WO2011049248A1 - 新規な共変性オルガノポリシロキサン - Google Patents
新規な共変性オルガノポリシロキサン Download PDFInfo
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- WO2011049248A1 WO2011049248A1 PCT/JP2010/069249 JP2010069249W WO2011049248A1 WO 2011049248 A1 WO2011049248 A1 WO 2011049248A1 JP 2010069249 W JP2010069249 W JP 2010069249W WO 2011049248 A1 WO2011049248 A1 WO 2011049248A1
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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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/12—Treatment with organosilicon compounds
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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
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
- A61K8/044—Suspensions
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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
- A61K8/04—Dispersions; Emulsions
- A61K8/06—Emulsions
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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
- A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
- A61K8/894—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone modified by a polyoxyalkylene group, e.g. cetyl dimethicone copolyol
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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
-
- 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
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
-
- 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
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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
- C08L83/04—Polysiloxanes
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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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- 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
- C08L83/16—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 all the silicon atoms are connected by linkages other than oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/28—Compounds of silicon
- C09C1/30—Silicic acid
- C09C1/3081—Treatment with organo-silicon compounds
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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
- 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
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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
- A61Q1/04—Preparations containing skin colorants, e.g. pigments for lips
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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
- A61Q15/00—Anti-perspirants or body deodorants
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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
Definitions
- the present invention relates to a novel co-modified organopolysiloxane having a group having a siloxane dendron structure and a hydrophilic group, a process for producing the same, a surfactant comprising the co-modified organopolysiloxane, and a powder treatment agent, and contains the same.
- the novel co-modified silicone having a siloxane dendron structure has various functional aspects, and has an aspect as an oil agent that imparts an excellent feel and texture when blended with cosmetics containing water. Moreover, it has the side as an outstanding emulsification adjuvant or emulsifier which can emulsify various oil agents stably. Furthermore, it has an aspect as an excellent dispersant or powder surface treatment agent for stably dispersing and blending powder in cosmetics.
- the polyether-modified silicone is usually produced by adding a polyether having a reactive unsaturated group to an organohydrogensiloxane, and has an advantage that the degree of freedom in structural design is high.
- the reason for this is that the compatibility between the unreacted polyether usually contained in the modified silicone and the copolymer as the reaction product is relatively good, so two-phase separation may not occur even in a mixture state. This is because there are many.
- silicone modified with polyglycerin, sugar, or polysaccharide has a problem in that the degree of freedom in structural design is low and the range of use does not widen.
- These polyhydric alcohol-modified silicones are usually produced by adding a polyhydric alcohol derivative having a reactive unsaturated group to an organohydrogensiloxane. In many cases, these polyhydric alcohol-modified silicones are reacted with the remaining polyhydric alcohol derivative. This is because the compatibility with the copolymer, which is a product, is low and two-phase separation occurs within a short time after production.
- Patent Document 8 a novel organopolysiloxane / glycerin derivative alternating copolymer has been proposed in Patent Document 8, and it is said that a high molecular weight polyglycerin-modified silicone can be obtained without problems such as cloudiness due to unreacted raw materials.
- this compound has a hydrophilic group incorporated in the main chain, as can be seen from its chemical structure. For this reason, properties are completely different from conventionally used hydrophilic silicones such as polyether-modified silicones, and considerable technology is required to stably blend in delicate formulations such as cosmetics, and the field of use is limited. There is a problem.
- silicone having one or more functional groups selected from the group consisting of a hydroxy group, a carboxy group, an amino group, an imino group, a mercapto group, and an epoxy group is added in the presence of an acidic or basic catalyst
- a method for producing a branched polyglycerol-modified silicone obtained by adding / grafting 3-epoxy-1-propanol has been proposed.
- the siloxane main chain is cleaved during graft polymerization, and two or more types of components having different properties are easily generated as a copolymer, and there are many problems in terms of quality and purification steps.
- silicone oil has a light touch and excellent stretchability, and has features such as excellent water repellency and high safety, but lacks a moisturizing feeling.
- a highly volatile material has a dry feel after application, and a low volatile property causes an unnatural residual feeling on the skin, and it is difficult to obtain a natural skin feeling after application.
- ester oil has a problem that it feels heavy and greasy when applied, but also has the advantage of providing a natural skin sensation after application.
- cosmetics formulated with ester oils have a moisturizing feeling after application, that is, it is difficult to give a fresh moisture during application and to maintain it.
- hydrocarbon oils are easy to blend into cosmetics and have good elongation, and those with high volatility have the advantage of providing a light and light feel when applied, but the skin becomes white after application because it easily dissolves sebum. There may be a feeling of dryness, itching and irritation due to dryness. Those having low volatility have a problem that the feel upon application is heavy and the oily feeling is large.
- oils are often used in cosmetic formulations in order to make use of each other's strengths and make up for the weaknesses.
- the value as a fee increases. This is due to the fact that the oily feeling is suppressed by the effect of water, and a refreshing skin sensation is easily obtained as compared with the case where water is not blended.
- Patent Documents 11 to 15 propose a method of using polyoxyalkylene-modified organopolysiloxane (polyether-modified silicone) having good compatibility with silicone oil as a surfactant for water-in-oil emulsions.
- polyether-modified silicone may be insufficient in emulsion stability due to a mixed oil agent system and the like, and care must be taken when formulating a cosmetic.
- Nonionic silicone surfactants for example, various glycerin-modified silicones have been reported, and it is said to improve the squeaky feeling peculiar to silicone and the poor adaptability to the skin.
- Patent Documents 18 to 19 and Patent Documents 20 to 25 relating to fluoroalkyl co-modification are mentioned as oil agents, and glycerin-modified silicone compounds such as Patent Documents 1, 4, and 5 as surfactants and patents that are cosmetics thereof.
- Documents 26 to 28 are mentioned.
- silicone-modified polyhydric alcohol-modified silicones for example, alkyl / linear siloxane branched / polyglycerin co-modified silicones
- cosmetics containing these have excellent adhesion to the skin, providing a smooth and non-sticky feeling. It is said that it has excellent emulsion stability.
- Patent Document 6 silicone-modified polyhydric alcohol-modified silicones (for example, alkyl / linear siloxane branched / polyglycerin co-modified silicones) have also been reported, and cosmetics containing these have excellent adhesion to the skin, providing a smooth and non-sticky feeling. It is said that it has excellent emulsion stability.
- pigments such as titanium oxide, zinc oxide, and bengara, and powders such as mica and sericite, such as basic cosmetics, cosmetics such as suncuts, nail color, nail coat, foundation, mascara, and eyeliner, etc.
- untreated powder is likely to agglomerate due to the charge and polarity of the powder surface, trace amounts of impurities, etc., improving the dispersibility and stability of the powder as well as the feel and water resistance when used in cosmetics.
- lipophilic treatment with oil agent or metal soap, hydrophilic treatment with surfactant or water-soluble polymer, treatment with silicone compound, silica treatment or alumina treatment, etc. are known.
- silicone compound having a reactive site in the molecule Since this forms a chemical bond with the surface of the powder, it is also effective in modifying the surface of the powder and at the same time blocking the surface activity.
- the treatment agent is not detached from the powder surface, and the change in characteristics due to the treatment can be reduced, so that the efficiency is improved.
- Patent Document 29 discloses a method of performing surface treatment with 12 to 60 parts by mass of methyl hydrogen polysiloxane with respect to 100 parts by mass of powders.
- this method since unreacted Si-H groups remain in the powder even after the surface treatment, there is a problem that hydrogen gas is generated depending on the liquid condition when the powder is blended in cosmetics. There is a point.
- Patent Document 30 proposes a method in which a polyether-modified silicone having an HLB value of 2 or more and 7 or less is used as a powder dispersion aid.
- this technique is effective when the oil agent is only a silicone system, but there are cases where the dispersion stability is insufficient in a mixed oil system with an organic system.
- Patent Document 31 reports a modified powder treated with polyglycerin-modified silicone. However, this does not have sufficient dispersibility in the oil agent and is likely to cause separation over time, and the redispersibility is poor, which may impair the quality and feeling of use of the cosmetic.
- Patent Document 32 reports a powder composition treated with a modified silicone having an alcoholic OH group and exemplifies a triglycerin-modified product.
- a triglycerin derivative whose hydroxyl group is protected with an acetal to silicone and then perform a deacetone reaction, which makes the production process longer and the reaction conditions of the deprotecting group after the addition reaction are severe.
- the silicone chain is cleaved, there is a problem that a desired product cannot be obtained with good reproducibility.
- Patent Document 33 reports a powder composition treated with a silicone-branched polyglycerin-modified silicone (for example, alkyl / linear siloxane branch / polyglycerin co-modified silicone) and a powder dispersion in oil containing the same. .
- a silicone-branched polyglycerin-modified silicone for example, alkyl / linear siloxane branch / polyglycerin co-modified silicone
- a powder dispersion in oil containing the same.
- Patent Document 34 reports a powder dispersion stabilizer composed of silicone-modified glycerin at both ends and a powder dispersion composition containing the powder dispersion stabilizer.
- this dispersion stabilizer exhibits an excellent effect when the oil agent is only a silicone type, but there is a problem that the effect is not recognized so much in a mixed oil agent system with an organic type.
- the dispersion stability in the mixed oil system was insufficient with the conventional technology relating to powder dispersion and surface treatment.
- a powder composition obtained by treating the powder surface with a treatment agent is prepared and then dispersed in an oil agent serving as a dispersion medium, the powder does not aggregate or settle.
- the degree of achievement of the prior art was insufficient even for the goal of providing a powder dispersion in oil with excellent stability.
- cosmetics with low water content such as oily cosmetics
- oily cosmetics generally have the following problems: 1) The oily feeling is very strong, and a sense of incongruity tends to occur in terms of stickiness, weight, film thickness, etc.
- 2) the fact that makeup after application to the skin is poor and that it easily adheres to and spreads on clothing is also known as a problem for oily makeup cosmetics such as lipsticks, eyeshadows, eyeliners and oily foundations. Yes.
- cosmetics characterized by containing a glycerin-modified silicone compound as an oil agent (Patent Document 18), and having an alkyl group having 1 to 10 carbon atoms
- An oily cosmetic comprising a polyglycerin-modified silicone compound as an oil component (Patent Document 19), comprising a long-chain alkyl group-containing polyglycerin-modified silicone compound having 11 to 30 carbon atoms Development of oily cosmetics (Patent Document 35) and the like has been carried out.
- an oil-based solid cosmetic (Patent Document 36) containing one or more of alkyl glyceryl ether-modified silicones, polyoxyalkylene-modified silicones, and alkyl glyceryl ether-modified silicones
- Patent Document 37 oily cosmetics
- Patent Document 38 oily cosmetics
- Japanese Examined Patent Publication No. 62-34039 JP 62-195389 A Patent No. 2583212
- Japanese Patent Publication No. 06-089147 Japanese Patent No. 1956013
- Japanese Patent No. 2613124 Japanese Patent Laid-Open No. 4-188895
- Japanese Patent No. 2844453 Japanese Patent No. 2844453
- Japanese Patent No. 3976226 Japanese Patent Laid-Open No. 2002-179798
- JP 2004-339244 Japanese Patent Laid-Open No. 2005-042097 Japanese Patent Laying-Open No. 2005-089494 JP 05-186596 A JP-A 61-293903
- JP-A-5-112424 (Patent No. 2601738) Japanese Patent No. 2719303 JP-A-10-167946 JP 10-316536 A JP 2002-38013 A JP 2004-169015 A JP 2006-218472 A WO2003-075864 (Patent No. 3625471) JP-A-6-305933 (Patent No. 3477222) JP 7-25728 A (Patent No. 3160427) Japanese Patent Laid-Open No. 7-33622 (Japanese Patent No. 3200247)
- the present invention has been made to solve the above-mentioned problems. First, it is easy to manufacture, and two-phase separation and sedimentation of unreacted raw materials hardly occur after manufacturing, making it chemically stable and practical. An object is to provide a novel organopolysiloxane having a hydrophilic group and a method for producing the same.
- an object of the present invention is to provide a surfactant composed of the organopolysiloxane, which can stably emulsify various oils and give a unique texture to the emulsion.
- the present invention is a powder treating agent comprising the organopolysiloxane, which has good dispersion stability in a mixed oil system, and is obtained by treating the powder surface with a treating agent.
- a powder treating agent comprising the organopolysiloxane, which has good dispersion stability in a mixed oil system, and is obtained by treating the powder surface with a treating agent.
- the composition is prepared, even when the dispersion method is used in an oil agent as a dispersion medium, it provides a powder dispersion in oil excellent in stability that does not cause aggregation or sedimentation of the powder.
- the purpose is to provide the following.
- an object of the present invention is to provide an external preparation of the organopolysiloxane, particularly use as a raw material for cosmetics and a cosmetic containing the organopolysiloxane.
- an object of the present invention when formulated in cosmetics containing water and oils, it works to suppress the oily feeling by making use of the effect of water, and as a result, it provides a fresh moisturizing effect to the skin and has an excellent effect of sustaining it.
- the purpose is to provide.
- an object of the present invention is to provide a cosmetic that ensures optical transparency and is excellent in storage stability when blended in an emulsion-type cosmetic.
- an object of the present invention is to provide a novel co-modified organopolysiloxane having a group having a carbosiloxane dendron structure in the molecule and a hydrophilic group such as polyether, a surfactant comprising the co-modified organopolysiloxane, and the co-polymer. It is achieved by a powder treatment agent comprising a modified organopolysiloxane and an external preparation containing them, particularly a cosmetic.
- the object of the present invention is to provide the following general formula (1) R 1 a L 1 b Q c SiO (4-abc) / 2
- R 1 is a monovalent organic group (excluding the group which is L1 or Q) or a hydrogen atom.
- Q is bonded to a silicon atom via a divalent or higher linking group, and at least one hydrophilicity selected from hydrophilic units represented by the following structural formulas (3
- R is a number in the range of 1-6
- W is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
- a, b, and c are numbers in a range that satisfies 1.0 ⁇ a ⁇ 2.5, 0.001 ⁇ b ⁇ 1.5, and 0.001 ⁇ c ⁇ 1.5.
- a novel co-modified organopolysiloxane having a group having a siloxane dendron structure and a hydrophilic group “[1] The following general formula (1) R 1 a L 1 b Q c SiO (4-abc) / 2 (1) A co-modified organopolysiloxane having a group having a siloxane dendron structure and a hydrophilic group represented by: ⁇ In general formula (1), R 1 is a monovalent organic group (excluding the group which is L 1 or Q) or a hydrogen atom.
- R 2 is an alkyl group or a phenyl group having 1 to 6 carbon atoms
- Z is .i a divalent organic group designates generation of a silylalkyl group represented by L i, the silylalkyl
- L i the silylalkyl
- the number of hierarchies, which is the number of repeating groups, is c it is an integer of 1 to c
- the number of hierarchies c is an integer of 1 to 10
- Li + 1 is the silylalkyl group when i is less than c
- C is a methyl group or a phenyl group
- a i is a number in the range of 0 to 3.
- R 1 is the same group as described above, and in the general formula (2), a hydrogen atom, substituted or non-substituted A substituted monovalent hydrocarbon group having 1 to 30 carbon atoms is preferred.)
- Q is bonded to a silicon atom via a divalent or higher linking group, and at least one hydrophilicity selected from hydrophilic units represented by the following structural formulas (3-1) to (3-4) It is a hydrophilic group containing a unit.
- R is a number in the range of 1-6
- W is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
- a, b, and c are numbers in a range that satisfies 1.0 ⁇ a ⁇ 2.5, 0.001 ⁇ b ⁇ 1.5, and 0.001 ⁇ c ⁇ 1.5.
- Q is bonded to a silicon atom via a divalent or higher linking group, and is selected from the hydrophilic units represented by the structural formulas (3-1) to (3-4).
- the co-modified organopolysiloxane according to any one of [1] to [2], wherein the co-modified organopolysiloxane is a hydrophilic group having a branch unit selected from the group described above.
- R 4 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an acyl group, and glycidyl.
- Formula (4-2): —R 3 (—O—X 2 ) p (4-2) ⁇ R 3 is the same group as described above, and p is the same number as described above.
- X 2 is a hydrophilic group represented by the following structural formula (4-2-1). (In the formula, at least one hydrophilic unit selected from the hydrophilic units represented by the general formulas (3-1) to (3-4) is bonded to each of two oxygen atoms.
- X 3 is a hydrophilic group represented by the following structural formula (4-3-1). (In the formula, at least one hydrophilic unit selected from the hydrophilic units represented by the general formulas (3-1) to (3-4) is bonded to each of two oxygen atoms. ) ⁇ Formula (4-4): —R 3 (—O—X 4 ) p (4-4) ⁇ R 3 is the same group as described above, and p is the same number as described above.
- X 4 is a hydrophilic group represented by the following structural formula (4-4-1). (In the formula, at least one hydrophilic unit selected from the hydrophilic units represented by the general formulas (3-1) to (3-4) is bonded to each of two oxygen atoms. ) ⁇
- n1 is a number in the range of 10 to 1,000
- n2 is a number in the range of 0 to 250
- n3 is a number in the range of 0 to 250.
- n2 0, at least one of R is L 1.
- n3 0, at least one of R is Q 1.
- Q 1 is each independently a hydrophilic group selected from the group consisting of the following structural formulas (4-1-2), (4-2-2), (4-3-2) and (4-4-2). Sex group.
- R 3 is a (p + 1) -valent organic group, p is a number of 1 or more and 3 or less.
- X1 is independently represented by the general formulas (3-1) to (3-4).
- at least one hydrophilic unit selected from the hydrophilic units selected, m is a number in the range of 1 to 100.
- R4 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an acyl group, and It is a group selected from the group consisting of glycidyl groups.
- each Z is independently a divalent organic compound represented by the following general formulas (5-1) to (5-7).
- each R 6 independently represents an optionally substituted linear or branched alkylene group having 2 to 22 carbon atoms, an alkenylene group, or an arylene group having 6 to 22 carbon atoms.
- R 7 is a group selected from divalent organic groups represented by the following formula.
- each R 6 independently represents an optionally substituted linear or branched alkylene group having 2 to 22 carbon atoms, an alkenylene group, or an arylene group having 6 to 22 carbon atoms. Is achieved.
- the object of the present invention is achieved by the invention of the surfactant and emulsion composition containing the above-mentioned co-modified organopolysiloxane, “[9] A surfactant containing the co-modified organopolysiloxane according to any one of [1] to [8]. [10] A surfactant containing the co-modified organopolysiloxane according to any one of (A) [1] to [8] and (A2) a hydrophilic compound having a reactive functional group.
- the object of the present invention is achieved by the invention of a powder treating agent, a powder composition, and a powder-in-oil dispersion containing the above-mentioned co-modified organopolysiloxane, [[12] A powder treating agent containing the co-modified organopolysiloxane according to any one of [1] to [8]. [13] A powder composition comprising the co-modified organopolysiloxane according to any one of (A) [1] to [8] and (D) a powder or powdery colorant.
- (D) 1.0 to 30 parts by mass of the co-modified organopolysiloxane according to any one of [A] [1] to [8] with respect to 100 parts by mass of the powder or powdery colorant
- the component (D) 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] or [14].
- [16] The powder composition according to [13] or [14], wherein the component (D) is an inorganic extender pigment.
- the object of the present invention is more suitably applied to the invention of an external preparation composition containing the above-mentioned co-modified organopolysiloxane, emulsion composition, powder composition or powder-in-oil dispersion, particularly cosmetics invention.
- the external preparation composition according to [18] which is a cosmetic or a medicine.
- a cosmetic comprising the emulsion composition according to [11].
- the object of the present invention is suitably achieved by a method for producing the above-mentioned co-modified organopolysiloxane by a hydrosilylation reaction.
- the production method includes: “[30] In the presence of a hydrosilylation reaction catalyst, the following general formula (1 ′) R 1 a H b + c SiO (4-abc) / 2 (1 ′) (Wherein R 1 , a, b and c are the same as above), a hydrophilic derivative (b) having one reactive unsaturated group in one molecule, and The co-modification according to any one of [1] to [8], which is obtained by reacting at least a siloxane dendron (c) having one reactive unsaturated group in one molecule.
