共変性オルガノポリシロキサンは、比較的低重合度であり、各種の粉体表面に配向して、適度な撥水性を付与できるため、特に化粧料用粉体の表面処理や分散に用いる粉体表面処理剤として極めて好適に用いることができる。
第一工程において、Si-H等の反応性官能基を有するオルガノハイドロジェンポリシロキサンに対して、分子鎖の片末端に1個の炭素-炭素二重結合を有するシロキサンデンドロン構造を有する化合物およびビスジメチルシリルエチレン基によって保護されたアリルアミンを共ヒドロシリル化させることで共変性オルガノポリシロキサン中間体を製造し、
第二工程において、共変性オルガノポリシロキサン中間体のアミノ基の脱保護反応を行い、
第三工程において、該脱保護反応後の反応性オルガノポリシロキサン中間体とサッカリド成分を有する化合物(特に、糖ラクトン化合物)を反応させることにより得ることができる。
本発明に係る新規な共変性オルガノポリシロキサン(以下、「(A)成分」ともいう)は、疎水性であり、高撥水性を呈するシロキサンデンドロン構造を有するシリルアルキル基と親水性のサッカリド成分を含有する基を同一分子内に有し、親油性原料と配合安定性に優れるため、各種処理剤および化粧料原料成分として有用であり、特に、化粧料に使用する表面処理剤、特に粉体の表面処理や粉体の分散に用いられる粉体処理剤として極めて有用である。特に、上記用途においては、共変性オルガノポリシロキサンの重合度が比較的低く、シロキサンデンドロン構造を有するシリルアルキル基とサッカリド成分を含有する基による変性率が一定の範囲にあることが好ましいため、最も好適には、前記の構造式(1-1)、(1-1-1)、(1-1-A)および(1-1-B)で表わされる鎖状構造の共変性オルガノポリシロキサンが特に好適に例示できる。
本発明に係る共変性オルガノポリシロキサンは、集積した親水基を持つため、各種粉体の表面に強く配向して適度な撥水性を付与できるため、化粧料用粉体の表面処理や分散を目的とし、粉体表面処理剤として好適に用いることができる。特に、本発明に係る共変性オルガノポリシロキサンは、公知の共変性オルガノポリシロキサンに比して、粉体処理剤として使用した場合、混合油剤系における分散安定性が更に良好であり、また、粉体表面を処理剤によって処理して得た粉体組成物を調製したのち、分散媒体となる油剤中にこれを分散させる方法をとった場合でも、従来の粉体処理剤では安定分散が困難であった粉体についても、凝集や沈降が起こらない安定性に優れた油中粉体分散物を与えることを特徴とする。
1.目的の粉体を、処理剤を配合した有機溶剤から選択される媒体中に分散して表面処理する方法。
2.粉体と粉体処理剤を混合したのち、ボールミル、ジェットミルなどの粉砕器を用いて表面処理する方法。
3.処理剤を溶剤に配合し、粉体を分散させて表面に吸着させた後、乾燥して焼結させる処理方法。
また、本発明は、(A)本発明に係る共変性オルガノポリシロキサンと(B)粉体又は着色剤を含有してなる粉体組成物に関する。粉体組成物は、上記の方法等により、(B)粉体又は着色剤と(A)本発明に係る共変性オルガノポリシロキサンを混合することにより得ることができ、粉体の表面処理、粉体の分散性の改善、化粧品原料用プレミックスなどその目的を問わない。
また、本発明でいう油中粉体分散物とは、上記の様にして得た粉体組成物を油剤中に分散したもの、或いは油剤中に共変性オルガノポリシロキサンを溶解または分散し、これに粉体を添加して混合分散したものを意味し、その形態は液状分散物である。かかる液状分散物は「スラリー」と呼ぶことがある。
1.前記の如くして得た粉体組成物を、エステル油やシリコーン油等の油剤中に添加して分散する方法。
2.上記の油剤中に共変性オルガノポリシロキサンを溶解または分散し、これに粉体を添加してボールミル、ビーズミル、サンドミル等の分散機器で混合する方法。
そして、得られた油中粉体分散物は、そのまま外用剤組成物(特に、化粧料)に配合することができる。
本発明に係る粉体組成物および油中粉体分散物等に用いる、(B)粉体又は着色剤は、化粧料の成分として一般に使用されるものであり、白色及び着色顔料、並びに、体質顔料を含む。白色及び着色顔料は化粧料の着色等に使用され、一方、体質顔料は、化粧料の感触改良等に使用される。本発明における「粉体」としては、化粧料に通常使用される白色及び着色顔料、並びに、体質顔料を特に制限なく使用することができる。本発明において、1種類又は2種類以上の粉体を配合することが好ましい。粉体の形状(球状、棒状、針状、板状、不定形状、紡錘状、繭状等)、粒子径(煙霧状、微粒子、顔料級等)、及び、粒子構造(多孔質、無孔質等)は何ら限定されるものではないが、平均一次粒子径が1nm~100μmの範囲にあることが好ましい。特に、これらの粉体又は着色剤を顔料として配合する場合、平均粒子径が1nm~20μmの範囲にある無機顔料粉体、有機顔料粉体、樹脂粉体から選択される1種類又は2種類以上を配合することが好ましい。
本発明に係る油中粉体分散物等に用いる油剤は、好適には、(C)5~100℃で液状であるシリコーンオイル、非極性有機化合物または低極性有機化合物から選択される1以上の油剤であり、非極性有機化合物及び低極性有機化合物としては、炭化水素油及び脂肪酸エステル油が好ましい。これらは、特にメークアップ化粧料の基材として広く用いられている成分であるが、これらの油剤には、公知の植物性油脂類、動物性油脂類、高級アルコール類、液状脂肪酸トリグリセライド、人工皮脂、フッ素系油から選択される1種類または2種類以上を併用しても良い。前記共変性オルガノポリシロキサンはこれらの非シリコーン系油剤に対しても優れた分散性を示すので、炭化水素油及び脂肪酸エステル油を安定に化粧料に配合でき、これらの非シリコーン系油剤による保湿特性を維持することができる。したがって、前記共変性オルガノポリシロキサンは、これらの非シリコーン系油剤の化粧料中における経時安定性を改善することができる。
<ビスジメチルシリルエチレンにより保護されたアリルアミンAの合成>
アリルアミン85.7g、トリエチルアミン379.4g、トルエン650gを仕込み、室温で攪拌しながらビスジメチルクロロシリルエチレン323.0g(33%トルエン溶液)を滴下した。その後、90℃で3時間エージングし、室温まで冷却したところ、塩酸塩の析出が見られた。飽和食塩水で有機層を洗浄した後、トルエン層を蒸留することにより保護されたアリルアミンAを213g得た。以下、実施例等で、当該ビスジメチルシリルエチレンにより保護されたアリルアミンを、「アリルアミンA」という。
<共変性オルガノポリシロキサン化合物P1の合成>
反応器に平均組成式MD15DH 3Mで表されるメチルハイドロジェンポリシロキサン61.3gにトリストリメチルシロキシビニルシラン32.4g、アリルアミンA6.3gを白金触媒0.1gの存在下、段階的に仕込み、窒素流通下で攪拌しながら75-90℃で10時間反応を行った。アルカリ分解ガス発生法(残存したSi-H基をKOHのエタノール/水溶液によって分解し、発生した水素ガスの体積から反応率を計算する)により反応が完結したことを確認した後、イソプロパノール(IPA)30gを加え、90℃で加熱し、アミノ基の脱保護を行った。アミノ%測定(塩酸によるアミノ残基の滴定)により、アミノ基の脱保護完結を確認した後、150℃で低沸分を留去したところ、平均組成式MD15DR1 2.4DRA 0.6M で表される中間体90gを得た。
次に、得られた中間体30gを、IPA30g中、グルコノラクトン2.2gと70℃で2時間作用させた。アミノ%測定により、アミノ基の消失を確認した後、110℃で低沸分を留去し、ろ過処理を行ったところ、平均組成式MD15DR1 2.4DR2 0.6Mで表されるシロキサンデンドロン構造およびグルコノラクトンに由来するサッカリド成分を含有する基(糖残基)を有する新規な共変性オルガノポリシロキサン32.5gを得た。
式中、R1、RAは下記に示した構造であり、R2はアミノプロピル基とグルコノラクトンの反応により得られたグルコノラクトンアミドプロピル基である。
R1= -C2H4-Si(OSiMe3)3
RA= -C3H6NH2
<共変性オルガノポリシロキサン化合物P2の合成>
反応器に平均組成式MD33DH 3Mで表されるメチルハイドロジェンポリシロキサン80gにトリストリメチルシロキシビニルシラン18.5g、アリルアミンA6.3gを白金触媒0.1gの存在下、段階的に仕込み、窒素流通下で攪拌しながら75-90℃で10時間反応を行った。アルカリ分解ガス発生法(残存したSi-H基をKOHのエタノール/水溶液によって分解し、発生した水素ガスの体積から反応率を計算する)により反応が完結したことを確認した後、イソプロパノール(IPA)20gを加え、90℃で加熱し、アミノ基の脱保護を行った。アミノ%測定(塩酸によるアミノ残基の滴定)により、アミノ基の脱保護完結を確認した後、150℃で低沸分を留去したところ、平均組成式MD33DR1 2DRA 1Mで表される中間体97.2gを得た。
次に、得られた中間体30gを、IPA40g中、グルコノラクトン1.5gと80℃で3時間作用させた。アミノ%測定により、アミノ基の消失を確認した後、110℃で低沸分を留去し、ろ過処理を行ったところ、平均組成式MD33DR1 2DR2 1Mで表されるシロキサンデンドロン構造およびグルコノラクトンに由来するサッカリド成分を含有する基(糖残基)を有する新規な共変性オルガノポリシロキサン24.2gを得た。
式中、R1、RAは下記に示した構造であり、R2はアミノプロピル基とグルコノラクトンの反応により得られたグルコノラクトンアミドプロピル基である。