- Siloxane dendron (c) having one reactive unsaturated group in one molecule has one carbon-carbon double bond at the end of the molecular chain represented by the following general formula (2 ′)
- General formula (2 ′): ⁇ In the formula, L ′ 1 is a methyl group or a silylalkyl group represented by the following general formula (2 ′′) when j 1.
- Z ′ is a divalent organic group.
- R 2 represents an alkyl group having 1 to 6 carbon atoms or a phenyl group
- Z represents a divalent organic group
- j represents a hierarchy of silylalkyl groups represented by L j
- L j + 1 is the silylalkyl group when j is less than c ′
- j c ′, it is a methyl group or a phenyl group.
- a j is a number in the range of 0 to 3.
- the production is easy, the two-phase separation and the precipitation of the unreacted raw material hardly occur after the production, the chemically stable and excellent practicality, the group having a siloxane dendron structure in the molecule and the hydrophilicity.
- a novel co-modified organopolysiloxane having a group and a process for producing the same can be provided.
- a surfactant comprising the co-modified organopolysiloxane, which can stably emulsify various oils and can impart a unique texture to the emulsion.
- a powder treating agent comprising the co-modified organopolysiloxane, having good dispersion stability in a mixed oil system, and a powder composition obtained by treating the powder surface with a treating agent After the preparation, a powder dispersion in oil excellent in stability that does not cause aggregation or sedimentation of the powder even when a method of dispersing it in an oil agent as a dispersion medium is used is provided. Things can be provided.
- the present invention it is possible to provide a preparation for external use of the co-modified organopolysiloxane, in particular, as a raw material for cosmetics, and a cosmetic containing the organopolysiloxane.
- a cosmetic containing the organopolysiloxane when formulated in cosmetics containing water and oils, it works to suppress the oily feeling by making use of the effect of water, and as a result, it provides a fresh moisturizing effect to the skin and has an excellent effect of sustaining it.
- when blended in an emulsion-type cosmetic it is possible to provide a cosmetic that ensures optical transparency and is excellent in storage stability, if desired.
- an oily cosmetic material substantially free of water that can give a natural and uncomfortable skin feeling and a sufficient moisturizing feeling after application.
- the novel co-modified organopolysiloxane according to the present invention is a co-modified organopolysiloxane having a group having a siloxane dendron structure and a hydrophilic group, and specifically includes the following general formula (1) R 1 a L 1 b Q c SiO (4-abc) / 2 (1)
- a co-modified organopolysiloxane having a group (-L 1 ) having a siloxane dendron structure and a hydrophilic group (-Q) represented by (Hereinafter, it is a group represented by L 1 in the general formula (1), and when i 1, the silylalkyl group represented by the following general formula (2) has a “carbosiloxane dendrimer” or “siloxane dendron structure” It may be expressed as a “silylalkyl group”).
- R 1 is a monovalent organic group or a hydrogen atom.
- the monovalent organic group which is R 1 does not include a group corresponding to the above L 1 or Q.
- R 1 include a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, or a chain or branched polysiloxane chain. .
- substituted or unsubstituted monovalent hydrocarbon group examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, and a dodecyl group.
- Saturated aliphatic hydrocarbon group saturated alicyclic hydrocarbon group such as cyclopentyl group and cyclohexyl group; aromatic hydrocarbon group such as phenyl group, tolyl group, xylyl group and naphthyl group; and carbon atoms of these groups
- Examples thereof include a group in which the bonded hydrogen atom is at least partially substituted with a halogen atom such as fluorine, or an organic group including an epoxy group, an acyl group, a carboxyl group, an amino group, a methacryl group, a mercapto group, and the like.
- alkoxy group examples include a methoxy group, an ethoxy group, an isopropanoxy group, and a higher alkoxy group.
- the chain or branched polysiloxane chain is a chain or branched polysiloxane chain that does not correspond to L 1 , and is bonded to the siloxane by a divalent linking group, and has a silanol terminal or a trimethylsiloxy terminal or n
- Examples include those having a polysiloxane chain structure composed of dimethylpolysiloxane units having a butyldimethylsiloxy terminal and a polymerization degree of 1 to 100.
- a part of the methyl group of the polysiloxane chain is substituted with a halogen atom such as phenyl group or fluorine, or an organic group containing an epoxy group, acyl group, carboxyl group, amino group, methacryl group, mercapto group, or the like. May be.
- a halogen atom such as phenyl group or fluorine
- the co-modified organopolysiloxane of the present invention introduces a modifying group other than a group having a siloxane dendron structure (—L 1 ) and a hydrophilic group (—Q) as R 1 for the purpose of imparting further functionality. Or it can be designed. That is, when R 1 is a substituted monovalent hydrocarbon group, the substituent can be appropriately selected according to the characteristics and application of the organic group exemplified above. For example, when used as a cosmetic raw material, a monovalent hydrocarbon group substituted with an amino group, aminoethylaminopropyl group, carboxyl group or the like is selected for the purpose of improving the feeling of use, feel or sustainability. Can do.
- an alkyl group having 8 to 20 carbon atoms can be selected.
- R 1 is preferably a monovalent hydrocarbon group or a monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms.
- the monovalent hydrocarbon group having no aliphatic unsaturated bond belonging to R 1 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 1 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 a carbosiloxane unit spreads in a dendrimer shape, and is a functional group exhibiting high water repellency compared to a linear or mere branched polysiloxane unit, Due to the good balance of the combination with the hydrophilic group, the co-modified organopolysiloxane according to the present application can be provided with excellent surface activity ability. Further, 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 2 represents an alkyl group having 1 to 6 carbon atoms or a phenyl group, and examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n- Examples thereof include linear, branched or cyclic alkyl groups such as butyl, i-butyl, s-butyl, pentyl, neopentyl, cyclopentyl and hexyl.
- R 1 is the same group as described above.
- R 1 is preferably a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms. Particularly preferred is a methyl group or a hydrogen atom.
- a i is a number in the range of 0-3.
- the number of layers c 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.
- a i each independently represents a number in the range of 0 to 3, and in the structure represented by the formulas (2-1) to (2-3) when the number of layers is 1 to 3, 1 , a 2 and a 3 are each independently a number ranging from 0 to 3.
- a i are particularly preferably numbers in the range of 0 to 1, and a 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.
- Z is each independently a group selected from divalent organic groups represented by the following general formulas (5-1) to (5-7).
- Z in L 1 is preferably a divalent organic group represented by the general formula (5-1) introduced by a reaction between a silicon-bonded hydrogen atom and an alkenyl group.
- Z is preferably a divalent organic group represented by the general formula (5-3) introduced by a reaction between a silicon-bonded hydrogen atom and an unsaturated carboxylic ester group.
- the silylalkyl group represented by L is a 2 ⁇ L c 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 or a hexylene group is particularly preferable, and an ethylene group is most preferable.
- each R 6 independently represents an optionally substituted linear or branched alkylene group having 2 to 22 carbon atoms, alkenylene. Or an arylene group having 6 to 22 carbon atoms. More specifically, R 6 is 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. And a branched alkylene group such as R6 is preferable, and R 6 is preferably a group selected from an ethylene group, a propylene group, a methylethylene group, or a hexylene group.
- R 7 is a group selected from divalent organic groups represented by the following formulae.
- Q is a hydrophilic group, which is bonded to a silicon atom via a divalent or higher valent linking group and is represented by the following structural formulas (3-1) to (3-4). Defined as a hydrophilic group containing at least one hydrophilic unit selected from sex units. Q that is a hydrophilic group is a portion that imparts hydrophilicity to the co-modified organopolysiloxane according to the present application, and is generally a functional group derived from a hydrophilic compound.
- Q defined as above is a mono- or higher-valent alcohol, a polyether compound, a polyglycerin compound, a polyglycidyl ether compound, a hydrophilic group, the molecular chain terminal of which may be partially blocked with a hydrocarbon.
- a functional group derived from a natural saccharide can be preferably exemplified.
- Suitable Q is a group derived from polyglycene, and it is particularly preferable that Q is a hydrophilic group having a triglycerin structure or a tetraglycerin structure.
- Q is bonded to a silicon atom via a divalent or higher valent linking group, and at least 1 selected from hydrophilic units represented by the following structural formulas (3-1) to (3-4) It is a hydrophilic group containing at least one kind of hydrophilic unit.
- the hydrophilic unit represented by the above formula (3-1) is an oxyalkylene unit.
- r is a number in the range of 1 to 6, and more preferably in the range of 2 to 4.
- One or more hydrophilic units represented by the above formula (3-1) can be contained in the hydrophilic group as Q.
- the hydrophilic unit represented by (3-1) is a polyoxyalkylene unit in which r is independently 2 to 4 and 2 to 50 hydrophilic units represented by formula (3-1) are linked.
- Q is preferably contained in a hydrophilic group.
- the hydrophilic group represented by the formula (3-1) is preferably contained in the hydrophilic group Q as a polyoxyalkylene unit having 4 to 50 linked units. It is more preferable that at least one polyoxyalkylene unit represented by -1) is contained in Q.
- t1 and t2 are each a number of 0 or more
- (t1 + t2) is a number in the range of 4 to 50, preferably a number in the range of 8 to 30.
- W is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and is preferably a hydrogen atom.
- W is a hydrogen atom
- aldehydes such as formaldehyde and allergenic compounds such as formates over time during storage.
- the hydrophilic units represented by the structural formulas (3-2) to (3-4) are mainly polyhydric alcohols containing glycerin, polyglycerins (also referred to as polyglycerols), polyglycidyl ethers, or terminals thereof. Although it is a hydrophilic unit contained in a hydrophilic group derived from a hydrophilic compound selected from a compound in which a hydroxyl group is partially blocked with a hydrocarbon group, it is not limited thereto.
- Q may be a hydrophilic group having no branched structure such as a linear polyoxyalkylene group.
- Q may be a hydrophilic group having a branched structure in a part of the functional group.
- Q is bonded to a silicon atom via a divalent or higher linking group and is at least 1 selected from hydrophilic units represented by the structural formulas (3-1) to (3-4). It may be a hydrophilic segment formed by linearly bonding a kind or more of hydrophilic units, and Q is bonded to a silicon atom via a divalent or higher linking group, and the structural formula (3- 1) containing at least one hydrophilic unit selected from the hydrophilic units represented by (3-4) and having the following structural formulas (3-5) to (3-7) The hydrophilic segment which has a branch unit selected from group represented by these may be sufficient.
- the divalent or higher valent linking group is a bonding site to the silicon atom contained in the hydrophilic group as Q, and the structure thereof is not particularly limited, but ethylene group, propylene group, butylene group, hexylene Alkylene groups such as ethylene phenylene groups, alkylene phenylene groups such as propylene phenylene groups, alkylene aralkylene groups such as ethylene benzylene groups; alkylenoxy phenylene groups such as ethylenoxy phenylene groups and propyleneoxy phenylene groups; Examples include alkylenoxy benzylene groups such as a nonoxy benzylene group, an ethylenoxy benzylene group, a propylenoxy benzylene group, and the groups shown below.
- the number of ether bonds in the divalent or higher linking group is preferably 0 to 3, more preferably 0 or 1.
- Q is more preferably a hydrophilic group represented by the following general formulas (4-1) to (4-3).
- R 3 is a (p + 1) -valent organic group, and p is a number of 1 or more and 3 or less. Examples of such R 3 include the same groups as the divalent or higher linking group.
- p is 1, and is a group selected from divalent organic groups represented by the following formulae.
- each R 6 independently has a substituent, a linear or branched alkylene group having 2 to 22 carbon atoms, an alkenylene group, or an arylene group having 6 to 22 carbon atoms. .
- X 1 is each independently at least one hydrophilic unit selected from the hydrophilic units represented by the general formulas (3-1) to (3-4), and m is in the range of 1 to 100 Is the number of
- X 1 is a hydrophilic unit (alkyleneoxy group) represented by the above general formula (3-1)
- m is preferably a number in the range of 4 to 50
- ⁇ X 1 It is particularly preferable that the structure represented by “ m ⁇ ” is a polyoxyalkylene unit represented by the above formula (3-1-1).
- X 1 includes the hydrophilic units represented by the general formulas (3-2) to (3-4), m is preferably a number in the range of 1 to 50, and in the range of 1 to 15. Is more preferable.
- R 4 is a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an acyl group, and a glycidyl group, and is preferably a hydrogen atom or a methyl group.
- R 3 is the same group as described above, and p is the same number as described above.
- X 2 is a hydrophilic group represented by the following structural formula (4-2-1).
- at least one or more hydrophilic units selected from the hydrophilic units represented by the general formulas (3-1) to (3-4) are independently bonded to the two oxygen atoms. .
- the hydrophilic unit may be further bonded to a branch unit selected from the groups represented by structural formulas (3-5) to (3-7), and the hydrophilic unit is branched in multiple layers.
- a dendritic polyether structure, a polyglycerol structure or a polyglycidyl ether structure may be formed.
- hydrophilic group shown by the following general formula (4-2-2) is illustrated as a hydrophilic group shown by general formula (4-2).
- p, R 3 , X 1 , R 4 and m are the same as described above.
- Formula (4-3) —R 3 (—O—X 3 ) p (4-3)
- R 3 is the same group as described above, and p is the same number as described above.
- X 3 is a hydrophilic group represented by the following structural formula (4-3-1).
- at least one or more hydrophilic units selected from the hydrophilic units represented by the general formulas (3-1) to (3-4) are independently bonded to the two oxygen atoms.
- the hydrophilic unit may be further bonded to a branch unit selected from the groups represented by structural formulas (3-5) to (3-7), and the hydrophilic unit is branched in multiple layers.
- a dendritic polyether structure, a polyglycerol structure or a polyglycidyl ether structure may be formed.
- hydrophilic group shown by the following general formula (4-3-2) is illustrated as a hydrophilic group shown by general formula (4-3).
- p, R 3 , X 1 , R 4 and m are the same as described above.
- Formula (4-4) —R 3 (—O—X 4 ) p (4-4)
- R 3 is the same group as described above, and p is the same number as described above.
- X 4 is a hydrophilic group represented by the following structural formula (4-4-1).
- at least one or more hydrophilic units selected from the hydrophilic units represented by the general formulas (3-1) to (3-4) are independently bonded to the two oxygen atoms. .
- the hydrophilic unit may be further bonded to a branch unit selected from the groups represented by structural formulas (3-5) to (3-7), and the hydrophilic unit is branched in multiple layers.
- a dendritic polyether structure, a polyglycerol structure or a polyglycidyl ether structure may be formed.
- hydrophilic group shown by the following general formula (4-4-2) is illustrated as a hydrophilic group shown by general formula (4-4).
- p, R 3 , X 1 , R 4 and m are the same as described above.
- a, b, and c are numbers within a range of 1.0 ⁇ a ⁇ 2.5, 0.001 ⁇ b ⁇ 1.5, and 0.001 ⁇ c ⁇ 1.5. is there. Within these numerical ranges, the co-modified organopolysiloxane according to the present application has a linear or branched polysiloxane main chain structure.
- a co-modified organopolysiloxane represented by the following structural formula (1-1) is preferably exemplified.
- R 1 can part of the carbon bonded hydrogen as part of the 1 selects a halogen atom, other monovalent substituted by organic hydrocarbon group or a long chain alkyl group such as a fluorine atom, and preferred. It may also contain hydrogen atoms bonded to Si atoms as a part of R 1 (-H).
- (n1 + n2 + n3) is a number in the range of 3 to 2,000, preferably in the range of 5 to 1,500, and more preferably in the range of 10 to 1,000.
- n1, n2 and n3 are numbers in the range from 0 to 2,000, n1 is a number in the range from 10 to 1,000, n2 is a number in the range from 1 to 250, and n3 is from 1 to 250. A number in the range is preferred.
- n1 is a number in the range of 10 to 1,000
- n2 is a number in the range of 1 to 50
- N3 is particularly preferably a number in the range of 1 to 50.
- the co-modified organopolysiloxane according to the present application is particularly preferably a co-modified organopolysiloxane represented by the following structural formula (1-1-1) or (1-1-2).
- Z and R 1 are the same groups as described above, and R is R 1 , L 1 described above, and Q 1 described below.
- n2 0, at least one of R is L 1.
- n3 0, at least one of R is Q 1.
- Q 1 is each independently a hydrophilic group selected from the group consisting of the following structural formulas (4-1-2), (4-2-2), (4-3-2) and (4-4-2). Sex group.
- R 3 , X 1 and R 4 are the same groups as described above, and p and m are the same numbers as described above.
- the co-modified organopolysiloxane according to the present application is a compound having a siloxane dendron structure having one carbon-carbon double bond at one end of a molecular chain and a reaction with respect to an organopolysiloxane having a reactive functional group. It can be obtained by addition reaction of a hydrophilic compound having a functional functional group.
- the type of addition reaction 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.
- the co-modified organopolysiloxane according to the present application is represented by the following general formula (1 ′) in the presence of a hydrosilylation reaction catalyst.
- R 1 a H b + c SiO (4-abc) / 2 (1 ′) (Wherein R 1 , a, b and c are the same as above), a hydrophilic derivative (b) having one reactive unsaturated group in one molecule, and It can be obtained by reacting at least a siloxane dendron (c) having one reactive unsaturated group in one molecule.
- the co-modified organopolysiloxane according to the present application includes a hydrophilic derivative (b) having one reactive unsaturated group in one molecule and a siloxane dendron (c) having one reactive unsaturated group in one molecule. ) At least in the coexistence state, the organohydrogensiloxane (a) represented by the component (b), the component (c) and the general formula (1 ′) are reacted together more preferably. can do.
- the siloxane In a state where these components do not coexist, specifically, when the method of reacting the component (b) after reacting the component (c) alone with the organohydrogenpolysiloxane is selected, the siloxane The proportion of the modified organopolysiloxane modified only with a group having a dendron structure is increased, and phase separation is caused due to poor compatibility with the surplus component (b) (specifically, polyglycerol monoallyl ether, etc.). May occur. As a result, a compound having an average composition formula as designed at the time of introduction of the functional group may not be obtained with respect to the content of silicon-bonded hydrogen atoms.
- the concentration of the hydrophilic group, particularly the polyhydric alcohol group such as polyglycerin, with respect to the Si-H group concentration of the reaction system is unsaturated.
- the concentration becomes relatively high as compared to the concentration, and the whole gels due to a dehydrogenation reaction or the like.
- organohydrogensiloxane (a) represented by the general formula (1 ′) an organohydrogensiloxane represented by the following structural formula (1-1) ′ is preferably exemplified.
- each R 1 is independently the same group as described above, and R ′ is a group selected from R 1 or a hydrogen atom.
- Hydrophilic derivatives (b) having one reactive unsaturated group per molecule include alkenyl groups at the ends of molecular chains such as allyl polyether, allyl polyglycerol, allyl polyglycidyl ether, polyglyceryl eugenol, glycerin monoallyl ether, etc. These are hydrophilic compounds having a reactive functional group, which can be synthesized by a known method, and some are commercially available.
- the siloxane dendron (c) having one reactive unsaturated group in one molecule has one carbon-carbon double bond at the molecular chain end represented by the following general formula (2 ′). It is a compound having a siloxane dendron structure.
- General formula (2 ′): ⁇ In the formula, L ′ 1 is a methyl group or a silylalkyl group represented by the following general formula (2 ′′) when j 1.
- Z ′ is a divalent organic group.
- R 1 is the same group as described above, and in general formula (2 ′′) And preferably a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms, particularly preferably a methyl group or a hydrogen atom.
- the hydrosilylation reaction is preferably performed in the presence of a catalyst, and examples thereof include platinum, ruthenium, rhodium, palladium, osmium, iridium, and the like, and a platinum compound is particularly effective because of its high catalytic activity.
- platinum compounds include: chloroplatinic acid; metal platinum; a metal platinum supported on a carrier such as alumina, silica, carbon black; platinum-vinylsiloxane complex, platinum-phosphine complex, platinum-phosphite complex And platinum complexes such as platinum alcoholate catalysts.
- the amount of the catalyst used is about 0.5 to 100 ppm as metallic platinum when a platinum catalyst is used.