R1= -C2H4-Si(OSiMe3)3
RA= -C3H6NH2
<共変性オルガノポリシロキサン化合物P3の合成>
反応器に平均組成式MD19DH 8Mで表されるメチルハイドロジェンポリシロキサン51.6gにトリストリメチルシロキシビニルシラン25.2g、アリルアミンA5.7g、1-ドデセン17.5gを白金触媒0.05gの存在下、段階的に仕込み、窒素流通下で攪拌しながら75-90℃で10時間反応を行った。アルカリ分解ガス発生法(残存したSi-H基をKOHのエタノール/水溶液によって分解し、発生した水素ガスの体積から反応率を計算する)により反応が完結したことを確認した後、メタノール30g/イソプロパノール(IPA)30gを加え、90℃で加熱し、アミノ基の脱保護を行った。アミノ%測定(塩酸によるアミノ残基の滴定)により、アミノ基の脱保護完結を確認した後、150℃で低沸分を留去したところ、平均組成式MD19DR1 3DRA 1DR3 4Mで表される中間体86.4gを得た。
次に、得られた中間体43gを、IPA40g中、グルコノラクトン1.9gと90℃で7時間作用させた。アミノ%測定により、アミノ基の消失を確認した後、110℃で低沸分を留去し、ろ過処理を行ったところ、平均組成式MD19DR1 3DR2 1DR3 4Mで表されるシロキサンデンドロン構造およびグルコノラクトンに由来するサッカリド成分を含有する基(糖残基)を有する新規な共変性オルガノポリシロキサン41gを得た。
式中、R1、RAおよびR3は下記に示した構造であり、R2はアミノプロピル基とグルコノラクトンの反応により得られたグルコノラクトンアミドプロピル基である。
R1= -C2H4-Si(OSiMe3)3
RA= -C3H6NH2
R3= -C12H25
反応器に平均組成式 MD350DRA 4M で表されるアミノ変性シリコーン50gを、IPA50g中、グルコノラクトン1.5gと90℃で作用させた。アミノ%測定(塩酸によるアミノ残基の滴定)により、アミノ基の脱保護完結を確認した後、110℃で低沸分を留去したところ、平均組成式MD350DR2 4Mで表されるグルコノラクトンに由来するサッカリド成分を含有する基(糖残基)を有するオルガノポリシロキサン47.7gを得た。
式中、RA下記に示した構造であり、R2はアミノプロピル基とグルコノラクトンの反応により得られたグルコノラクトンアミドプロピル基である。
RA= -C3H6NH2
比較実験に用いたオルガノポリシロキサン化合物R2は、以下の製品である。
ES5612:ポリエーテル変性シリコーン(商品名:ES5612、東レ・ダウコーニング社製)
R1= -C2H4-Si(OSiMe3)3
R2= アミノプロピル基とグルコノラクトンの反応により得られたグルコノラクトンアミドプロピル基
R3= -C12H25
以下の[分散体の調製1]~[分散体の調製5]に示す組成及び製法でスラリー状の微粒子分散体を調製し、その分散特性を粘度の経時変化から評価した。スラリーの粘度は、1000mPasを基準とし、それ以下の場合を低粘度、それ以上の場合は高粘度とした。また、スラリー作成段階において、ペイントシェイカー攪拌後に、ゲル化してしまった場合は、スラリー製造不可とした。結果表2に示す。また、各分散体の調製において用いた成分は、以下の通りである。
(1) 微粒子粉体:微粒子酸化チタン
商品名:MT-01(テイカ社製)
粒子径:10nm
(2) 分散媒:デカメチルシクロペンタシロキサン
商品名:DC245(東レ・ダウコーニング社製)
微粒子酸化チタン20g、実施例1の共変性オルガノポリシロキサン(P1)5gおよびデカメチルシクロペンタシロキサン25gを混合し、ジルコニアビーズ(0.8mmΦ)200gを加え、ペイントシェイカー(PAINT SHAKER 浅田鉄工株式会社製)にて15時間混合してスラリー状の分散体(TP1)を作成した。
[分散体の調製1]において、実施例1の共変性オルガノポリシロキサン(P1)の代わりに、実施例2の共変性オルガノポリシロキサン(P2)を用いた他は同様にして、スラリー状の分散体(TP2)を作成した。
[分散体の調製1]において、実施例1の共変性オルガノポリシロキサン(P1)の代わりに、実施例3の共変性オルガノポリシロキサン(P3)を用いた他は同様にして、スラリー状の分散体(TP3)を作成した。
[分散体の調製1]において、実施例1の共変性オルガノポリシロキサン(P1)の代わりに、比較例1の共変性オルガノポリシロキサン(R1)を用いた他は同様にして、スラリー状の分散体(TR1)を作成した。
[分散体の調製1]において、実施例1の共変性オルガノポリシロキサン(P1)の代わりに、比較例2の共変性オルガノポリシロキサン(R2)を用いた他は同様にして、スラリー状の分散体(TR2)を作成した。