- the crude product of the co-modified organopolysiloxane obtained by the above addition reaction can be purified by subjecting it to a non-bromide treatment by a hydrogenation reaction in a solvent or in the absence of a solvent in the presence of a hydrogenation catalyst.
- a refined product is preferably used in the case of use in an external preparation that requires a reduction in the amount and compatibility with other cosmetic ingredients.
- a stripping process is performed in which a light product is distilled off by contacting nitrogen gas under reduced pressure with a crude product or hydrogenated product of a co-modified organopolysiloxane. It is preferable.
- Such hydrogenation reaction and stripping step can be carried out using any known organopolysiloxane copolymer, solvent used for purification of polyether-modified silicones, reaction conditions, reduced pressure conditions and the like without any particular limitation. Can do.
- the crude product of the co-modified organopolysiloxane obtained by the above addition reaction hydrolyzes an unreacted unsaturated compound by adding an acidic substance, and then contacts nitrogen gas under reduced pressure to make a light product.
- the stripping step of distilling off low bromide can be simply carried out.
- the co-modified organopolysiloxane according to the present invention obtained by the above-described production method can be easily produced, and the modification rate and the type of the modifying group can be easily controlled simply by changing the raw material preparation. Functional molecular design is easy. Furthermore, the obtained co-modified organopolysiloxane has the advantage that it is chemically stable and excellent in practical use, with little phase separation or unreacted raw material precipitation after production.
- the novel co-modified organopolysiloxane according to the present invention (hereinafter also referred to as “component (A)”) is hydrophobic and has the same molecule as a silylalkyl group having a siloxane dendron structure exhibiting high water repellency and a hydrophilic group.
- component (A) is hydrophobic and has the same molecule as a silylalkyl group having a siloxane dendron structure exhibiting high water repellency and a hydrophilic group.
- the hydrophilic group is preferably a polyhydric alcohol such as polyether or glycerin, or a derivative such as polyglycerin or polyglycidyl ether
- the novel co-modified organopolysiloxane of the present invention is particularly useful as a nonionic surfactant. Is suitable, and various oil agents can be stably emulsified, and there is an advantage that a unique texture and excellent feel can be imparted to the e
- the novel organopolysiloxane copolymer of the present invention exhibits an excellent effect on surface activity (dispersibility, emulsification) in a small amount.
- agents especially cosmetics, foam stabilizers for urethane foam production, mold release agents, antifoaming agents, fiber treatment agents, adhesives, antifogging agents, glazing agents, water repellents, paints, resin additives, electrification
- the polysiloxane chain part is selected in the range of about 2 to 10 polymerization degree and highly volatile polyether is used as the hydrophilic group, it should be used suitably for applications such as cleaning of electric and electronic parts. Can do.
- the novel co-modified organopolysiloxane (A) according to the present invention is an excellent surfactant alone, but a reaction such as an alkenyl group at the end of the molecular chain of allyl polyether, allyl polyglycerol, allyl polyglycidyl ether, etc. It can also be suitably used as a mixture with the hydrophilic compound (A2) having a functional functional group.
- the hydrophilic compound having a reactive functional group is used for the production of the novel co-modified organopolysiloxane according to the present invention from the viewpoint of uniform miscibility with the co-modified organopolysiloxane (A), emulsification characteristics, and dispersibility.
- the same compounds as the hydrophilic compound to be used are exemplified and preferred.
- composition obtained by mixing the co-modified organopolysiloxane (A) according to the present invention and the hydrophilic compound (A2) having a reactive functional group has a ratio represented by component (A) / component (A2) of 50. / 50 to 99.5 / 0.5 is preferable, and 80/20 to 99/1 is particularly preferable.
- the emulsion composition containing the co-modified organopolysiloxane (A) according to the present invention will be described.
- the co-modified organopolysiloxane (A) according to the present invention or a mixture of the co-modified organopolysiloxane (A) and the hydrophilic compound (A2) having a reactive functional group is useful as a surfactant.
- Various oil agents and water can be stably emulsified to form an emulsion composition.
- the type of emulsion may be an oil-in-water emulsion or a water-in-oil emulsion, and an emulsion composition (such as an O / W / O emulsion) having such an emulsion as an internal phase (dispersed particles).
- an emulsion composition such as an O / W / O emulsion having such an emulsion as an internal phase (dispersed particles).
- the emulsion composition according to the present invention is preferably an emulsion composition containing (A) a co-modified organopolysiloxane, (B) water, and an oil, and can be used as a raw material for external preparations and particularly cosmetics. it can.
- Water does not contain components harmful to the human body and may be clean, and examples thereof include tap water, purified water, mineral water, and deep sea water.
- the amount of water used and the blending ratio are not limited, but it is preferably in the range of 5 to 99% by weight of the whole emulsion, particularly in the range of 10 to 80% by weight. It is preferable.
- the oil agent is preferably (C) one or more oil agents selected from silicone oil, hydrocarbon oil or ester oil that is liquid at 5 to 100 ° C.
- these oil agents can be emulsified by combining one or two or more kinds selected from known vegetable oils, animal fats, higher alcohols, liquid fatty acid triglycerides, and artificial sebum.
- the silicone oil as component (C) is a linear organopolysiloxane represented by the following general formula (1) or a cyclic organopolysiloxane represented by the general formula (2) and the general formula (3).
- the branched organopolysiloxanes shown are mentioned.
- R 1 represents a hydrogen atom, a hydroxyl group, a monovalent unsubstituted or fluorine-substituted alkyl group having 2 to 30 carbon atoms, an aryl group, an amino-substituted alkyl group, an alkoxy group.
- n is an integer from 0 to 1000
- m + n is an integer from 1 to 2000
- x, y is 0, 1, 2, or 3
- p and q are integers from 0 to 8 and 3 ⁇ p + q ⁇ 8
- r is an integer from 1 to 4
- u is an integer from 0 to 500.
- silicone oils having these structures include hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane as cyclic organopolysiloxanes.
- linear organopolysiloxanes examples include trimethylsiloxy group-blocked dimethylpolysiloxanes at both ends of the molecular chain (dimethylsilicone having a low viscosity ranging from 2 cst and 6 cst to high viscosity such as 1 million cst), organohydrogenpolysiloxane, trimethyl at both ends of the molecular chain.
- the hydrocarbon oil as component (C) includes liquid paraffin, light liquid isoparaffin, heavy liquid isoparaffin, petrolatum, n-paraffin, isoparaffin, isododecane, isohexadecane, polyisobutylene, hydrogenated polyisobutylene, polybutene, ozokerite, ceresin. , Microcrystalline wax, paraffin wax, polyethylene wax, polyethylene / polypropylene wax, squalane, squalene, pristane, polyisoprene and the like.
- ester oil as component (C) examples include hexyldecyl octanoate, cetyl octanoate, isopropyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, oleyl oleate, decyl oleate, myristic acid Octyldodecyl, hexyldecyl dimethyloctanoate, cetyl lactate, myristyl lactate, diethyl phthalate, dibutyl phthalate, lanolin acetate, ethylene glycol monostearate, propylene glycol monostearate, propylene glycol dioleate, glyceryl monostearate, monoolein Glyceryl acid, glyceryl tri-2-ethylhexanoate, trimethylolpropane tri-2-ethylhexan
- Methods for dispersing and emulsifying oil and water include homomixers, paddle mixers, Henschel mixers, homodispers, colloid mills, propeller stirrers, homogenizers, inline continuous emulsifiers, ultrasonic emulsifiers, vacuum kneaders, etc.
- the method of dispersing this composition in water by a mechanical force using an apparatus is illustrated.
- the emulsion composition 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 emulsion composition can be blended with other cosmetic raw material components to be described later in the aqueous phase or oil phase, and the emulsion composition containing these cosmetic raw material components is included in the present invention.
- the emulsion composition containing the co-modified organopolysiloxane of the present invention comprises an aqueous phase containing the component (B) and an oil phase containing the component (A) and the component (C) which is an oil agent.
- the transparency of the two phases can be adjusted by adjusting the difference in refractive index at room temperature to 0.0020 units or less and emulsifying. More specifically, the method for adjusting the transparency of the emulsion composition of the present invention includes the following procedures (i) to (iv).
- Oil phase components such as (A) co-modified organopolysiloxane, (C) component volatile oil, non-volatile oil, solubilizer and the like are mixed by any method known in the art. Similarly, the aqueous phase component is mixed in a separate container.
- the refractive index (RI) of each phase is measured separately at room temperature (25 ° C.).
- the refractive index of each phase is adjusted so that the difference in refractive index between these two phases is at least within 0.0020 units, thereby ensuring the optical transparency of the final mixture.
- These two phases are emulsified. The emulsification can be carried out by a desired emulsification means. In general, these two phases are gradually poured into the oil phase while stirring using a mechanical means such as a shear mixer. The phases are combined as an emulsion.
- the method for adjusting the transparency of the emulsion of the present invention can be suitably used particularly in the preparation of a water-in-oil emulsion composition, and the resulting emulsion composition is subjected to high shear conditions under a homogenizer or other suitable apparatus.
- the transparency and stability can be further improved.
- the difference in refractive index between these two phases is within the refractive index (RI) unit of at least about 0.0020. It is preferably within a unit of about 0.00010, and most preferably there is no difference in refractive index between the two.
- an opaque emulsion composition can be obtained by performing an emulsification treatment without adjusting the refractive index of each phase.
- the adjustment of the refractive index can be easily performed by diluting the aqueous phase with an additional amount of water.
- the emulsion composition containing the co-modified organopolysiloxane according to the present invention has its aqueous phase.
- a refractive index (RI) adjusting agent can be blended in the oil phase to adjust the difference in refractive index between the oil phase and the aqueous phase, thereby ensuring optical transparency of the emulsion composition. That is, when the difference in refractive index between both phases is 0 or very small, the emulsion composition as a whole becomes transparent or translucent.
- the type and amount of the refractive index adjusting agent vary depending on the refractive index of the water phase and the oil phase, and are generally present in an amount sufficient to adjust the refractive index of the water phase and the oil phase so as to obtain optical transparency. .
- the refractive index adjusting agent can be used without particular limitation as long as it is a compound having an action of increasing the refractive index value of the aqueous phase of the composition or a component that decreases the refractive index value of the oil phase of the composition. .
- the addition of the refractive index adjusting agent may be performed at any of the steps (i) to (iv) described above, but practically, each phase is adjusted using the refractive index adjusting agent in the procedure (iii). It is preferable to adjust the refractive index.
- Ingredients used as refractive index adjusters for the aqueous phase include polyhydric alcohols and derivatives thereof, sugar alcohols and derivatives thereof, polyoxyalkylene group-containing alcohols, polyoxyalkylene group-containing ethers, silicone-polyether copolymer Examples include coalesced substances, arbitrary water-soluble polar substances, water-soluble inorganic salts, organic acid salts and amino acids. One or more of these water phase refractive index modifiers may be used in combination. Components which are a part of the components (E), (F), (G) and (K) described later can be suitably used as the refractive index adjuster for these aqueous phases.
- the refractive index adjuster of the aqueous phase is propylene glycol, dipropylene glycol, glycerin, sorbitol, mannitol, xylitol, pentaerythritol, trimethylolpropane, hexylene glycol, octylene glycol, 1,2-butane.
- the components used as the refractive index adjusting agent of the oil phase include those exemplified as the component (C) among the “oil agents” in the present invention, oils and fats commonly used in cosmetics, higher alcohols, higher fatty acids, and organic lipophilicity. What is chosen from surfactant etc. can be illustrated.
- the oil agent is different from the oil agent used as the base oil of the oil phase of the emulsion.
- One or more of these water phase refractive index modifiers may be used in combination.
- a mixture of two kinds of base oils may be used for the purpose of adjusting the refractive index of the oil phase.
- oil phase refractive index adjuster examples include silicone oils, ester oils such as lauryl myristate, diisopropyl sebacate, diisopropyl adipate, and C8-C18 alkyl benzoates, mineral oil, polydecene, hydrogenated polyisobutene, and the like.
- ester oils such as lauryl myristate, diisopropyl sebacate, diisopropyl adipate, and C8-C18 alkyl benzoates
- mineral oil polydecene, hydrogenated polyisobutene, and the like.
- hydrocarbon oil oleyl alcohol, batyl alcohol, lanolin alcohol, cholesterol, phytosterol, long chain alcohol such as octyldodecanol, PPG-3 myristyl ether, PPG-14 butyl ether, POE (20) glyceryl triisostearate or other mixtures is there.
- the co-modified organopolysiloxane according to the present invention has good dispersion stability in a mixed oil system when used as a powder treating agent, and a powder composition obtained by treating the powder surface with a treating agent. It is characterized by providing a powder-in-oil dispersion with excellent stability that does not cause suspicion or settling of the powder even when a method of dispersing it in an oil agent as a dispersion medium is prepared. To do.
- Powders that can be treated with the co-modified organopolysiloxane according to the present invention are powders and / or colorants used in cosmetics, and these powders and / or colorants are used in ordinary cosmetics. If used, its shape (spherical, rod-like, needle-like, plate-like, irregular shape, spindle shape, etc.), particle size (smoke-like, fine particles, pigment grade, etc.), particle structure (porous, non-porous) Any of these can be used regardless of the quality, etc., but when these powders and / or colorants are blended as pigments, inorganic pigment powders having an average particle diameter in the range of 1 nm to 20 ⁇ m, It is preferable to blend one type or two or more types selected from organic pigment powder and resin powder.
- the powder or powdery colorant as component (D) examples include inorganic powder, organic powder, surfactant metal salt powder (metal soap), colored pigment, pearl pigment, metal powder pigment and the like. Further, a composite of these pigments can also be used.
- the inorganic powder titanium oxide, zirconium oxide, zinc oxide, cerium oxide, magnesium oxide, barium sulfate, calcium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, talc, mica, kaolin, sericite, Muscovite, synthetic mica, phlogopite, saucite, biotite, lithia mica, silicic acid, anhydrous silicic acid, aluminum silicate, sodium silicate, sodium magnesium silicate, magnesium silicate, magnesium aluminum silicate, calcium silicate , Barium silicate, strontium silicate, metal tungstate, hydroxyapatite, vermiculite, hydrite, bentonite, montmorillonite, hectorite,
- Laked natural pigments such as carminic acid, laccaic acid, calsamine, bradylin, crocin, etc .
- metal powders such as aluminum, gold, silver, copper, platinum, and stainless steel.
- powders that absorb and scatter ultraviolet rays such as fine particle titanium oxide, fine particle iron-containing titanium oxide, fine particle zinc oxide, fine particle cerium oxide, and composites thereof, may be mentioned.
- these powders and / or colorants have been subjected to water repellency treatment.
- these powders and / or colorants were combined with each other, or surface treatment was performed with a general oil agent, a silicone compound other than the co-modified organopolysiloxane according to the present invention, a fluorine compound, a surfactant, or the like.
- a thing can also be used and it can use 1 type, or 2 or more types as needed.
- water-repellent treatments include those obtained by treating the above powder and / or colorant with various water-repellent surface treatment agents, such as methylhydrogenpolysiloxane treatment, silicone resin treatment, and silicone.
- Organosiloxane treatment such as gum treatment, acrylic silicone treatment, fluorinated silicone treatment, metal soap treatment such as zinc stearate treatment, silane treatment such as silane coupling agent treatment, alkylsilane treatment, perfluoroalkylsilane, perfluoroalkylphosphorus Fluorine compound treatment such as acid ester salt, perfluoropolyether treatment, amino acid treatment such as N-lauroyl-L-lysine treatment, oil agent treatment such as squalane treatment, acrylic treatment such as alkyl acrylate treatment, etc. Use in combination of one or more It is possible.
- the blending amount of the co-modified organopolysiloxane and the powder and / or colorant is 100% for the powder and / or colorant.
- the amount is preferably from 0.1 to 30 parts by mass, particularly preferably from 0.5 to 10 parts by mass with respect to parts by mass.
- the amount of these powders and / or colorants added to an external preparation composition, particularly cosmetics is preferably in the range of 0.1 to 99% by mass of the total cosmetics.
- the blending amount in the case of a powdered solid cosmetic is preferably in the range of 80 to 99% by mass of the entire cosmetic.
- 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 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 solution in which a co-modified organopolysiloxane is dissolved or dispersed in an oil agent.
- the powder is added and mixed and dispersed, and its form is a liquid dispersion.
- 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 such as ester oil or silicone oil. 2.
- the powder composition and the powder-in-oil dispersion containing the co-modified organopolysiloxane according to the present invention can be suitably used as an external preparation composition, particularly as a cosmetic or a cosmetic raw material.
- the co-modified organopolysiloxane according to the present invention is particularly useful as a cosmetic raw material, a pharmaceutical raw material, or an external preparation composition, and a cosmetic containing the co-modified organopolysiloxane has an advantage of excellent characteristics.
- a cosmetic containing the co-modified organopolysiloxane has an advantage of excellent characteristics.
- cosmetics also referred to as oily cosmetics
- the oil agent used in this case can include the same components as described above.
- one or more polyhydric alcohols and / or lower monohydric alcohols can be used as the component (E) depending on the purpose.
- Examples of the lower alcohol include ethanol, isopropanol, n-propanol, t-butanol, and s-butanol.
- Examples of the polyhydric alcohol include 1,3-butylene glycol, 1,2-butylene glycol, propylene glycol, and trimethylene.
- Dihydric alcohols such as glycol, tetramethylene glycol, 2,3-butylene glycol, pentamethylene glycol, 2-butene-1,4-diol, dibutylene glycol, pentyl glycol, hexylene glycol, octylene glycol, glycerin, tri Trihydric alcohols such as methylolpropane and 1,2,6-hexanetriol, polyhydric alcohols more than tetravalent such as pentaerythritol and xylitol, sorbitol, mannitol, maltitol, maltotriose Sucrose, erythritol, glucose, fructose, starch hydrolyzate, maltose, xylitose, sugar alcohols such as amylolytic sugar reducing alcohol.
- Trihydric alcohols such as methylolpropane and 1,2,6-hexanetriol
- polyhydric alcohol polymers such as diethylene glycol, dipropylene glycol, triethylene glycol, polypropylene glycol, tetraethylene glycol, diglycerin, polyethylene glycol, triglycerin, tetraglycerin, polyglycerin, etc. Etc. are exemplified.
- 1,3-butylene glycol, sorbitol, dipropylene glycol, glycerin, and polyethylene glycol are particularly preferable.
- the blending amount is preferably in the range of 0.1 to 50% by weight of the entire cosmetic.
- the polyhydric alcohol can be added in an amount of about 5 to 30% by mass for the purpose of improving the storage stability of the cosmetic, and is included in one preferred embodiment of the present invention.
- inorganic salts and / or organic acid salts can be used as the component (F) depending on the purpose.
- inorganic salts include alkali metal salts such as hydrochloric acid, sulfuric acid, nitric acid, carbonic acid, and phosphoric acid, alkaline earth metal salts, aluminum salts, zinc salts, and ammonium salts.
- Preferred inorganic salts include chlorides such as sodium chloride, potassium chloride, magnesium chloride, calcium chloride, aluminum chloride, zinc chloride, and ammonium chloride, and sulfides such as sodium sulfate, potassium sulfate, magnesium sulfate, aluminum sulfate, zinc sulfate, and ammonium sulfate.
- chlorides such as sodium chloride, potassium chloride, magnesium chloride, calcium chloride, aluminum chloride, zinc chloride, and ammonium chloride
- sulfides such as sodium sulfate, potassium sulfate, magnesium sulfate, aluminum sulfate, zinc sulfate, and ammonium sulfate.
- carbonates such as sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbon
- Phosphorus oxides can be mentioned, among which sodium chloride, potassium chloride, magnesium chloride, calcium chloride, sodium sulfate, potassium sulfate, magnesium sulfate and aluminum sulfate are particularly preferable.
- Organic acid salts include sodium acetate, potassium acetate, sodium ascorbate, etc., as well as sodium citrate, sodium lactate, sodium glycolate, sodium malate, sodium tartrate and other ⁇ -hydroxy acid salts, sodium aspartate, aspartate Potassium, magnesium aspartate, calcium aspartate, sodium glutamate, potassium glutamate, magnesium glutamate, calcium glutamate, arginine-glutamate, ornithine-glutamate, lysine-glutamate, lysine-aspartate, ornithine-aspartate, etc.