○○:低粘度のスラリー製造可、経時での増粘なし。
○×:低粘度のスラリー製造可、経時でゲル化。
△○:高粘度のスラリー製造可、経時で減粘。
×-:スラリーの製造不可。
以下、本発明の化粧料について、本発明に係る新規な共変性オルガノポリシロキサンP1~P3を配合した以下の具体的な処方による実施例を示して説明するが、本発明の化粧料は、これらの処方例に記載の種類、組成に限定されるものでない。なお、処方中、部は重量(質量)部を示す。
[処方例1]リキッドファンデーション(W/O型)
[処方例2]リキッドファンデーション(W/O型)
[処方例3]リキッドファンデーション(O/W型)
[処方例4]サンスクリーンクリーム(W/O型)
[処方例5]サンスクリーン(シェーキングタイプ)
[処方例6]下地クリーム
[処方例7]口紅
[処方例8]液状口紅
[処方例9]リップスティック
[処方例10]アイシャドウ
[処方例11]マスカラ
(成分)
1. ジメチルシロキサン(2cs) 30部
2. イソノナン酸イソトリデシル 3部
3. ネオペンタン酸イソトリデシル 2部
4. ポリエーテル変性シリコーン(注1) 1.5部
5. 共変性オルガノポリシロキサンP2 0.5部
6. 有機変性粘土鉱物(ベントン38V) 1.5部
7. メトキシケイ皮酸オクチル 5部
8.シリコーン処理酸化チタン 8.5部
9.シリコーン処理赤酸化鉄 0.4部
10.シリコーン処理黄酸化鉄 1部
11.シリコーン処理黒酸化鉄 0.1部
12.デカメチルシクロペンタシロキサン、ジメチコンクロスポリマー(注2) 2部
13.1,3-ブチレングリコール 5部
14.グリセリン 3部
15.塩化ナトリウム 0.5部
16.防腐剤 適量
17.精製水 残量
18.香料 適量
注1)東レ・ダウコーニング社製ES-5300を使用した。
注2)Dow Corning社製DC9040を使用した。
工程1: 成分1、4、6、7、12を撹拌混合した。
工程2: 成分2、3、5、8~11を、3本ロールを用いて混練混合した。
工程3: 撹拌下、工程1で得られた混合物に工程2の混合物を加え、更に撹拌混合した。
工程4: 成分13~18を均一に溶解した水相を、工程3で得られた混合物に加えて乳化し、容器に充填して製品を得た。
(成分)
1. イソドデカン 20部
2. イソヘキサデカン 10部
3. イソノナン酸イソトリデシル 3部
4. トリカプリルカプリン酸グリセリル 2部
5. ポリエーテル変性シリコーン(注1) 1.5部
6. 共変性オルガノポリシロキサンP3 0.5部
7. 有機変性粘土鉱物(ベントン38V) 1.5部
8. メトキシケイ皮酸オクチル 5部
9. オクチルシラン処理酸化チタン 8.5部
10.オクチルシラン処理赤酸化鉄 0.4部
11.オクチルシラン処理黄酸化鉄 1部
12.オクチルシラン処理黒酸化鉄 0.1部
13.(ジメチコン/ビス-イソブチルPPG/20)クロスポリマー(注2) 2部
14.イソドデカン/(アクリレーツ/メタクリル酸ポリトリメチルシロキシ)コポリマー(注3) 1部
15.トリメチルシロキシケイ酸 1部
16.1,3-ブチレングリコール 5部
17.グリセリン 3部
18.塩化ナトリウム 0.5部
19.防腐剤 適量
20.精製水 残量
21.香料 適量
注1)東レ・ダウコーニング社製ES-5300を使用した。
注2)Dow Corning社製EL-8051を使用した。
注3)東レ・ダウコーニング社製FA-4002IDを使用した。
工程1: 成分1、2、5、7、8、13、14、15を撹拌混合した。
工程2: 成分3、4、6、9~12を、3本ロールを用いて混練混合した。
工程3: 撹拌下、工程1で得られた混合物に工程2の混合物を加え、更に撹拌混合した。
工程4: 成分16~21を均一に溶解した水相を、工程3で得られた混合物に加えて乳化し、容器に充填して製品を得た。
(成分)
1. カルボキシデシルトリシロキサン 1部
2. ポリソルベート80 1.2部
3. セスキオレイン酸ソルビタン 0.2部
4. ステアリン酸グリセリル 1.5部
5. ベヘニルアルコール 2.5部
6. シクロペンタシロキサン 8部
7. ジメチコン(6cs) 3部
8. スクワラン 3部
9. イソノナン酸イソトリデシル 3部
10.トリカプリルカプリン酸グリセリル 3部
11.共変性オルガノポリシロキサンP3 0.2部
12.シリコーン処理酸化チタン 8.5部
13.シリコーン処理赤酸化鉄 0.4部
14.シリコーン処理黄酸化鉄 1部
15.シリコーン処理黒酸化鉄 0.1部
16.1.3-ブチレングリコール 8部
17.水酸化ナトリウム水溶液(1%) 15部
18.カルボマー(2%) 10部