- Examples include amino acid salts and sodium alginate. Of these, sodium acetate, sodium citrate, sodium lactate, and sodium glutamate are particularly preferable.
- the blending amount is 0.1 to 8% by weight, preferably 0.5 to 5% by weight of the total cosmetic.
- silicone surfactants excluding those which are co-modified organopolysiloxanes as component (A)
- component (G) can be used.
- silicone surfactants are not limited, but preferred are linear polyoxyalkylene-modified organopolysiloxanes (polyether-modified with polyoxyalkylene groups bonded to the side chain and / or terminal).
- silicone surfactants as a component that functions as an emulsifier for oils or a cleaning component, typically, polyglyceryl-modified silicone, glyceryl-modified silicone, sugar-modified silicone fluorine-based surfactant, polyoxyethylene, Examples thereof include polyoxypropylene block polymers and alkylpolyoxyethylene / polyoxypropylene block polymer ethers.
- 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.
- the crosslinkable organopolysiloxane used according to the purpose in the cosmetic of the present invention has a structure in which an organopolysiloxane chain is three-dimensionally cross-linked by reaction with a crosslinkable component and the like, such as a polyoxyalkylene unit.
- a crosslinkable component and the like such as a polyoxyalkylene unit.
- a non-emulsifying material having no hydrophilic part is preferred.
- Such a crosslinkable organopolysiloxane can be used without limitation regardless of the physical form such as dilution and properties, the production method, and the like, but particularly preferred are ⁇ , described in US Pat. No. 5,654,362.
- ⁇ -diene cross-linked silicone elastomer (commercially available products are DC 9040 Silicone Elastomer Blend, DC 9041 Silicone Elastomer Blend, DC 9045 Silicone Elastomer Blend, DC 9046 Silicone Elastomer, USA).
- the INCI name International Nomenclature Cosmetic labeling names
- (dimethicone / vinyl dimethicone) cross polymer the dimethicone / phenylvinyl dimethicone) cross polymer
- (PEG-8-30 / C6-C30 alkyl dimethicone) cross polymer the vinyl dimethicone / C6-C30 alkyl dimethicone) cross polymer
- (dimethicone / polyglycerin) cross polymer and the like.
- the co-modified organopolysiloxane according to the present invention functions as a surfactant or a surfactant aid. Therefore, there is an advantage that a uniform emulsification system can be formed. Furthermore, since the crosslinkable organopolysiloxane functions as a surfactant, it is possible to stably form a hydrogel structure even in a small amount of use, and to obtain a hydrous or emulsion cosmetic that is soft and excellent in water retention. is there.
- the organopolysiloxane elastomer spherical powder used according to the purpose in the cosmetic of the present invention is the same component as the spherical silicone rubber powder previously mentioned as the component (D), and the co-modified organo according to the present invention in advance.
- the powder processing by polysiloxane may be made
- Such an organopolysiloxane elastomer spherical powder preferably has a primary particle size in the range of 0.1 to 50 ⁇ m.
- the organopolysiloxane elastomer spherical powder may or may not be surface-treated with silicone resin or silica.
- organopolysiloxane elastomer spherical powders examples include Trefill E-506S, Trefill E-508, 9701, Cosmetic Powder, 9702 Powder manufactured by Toray Dow Corning.
- the organopolysiloxane elastomer spherical powder can also be used in the cosmetic of the present invention in the form of an aqueous dispersion.
- examples of such commercially available aqueous dispersions include BY 29-129 and PF-2001 PIF Emulsion manufactured by Toray Dow Corning.
- a silicone elastomer powder When a silicone elastomer powder is added to the cosmetics according to the present invention, it gives a rich feeling as obtained when dispersed in an oil, makes the skin unevenness inconspicuous, and unlike oils, it has an oily texture and texture. There is an advantage of giving a natural impression by suppressing the glow of the skin.
- silicone elastomers can be blended in one kind or two or more kinds according to the purpose, and within the range of 0.05 to 25% by mass of the whole cosmetic depending on the purpose and the intention of the blending. It is preferable to mix, and it is especially preferable to mix in the range of 0.1 to 15% by mass.
- the silicone resin used according to the purpose in the cosmetic of the present invention includes trialkylsiloxy units (M units), dialkylsiloxy units (D units), monoalkylsiloxy units (T units), and tetrafunctional siloxy units. It is preferably a solid silicone network compound that is an MQ resin, MDQ resin, MTQ resin, MDTQ resin, TD resin, TQ resin, or TDQ resin composed of any combination of (Q units).
- the substituent on silicon of these silicone resins may contain not only an alkyl group but also a substituted alkyl group, a phenyl group, an aryl group, and the like.
- fluorine-modified silicone resins trimethylsiloxysilicic acid (MQ resin), and dimethylsiloxy group-containing trimethylsiloxysilicic acid (MDQ resin) are particularly preferred because of their excellent usability.
- MQ resin trimethylsiloxysilicic acid
- MDQ resin dimethylsiloxy group-containing trimethylsiloxysilicic acid
- the acrylic silicone dendrimer copolymer used according to the purpose in the cosmetic of the present invention has a carbosiloxane dendrimer structure in the side chain described in Japanese Patent No. 4009382 (Japanese Patent Laid-Open No. 2000-063225).
- a vinyl polymer is particularly preferably exemplified.
- commercially available products include FA 4001 CM Silicone Acrylate manufactured by Toray Dow Corning, FA 4002 ID Silicone Acrylate, and the like.
- the surface protection characteristics such as sebum resistance are improved by the strong water repellency due to the carbosiloxane dendrimer structure, and the product of the present invention.
- High emulsification stability can be maintained, so that there is an advantage that a good feel and gloss can be given at the time of application, and unevenness such as wrinkles and pores of the applied skin can be effectively made inconspicuous.
- the co-modified organopolysiloxane according to the present invention has an advantage that it can suppress kinks and makeup on the skin because other oil agents, powders or colorants and an acrylic silicone dendrimer copolymer are suitably adapted.
- the powder composition for cosmetics having excellent blending stability by treating the powder or colorant with the co-modified organopolysiloxane of the present invention and the acrylic silicone dendrimer copolymer using a known method.
- Product can be prepared.
- the blending amount of the acrylic silicone dendrimer copolymer is appropriately selected according to the purpose and the intention of blending, but it is preferably blended within the range of 1 to 99% by weight of the whole cosmetic, and 30 to 70% by weight. It is particularly preferable to blend in the range of%.
- silicone raw rubber also called silicone gum
- silicone raw rubber can be blended depending on the purpose. Since silicone raw rubber has a high degree of polymerization, it is distinguished from the above oily silicones in that it has a measurable plasticity.
- silicone raw rubber include substituted or unsubstituted organopolysiloxane having a dialkylsiloxy unit (D unit), such as dimethylpolysiloxane, methylphenylpolysiloxane, methylfluoroalkylpolysiloxane, or the like, or a microcrosslinked structure thereof. Among them, dimethylpolysiloxane raw rubber having a polymerization degree of 3000 to 20000 is preferable.
- D unit dialkylsiloxy unit
- Silicone gum has an ultra-high degree of polymerization, so it forms a protective film with excellent persistence to hair and skin and excellent breathability. For this reason, it is a component which can give gloss and luster especially to hair, and can give a texture with tension and firmness to the whole hair during and after use.
- the blending amount of the silicone gum is in the range of 0.05 to 30% by mass, preferably in the range of 1 to 15% by mass with respect to the entire cosmetic.
- Silicone gum can be easily blended if an emulsified composition prepared in advance through an emulsification step (including emulsion polymerization) is used, and can be stably blended in various cosmetics in the present invention.
- the cosmetic of the present invention is a hair cosmetic or the like, if the amount of the silicone gum is less than the lower limit, the specific feel and the gloss imparting effect on the hair may be insufficient.
- a polyamide-modified silicone is useful as a thickening / gelling agent for oily raw materials, particularly silicone oil, as in the oil-soluble gelling agent described later.
- the affinity with an oil agent such as silicone oil is further improved. Therefore, the cosmetic according to the present invention is applied when applied to the skin or hair. Elongation and comfort are good, and it has excellent stability and adhesion. In addition, it is excellent in glossy transparency and gloss, and it is possible to adjust the viscosity and hardness (flexibility) of the entire cosmetics including oily raw materials as appropriate. There is an advantage in quality that the feeling) can be suppressed.
- the use of the polyamide-modified silicone and the co-modified organosiloxane of the present invention improves the dispersion stability of fragrances, powders, and the like, and thus has a characteristic that a uniform and fine makeup feel lasts for a long time.
- the amount of polyamide-modified silicone used is appropriately selected according to its purpose and intention of blending, but when used as a gelling agent for oily raw materials, The range is 0.5 to 80 parts by mass, and the range of 1 to 50 parts by mass is more preferable.
- the alkyl-modified silicone wax used according to the purpose in the cosmetic of the present invention may be a wax-like alkyl-modified silicone at room temperature, such as a molecular long-chain trimethylsiloxy group-blocked methyl long-chain alkylpolysiloxane, Examples thereof include a dimethylpolysiloxane / methyl long chain alkylsiloxane copolymer blocked with a trimethylsiloxy group at both molecular chain ends, and a long chain alkyl-modified dimethylpolysiloxane with both molecular chain terminals. Examples of these commercially available products include AMS-C30 Cosmetic Wax, 2503 Cosmetic Wax (manufactured by Dow Corning, USA).
- the affinity with the oily raw material is improved, and the moldability and the uniform dispersibility of each component are excellent.
- Cosmetics can be obtained. Especially in systems containing powder or colorant, it has the quality advantage that the system containing alkyl-modified silicone wax does not easily separate, and has excellent shape retention strength, and it is oily that stretches smoothly and evenly during application. Cosmetics can be provided.
- the above-mentioned alkyl-modified silicone wax preferably has a melting point of 60 ° C. or higher from the standpoint of cosmetic durability and high-temperature stability.
- the blending amount is appropriately selected according to the purpose and the intention of blending, but can be blended in the range of usually 1 to 50% by mass with respect to the entire cosmetic. In order to improve the moldability of the oily cosmetic and the longevity of the makeup, it is preferably blended in the range of 5 to 40% by mass.
- the alkyl-modified silicone wax has high affinity with silicone oils having a long-chain alkyl group, such as the above-mentioned alkyl-modified silicone, and cross-linkable organopolysiloxanes. Therefore, it is also preferable to use these alkyl-modified silicone wax in combination with these optional components. .
- alkyl-modified silicone resin wax used according to the purpose in the cosmetic of the present invention for example, a silsesquioxane resin wax described in JP-T-2007-532754 is preferable.
- an alkyl-modified silicone resin wax in combination with the organosiloxane copolymer of the present invention and blending it with the cosmetic of the present invention, it has the advantage of improving the conditioning effect on the skin or hair and imparting a fine and moist feel. is there.
- the blending amount of the alkyl-modified silicone resin wax is appropriately selected according to the purpose and the intention of blending, but is usually in the range of 0.5 to 50% by weight with respect to the entire cosmetic. Can be blended. A range of 1 to 30% by mass is particularly preferable in order to achieve sebum durability and a delicate feel to the cosmetic.
- the external preparation composition, cosmetics or cosmetic raw materials according to the present invention may further contain component (J), which is another surfactant, as necessary.
- component (J) is another surfactant, as necessary.
- (J) from the group consisting of an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, and a semipolar surfactant
- an anionic surfactant e.g., a cationic surfactant, e.g., a cationic surfactant, e.g., a nonionic surfactant, an amphoteric surfactant, and a semipolar surfactant
- One or two or more kinds of surfactants selected can be used in combination.
- a silicone-based nonionic surfactant e.g., silicone-based nonionic surfactant.
- the blending amount of these surfactants is in the range of 0.1 to 25% by mass, and preferably in the range of 0.5 to 10% by
- the cosmetic according to the present invention is a skin-cleaning or hair-cleaning cosmetic
- it may be blended within the range of 0.1 to 90% by mass of the entire cosmetic for the purpose of improving cleaning properties.
- organopolysiloxane of the present invention when used as a cleaning agent, two or more kinds of surfactants can be preferably blended from the viewpoint of cleaning activity. More specifically, as an anionic surfactant, saturated or unsaturated fatty acid salts (for example, sodium laurate, sodium stearate, sodium oleate, sodium linolenate, etc.), alkyl sulfates, alkylbenzene sulfonic acids (for example, hexylbenzene) Sulfonic acid, tocylbenzenesulfonic acid, dodecylbenzenesulfonic acid, etc.) and salts thereof, polyoxyalkylene alkyl ether sulfate, polyoxyalkylene alkenyl ether sulfate, polyoxyethylene alkyl sulfate ester, sulfosuccinic acid alkyl ester salt, polyoxy Alkylsulfosuccinic acid alkyl
- Nonionic surfactants include polyoxyalkylene ethers, polyoxyalkylene alkyl ethers, polyoxyalkylene fatty acid esters, polyoxyalkylene fatty acid diesters, polyoxyalkylene resin acid esters, polyoxyalkylene (cured) castor oil Polyoxyalkylene alkylphenols, polyoxyalkylene alkyl phenyl ethers, polyoxyalkylene phenyl phenyl ethers, polyoxyalkylene alkyl esters, polyoxyalkylene alkyl esters, sorbitan fatty acid esters, polyoxyalkylene sorbitan alkyl esters, Polyoxyalkylene sorbitan fatty acid esters, polyoxyalkylene sorbit fatty acid esters, polyoxyalkylene Glycerin fatty acid esters, polyglycerol alkyl ethers, polyglycerol fatty acid esters, sucrose fatty acid esters, fatty acid alkanolamides, alkyl gluco
- polyglyceryl-modified silicone those having an alkyl branch, a straight-chain silicone branch, etc., as necessary at the same time as a hydrophilic group can be suitably used.
- Amphoteric surfactants such as imidazoline type, amide betaine type, alkyl betaine type, alkyl amide betaine type, alkyl sulfobetaine type, amide sulfobetaine type, hydroxysulfobetaine type, carbobetaine type, phosphobetaine type, aminocarboxylic acid type, amide Amino acid type amphoteric surfactants are exemplified. Specifically, 2-undecyl-N, N, N- (hydroxyethylcarboxymethyl) -2-imidazoline sodium, 2-cocoyl-2-imidazolinium hydroxide-1-carboxyethyloxy disodium salt, etc.
- Imidazoline-type amphoteric surfactants alkylbetaine-type amphoteric surfactants such as lauryldimethylaminoacetic acid betaine and myristylbetaine; palm oil fatty acid amidopropyldimethylaminoacetic acid betaine, palm kernel fatty acid amidopropyldimethylaminoacetic acid betaine, beef tallow fatty acid amidopropyl Dimethylaminoacetic acid betaine, hardened tallow fatty acid amidopropyl dimethylaminoacetic acid betaine, lauric acid amidopropyl dimethylaminoacetic acid betaine, myristic acid amidopropyl dimethylaminoacetic acid betaine, palmitic acid amide
- Amidobetaine type amphoteric surfactants such as propyldimethylaminoacetic acid betaine, stearic acid amidopropyl dimethylaminoacetic acid betaine, oleic acid amidopropyldi
- the semipolar surfactant examples include alkylamine oxide type surfactants, alkylamine oxides, alkylamidoamine oxides, and alkylhydroxyamine oxides.
- Alkyldimethylamine oxide having 10 to 18 carbon atoms and 8 to 18 carbon atoms are exemplified.
- Alkoxyethyldihydroxyethylamine oxide and the like are preferably used.
- one or more water-soluble polymers can be used as the component (K) depending on the purpose.
- Water-soluble polymers can be used to prepare cosmetics in the desired dosage form, stabilize the aqueous phase, adjust the refractive index, and feel the skin and hair, improve the conditioning effect, etc.
- Any amphoteric, cationic, anionic, nonionic, or water-swellable clay mineral can be used as long as it is blended for the purpose of improving the viscosity and used in ordinary cosmetics. Since these water-soluble polymers have a thickening effect on the water-containing component, they are particularly useful for obtaining gel-like water-containing cosmetics, water-in-oil emulsion cosmetics, and oil-in-water emulsion cosmetics.
- Examples of natural water-soluble polymers include gum arabic, gum tragacanth, galactan, guar gum, carob gum, caraya gum, carrageenan, pectin, agar, quince seed (malmello), alge colloid (gypsum extract), starch (rice, corn, potato, Wheat), plant polymers such as glycyrrhizic acid, microbial polymers such as xanthan gum, dextran, succinoglucan and pullulan, and animal polymers such as collagen, casein, albumin and gelatin.
- semi-synthetic water-soluble polymers include starch polymers such as carboxymethyl starch and methylhydroxypropyl starch, methylcellulose, nitrocellulose, ethylcellulose, methylhydroxypropylcellulose, hydroxyethylcellulose, sodium cellulose sulfate, and hydroxypropyl.
- starch polymers such as carboxymethyl starch and methylhydroxypropyl starch, methylcellulose, nitrocellulose, ethylcellulose, methylhydroxypropylcellulose, hydroxyethylcellulose, sodium cellulose sulfate, and hydroxypropyl.
- examples thereof include cellulose polymers such as cellulose, sodium carboxymethyl cellulose (CMC), crystalline cellulose, and cellulose powder, and alginic acid polymers such as sodium alginate and propylene glycol alginate.
- Examples of the synthetic water-soluble polymers include polyvinyl polymers such as polyvinyl alcohol, polyvinyl methyl ether polymers, polyvinyl pyrrolidone, carboxyvinyl polymers (CARBOPOL 940, 941; BF Goodrich), polyethylene glycol 20,000, Polyoxyethylene polymer such as polyethylene glycol 6,000, polyethylene glycol 4,000, polyoxyethylene polyoxypropylene copolymer, PEG / PPG-36 / 41 dimethyl ether, PEG / PPG-14 / 7 dimethyl ether, etc. Examples thereof include polymer polymers, acrylic polymers such as sodium polyacrylate, polyethyl acrylate, and polyacrylamide, polyethyleneimine, and cationic polymers.
- polyvinyl polymers such as polyvinyl alcohol, polyvinyl methyl ether polymers, polyvinyl pyrrolidone, carboxyvinyl polymers (CARBOPOL 940, 941; BF Goodrich), polyethylene glycol 20,000
- quaternary nitrogen-modified polysaccharides for example, cation-modified cellulose, cation-modified hydroxyethyl cellulose, cation-modified guar gum, cation-modified locust
- quaternary nitrogen-modified polysaccharides are particularly suitable as components that can be blended in hair cosmetics.
- dimethyldiallylammonium chloride derivatives eg, dimethyldiallylammonium chloride-acrylamide copolymer, polydimethylmethylenepiperidinium chloride, etc.
- vinylpyrrolidone derivatives eg, vinylpyrrolidone, dimethylaminoethyl methacrylate
- acid copolymer salts vinylpyrrolidone / methacrylamidopropyltrimethylammonium chloride copolymer, vinylpyrrolidone / methylvinylimidazolium chloride copolymer, etc.
- one or more ultraviolet protection components can be used as the component (L) depending on the purpose.
- PABA paraaminobenzoic acid
- PABA monoglycerin ester N, N-dipropoxy PABA ethyl ester, N, N-diethoxy PABA ethyl ester, N, N-dimethyl PABA ethyl ester, N, N-dimethyl PABA
- Benzoic acid UV absorbers such as butyl ester, anthranilic acid UV absorbers such as homomenthyl-N-acetylanthranylate, amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, p-isopropanol Salicylic acid ultraviolet absorbers such as phenyl salicylate, octylcinnamate, e
- PABA paraaminobenzoic acid
- organic ultraviolet absorbers are generally highly polar and hardly soluble, it has been difficult to stably add a desired amount in a water-in-oil (W / O) emulsified cosmetic stably.
- W / O water-in-oil
- the co-modified organopolysiloxane of the present invention having a group having a carbosiloxane dendron structure, a long-chain alkyl group, and a hydrophilic group is used as an emulsifier, and an intermediate polar oil such as ester oil is used in combination as a binder, Even when the phase contains a low polarity oil such as silicone oil or hydrocarbon oil, a stable UV absorber-containing W / O emulsified cosmetic can be obtained.