19.精製水 残量
工程1: 1~6および8~10を攪拌混合した。
工程2: 7および11~15を、3本ロールを用いて混練混合した。
工程3: 撹拌下、工程1で得られた混合物に工程2の混合物を加え、更に撹拌混合した。
工程4: 成分16~19を均一に溶解した水相を、工程3で得られた混合物に加えて乳化し、容器に充填して製品を得た。
(成分)
1. ジメチコン(2cs) 3.8部
2. イソノナン酸イソトリデシル 4部
4. ポリエーテル変性シリコーン(注1) 2部
5. パラメトキシケイ皮酸オクチル 5部
6.ジエチルアミノヒドロキシベンゾイル安息香酸ヘキシル 2部
7. 有機変性ベントナイト 1.2部
8. 酸化チタン分散体(酸化チタン40wt%)(注2) 20部
9.ジメチコン/(アクリレーツ/メタクリル酸ポリトリメチルシロキシ)コポリマー 3部
10.1.3-ブチレングリコール 7部
11.クエン酸ナトリウム 0.2部
12.塩化ナトリウム 0.5部
13.精製水 残量
注1)東レ・ダウコーニング社製ES-5300を使用した。
注2)実施例に記載の分散体TP3を使用した。
工程1: 成分1~9を混合する。
工程2: 成分10~13を混合する。
工程3: 工程1で得られた混合物に、工程2で得られた水相を攪拌下に添加し、乳化した後、容器に充填して製品を得た。
(成分)
1. メトキシ桂皮酸オクチル 8部
2. パルミチン酸オクチル 7部
3. ジエチルアミノヒドロキシベンゾイル安息香酸ヘキシル 2部
4. 酸化チタンスラリー(注1) 25部
5. シクロペンタシロキサン 18.2部
6. ジメチコンクロスポリマー 3部
7. トリメチルシロキシケイ酸 3.3部
8.ポリエーテル変性シリコーン(注2) 1.5部
9. 防腐剤 0.1部
10. エタノール 5部
11. 1,3-ブチレングリコール 3部
12.精製水 残量
注1)実施例に記載の分散体TP3を使用した。
注2)東レ・ダウコーニング(株)社製ES-5300を使用した。
工程1:成分1~9を混合する。
工程2:工程1の混合物に成分10~12の混合物を添加し、乳化する。
(成分)
1. ジメチルポリシロキサン(2mm2/s) 2部
2. デカメチルシクロペンタシロキサン 10部
3. ポリエーテル変性シリコーン(注1) 2部
4. イソオクタン酸セチル 5部
5. 共変性オルガノポリシロキサンP2 0.5部
6. パラメトキシケイ皮酸2-エチルヘキシル 2部
7. シリコーンエラストマー(注2) 4部
8.シリコーン処理酸化チタン 6部
9.シリコーン処理赤酸化鉄 0.3部
10.シリコーン処理黄酸化鉄 0.7部
11.シリコーン処理黒酸化鉄 0.07部
12. 有機変性ベントナイト 0.5部
13. 硫酸バリウム 2部
14.タルク 1部
15.ナイロンパウダー 3部
16.防腐剤 適量
17.キサンタンガム 0.1部
18.L-アスコルビン酸リン酸エステルマグネシウム 0.3部
19.精製水 残量
注1)東レ・ダウコーニング社製、ES-5612を用いた。
注2)Dow Corning社製、9045Silicone Elastomer Blendを用いた。
工程1:成分1~15を混合、分散する。
工程2:成分16~19を混合する。
工程3:工程1で得られた混合物に、工程2で得られた混合物を加えて室温で乳化し、容器に充填して製品を得た。
(成分)
1. トリエチルヘキサノイン 10.0部
2. エチルヘキサン酸セチル 17.0部
3. セスキイソステアリン酸ソルビタン 4.0部
4. マイクロクリスタリンワックス 10.0部
5. パラフィンワックス 15.0部
6. リンゴ酸ジイソステアリル 7.0部
7. トリイソステアリン酸グリセリル 9.0部
8. ジカプリン酸プロピレングリコール 7.0部
9. ステアリン酸イヌリン(製品名:千葉製粉社製レオパールISL2) 2.0部
10.共変性オルガノポリシロキサンP3 1.0部
11.ポリエーテル変性シリコーン(注1) 2.0部
12.イソドデカン/(アクリレーツ/メタクリル酸ポリトリメチルシロキシ)コポリマー(注2) 3.0部
13.トリメチルシロキシケイ酸のジメチルポリシロキサン(100cst)溶液(有効成分33%) 2.0部
14.黄色4号 適量
15.酸化チタン 1.0部
16.黒酸化鉄 1.0部
17.マイカ 1.0部
18.赤104 適量
19.精製水 7.0部
20.1,3-ブチレングリコール 1.0部
21.防腐剤 適量
22.香料 適量
注1)東レ・ダウコーニング社製ES-5300を使用した。
注2)東レ・ダウコーニング社製FA-4002IDを使用した。
工程1:成分1~18を加熱溶解する。
工程2:成分19~21を混合する。