- the blending amount is preferably 0.1 to 10% by mass of the organic ultraviolet absorber and 0.005 to 5% by mass of the binder.
- an inorganic UV protection component can be blended in addition to the UV protection component described above depending on the purpose.
- Such an inorganic ultraviolet protective component may be formulated by blending the inorganic powder exemplified in the above (D) powder and / or colorant as an ultraviolet dispersant, specifically, titanium oxide.
- Metal oxides such as zinc oxide, cerium oxide, low-order titanium oxide, iron-doped titanium oxide, metal hydroxides such as iron hydroxide, plate-like iron oxide, metal flakes such as aluminum flakes, ceramics such as silicon carbidekind.
- at least one selected from fine metal oxides or fine metal hydroxides having an average particle diameter in the range of 1 to 100 nm is particularly preferable.
- These powders are conventionally known surface treatments such as fluorine compound treatment (perfluoroalkyl phosphate treatment, perfluoroalkylsilane treatment, perfluoropolyether treatment, fluorosilicone treatment, fluorinated silicone resin treatment are preferred), silicone Treatment (methylhydrogenpolysiloxane treatment, dimethylpolysiloxane treatment, vapor phase tetramethyltetrahydrogencyclotetrasiloxane treatment is preferred), silicone resin treatment (trimethylsiloxysilicate treatment is preferred), pendant treatment (vapor phase silicone) Method of adding an alkyl chain after the treatment), silane coupling agent treatment, titanium coupling agent treatment, silane treatment (alkyl silane or alkylsilazane treatment is preferred), oil agent treatment, N-acylated lysine It is preferable that the surface treatment is performed by treatment, polyacrylic acid treatment, metal soap treatment (preferably stearic acid or myristic acid salt), acrylic resin treatment, metal oxide treatment, etc., and more preferably
- the surface of fine particle titanium oxide is coated with a metal oxide such as silicon oxide or alumina, and then surface-treated with alkylsilane.
- the surface treatment amount is preferably in the range of 0.1 to 50% by mass in total of the surface treatment amount with respect to the powder mass.
- the cosmetics of the present invention include oils and higher alcohols and higher fatty acids that are commonly used in cosmetics other than the oil used as the component (C) of the present invention. Can be used within a range not impairing the above.
- the cosmetic of the present invention includes oil-soluble gelling agents, organically modified clay minerals, antibacterial and preservatives, physiologically active ingredients, skin-beautifying ingredients, pH adjusters, antioxidants, Various components such as a solvent, a chelating agent, a moisturizing component, and a fragrance can be used as long as the object of the present invention is not impaired.
- oils and fats, higher alcohols and higher fatty acids include natural animal and vegetable oils and semi-synthetic oils such as avocado oil, linseed oil, almond oil, ibotarou, eno oil, olive oil, cacao butter, capok wax, kaya oil, carnauba wax , Liver oil, candelilla wax, beef tallow, beef leg fat, beef bone fat, hydrogenated beef tallow, kyounin oil, whale wax, hydrogenated oil, wheat germ oil, sesame oil, rice germ oil, rice bran oil, sugarcane wax, sasanqua oil, safflower Oil, shea butter, cinnamon oil, cinnamon oil, jojoba wax, olive squalane, shellac wax, turtle oil, soybean oil, tea seed oil, camellia oil, evening primrose oil, corn oil, lard oil, rapeseed oil, Japanese kiri oil, nukarou, Germ oil, horse fat, persic oil, palm oil, palm kernel oil, castor oil,
- POE means polyoxyethylene.
- the higher alcohol include lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, behenyl alcohol, hexadecyl alcohol, oleyl alcohol, isostearyl alcohol, hexyl decanol, octyldodecanol, cetostearyl alcohol, 2-decyltetradecyl. Nord, cholesterol, sitosterol, phytosterol, lanosterol, POE cholesterol ether, monostearyl glycerin ether (batyl alcohol), monooleyl glyceryl ether (ceralkyl alcohol) and the like.
- Examples of the higher fatty acid include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, undecylenic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA), Examples include isostearic acid and 12-hydroxystearic acid.
- oil-soluble gelling agents include amino acid derivatives such as N-lauroyl-L-glutamic acid and ⁇ , ⁇ -di-n-butylamine, dextrin palmitate, dextrin stearate, dextrin 2-ethylhexanoate palmitate
- Dextrin fatty acid esters such as esters, sucrose fatty acid esters such as sucrose palmitate, sucrose stearate, fructooligosaccharide fatty esters such as inulin stearate, fructooligosaccharide 2-ethylhexanoate, monobenzylidene sorbitol, di
- gelling agents selected from benzylidene derivatives of sorbitol such as benzylidene sorbitol.
- organically modified viscosity mineral examples include dimethylbenzyl dodecyl ammonium montmorillonite clay, dimethyl dioctadecyl ammonium montmorillonite clay, dimethyl alkyl ammonium hectorite, benzyl dimethyl stearyl ammonium hectorite, distearyl dimethyl ammonium chloride-treated aluminum magnesium silicate, and the like.
- these commercially available products include Benton 27 (benzyldimethylstearyl ammonium chloride-treated hectorite: National Red), Benton 38 (distearyldimethylammonium chloride-treated hectorite: National Red), and the like.
- an antiperspirant active ingredient and a deodorant agent can be blended.
- Antiperspirant active ingredients can be exemplified by astringent salts such as aluminum chlorohydrate or aluminum-zirconium tetrachlorohydrex glycine (ZAG), such as aluminum, hafnium, zinc and zirconium salts such as aluminum halide, aluminum hydroxyhalide, Zirconium halide, zirconium oxyhalide, zirconium hydroxyhalide, zirconyl hydroxide, aluminum zirconium chloride, zirconium lactate-aluminum, basic aluminum halide such as Al 2 (OH) 5 Cl, aluminum bromide, buffered aluminum sulfate, alum, baked Alum and their various water, alcohol or glycine complexes (eg aluminum containing aluminium, zirconium and glycine) Um Zirconium Chlorohydrate and Glycine Complex (ZAG Complex)) can also be used.
- ZAG aluminum-zirconium tetrachlorohydrex glycine
- antiperspirant active ingredients may be used alone or in combination of two or more.
- these antiperspirant active ingredients are one of the water phase ingredients.
- soybean extracts and isoflavones are also known to have an antiperspirant effect. Since these are low in water solubility, they are preferably used by dissolving in an oil phase.
- the amount of the antiperspirant active ingredient is an amount sufficient to reduce sweating and that the content is suppressed to a small amount. sell.
- the antiperspirant composition contains 5 to 25% by mass of an antiperspirant active ingredient based on the total cosmetics from the viewpoint of antiperspirant effect and feel.
- a water-soluble antiperspirant active ingredient for economic reasons, it is preferable to maximize the proportion of water in the composition while maintaining the antiperspirant effect, but the antiperspirant active ingredient is saturated with respect to the aqueous phase. It can also be added up to the amount.
- a deodorant agent can be blended together with the antiperspirant component or in place of the antiperspirant component.
- Deodorant agents can include deodorants, perfumes, and substances that prevent or remove odors from sweat.
- deodorants are antibacterial agents (bactericides or fungicides), bacteriostatic agents, odor adsorbing substances, deodorants, fragrances, etc. Blended. Needless to say, these deodorant agents are also useful in cosmetics other than antiperspirants, and can be suitably blended in the cosmetics of the present invention.
- Antibacterial agents include, for example, alkyltrimethylammonium bromide, cetylpyridinium chloride, benzethonium chloride, benzalkonium chloride, chlorhexidine hydrochloride, chlorhexidine gluconate, diisobutylphenoxyethoxyethyldimethylbenzylammonium chloride, N-lauroyl sarcosine sodium, N-palmitoyl sarcosine Sodium, N-myristoylglycine, N-lauroylsarcosine potassium, trimethylammonium chlorite, aluminum chlorohydroxylactate sodium, triethyl citrate, tricetylmethylammonium chloride, 1,5-pentanediol, 1,6-hexanediol, 2, 4,4'-trichloro-2'-hydroxydiphenyl ether (triclosan) 3,4,4′-trichlorocarbanilide (triclocarban); diaminoal
- glyceryl monoalkyl ethers such as 1-heptyl glyceryl ether, 1- (2-ethylhexyl) glyceryl ether, 1-octyl glyceryl ether, 1-decyl glyceryl ether and 1-dodecyl glyceryl ether are used. I can do it.
- the odor adsorbing substance can be used without particular limitation as long as it is a substance that adsorbs odor-causing substances and reduces odor. Includes those that exhibit properties.
- odor adsorbing substance zinc oxide, magnesium oxide, zeolite, metasilicate aluminate, silicic anhydride, colloidal silica, talc, mica, hydroxyapatite, cellulose, corn starch, silk, nylon powder, crosslinkable organopolysiloxane powder, organopolysiloxane Elastomer spherical powder or the like can be used as an odor adsorbing substance.
- carbonates and hydrogen carbonates such as alkali metal carbonates and alkali metal hydrogen carbonates, ammonium salts, tetraalkylammonium salts and the like can be used, and sodium and potassium salts of these odor adsorbents are more preferable.
- organic or inorganic porous particles for example, silver ion-carrying zeolite, silver ion / zinc ion / ammonium ion-carrying zeolite
- metal ions such as silver, copper, zinc, and cerium
- silver cancrinite An aggregate of acicular crystals can also be used. These can be suitably used as deodorant agents in that they act both as antibacterial agents and odor adsorbing substances.
- Various extracts derived from animals / plants / microorganisms / fungi such as urgon, gobishi, gardenia, hamamelis and herbs can also be suitably used as deodorant agents. Although some of these components overlap with the physiologically active components described later, it is useful and preferable for cosmetic composition design to select these extracts for the purpose of acting as a deodorant agent. .
- the odor-adsorbing substance is preferably contained in the total composition in an amount of 0.001 to 60% by weight, more preferably 0.01 to 30% by weight, and even more preferably 0.01 to 3% by weight. If the content of the odor adsorbing substance is within this range, it is useful in that the deodorizing performance can be improved without deteriorating the strength and feel of the preparation.
- Suitable perfumes include any topical material that provides a composition that is known or otherwise effective in masking malodors associated with sweating or otherwise has the desired fragrance. These include any perfume or perfume chemical, such as perfume precursors and deodorant fragrances, suitable for topical application to the skin, and may be perfume ingredients that are scented as needed.
- Antibacterial and antiseptics can be blended with the cosmetics of the present invention for the purpose of preventing corruption.
- Antibacterial and antiseptics include, for example, paraoxybenzoic acid alkyl esters, benzoic acid, sodium benzoate, sorbic acid, potassium sorbate, phenoxyethanol, and the like, and antibacterial agents include benzoic acid, salicylic acid, carboxylic acid, sorbic acid, alkyl paraoxybenzoate. Examples include esters, parachlorometacresol, hexachlorophene, benzalkonium chloride, chlorhexidine chloride, trichlorocarbanilide, triclosan, and photosensitizers.
- Physiologically active ingredients include substances that impart some physiological activity to the skin when applied to the skin.
- anti-inflammatory agents include substances that impart some physiological activity to the skin when applied to the skin.
- anti-inflammatory agents include substances that impart some physiological activity to the skin when applied to the skin.
- anti-inflammatory agents include substances that impart some physiological activity to the skin when applied to the skin.
- anti-inflammatory agents include substances that impart some physiological activity to the skin when applied to the skin.
- anti-inflammatory agents include substances that impart some physiological activity to the skin when applied to the skin.
- anti-inflammatory agents include anti-inflammatory agents, anti-aging agents, squeeze agents, antioxidants, hair growth agents, hair restorers, moisturizers, blood circulation promoters, antibacterial agents, bactericides, desiccants, cooling agents, warming agents, vitamins , Amino acids, wound healing promoters, stimulation relieving agents, analgesics, cell activators, enzyme components, and the like.
- natural plant extract components seaweed extract components, and herbal medicine components are particularly preferable.
- Ashitaba extract avocado extract, Achacha extract, Altea extract, Arnica extract, Aloe extract, Apricot extract, Apricot kernel extract, Ginkgo biloba extract, Fennel extract, Turmeric extract, Oolong tea extract, Ages extract, Echinashi leaf extract , Ogon extract, Oat extract, Auren extract, Barley extract, Hypericum extract, Odrianthus extract, Dutch mustard extract, Orange extract, Seawater dried product, Seaweed extract, Hydrolyzed elastin, Hydrolyzed wheat powder, Hydrolyzed silk, Chamomile extract, Carrot Extract, Kawaramugi extract, licorice extract, calcade extract, oyster extract, kiwi extract, kina extract, cucumber extract, guanosine, gardenia extract, kumazasa extract, kura Extract, walnut extract, grapefruit extract, clematis extract, chlorella extract, mulberry extract, gentian extract, tea extract, yeast extract, burdock extract, fermented rice bran
- Biopolymers such as deoxyribonucleic acid, mucopolysaccharide, sodium hyaluronate, sodium chondroitin sulfate, collagen, elastin, chitin, chitosan, hydrolyzed eggshell membrane, glycine, valine, leucine, isoleucine, serine, threonine, phenylalanine, arginine , Lysine, aspartic acid, glutamic acid, amino acids such as cystine, cysteine, methionine, tryptophan, hormones such as estradiol, etenyl estradiol, oily components such as sphingolipids, ceramides, cholesterol derivatives, phospholipids, ⁇ -aminocaproic acid, glycyrrhizic acid , ⁇ -glycyrrhetinic acid, lysozyme chloride, guaiazulene, hydrocortisone, allanto
- Examples of skin beautifying ingredients include placenta extract, whitening agents such as arbutin, glutathione, and yukinoshita extract, cell activators such as royal jelly, skin roughening agents, nonyl acid wallenyl amide, nicotinic acid benzyl ester, nicotinic acid ⁇ -Butoxyethyl ester, capsaicin, gingerone, cantalis tincture, ictamol, caffeine, tannic acid, ⁇ -borneol, tocopherol nicotinate, inositol hexanicotinate, cyclandrate, cinnarizine, torazoline, acetylcholine, verapamil, cephalanthin, ⁇ - Examples include blood circulation promoters such as oryzanol, skin astringents such as zinc oxide and tannic acid, antiseborrheic agents such as sulfur and thiantol, and vitamins include vitamin A oil, reti
- pH adjuster examples include lactic acid, citric acid, glycolic acid, succinic acid, tartaric acid, dl-malic acid, potassium carbonate, sodium hydrogen carbonate, ammonium hydrogen carbonate and the like.
- solvent in addition to water, light isoparaffin, ethers, LPG, N-methylpyrrolidone, next-generation chlorofluorocarbon and the like can be mentioned.
- antioxidant examples include tocopherol, butylhydroxyanisole, dibutylhydroxytoluene, phytic acid, and the like.
- chelating agent examples include alanine, sodium edetate, sodium polyphosphate, sodium metaphosphate, and phosphoric acid. .
- moisturizing components examples include hyaluronic acid, chondroitin sulfate, pyrrolidone carboxylate, polyoxyethylene methyl glucoside, polyoxypropylene methyl glucoside and the like. Needless to say, the polyhydric alcohols described above exhibit a moisture retaining function on the skin or hair.
- these moisturizing ingredients can be used in combination with other oily raw materials, by selecting a gel cosmetic dosage form, or in combination with film-forming ingredients. Moisturizing properties may be improved.
- the external preparation composition according to the present invention is not particularly limited as long as it is a composition that can be applied to the human body as a cosmetic or a medicine.
- the cosmetics of the present invention include skin products such as skin cleanser products, skin care products, makeup products, antiperspirant products, UV protection products; hair cleanser 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 above cosmetics for skin can be used for any part of the scalp, face (including lips, eyebrows, cheeks), fingers, nails and whole body.
- makeup products such as nail lacquer, enamel remover and nail polish
- the above cosmetics for hair include detergents for hair such as shampoo and rinse-in shampoo; hair-styling products such as hair oil, hair wax, curl retainer for hair, set agent, hair cream, hair spray, hair liquid, etc .; hair dye, hair Hair coloring products such as color sprays, hair color rinses and hair color sticks; hair tonic products such as hair tonics, hair treatment essences and hair packs; hair rinses such as oil rinses, cream rinses, treatment rinses, hair conditioners and hair treatments Or a hair conditioning product is illustrated.
- Examples of the cosmetic for bath include bath oil, bath salt, and foam bath.
- the form of the external preparation composition according to the present invention is not particularly limited, and is liquid, W / O emulsion, O / W emulsion, W / O cream, O / W cream, solid It can be preferably applied to a shape (stick shape, etc.), a paste shape, a gel shape, a powder shape, a multilayer shape, a mousse shape, a mist shape, a granule shape, a flake shape, a meteorite shape, and the like.
- Particularly preferred forms are W / O emulsion, W / O cream, solid, paste, gel, and powder.
- the external preparation composition according to the present invention is not particularly limited, and includes a jar, a pump, a tube, a bottle, a pressure can discharge container, a pressure-resistant aerosol container, a light shielding container, a compact container, a metal plate, An arbitrary container such as a stick container, a feeding container, a spray container, or a container with a partition provided with a mixed solution discharge port can be filled. Tubes tend to be separated in ordinary silicone preparations. However, since the external preparation composition according to the present invention, especially cosmetics, is excellent in stability, it should be stored stably even when filled in such tube containers. There is an advantage that it is possible.
- the co-modified organopolysiloxane according to the present invention is a cosmetic raw material excellent in versatility, and can be widely used as a composition applied to the human body as a cosmetic or a medicine. Therefore, more specifically, the antiperspirant composition will be described as an example.
- the antiperspirant composition according to the present invention can be selected from any of water-in-oil emulsions (water-based preparations), stick-form preparations, and aerosol preparations such as sprays.
- the above cosmetic ingredients can be appropriately selected and used according to the type of preparation.
- the antiperspirant active ingredient to be blended in the water phase or oil phase is as described above, and it is preferable to blend the deodorant component as desired.
- Water-in-oil emulsion antiperspirant composition In the water-in-oil emulsion antiperspirant composition according to one embodiment of the present invention, an oil phase component containing a co-modified organopolysiloxane (co-modified organopolysiloxane, volatile oil, non-volatile oil, solubilized
- the aqueous phase components are mixed by any method.
- the refractive index of each phase is adjusted as described in “Transparency Adjustment Method for Emulsions Containing Co-modified Organopolysiloxane of the Present Invention” to control a water-in-oil emulsion type. It is preferred to improve the transparency and stability of the sweat composition.
- the co-modified organopolysiloxane of the present invention can give a natural feeling of application without a moisturizing feeling and a sense of incongruity by blending with a water-in-oil emulsion antiperspirant composition.
- the co-modified organopolysiloxane of the present invention can also act as an emulsifier for stably emulsifying and dispersing an aqueous phase containing an antiperspirant active ingredient in oil.
- the amount used is 0.1 to 10 parts, preferably 0.5 to 5 parts, based on 100 parts by mass of the entire composition.
- the antiperspirant of the present invention there is an advantage that a water-in-oil emulsion type transparent antiperspirant composition excellent in transparency can be obtained by using the above-described method for adjusting the transparency of the emulsion.
- the amount of volatile oil that is the base oil of the water-in-oil emulsion antiperspirant composition is 5 to 40 parts, preferably 10 to 30 parts, and even more preferably when the total composition is 100 parts by mass. 15 to 20 parts.
- the volatile oil among those exemplified as the component (C) in the present invention, those whose vapor pressure is measured at 25 ° C. can be used. That is, the volatile oil has a vapor pressure at 25 ° C. of 0.01 to 8 hPa, preferably 0.02 to 2.0 hPa, and a boiling point at 1 atm of less than 250 ° C.
- the types and amounts of the antiperspirant active component and the deodorant component are as described above, and can be appropriately adjusted as desired.
- the amount of the non-volatile oil used is 1 to 10 parts by mass, preferably 2 to 8 parts by mass as described above.
- solubilizer In the water-in-oil emulsion type transparent antiperspirant composition of the present invention, a solubilizer can be used.
- oil agent (C) component in the present invention
- oils and fats usually used in cosmetics, higher alcohols, higher fatty acids, organic lipophilic surfactants, etc.
- it is selected from the oil agent used as the base oil, the oil agent used as the refractive index adjusting agent, and the oil agent different from the non-volatile oil.
- the refractive index adjusting agent, base oil, and non-volatile oil may serve as a solubilizer.
- the amount of solubilizer used is about 0.1 to about 20 parts, preferably 1.0 to 10.0 parts by weight of the total composition.
- components (D) and (H) in the present invention may be components (D) and (H) in the present invention.
- the proportion of these components is generally 0 to 8 parts by mass when the total composition is 100 parts by mass, but is not limited.
- a surfactant may also be added to the water-in-oil emulsion antiperspirant composition of the present invention.
- These are represented by component (J) in the present invention and include any hydrophilic emulsifier having an HLB of more than 8.
- the blending amount is generally 0 to 2 parts by mass based on 100 parts by mass of the total composition. However, it will be appreciated by those skilled in the art that this ratio is adjusted based on the required HLB of the system.
- hydrophilic nonionic surfactants preferred as surfactants include POE-sorbitan fatty acid esters; POE sorbite fatty acid esters; POE-glycerin fatty acid esters; POE-fatty acid esters; POE-alkyl ethers; Types: POE / POP-alkyl ethers; tetra-POE / tetra-POP-ethylenediamine condensates; POE-castor oil hardened castor oil derivatives; POE-honey bee lanolin derivatives; alkanolamides; POE-propylene glycol fatty acid esters; Alkylamines; POE-fatty acid amides; sucrose fatty acid esters; alkylethoxydimethylamine oxides; trioleyl phosphates and the like.
- the external preparation of the present invention (as an example of an antiperspirant composition) includes a thickener, an oil-soluble gelling agent, an organically modified clay mineral, a physiologically active component, a skin beautifying component, and pH adjustment.
- a thickener such as an agent, an antioxidant, a solvent, a chelating agent, a moisturizing component, and a drug can be used as long as the object of the present invention is not impaired.
- the antiperspirant composition according to the present invention is used by applying an amount sufficient to suppress sweat and / or odor to the armpits and other parts.
- About 0.1 to 10 g is preferably applied to the target site on the skin, more preferably 0.1 to 5 g, and even more preferably 0.1 to 1 g.
- the stick-like antiperspirant composition is one form of a solid antiperspirant composition, and may be a form containing water, such as a solid W / O emulsion, or an external preparation composition substantially free of water. It can also be.
- a system that does not substantially contain water will be described as an example.
- the non-aqueous stick-like antiperspirant composition is excellent in stability and is advantageous when it is desired to obtain a dry feeling.
- an oil phase component such as a co-modified organopolysiloxane, a volatile oil agent, a higher alcohol, a wax, and a non-volatile oil agent is mixed to obtain a higher alcohol.
- Heating and stirring at a temperature at which solid components such as wax and wax melt (for example, about 80 ° C.) form a single liquid phase.
- the remaining components other than the antiperspirant active component are added while stirring, and further the active component is added.
- stirring operation can be performed by stirring means using well-known mechanical force, such as a mixer.
- the co-modified organopolysiloxane of the present invention can give a natural feeling of application without a moisturizing feeling and an uncomfortable feeling by blending it into a non-aqueous stick-like antiperspirant composition. Therefore, when a dry feeling is too strong, it can be relieved and a natural feeling of use can be brought about. Further, the co-modified organopolysiloxane of the present invention has the effect of suppressing the particle aggregation by effectively adsorbing on the surface of the powder or solid fine particles, and stably dispersing the powder or solid fine particles in the oil. .
- the non-aqueous stick-like antiperspirant composition containing the co-modified organopolysiloxane of the present invention has the advantage that there is little white residue after coating and drying. Furthermore, since the co-modified organopolysiloxane of the present invention has good compatibility with solid oils such as higher alcohols and waxes, it is possible to control stick hardness and to generate white deposits derived from solid oils after coating and drying. It has a mitigating effect.
- the amount used is 0.1 to 10 parts by mass, preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the entire composition.
- non-aqueous stick-like antiperspirant composition according to the present invention, one or more volatile oils can be used, and the total composition has 5 to 70% by weight, more preferably 10 to 60% by weight, It is preferable because a good feel can be obtained.
- the components exemplified above can be used as the antiperspirant active component without any particular limitation.
- a water-soluble salt or the like is preferably used as it is as a solid and is dispersed as fine particles in the composition.
- the average particle size of the fine particles of the antiperspirant active component is preferably about 0.1 to 100 ⁇ m, more preferably 0.1 to 20 ⁇ m, and even more preferably 0.1 to 10 ⁇ m.
- one or more antiperspirant active ingredients can be used, preferably 10 to 70% by mass, more preferably 15 to 50% by mass, and further 15%. Containing ⁇ 25% by mass is more preferable because the effect of suppressing sweat and odor can be sufficiently obtained and the feel is good.
- the same deodorant agent as described above can be blended together with / or in place of the antiperspirant active ingredient, and the type, amount used, etc. are as described above.
- the higher alcohol that can be used in the non-aqueous stick-type antiperspirant composition according to the present invention has 12 to 50 carbon atoms, preferably 16 to 30 carbon atoms, and more preferably 18 to 24 carbon atoms. If it is in this range, a good feel can be obtained.
- cetyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol and the like are exemplified.
- One or more types of higher alcohols can be used, and the total alcohol is contained in an amount of 1 to 50% by weight, preferably 5 to 35% by weight, more preferably 10 to 25% by weight. If it is in this range, it is possible to obtain a good feel as well as moderate shaping.
- Hydrocarbon oil such as silicone oil, mineral oil, polydecene, hydrogenated polyisobutene, (G) component in the present invention, ether oil such as dioctyl ether, carbonate oil such as dioctyl carbonate and dioctadecyl carbonate, isopropyl palmitate, isopropyl myristate , Ester oils such as lauryl myristate, diisopropyl sebacate, diisopropyl adipate, C8-C18 alkyl benzoates, polyalkylene glycols such as PPG-3 myristyl ether and PPG-14 butyl ether and their derivatives, isostearyl alcohol And oleyl alcohol, 2-ethylhexyl alcohol, and organic lipophilic surfactants.
- ether oil such as dioctyl ether
- carbonate oil such as dioctyl carbonate and dioctadecyl carbonate
- these non-volatile oils can be used, and are contained in an amount of 1 to 30% by weight, preferably 5 to 15% by weight in the total composition.
- the non-aqueous stick-like antiperspirant composition according to the present invention can further contain a wax and is preferable because the high-temperature stability is improved.
- the wax include the component (C), fats and oils, and higher fatty acids that are solid at room temperature. Furthermore, what is solid at room temperature among the said (H) component is illustrated.
- hydrogenated castor oil, fatty acid, waxy modified silicone, glycerol monostearate, 2-8178 Gelrant, 2-8179 Gelrant, etc. manufactured by Dow Corning, USA
- AMS-C30 Cosmetic Wax, 2503 Cosmetic Wax, etc. US Dow Corning Co., Ltd. alkyl-modified silicone resin wax, etc.
- the resulting stick-like antiperspirant composition is imparted with appropriate hardness and stability.
- One or more kinds of the above-mentioned waxes can be used, and it is preferable to contain 1 to 10% by weight, and further 2 to 8% by weight in the total composition because of excellent stability and good feel.
- components (D) and (H) described above are the components (D) and (H) described above, and the ratio of these components is usually the total amount of the composition. From about 0 parts to about 8 parts, but is not limited.
- thickeners, oil-soluble gelling agents, organically modified clay minerals, bioactive ingredients, skin-beautifying ingredients, pH adjusters, antioxidants, solvents, chelating agents, moisturizing ingredients, chemicals Etc. can be used as long as the object of the present invention is not impaired.
- the antiperspirant composition according to the present invention is used by applying an amount sufficient to suppress sweat and / or odor to the armpits and other parts.
- About 0.1 to 10 g is preferably applied to the target site on the skin, more preferably 0.1 to 5 g, and even more preferably 0.1 to 1 g.
- the stick composition of the present invention is preferably applied once or twice a day in order to effectively suppress sweat and / or odor.
- aerosol antiperspirant composition which is one of the external preparation compositions containing the co-modified organopolysiloxane according to the present invention and is one embodiment of the present invention.
- the aerosol antiperspirant composition may be in a form containing water, or may be a preparation for external use which does not substantially contain water.
- Non-aqueous aerosol antiperspirant composition is advantageous for obtaining a dry and smooth use feeling, while water-containing aerosol antiperspirant composition is effective in antiperspirant action and provides a refreshing feeling. There is an advantage that it is easy.
- the aerosol antiperspirant composition according to the present invention includes a propellant, a powder component dispersed therein (an antiperspirant active component, a deodorant agent, a usability improving component, etc.), a co-modified organopolysiloxane, and A liquid oil agent etc. can be mix
- the antiperspirant active component may be a powder or a solution. In the case of a powder, it is preferably dispersed as fine particles in the composition. The average particle size of the fine particles is preferably about 0.1 to 100 ⁇ m, more preferably 0.1 to 20 ⁇ m, and even more preferably 0.1 to 10 ⁇ m.
- an aqueous solution can also be used, but in order to further improve the storage stability of the composition, the AP active ingredient is propylene glycol, polyethylene glycol, alkyl glycerol ether, alkyl etherified saccharide, alkyl etherified sugar alcohol, etc. It is more preferable to use a material complexed or dissolved with the polyols.
- the antiperspirant active component that can be used in the aerosol antiperspirant composition according to the present invention include the same components as described above.
- One or more antiperspirant active ingredients can be used, preferably 0.001 to 20.0% by weight, more preferably 0.1 to 10.0% by weight, based on the total amount of the aerosol antiperspirant composition.
- the deodorant agent that can be blended together with or in place of the antiperspirant active ingredient includes an antibacterial agent (bactericide or antifungal agent), bacteriostatic agent, odor adsorbing substance, deodorant Agents, fragrances and the like. Specific examples of these components are as described above, and a preferable blending amount is 0.01 to 10.0% by weight, more preferably 0.1 to 3.0% by weight, based on the total amount of the aerosol antiperspirant composition.
- the co-modified organopolysiloxane of the present invention when blended in an aerosol antiperspirant composition, suppresses particle aggregation by effectively adsorbing to the surface of the powder or solid fine particles. It has the effect of stably and uniformly dispersing in the system.
- the aerosol antiperspirant composition blended with the co-modified organopolysiloxane of the present invention reduces aerosol valve clogging, makes the white color after use inconspicuous, and improves the uniform adhesion to the skin.
- the AP active ingredient and deodorant may cause dryness and tension to be sensed on the skin after use, resulting in reduced dry skin and reduced skin elasticity and unnatural skin sensation.
- the particle diameter of the powder is preferably 1 to 20 ⁇ m, more preferably 5 to 15 ⁇ m, in order to give a smooth feel to the skin.
- the particle diameter is larger than 20 ⁇ m, roughness is felt, and when the particle diameter is 1 ⁇ m or less, a problem of particle scattering may occur.
- propellant used in the present invention examples include gaseous solvents such as propane, n-butane, isobutane, isopentane, pentane, dimethyl ether, liquefied petroleum gas (LPG), and liquefied natural gas.
- LPG liquefied petroleum gas
- LPG dimethyl ether
- isopentane are preferable.
- chlorofluorocarbons and chlorofluorocarbons such as 1,1-difluoroethane can also be blended, but are not preferable due to environmental problems.
- Carbon dioxide gas and nitrogen gas can also be used from the environmental and safety aspects.
- the filling amount of the propellant is not particularly limited and is appropriately determined according to a conventional method.
- a usability improving component may be mentioned.
- the usability improving component has an action of imparting a smooth feeling to the skin, and is an inorganic powder such as silica gel, talc, bentonite, kaolinite, true spherical silica, smectite, and materials subjected to surface treatment on these, Composites such as polyethylene powder, nylon powder, polystyrene powder, crosslinkable organopolysiloxane powder, organopolysiloxane elastomer spherical powder, organic powder such as silicone resin powder, and inorganic powder containing metal oxide Examples thereof include powders. That is, the usability improving component here may be the components (D) and (H) in the present invention. These usability improving components can also be used in combination of one or more.
- the liquid oil agent has the effect of uniformly adhering the powder onto the skin and improving the feeling of use, and can be used alone or in combination of two or more.
- the liquid oil agent preferably contains silicone oil.
- the silicone oil preferably has a viscosity range of 100,000 cst (25 ° C.) or less, more preferably 100 cst (25 ° C.) or less, in order to obtain a smooth feel without stickiness.
- the blending amount of the liquid oil is preferably 0.1 to 50% by weight, more preferably 0.5 to 25% by weight based on the total amount of the aerosol antiperspirant composition. If the blending amount is less than 0.1% by weight, the oily feel will not be smooth and the skin will not be familiar. If blending more than 50% by weight, the feeling of use will be reduced due to slipping and the formulation will be stable. May have adverse effects.
- the liquid oil agent previously emulsified and made into the form of O / W emulsion can also be mix
- an O / W emulsion having good blending stability can be obtained by using a phosphoric acid surfactant and a general nonionic surfactant in combination.
- the aerosol antiperspirant composition according to the present invention, water, ethanol, IPA, polyhydric alcohol, surface activity is further used for the purpose of more effectively expressing the antiperspirant action by dissolving the antiperspirant active component in the system.
- An agent or the like may be blended.
- some monohydric alcohols such as ethanol and IPA
- some polyhydric alcohols such as propylene glycol and 1,3-butylene glycol are inflamed or inflamed on the sensitive axillary part of the skin during and after application when the compounding amount is large. Prone to irritation.
- the amount of the lower monohydric alcohol used is desirably 50% by weight or less based on the total amount of the aerosol antiperspirant composition.
- the amount of polyhydric alcohol that tends to cause irritation or the like in sensitive parts of the skin is 20% by weight or less based on the total amount of the aerosol antiperspirant composition.
- a preferred polyhydric alcohol is the component (E), which is exemplified as the “refractive index adjusting agent for water phase”.
- the weight ratio of the antiperspirant active ingredient is preferably in the range of 1 / 0.5 to 1/2. Within this range, it can be expected that the antiperspirant action is further improved and the onset thereof is accelerated without causing stickiness.
- the blending of the surfactant is effective for improving the stability of the aerosol antiperspirant composition containing water. That is, a non-aqueous aerosol antiperspirant composition is prepared by first mixing a component excluding a propellant and powder to prepare a stock solution, and uniformly dispersing the powder in this stock solution and then filling the propellant. Since it is usually manufactured, stability problems are unlikely to occur. On the other hand, when an aerosol antiperspirant composition containing water is produced by the same method, the stability of the system decreases when a propellant such as liquefied petroleum gas (LPG) is mixed, and components such as an antiperspirant component Has a problem that it is likely to precipitate as starch.
- LPG liquefied petroleum gas
- Suitable surfactants include one or more nonionic or weakly acidic surfactants from the viewpoint of the antiperspirant active component being acidic and the effect of stabilizing the dispersion of the aerosol antiperspirant composition system. Agents are preferred. Among these, polyoxyethylene polyoxypropylene cetyl ether phosphoric acid and polyoxyethylene oleyl ether phosphoric acid are preferable.
- the blending amount of the surfactant is preferably 0.1 to 25% by weight, more preferably 0.1 to 10% by weight, based on the total amount of the aerosol antiperspirant composition.
- the blending amount is less than 0.1% by weight, the effect of improving the stability of the preparation is poor.
- the blending amount exceeds 25% by weight, it is not economical and the usability is also lowered.
- components (F), (G), (H), and (J) in the present invention are the components (F), (G), (H), and (J) in the present invention. From about 0 to about 8 parts based on the total amount of the product, but not limited.
- thickeners, oil-soluble gelling agents, organically modified clay minerals, bioactive ingredients, skin-beautifying ingredients, pH adjusters, antioxidants, solvents, chelating agents, moisturizing ingredients, chemicals Etc. can be used as long as the object of the present invention is not impaired.
- the aerosol antiperspirant composition according to the present invention can be sprayed using an ordinary aerosol container or an aerosol container having a resin-coated inner surface for the purpose of rust prevention or the like. It is also possible to spray using a double container using an inner bag.
- the antiperspirant composition according to the present invention is used by spraying it on the armpits or other parts and applying a sufficient amount to suppress sweat and / or odor. It is preferable to apply about 0.1 to 5 g, more preferably 0.1 to 3 g, and more preferably 0.1 to 1 g to the target site on the skin. Further, the aerosol antiperspirant composition according to the present invention is preferably applied by spraying once or twice a day in order to effectively suppress sweat and / or odor.
- Me represents a methyl (—CH 3 ) group
- Me 3 SiO group (or Me 3 Si group) is “M”
- Me 2 SiO group is “D”
- MeHSiO group is “M”.
- H ' the units modified by any substituent methyl group in M and D is denoted by M R and D R.
- IPA shows isopropyl alcohol in a manufacture example.
- Example 1 ⁇ Silicone Compound No. Synthesis of 1> 19.
- 8 g vinyltristrimethylsiloxysilane represented by an average composition formula CH 2 ⁇ CH—Si (OSiMe 3 ) 3 .
- 8 g 3.3 g of glycerin monoallyl ether represented by the structural formula CH 2 ⁇ CH—CH 2 —OCH 2 CH (OH) CH 2 OH, and 90 g of isopropyl alcohol (IPA) were charged, and the mixture was stirred while flowing under nitrogen. Warmed to ° C.
- IPA isopropyl alcohol
- R * 21 and R * 31 represent the following.
- R * 21 -C 3 H 6 OCH 2 CH (OH) CH 2 OH
- R * 31 -C 2 H 4 Si (OSiMe 3) 3
- the product was a pale yellow translucent uniform viscous liquid.
- Example 2 ⁇ Silicone Compound No. Synthesis of 2>
- 90 g of IPA were charged, and the mixture was heated to 70 ° C. while stirring under a nitrogen stream. .
- Example 3 ⁇ Silicone Compound No. Synthesis of 3> 7.
- 2 g, 7.9 g of glycerol monoallyl ether represented by the structural formula CH 2 ⁇ CH—CH 2 —OCH 2 CH (OH) CH 2 OH, and 90 g of IPA were charged and heated to 70 ° C. with stirring under a nitrogen stream. .
- Example 4 ⁇ Silicone Compound No. Synthesis of 4>
- 6 g, 14.7 g of glycerol monoallyl ether represented by the structural formula CH 2 ⁇ CH—CH 2 —OCH 2 CH (OH) CH 2 OH, and 90 g of IPA were charged, and the mixture was heated to 40 ° C. with stirring under a nitrogen stream. .
- Example 5 ⁇ Silicone Compound No. Synthesis of 5> 7.
- Example 6 ⁇ Silicone Compound No. Synthesis of 6>
- MD 72 DH 12 M vinyltristrimethylsiloxysilane represented by an average composition formula CH 2 ⁇ CH—Si (OSiMe 3 ) 3 66. 3 g
- 24.3 g of polyglycerol monoallyl ether 200 g of IPA, 0.23 g of a 2.3 wt% sodium acetate / methanol solution were charged,
- the polyglycerin monoallyl ether is synthesized by ring-opening polymerization of 3 mol of glycidol with respect to 1 mol of glycerin monoallyl ether. Since glycerin monoallyl ether has two hydroxyl groups and glycidol can react with both, the polyglycerin moiety includes not only a chain structure but also a branched structure.
- R * 22 is a hydrophilic group represented by -C 3 H 6 O-X, X is a tetraglycerol moiety. The product was a milky white uniform gum.
- Example 7 ⁇ Silicone Compound No. Synthesis of 7>
- 105.5 g of methyl hydrogen polysiloxane represented by an average composition formula MD 72 DH 12 M, vinyltristrimethylsiloxysilane 64. 5 represented by an average composition formula CH 2 ⁇ CH—Si (OSiMe 3 ) 3 . 0 g, 30.5 g of polyglyceryl eugenol, and 200 g of IPA were charged and heated to 60 ° C. with stirring under a nitrogen stream.