工程3:工程1の混合物に工程2の混合物を添加して更に撹拌混合する。
工程4:工程3の混合物に、成分22を加えて密閉容器に充填し製品を得た。
(成分)
1.フェニルメチルシリコーン 10部
2.ミリスチン酸イソプロピル 10部
3.シクロペンタシロキサン/(アクリレーツ/メタクリル酸ポリトリメチルシロキシ)コポリマー(注1) 5部
4.煙霧状無水ケイ酸 0.1部
5.球状ウレタン粉末 5部
6.シクロペンタシロキサン/トリメチルシロキシケイ酸(注2) 5部
7.共変性オルガノポリシロキサンP2 1部
8.ポリエーテル変性シリコーン(注3) 1.5部
9.オクチルメトキシシンナメート 1部
10.赤色202号 0.5部
11.酸化チタン 0.5部
12.雲母チタン 3部
13.香料 0.1部
14.エタノール 10部
15.防腐剤 0.2部
16.塩化ナトリウム 0.1部
17.精製水 残量
注1)東レ・ダウコーニング社製FA-4001CMを使用した。
注2)東レ・ダウコーニング社製BY11-018を使用した。
注3)東レ・ダウコーニング社製ES-5300を使用した。
A : 成分1~12を分散混合する。
B : 別に、成分13~17を均一に溶解する。
C : AにBを加えて乳化し、脱泡後、容器に充填して油中水型乳化口紅を得る。
(成分)
1.ポリエチレンーポリプロピレンコポリマー 5部
2.キャンデリラワックス 5部
3.カルナウバワックス 5部
4.ワセリン 10部
5.2-エチルヘキサン酸セチル 10部
6.ジグリセリンジイソステアレート 14.5部
7.マカデミアナッツ油 7部
8.ステアリン酸イヌリン(千葉製粉社製レオパールISK2) 23部
9.共変性オルガノポリシロキサンP3 2部
10.赤色201号 1部
11.赤色202号 3部
12.黄色4号アルミニウムレーキ 3部
13.酸化チタン 1部
14.黒酸化鉄 0.5部
15.酸化鉄雲母チタン 10部
16.防腐剤 適量
17.香料 適量
A:成分1~9を加温溶解し、成分10~16を加え均一に混合する。
B:Aに成分17を加えて容器に充填し、リップスティックを得る。
(成分)
1.ジメチルポリシロキサン(2cs) 13部
2.ジメチルポリシロキサン(6cs) 12部
3.共変性オルガノポリシロキサンP2 1部
4.PEG10-ジメチコン 1部
5.シリコーン処理酸化チタン 6.2部
6.シリコーン処理セリサイト 4部
7.シリコーン処理マイカ 6部
8.マイクロクリスタリンワックス 2部
9.キャンデリラロウ 1部
10.ジメチルシリル化シリカ 2部
11.塩化ナトリウム 2部
12.プロピレングリコール 8部
13. 防腐剤 適量
14. 香料 適量
15. 精製水 残余
A : 成分1~10を添加して均一に分散する。
B : 成分11~15を均一溶解する。
C : 攪拌下、AにBを徐添して乳化し、アイシャドウを得る。
(成分)
1. パラフィンワックス 5部
2. 軽質流動イソパラフィン 残量
3. カプリルメチコン 3部
4. トリメチルシロキシケイ酸 0.5部
5. 共変性オルガノポリシロキサンP3 0.5部
6. ジイソステアリン酸ポリグリセリルー2 3部
7. トリオクタノイン 6部
8. ジメチコン 5部
9. 有機変性ベントナイト 2部
10. シクロペンタシロキサン、ジメチコンクロスポリマー(注1 5部
11. フッ素化合物表面処理黒酸化鉄 6部
12.ショ糖脂肪酸エステル 4部
13.ミツロウ 5部
14.ロジン酸ペンタエリスリット 5部
15.防腐剤 適量
16.ポリビニルアルコール 1部
17.精製水 30部
注1):Dow Corning社製DC-9040を使用した。
成分1~14を加温溶解後、充分に混合分散した。これに、成分15から17の混合物を添加し、乳化し、容器に充填して製品を得た。
[例1 乳化ファンデーション]
[例2 液状ファンデーション]
[例3 ファンデーション]
[例4 油中水型クリーム]
[例5 油中水型乳化組成物]
[例6 油中水型乳化口紅(液状)]
[例7 液状口紅]
[例8 口紅]
[例9 日焼け止め乳液]
[例10 乳液]
[例11 サンカットクリーム]
[例12 UVカット油中水型乳液]
[例13 サンスクリーン剤]
[例14 油中水型乳化サンスクリーン]
[例15 O/Wクリーム]
[例16 アイシャドウ]
[例17 マスカラ]
[例18 マスカラ]
[例19 固形パウダーアイシャドウ]
[例20 プレストパウダー化粧料]
[例21 パウダーファンデーション]
[例22 プレスドファンデーション]
[例23 クリーム]
[例24 ファンデーション]
[例25 油中水乳化型日焼け止め料]
[例26 リップスティック]
[例27 口紅]
[例28 ファンデーション]
[例29 制汗エアゾール化粧料]