- the polyglyceryl eugenol is synthesized by ring-opening polymerization of 4 moles of glycidol with respect to 1 mole of eugenol.
- the polyglycerin portion mainly composed of tetraglycerin can include not only a chain structure but also a branched structure.
- the product was a milky white uniform gum.
- Example 8 ⁇ Silicone Compound No. Synthesis of 8>
- 112.3 g of methyl hydrogen polysiloxane represented by an average composition formula MD 72 DH 12 M, vinyltristrimethylsiloxysilane 45. 5 represented by an average composition formula CH 2 ⁇ CH—Si (OSiMe 3 ) 3 . 4 g, 32.5 g of polyglyceryl eugenol, and 200 g of IPA were charged and heated to 55 ° C. with stirring under a nitrogen stream.
- Example 9 ⁇ Silicone Compound No. Synthesis of 9>
- 9 g, 8.2 g of glycerin monoallyl ether represented by the structural formula CH 2 ⁇ CH—CH 2 —OCH 2 CH (OH) CH 2 OH, and 60 g of IPA were charged and heated to 60 ° C. while stirring under a nitrogen stream. .
- Example 10 ⁇ Silicone Compound No. Synthesis of 10> 16.
- 160.9 g of methyl hydrogen polysiloxane represented by an average composition formula MD 45 DH 2 M and vinyl tristrimethylsiloxysilane represented by an average composition formula CH 2 ⁇ CH—Si (OSiMe 3 ) 3 6 g, 20.5 g of polyglycerol monoallyl ether, and 200 g of IPA were charged, and the mixture was heated to 65 ° C. with stirring under a nitrogen flow.
- the polyglycerol monoallyl ether is synthesized by ring-opening polymerization of 3 mol of glycidol per 1 mol of glycerol monoallyl ether. Since glycerin monoallyl ether has two hydroxyl groups and glycidol can react with both, the polyglycerin moiety includes not only a chain structure but also a branched structure.
- R * 22 is —C 3 H 6 O—X, X is a tetraglycerin moiety.
- the product was a milky white uniform viscous liquid.
- Example 11 ⁇ Silicone Compound No. Synthesis of 11>
- Example 12 ⁇ Silicone Compound No. Synthesis of 12> 15.
- 1 g, 25.9 g of polyglyceryl eugenol, and 200 g of IPA were charged and heated to 70 ° C. with stirring under a nitrogen stream.
- R * 31 -C 2 H 4 Si (OSiMe 3) 3
- the polyglyceryl eugenol is synthesized by ring-opening polymerization of 4 moles of glycidol per mole of eugenol.
- the polyglycerin moiety can include not only a chain structure but also a branched structure. This product was a milky white uniform viscous liquid.
- Example 13 ⁇ Silicone Compound No. Synthesis of 13>
- the product is a milky white uniform viscosity It was a thick liquid.
- Example 14 ⁇ Silicone Compound No. Synthesis of 14> A reactor is charged with 100.0 g of methyl hydrogen polysiloxane represented by the average composition formula MD 43 DH 7 M, 27.9 g of polyoxyethylene (10) monoallyl ether, 0.055 g of natural vitamin E, and under nitrogen flow. The mixture was heated to 65 ° C. with stirring. 0.018 g of a toluene solution (Pt concentration: 2.2 wt%) of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex was added and reacted at 80 ° C. for 3.5 hours. .
- a toluene solution Pt concentration: 2.2 wt%
- the product as a whole was a very viscous off-white liquid, but was not uniform and partially caused phase separation (viscous light brown phase). This is because the presence ratio of silicone modified only with -C 2 H 4 Si (OSiMe 3 ) 3 is increased because vinyltristrimethylsiloxysilane was previously reacted alone with methylhydrogenpolysiloxane. It is considered that phase separation occurred due to poor compatibility with excess polyglycerin monoallyl ether. In addition, there is a problem that it is difficult to obtain a compound having an average composition formula of MD 72 DR * 31 9 DR * 22 3 M, which is the original design, by this method.
- the cause of gelation is considered as follows. Since polyglycerol monoallyl ether was first reacted with methyl hydrogen polysiloxane alone, the polyhydric alcohol group concentration relative to the Si-H group concentration in the reaction system was relatively high compared to the unsaturated group concentration. there were. For this reason, it is considered that the dehydrogenation reaction preferentially proceeds beyond the effect of suppressing the side reaction by sodium acetate, resulting in gelation of the reaction solution.
- Comparative Example 2 ⁇ Synthesis of Comparative Silicone Compound RE4> A reactor was charged with 129.4 g of methyl hydrogen polysiloxane represented by the average composition formula MD 45 DH 2 M, 40.0 g of polyoxyethylene (10) monoallyl ether, and 51 g of toluene, and stirred under nitrogen flow. Warmed to 75 ° C. 0.017 g of 10 wt% IPA solution of chloroplatinic acid was added, and the reaction was carried out at 73 to 93 ° C. for 1.5 hours. When 2 g of the reaction solution was sampled and confirmed by an alkali decomposition gas generation method, the reaction was complete.
- methyl hydrogen polysiloxane represented by the average composition formula MD 45 DH 2 M
- 40.0 g of polyoxyethylene (10) monoallyl ether 40.0 g of polyoxyethylene (10) monoallyl ether
- 51 g of toluene toluene
- Comparative Example 3 ⁇ Synthesis of Comparative Silicone Compound RE5> A reactor was charged with 89.9 g of methyl hydrogen polysiloxane represented by the average composition formula MD 63 DH 22 M, 36.4 g of polyoxyethylene (10) monoallyl ether, 73.7 g of 1-hexadecene, and 60 g of toluene. The mixture was heated to 40 ° C. with stirring under a nitrogen stream. 0.06 g of an IPA solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt concentration: 4.5 wt%) was added and reacted at 80-110 ° C. for 2.5 hours. I did it.
- Pt concentration platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex
- reaction solution was sampled, and it was confirmed that the reaction was completed by an alkali decomposition gas generation method.
- the reaction solution was heated under reduced pressure to distill off the low boiling point, thereby obtaining an alkyl / polyether co-modified silicone represented by an average composition formula MD 63 D R * 12 18 D R * 24 4 M.
- R * 12 -C 16 H 33
- R * 24 -C 3 H 6 O (C 2 H 4 O) 10 H
- the product was a light brown translucent uniform liquid.
- Comparative Example 4 ⁇ Synthesis of Comparative Silicone Compound RE6> 116.2 g of methyl hydrogen polysiloxane represented by average composition formula MD 406 DH 4 M in the reactor, average composition formula CH 2 ⁇ CH—CH 2 —O (C 2 H 4 O) 19 (C 3 H 6 O) 34.0 g of allyl polyether represented by 19 H, 45 g of IPA, 0.03 g of natural vitamin E, 0.15 g of 1.5 wt% sodium acetate / methanol solution were charged and heated to 50 ° C. with stirring under a nitrogen stream. did. 0.39 g of 1 wt% IPA solution of chloroplatinic acid was added, and the reaction was performed at 80 to 85 ° C. for 4 hours.
- Comparative Example 6 Synthesis of Comparative Silicone Compound RE8>
- a mixture of 30.9 g of polysiloxane and 0.10 g of a toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt concentration 0.5 wt%) was added dropwise at room temperature. To obtain a linear siloxane branched polysiloxane intermediate.
- Comparative Example 7 ⁇ Synthesis of Comparative Silicone Compound RE9> 212.5 g of methyl hydrogen polysiloxane represented by the average composition formula MD 406 DH 4 M in the reactor, glycerin mono represented by the structural formula CH 2 ⁇ CH—CH 2 —OCH 2 CH (OH) CH 2 OH Allyl ether (4.9 g) and IPA (90 g) were charged, and the mixture was heated to 70 ° C. with stirring under a nitrogen flow. 0.053 g of an IPA solution (Pt concentration: 4.5 wt%) of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex was added, and the reaction was performed at 80 ° C. for 3 hours.
- IPA solution Pt concentration: 4.5 wt%) of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex
- reaction solution 2 g was sampled, and it was confirmed that the reaction was completed by an alkali decomposition gas generation method.
- the reaction solution was heated under reduced pressure to distill off the low boiling point, thereby obtaining a glycerin-modified silicone represented by an average composition formula MD 406 DR * 21 4 M.
- R * 21 -C 3 H 6 OCH 2 CH (OH) CH 2 OH
- the product was a light tan translucent uniform viscous liquid.
- Comparative Example 8 ⁇ Synthesis of Comparative Silicone Compound RE10> 155.9 g of methyl hydrogen polysiloxane represented by the average composition formula MD 72 DH 12 M in the reactor, glycerin mono represented by the structural formula CH 2 ⁇ CH—CH 2 —OCH 2 CH (OH) CH 2 OH 13.0 g of allyl ether, 41.1 g of 1-decene and 63 g of IPA were charged and heated to 45 ° C. with stirring under a nitrogen stream.
- glycerin mono represented by the structural formula CH 2 ⁇ CH—CH 2 —OCH 2 CH (OH) CH 2 OH 13.0 g of allyl ether
- 41.1 g of 1-decene and 63 g of IPA were charged and heated to 45 ° C. with stirring under a nitrogen stream.
- composition formulas of “silicone compound No. 1” to “silicone compound No. 14” according to the present invention synthesized by the above method and “comparative silicone compound RE3” to “comparative silicone compound RE11” according to comparative examples are as follows. Summarize as follows.
- R * 26 -C 3 H 6 O (C 2 H 4 O) 19 (C 3 H 6 O) 19 H
- R * 27 -C 3 H 6 O-X represented by a hydrophilic group (X is triglycerol partial)
- R * 28 -C 3 H 6 O-X represented by a hydrophilic group (X is diglycerin portion)
- R * 31 -C 2 H 4 Si (OSiMe 3) 3 ⁇ Group having linear polysiloxane structure:
- R * 41 -C 2 H 4 SiMe 2 (OSiMe 2) 6 OSiMe 3
- Examples 15 to 23 and Comparative Examples 12 to 20 W / (Si + O), W / Si emulsified cosmetic]
- W / (Si + O) and W / Si emulsions were prepared by mixing and emulsifying each component according to the following procedure with the compositions shown in Tables 2 to 7.
- W is an abbreviation for an aqueous phase
- Si is an abbreviation for a silicone-based oil agent
- O is an abbreviation for another organic oil agent. is there.
- Si + O represents an oil phase composed of a mixed oil of silicone oil and other organic oil agents.
- Preparation Procedure 1 A 200 ml container was charged with dimethylpolysiloxane (2cst) as a base oil, an oil combined with the base oil, and a hydrophilic silicone compound as a surfactant. 2. Mixing with a spatula was performed to disperse and dissolve the surfactant in the oil. (Oil phase A) 3. The sawtooth of the homodisper was immersed in the oil phase A, and after stirring the container, stirring was started. Stirring was performed until the whole became a uniform solution. 4). Salt and ion-exchanged water were charged into another cup and mixed with a spatula to dissolve. (Water phase B) 5.
- 2cst dimethylpolysiloxane
- the rotation speed of the homodisper was increased to 3000 rpm, and the aqueous phase B was poured into the oil phase A at a substantially constant speed over about 40 seconds with stirring. 6). Stirring was continued for another 2 minutes and then temporarily stopped, and the oil adhering to the inner wall of the container was scraped off with a spatula and mixed with the produced emulsion. 7). Stirring was performed for 3 minutes at a rotation speed of 3000 rpm of the homodisper to obtain an emulsified cosmetic.
- the emulsion formulation (composition) is shown in “Table 3” to “Table 8” below.
- Table 3 dimethylpolysiloxane (2cst) was 200 FLUID 2 CS manufactured by Dow Corning. (Abbreviated as “2cst” in the table)
- 2cst FLUID 2 CS manufactured by Dow Corning.
- 6cst oil agent used together with this.
- Extract 6 emulsions were prepared per Example and Comparative Example, the total number of evaluated emulsion samples was 108 (9 ⁇ 6 + 9 ⁇ 6).
- Feel 1-1 Place the emulsion from the back of the hand to the tip of the finger (0.1 g x 2 times) and the arm (0.2 g x 1 time. However, in the case of the emulsion using isododecane and isoparaffin as the oil, 0.2 g x 2 times. ) Sensory evaluation was carried out from four sides with respect to the feel and feel when applied, and a score of 0 (bad) to 5 (good) was assigned to each side to determine superiority or inferiority.
- Viscosity stability 2-1 The viscosity of the emulsion after preparation was measured using an E-type viscometer manufactured by Tokyo Keiki Co., Ltd .: VISCOMIC EMD. (Cone rotor small: 3 ° ⁇ R9.7, 25 ° C., 2.5 rpm)
- 2-2 Next, 25 g ⁇ 2 emulsions were placed in 2 ⁇ 35 ml glass bottles, stoppered and placed in a high temperature bath at 0 ° C. and 40 ° C. for 2 weeks. Then, it took out, returned to room temperature, and implemented the viscosity measurement similarly.
- 2-3 The viscosity value after the lapse of time was displayed as a relative value when the initial viscosity value was set to 100%, and was summarized in a list for each oil agent system. (Tables 32 to 37)
- Evaluation results The following is a list of the total points of the emulsion feel evaluation according to the difference between the oil system and the active agent.
- the total score of the example prescription is 168 to 214 points, and the total score (overall score) of feeling and use feeling is higher than the prescription of the comparative example (160 points at the highest), and various oil systems are used However, it was found that a stable and excellent emulsion was obtained. This is the effect of using the novel hydrophilic silicone having a siloxane dendron structure of the present invention as an emulsifier.
- Comparative Example 7-1 Although emulsification was attempted, an aqueous phase and an oil phase were separated, and no emulsion was formed.
- Example 9 In order to clarify what the characteristics of the touch surface of the novel hydrophilic silicone having the siloxane dendron structure of the present invention are, the total score of Example 9 sample and the sample of Comparative Example 9 sample for each oil agent system and evaluation side The total score was calculated, and the difference (Example total score-Comparative example total score) was determined and summarized in Tables 30 to 32.
- the low-viscosity silicone oil that is not so volatile has the advantage of providing a light and light feel when applied, but has the problem of creating an unnatural residual feeling (uncomfortable feeling) on the skin after application. Therefore, when the oil system is composed only of such silicone oil, it is difficult to obtain a natural skin sensation after application of the W / Si emulsion.
- novel hydrophilic silicone of the present invention is used as an emulsifier, it is clearly different from the case of using a conventionally known silicone surfactant, and it is clear that a sustained moisturizing feeling and a natural skin sensation are easily obtained. Became.
- the product of the present invention is superior to existing active agents in that the feeling of finger residue is reduced and the freshness can be imparted only during application.
- Ester oil has a problem that it feels heavy and oily when applied, but has the advantage of providing a natural skin sensation after application.
- the oily feeling is very strong, when the oil system contains an ester oil, it has been difficult to obtain a moisturizing feeling after application, that is, to give freshness during application and to maintain it.
- the novel hydrophilic silicone of the present invention is used as an emulsifier, it is greatly different from the case of using a conventionally known silicone surfactant, and even when ester oil is contained in an oil system, a fresh tactile sensation is obtained at the time of application. It became clear that it was easy to obtain, and it was easy to obtain a sustained moisturizing feeling. In addition, it was shown that the product of the present invention is superior to existing active agents in that it can reduce the feeling of finger residue and improve the spreadability at the time of application.
- highly volatile hydrocarbon oils have the advantage of providing a light and light feel when applied, but the skin becomes whiter after application due to the ease of dissolving sebum, and the skin feels dry, itchy and irritating. There is. Therefore, when the oil system contains such hydrocarbon oil, it is difficult to obtain a natural skin feeling and a continuous moisturizing feeling after application of the W / (Si + O) emulsion.
- the novel hydrophilic silicone of the present invention is used as an emulsifier, it is significantly different from the case where a conventionally known silicone surfactant is used, and even if a hydrocarbon oil having a large volatility is contained in the oil system, it can be sustained. It became clear that a natural moisturizing feeling and natural skin sensation were easily obtained. In addition, it was shown that the product of the present invention is superior to existing active agents in that the spreadability at the time of application can be improved.
- Viscosity stability As shown in Tables 33 to 38 below, the emulsion obtained by using the novel hydrophilic silicone having a siloxane dendron structure of the present invention as an emulsifier is any oil agent system. However, there was little change in viscosity with temperature and time, and the fluctuation was within the initial value ⁇ 8%. On the other hand, it has been found that the viscosity of an emulsion obtained by using an existing silicone surfactant as an emulsifier varies up to an initial value ⁇ 10% or more depending on the type of oil agent system.
- the emulsions obtained using the novel hydrophilic silicones of the present invention as emulsifiers are more resistant to various oil systems compared to the emulsions of the comparative examples.
- a matte feeling can be given, or a pearly luster with a high-class feeling can be given.
- It is effective that the gloss of the emulsion is not too strong, which leads to suppression of oily glare after application to the skin and excessive oiliness. That is, it has been clarified that the novel hydrophilic silicone of the present invention gives a unique and excellent texture to the emulsion.
- Examples 24-43 W / (Si + O), W / Si emulsified cosmetic] W / (Si + O) and W / Si emulsions were prepared by mixing and emulsifying the compositions shown in Tables 43 to 51 according to the following procedures.
- Tactile evaluation Tables 52 and 53 below show a list of total points for the evaluation of the feeling of the emulsion according to the difference between the oil system and the activator system. Examples are formulations using a novel hydrophilic silicone having a siloxane dendron structure of the present invention and an existing silicone surfactant as an emulsifier.
- Comparative Examples 17, 18, 19, and 20 which are prescriptions using an existing (poly) glycerin-modified silicone as an emulsifier, were used as comparative examples here.
- the example formulation had a high total score (overall score) of feel and use feeling compared to the formulation of the comparative example, and it was found that even when various oil systems were used, a stable and excellent emulsion was obtained. .
- Table 54 shows a list of the total points for the evaluation of the feel of emulsions containing glycerin as a polyhydric alcohol, ethanol as a lower monohydric alcohol, and sodium citrate as an organic acid salt. In addition, for comparison with this, Table 54 shows a part of the touch evaluation of Example emulsions containing inorganic salts (salts).
- Example 27 corresponds to the evaluation data (without additive) of Example 20 immediately below.
- Example total score-Comparison implementation Example total points
- the emulsion formulation containing at least the novel hydrophilic silicone, oil agent and water of the present invention is selected from the group consisting of glycerin (polyhydric alcohol), ethanol (lower monohydric alcohol), and sodium citrate (organic acid salt). It was found that by further blending at least one selected, freshness at the time of application and moisturizing feeling after application were improved as compared with the case of further adding salt (inorganic salt). Polyols such as polyhydric alcohols are said to have a sticky feeling after coating, but the above effects were obtained without such inconvenience in the blending of the present invention. (Refer to the evaluation content described in the item [Emulsion Evaluation] first. Side 5: Stickiness was also confirmed in the evaluation of moisturizing feeling.)
- Examples 44 to 49 and Comparative Examples 21 to 28 Powder dispersion in oil
- a powder-in-oil dispersion was prepared by mixing and dispersing the compositions (prescriptions) shown in Table 68 (Examples) / Table 69 (Comparative Examples) according to the following procedure.
- the numerical unit is all g.
- Examples 50 to 53 and Comparative Examples 29 to 36 powder compositions
- the compositions (prescriptions) shown in Table 70 (Examples) / Table 71 (Comparative Examples) were processed according to the following procedures to prepare the powder compositions according to the present invention and the powder compositions as comparative examples.
- a powder composition was prepared by dissolving a prescribed amount of a silicone compound (surface treatment agent) in the table in isopropyl alcohol, adding and dispersing the powder, and distilling off the solvent.
- a silicone compound surface treatment agent
- the following powder was used.
- ⁇ Settling property 0.2% or less ⁇ : Settling property 0.2% ⁇ 2.0% ⁇ : Settling property 2.0% to 2.8% ⁇ : Sedimentation property 2.8% or more
- XX Dispersion stability test could not be performed due to the properties of the sample.
- the compounding amount was 35 for D5 to 5.0 g of the powder dispersion D5 was 37.45 g with respect to 0.0 g and 2.55 g of the powder composition.