[例30 非水加圧制汗剤製品]
[例31 エアゾール型制汗剤組成物]
[例32 制汗ローション組成物]
[例33 W/Oエマルション型皮膚外用剤]
[例34 非水制汗デオドラントスティック組成物]
[例35 W/O固形制汗スティック組成物]
[例36 W/Oエマルション型制汗クリーム組成物]
[例37 マスカラ]
[例38 アフターシェーブクリーム]
[例39 固形状ファンデーション]
[例40 日中用美白クリーム]
[例41 サンタンクリーム]
[例42 ポリオール/O型非水エマルション皮膚外用剤]
[例43 ポリオール/O型非水エマルション皮膚外用剤]
Claims (20)
- 下記一般式(1)
R1 aR2 bL1 cQdSiO(4―a―b―c―d)/2 (1)
で表される、シロキサンデンドロン構造を有する基(L1)およびサッカリド成分を含有する基(Q)を有する共変性オルガノポリシロキサン。
{一般式(1)中、
R1は置換もしくは非置換の炭素原子数1~30の一価炭化水素基または水素原子である。
R2は、炭素原子数6~30の、置換もしくは非置換の、直鎖状もしくは分岐状の一価炭化水素基、または、下記一般式(2-1);
一般式(3):
Qはサッカリド成分を含有する基であり、式X-(G1)n-(G2)mを有し、式中G1は、炭素原子数5~12のサッカリド成分であり、n+mは1~10であり、nまたはmは0であることができ、G2は、有機または有機ケイ素基で追加的に置換されていてもよい、炭素原子数5~12のサッカリド成分であり、
Xは連結基であって、以下の:
-R5-NHC(O)-R6-;
-R5-NHC(O)O-R6-;
-R5-NH-C(O)-NH-R6-;
-R5-O-R6-;
-R5-CH(OH)-CH2-O-R6-;
-R5-S-R6-;
-R5-CH(OH)-CH2-NH-R6-;および
-R5-N(R1)-R6-
からなる群から独立して選択され、R5およびR6は、(Ra)u(Rb)v(Rc)xを含む二価のスペーサー基であり、ここでu、vおよびxの少なくとも1つは1でなければならず、RaおよびRcは、炭素原子数1~12のアルキレン基または(RdO)pで表されるポリオキシアルキレン基のいずれかであり、ここでRdはHまたは炭素原子数1~12であり、pは1~50の任意の整数であり、各(RdO)は、同じであっても異なっていてもよく、Rbは-N(Re)-であり、ここでReはHまたは炭素原子数1~12のアルキル基であり、またはX-Yであり、ここでXは以前に定義した通りかR5であり、Yはカルボン酸、ホスフェート、サルフェート、スルホネート、または第四級アンモニウム基である。)
a、b、c及びdは、1.0≦a+b≦2.5、 0.001≦c≦1.5、及び0.001≦d≦1.5となる範囲の数である。} - 前記のQが、アミノ基とヒドロキシ官能サッカリドの反応により得られるサッカリド成分を含有する基である、請求項1に記載の共変性オルガノポリシロキサン。
- 前記のQが、ケイ素原子に結合し、
-R12-(N(R13)-R14)w-NR15R16
(式中、R12は炭素数2~8のアルキレン基であり、
R13、R15、R16は水素原子又は炭素数1~10の一価有機基であるが、全てのR13、R15およびR16のうち少なくとも一つは水素原子であり、
R14は炭素数1~4のアルキレン基であり、wは0≦w≦6の範囲の数である。)
で示されるアミノ基と、
糖ラクトン化合物の反応により得られる糖ラクトンアミドアルキル基である、請求項1または請求項2に記載の共変性オルガノポリシロキサン。 - 構造式(1-1)または構造式(1-1-1)において、L1が下記一般式(2-1)または一般式(2-2)で表される官能基であり、
一般式(2-1):
Qがケイ素原子に結合し、
-R12-(N(R13)-R14)w-NR15R16
(式中、R12は炭素数2~8のアルキレン基であり、
R13、R15、R16は水素原子又は炭素数1~10の一価有機基であるが、全てのR13、R15およびR16のうち少なくとも一つは水素原子であり、
R14は炭素数1~4のアルキレン基であり、wは0≦w≦6の範囲の数である。)
で示されるアミノ基と、
糖ラクトン化合物の反応により得られる糖ラクトンアミドアルキル基(Q1)である、請求項4または請求項5に記載の共変性オルガノポリシロキサン。 - 以下の工程(I)~工程(III)を含む、請求項1~7のいずれかに記載の共変性オルガノポリシロキサンの製造方法。
工程(I):シロキサンデンドロン構造を有する化合物、
直接または脱保護反応後に、サッカリド成分を有する化合物と反応可能な官能基を有する化合物、および
オルガノハイドロジェンポリシロキサンを、
共ヒドロシリル化させることにより、直接または脱保護反応後にサッカリド成分を有する化合物と反応可能な官能基を持った共変性オルガノポリシロキサン中間体を製造する工程
工程(II):工程(I)で得られた共変性オルガノポリシロキサン中間体を、その必要に応じ、脱保護反応することにより、サッカリド成分を有する化合物と反応可能な官能基を持った共変性オルガノポリシロキサン中間体を製造する工程
工程(III): 工程(I)または工程(II)で得られた共変性オルガノポリシロキサン中間体と、
サッカリド成分を有する化合物を反応させる工程。 - 前記の工程(II)が必須の工程であり、
脱保護反応後に、サッカリド成分を有する化合物と反応可能な官能基を有する化合物が、オルガノシリル基によって保護されたアリルアミンであることを特徴とする、請求項8に記載の共変性オルガノポリシロキサンの製造方法。 - 前記のオルガノシリル基が、ビスジメチルシリルエチレン基であることを特徴とする、請求項9に記載の共変性オルガノポリシロキサンの製造法。
- 請求項1~7のいずれかに記載の共変性オルガノポリシロキサンを含有する表面処理剤。
- 請求項1~7のいずれかに記載の共変性オルガノポリシロキサンを含有する粉体処理剤。
- (A)請求項1~7のいずれか1項に記載の共変性オルガノポリシロキサン
および(B)粉体又は着色剤
を含有してなる粉体組成物。 - 前記の(B)成分が、平均粒子径が1nm~20μmの範囲にある無機顔料粉体、有機顔料粉体、樹脂粉体よりなる群より選ばれる1種又は2種類以上である請求項13に記載の粉体組成物。
- (A)請求項1~7のいずれかに記載の共変性オルガノポリシロキサン、(B)粉体又は着色剤および(C)5~100℃で液状であるシリコーンオイル、非極性有機化合物または低極性有機化合物から選択される1以上の油剤を含有してなる油中粉体分散物。
- 請求項1~7のいずれかに記載の共変性オルガノポリシロキサンを含有する外用剤組成物。
- 化粧料または医薬である請求項16に記載の外用剤組成物。
- 請求項13または請求項14に記載の粉体組成物を含有する化粧料。
- 請求項15に記載の油中粉体分散物を含有する化粧料。
- (A)請求項1~7のいずれかに記載の共変性オルガノポリシロキサン、
(B)粉体又は着色剤 および
(C)5~100℃で液状であるシリコーンオイル、非極性有機化合物または低極性有機化合物 を含有してなる、メークアップ化粧料。
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KR1020157011238A KR20150064156A (ko) | 2012-10-02 | 2013-10-02 | 신규한 동시 개질된 유기폴리실록산, 이를 포함하는 분말 처리제, 및 분말 조성물 |
CN201380056630.4A CN104769015A (zh) | 2012-10-02 | 2013-10-02 | 新型共改性的有机聚硅氧烷、包含该共改性的有机聚硅氧烷的粉末处理剂以及粉末组合物 |
EP13844232.2A EP2905300A4 (en) | 2012-10-02 | 2013-10-02 | NOVEL COMODIFIED ORGANOPOLYSILOXAN, POWDER PROCESSING AGENT THEREFOR AND POWDER COMPOSITION |
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JP7078245B2 (ja) | 2017-06-27 | 2022-05-31 | 株式会社トキワ | 油性固形化粧料 |
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CN111819247A (zh) * | 2019-02-22 | 2020-10-23 | 浙江三时纪新材科技有限公司 | 一种球形或角形粉体填料的制备方法、由此得到的球形或角形粉体填料及其应用 |
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EP2905300A1 (en) | 2015-08-12 |
KR20150064156A (ko) | 2015-06-10 |
CN104769015A (zh) | 2015-07-08 |
US20150239924A1 (en) | 2015-08-27 |
US9441009B2 (en) | 2016-09-13 |
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JP2014070220A (ja) | 2014-04-21 |
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