- Example 44 to Example 53 and Comparative Example 21 to Comparative Example 36 were combined with the D5 / IOTG solution so that the powder concentration was 5.1 wt%. After mixing, this mixed solution was put into a 50 ml settling tube, and the sedimentation property after 2 days was visually observed and evaluated according to the following criteria. The results are shown in Table 72. ⁇ : Settling property 0.2% or less ⁇ : Settling property 0.2% ⁇ 2.0% ⁇ : Settling property 2.0% to 2.8% X: Sedimentation property 2.8% or more xx: The dispersion stability test could not be performed due to the properties of the sample.
- the blending amount was 23.6 g for D5 and 11.4 g for IOTG with respect to 5.0 g of the powder dispersion.
- D5 was 26.2g and IOTG was 11.2g with respect to 2.55g of powder compositions.
- the powder compositions (Comparative Example 29 to Comparative Example 36) prepared by using an existing silicone surfactant as a powder surface treatment agent have insufficient dispersion stability when dispersed in an oil agent.
- the powder composition prepared using the novel co-modified organopolysiloxane of the present invention as a surface treating agent (Example 50 to Example) No. 53) was found to be capable of forming a uniform dispersion having excellent dispersion stability and less powder settling even when diluted with an oil to give a powder dispersion in oil.
- the powder dispersion and powder composition of the present invention are used not only when the dispersion medium is decamethylcyclopentasiloxane (low viscosity silicone oil) but also with glyceryl tri-2-ethylhexanoate (IOTG: ester oil). Even in the case of the mixed oil, the dispersion stability was good.
- the dispersion medium is decamethylcyclopentasiloxane (low viscosity silicone oil) but also with glyceryl tri-2-ethylhexanoate (IOTG: ester oil). Even in the case of the mixed oil, the dispersion stability was good.
- Examples 54 to 58 and Comparative Examples 37 to 40 show the results of preparing a lip gloss as an example of a cosmetic according to the present invention, which is substantially free of water, and evaluating its feel.
- Lip gloss was prepared by mixing and molding the formulations (compositions) shown in Tables 74 to 76 according to the following procedures. In addition, the unit of the numerical value in a table
- surface is wt%. [Preparation procedure] 1. Components 1 to 15 were heated at 40 to 50 ° C. and uniformly mixed and dispersed. 2. After degassing, it was filled and molded at room temperature.
- the obtained lip gloss was tested and sensory evaluated by the following method.
- the obtained evaluation results are shown in Tables 73 to 75.
- [Test procedure] (1) 0.05 g of the obtained lip gloss was uniformly applied to 1 cm ⁇ 3 cm on clean skin (back of hand). Note) Since the lip gloss tends to enter the lip of the lip and easily bleed there, the back of the hand is also used as the test surface, which is similarly foldy and concentrated in the tactile nerve, and is easy to visually observe. (2) One hour after application, the following five items were evaluated.
- Examples 59 to 63 and Comparative Examples 41 to 44 show the results of preparing an oily foundation as an example of a cosmetic according to the present invention and substantially free of water, and evaluating the properties thereof.
- An oily foundation was prepared by mixing and molding the formulations (compositions) shown in Tables 77 to 79 according to the following procedure. In addition, the unit of the numerical value in a table
- surface is wt%. [Preparation procedure] 1. Ingredients 1 to 14 were heated at 90 ° C. and dissolved. 2. Components 15 to 18 were added to this and mixed and deaerated uniformly. 3. Poured into a mold, cooled and molded.
- Example 64 ⁇ Silicone Compound No. Synthesis of 15> Step 1 : 94.5 g of methylhydrogenpolysiloxane represented by an average composition formula MD 37 DH 13 M and vinyltristrimethylsiloxy represented by an average composition formula CH 2 ⁇ CH—Si (OSiMe 3 ) 3 in a reactor 8.3 g of silane was charged, and an IPA solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt concentration 0.4 wt%) was 0 at room temperature while stirring under nitrogen flow. .25 g was added. The reaction was carried out for 1 hour while heating in an oil bath set at 65 ° C.
- Pt concentration 0.4 wt% platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex
- Step 2 When 34.5 g of 1-hexadecene was added to the reaction solution, the temperature rose from 35 ° C. to 60 ° C. due to heat generation. After performing the reaction for 1.5 hours while heating in an oil bath set at 65 ° C., it was confirmed that there was no problem in the reaction rate by the same method as described above.
- Step 3 28.1 g of polyoxyethylene (10) monoallyl ether, 0.02 g of natural vitamin E and 60 g of IPA were added to the reaction solution, and 0.25 g of the same platinum catalyst solution as above was added. There was a temperature rise of about 5 ° C.
- Step 4 When 34.5 g of 1-hexadecene was added, the temperature increased by about 10 ° C. due to heat generation. The reaction was complete when the reaction was confirmed for 3 hours while heating in an oil bath set at 85 ° C. The reaction solution is heated under reduced pressure to distill off the low boiling point, and further filtered to obtain a siloxane represented by the average composition formula MD 37 D R * 12 10 D R * 31 1 D R * 24 2 M A novel polyether-modified silicone having a dendron structure and a long-chain alkyl group was obtained.
- R * 12 -C 16 H 33
- R * 31 -C 2 H 4 Si (OSiMe 3) 3
- R * 24 -C 3 H 6 O (C 2 H 4 O) 10 H
- This product was a light brown, almost clear, uniform liquid.
- Example 65 ⁇ Silicone Compound No. Synthesis of 16> Step 1 : 94.6 g of methyl hydrogen polysiloxane represented by average composition formula MD 330 DH 80 M, vinyl tristrimethylsiloxy represented by average composition formula CH 2 ⁇ CH—Si (OSiMe 3 ) 3 in the reactor 10.4 g of silane was charged and an IPA solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt concentration 0.4 wt%) was stirred at 35 ° C. while stirring under a nitrogen flow. 0.25 g was added.
- Pt concentration 0.4 wt% platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex
- Step 2 35.3 g of allyl polyether represented by the average composition formula CH 2 ⁇ CH—CH 2 —O (C 2 H 4 O) 19 (C 3 H 6 O) 19 H and natural vitamin E are added to the reaction solution.
- Step 3 13.0 g of 1-hexadecene was added to the reaction solution at about 65 ° C. When the temperature rise due to heat generation subsided, 13.0 g of 1-hexadecene (second time) was added and reacted in the same manner.
- Step 4 After adding 200 g of diluent caprylyl methicone (SS-3408) and dissolving, it was heated under reduced pressure to distill off IPA and low boiling point.
- SS-3408 diluent caprylyl methicone
- Examples 66 to 67 and Comparative Examples 45 to 46 show the results of preparing a water-in-oil transparent antiperspirant composition as an example of the cosmetic according to the present invention and evaluating its properties.
- a water-in-oil emulsion antiperspirant composition was prepared by mixing and emulsifying each component according to the following procedure with the formulation (composition) shown in Table 80.
- the final ⁇ 1.0 part of ion-exchanged water (No. 14) was added in small portions in order to match the RI value of the aqueous phase to the RI of the oil phase within ⁇ 0.0001 units. This process was repeated until the desired RI value match was reached. 7).
- the rotation speed of the homodisper was set to 3000 rpm, and the aqueous phase B was poured into the oil phase A at a substantially constant speed over about 2 minutes with stirring. 8). Stirring was continued for another 2 minutes and then temporarily stopped, and the oil adhering to the inner wall of the container was scraped off with a spatula and mixed with the produced emulsion. 9. Stir for 3 minutes at 3000rpm, homodisper speed, and finish.
- “Tactile sensation” The feel when the antiperspirant composition was applied to the forearm portion 0.2 g ⁇ 1 time was judged from superiority or inferiority from the viewpoint of less stickiness after application. ⁇ There was little stickiness and I did not mind. ⁇ I was concerned about stickiness. “Non-whitening performance”: The antiperspirant composition was applied to the forearm part 0.2 g ⁇ 1 time, dried for 15 minutes, and then the whiteness of the appearance was visually determined. ⁇ I did not know the whiteness. ⁇ It looked somewhat whitish. ⁇ It looked whitish. “Stability”: The appearance of the antiperspirant composition after the storage stability test was visually observed. ⁇ Translucent to transparent with little change in appearance compared to the initial stage. ⁇ : Transparency slightly decreased. X: Opaque or non-uniform appearance.
- Examples 68 to 69 and Comparative Examples 47 to 48 show the results of preparing a non-aqueous stick-type antiperspirant composition as an example of the cosmetic according to the present invention and evaluating its properties.
- a non-aqueous stick-type antiperspirant composition was prepared by heat mixing and cooling and solidifying each component according to the following procedure with the formulation (composition) shown in Table 81.
- ⁇ Natural without any sense of incongruity, but slightly dry. ⁇ There was a sense of incongruity. “No stickiness”: After applying the antiperspirant composition to the back of the hand 0.2 g ⁇ 1 time, superiority or inferiority was determined from the viewpoint of no stickiness when the application part was touched with a finger. ⁇ It was not sticky at all. ⁇ It was hardly sticky. ⁇ Slightly sticky. ⁇ I was concerned about stickiness. “Non-whitening performance”: The antiperspirant composition was applied to the forearm portion 0.2 g ⁇ 1 time, dried after 5 minutes, and then the apparent whiteness was visually determined. ⁇ Whiteness was hardly noticeable. ⁇ It looked somewhat white. ⁇ It looked whitish.
- Perfume appropriate amount (production method) A: Components 1 to 4 and components 12 and 13 are dissolved by heating at 50 ° C., and components 8 to 11 are added and dispersed by stirring. B: On the other hand, components 5 to 7 and component 14 are stirred and mixed at 70 ° C. and dissolved. C: Both A and B are returned to room temperature, B is added while stirring the previously prepared A with a homomixer, and sufficiently stirred. Thereafter, deaeration and filling are performed to obtain an emulsified foundation. (effect) When applied, it is very light and stretchy and has a moist feel, but there is no stickiness after application, and a unique feeling of use that maintains a moderate moisturizing feeling can be obtained. The stability over time of the product is also good.
- Example 2 Liquid Foundation] (Ingredient) (Wt%) 1. Decamethylcyclopentasiloxane 25.0 2. Dimethylpolysiloxane (2cst) 18.0 3. Dimethylpolysiloxane (6 cst) 2.0 4. Cetyl 2-ethylhexanoate 5.0 5. Composition of Example 8 (containing silicone compound No. 8) 7.0 6). Ethanol 8.0 7). Ion exchange water 2.0 8). Polymethylsilsesquioxane powder 13.0 9. Titanium dioxide 13.0 10. Mica 2.0 11. Iron oxide 1.0 12 Polyethylene powder 1.0 13. Polystyrene powder 1.0 14 Cellulose powder 1.0 15. Polyamide resin powder 1.0 16. Paraben proper amount17. Antioxidant adequate amount 18.
- Perfume appropriate amount (production method) A: Components 1 to 5 and components 16 to 18 are mixed and dissolved at room temperature, and then component 6 is added and thoroughly mixed while stirring with a homomixer. B: Then, component 7 is added while continuing stirring with a homomixer. C: Components 8 to 15 are added thereto, mixed and dispersed with a homomixer, degassed and filled to obtain a liquid foundation. (effect) When applied, there is no stickiness, it grows lightly, and the slipperiness is very good. After application, a moderate moisturizing feeling and plain feeling of natural use will persist. The stability of the product over time is also excellent, and the makeup lasting is also good.
- B Components 14 to 15 and 17 are dissolved by heating.
- C While stirring, B is gradually added to A to emulsify, and cooled to add component 16 to obtain a foundation.
- Example 4 Water-in-oil cream] (Ingredient) (Wt%) 1. Dimethyl distearyl ammonium hectorite 1.0 2. Dioctadecylmethylammonium salt modified montmorillonite 1.0 3. Dimethylpolysiloxane (6 cst) 5.0 4). 2-Ethylhexyl paramethoxycinnamate 2.0 5. Dienepentanoic acid diethylpentanediol 3.0 6). DC 9011 Silicone Elastomer Blend * 4) 6.0 7). Composition of Example 2 (containing silicone compound No. 2) 1.0 8). Dipropylene glycol 10.0 9. Sodium citrate 0.2 10. Ethanol 3.0 11. Preservative appropriate amount 12.
- Perfume proper amount13 Purified water 67.8 * 4) Diluted cross-linked polyether-modified silicone with decamethylcyclopentasiloxane (15% elastomer component) (Production method) A: Components 1 to 7 are mixed. B: Components 8 to 13 are mixed and dissolved, and added to the above A, followed by stirring and emulsification to obtain a water-in-oil cream. (effect) There is almost no oiliness and stickiness, light spreading is light, and a fresh and refreshing feeling is obtained. Good familiarity with the skin, moisturizing feeling is maintained. Also, a natural matte finish can be obtained. The stability over time of the product is also good.
- Pseudo ceramide 5.0 14 Magnesium stearate 1.0 15. Magnesium sulfate 1.0 16. Methyl paraoxybenzoate 0.2 17. Glycerin 16.0 18. Dipropylene glycol 0.5 19. Purified water 43.6 * 5) Phenyl trimethicone * 6) Diluted cross-linked organopolysiloxane (dimethicone crosspolymer) with decamethylcyclopentasiloxane (12% elastomer component) (Production method)
- component 15 and components 17 to 19 are mixed to form a solution.
- C C is gradually added while maintaining B at 80 ° C. and stirring uniformly. The mixture is further cooled to room temperature with stirring to obtain a water-in-oil emulsion composition.
- effect It is suitable for skin care, particularly face care, and can provide a natural skin sensation with a smooth application feeling and no discomfort. It has a slightly matte finish and has the effect of making skin wrinkles less noticeable.
- silicone compound No. 13 can be expected to promote transdermal absorbability of ceramides. In addition, it is expected that the efficacy of the ceramide itself will be enhanced by being absorbed through the skin.
- Example 7 Liquid Lipstick] (Ingredient) (Wt%) 1. Composition of Example 14 (containing silicone compound No. 14) 10.0 2. Silicic anhydride (average primary particle size 10 nm) 1.5 3. Diisostearyl malate 15.0 4). Octyldodecanol 4.0 5. Methyltrimethicone (M3T) 1.0 6). Heavy liquid isoparaffin 35.0 7). Squalane 9.0 8). Sunflower oil 5.0 9. Trioctanoin 5.0 10. Vaseline 5.0 11. Microcrystalline wax 2.0 12 Red No. 202 0.8 13. Titanium oxide 0.7 14 Titanium oxide coated glass powder 2.0 15. Titanium oxide coated silica powder 2.0 16.
- N ⁇ -lauroyl-L-lysine 2.0 (Production method) The above components 3 to 9 are mixed and heated to 90 ° C., then component 2 is added, dispersed uniformly using a homomixer, and further component 1 is added. While maintaining the temperature at 90 ° C., ingredients 10 to 16 are added, applied to a homomixer, filled into a container, and then cooled to obtain a liquid lipstick. (effect) When applied to the lips, it spreads smoothly and is easy to apply, with a non-sticky feel and good gloss on the lips.
- Preservative Appropriate amount * 9 Heat treatment after adding 3% silicone compound to Bengala (manufacturing method)
- E Ingredients 1 to 7 are melted at 80 ° C., and D is added while stirring to uniformly disperse.
- Example 10 Latex (Ingredient) (Wt%) 1. Decamethylcyclopentasiloxane 15.0 2. Methylphenylpolysiloxane 5.0 3. Squalene 5.0 4). Tetra-2-ethylhexanoic acid pentaerythritol 5.0 5. Composition of Example 8 (containing silicone compound No. 8) 1.0 6). BY 22-008M * 12) 2.0 7). 9701 Cosmetic Powder * 13) 2.0 8). Hydrophobized silica 0.5 9. Magnesium ascorbate phosphate 1.0 10. Sodium chloride 1.0 11. Polyethylene glycol 11000 1.0 12 Propylene glycol 8.0 13. Preservative appropriate amount14. Perfume appropriate amount 15.
- Example 11 Sun Cut Cream
- (Ingredient) (Wt%) 1. Decamethylcyclopentasiloxane 17.5 2. FA 4002 ID * 14) 12.0 3. Glyceryl triisooctanoate 5.0 4). Octyl paramethoxycinnamate 6.0 5. SS-2910 * 15) 1.0 6).
- Composition of Example 12 (containing silicone compound No. 12) 0.5 7). Organically modified bentonite 0.2 8). Silicone-treated zinc oxide 20.0 9.9702 Powder * 16) 3.0 10. Sodium chloride 0.5 11.1,3-butylene glycol 2.0 12 Preservative appropriate amount13. Perfume appropriate amount14.
- Example 14 Water-in-oil emulsification sunscreen] (Ingredient) (Wt%) 1. SH 556 * 22) 5.0 2. Octyl methoxycinnamate 5.0 3. Powder dispersion in oil of Example 49 25.0 4). Composition of Example 10 (containing silicone compound No. 10) 1.0 5. Dipropylene glycol 5.0 6). PEG (10) / PPG (14) dimethyl ether 1.5 7). Sodium carboxymethylcellulose 0.1 8). Succinoglycan 0.3 9. Chelating agent appropriate amount10. Preservative appropriate amount11. Buffering agent appropriate amount12. Purified water 57.1 * 22) Phenyl trimethicone (production method) A: After components 1, 2, and 4 are uniformly mixed, component 3 is added.
- Stearyl dimethicone * 24) Aqueous dispersion of organopolysiloxane elastomer spherical powder (63% active ingredient) (Production method)
- Example 16 Eyeshadow (Ingredient) (Wt%) 1. Decamethylcyclopentasiloxane 13.0 2. Dimethylpolysiloxane (6 cst) 10.0 3. Methyl trimethicone (M3T) 2.0 4). Composition of Example 1 (containing silicone compound No. 1) 2.0 5. PEG (10) lauryl ether 0.5 6). Silicone-treated chromium oxide * 25) 6.2 7). Silicone treated ultramarine blue * 25) 4.0 8). Silicone-treated titanium-coated mica * 25) 6.0 9. Sodium chloride 2.0 10. Propylene glycol 8.0 11. Preservative appropriate amount 12. Perfume proper amount13.
- Example 17 Mascara] (Ingredient) (Wt%) 1. Isododecane 23.0 2. Methyltrimethicone (M3T) 1.0 3. Dimethyl palmityl polysiloxane 1.0 4). Dimethylpolysiloxane (100,000 cst) 1.0 5. Microcrystalline wax 5.0 6). Beeswax 3.0 7). Composition of Example 4 (containing silicone compound No. 4) 3.0 8). Silicone-coated black iron oxide 14.0 9. Bentonite 2.0 10. Nylon fiber (average length 2 ⁇ m) 2.0 11. P-Hydroxybenzoate ester 0.5 12 Absolute ethanol 2.5 13.
- Example 18 Mascara] (Ingredient) (Wt%) 1. Decamethylcyclopentasiloxane 19.4 2. Light liquid isoparaffin 14.6 3. Methyltrimethicone (M3T) 1.5 4). FA 4001 CM * 26) 31.0 5. Dextrin fatty acid ester 15.0 6). Composition of Example 3 (containing silicone compound No. 3) 3.0 7). Organically modified bentonite 1.5 8). Hydrophobized silicic acid anhydride 2.0 9. Nylon fiber (average length 2 ⁇ m) 2.0 10.
- B Components 6 to 10 are dissolved by heating.
- C B is sprayed on A and further stirred. Thereafter, it is pulverized and compression molded by a molding machine to obtain a solid powder eye shadow. (effect) Excellent usability and finish. Since the powder has good adhesion and is excellent in water resistance, water repellency and sweat resistance, it has a long lasting makeup.
- Example 20 Pressed Powder Cosmetic
- (Wt%) Silicone-treated titanium oxide 10.0 2. Silicone-treated mica 50.8 3. Silicone-treated talc 10.0 4). Silicone-treated yellow iron oxide 1.5 5. Silicone treated bengara 0.5 6). Silicone-treated black iron oxide 0.2 7). Paraffin wax 2.0 8). Squalane 1.4 9. 2-Ethylhexyl palmitate 2.0 10. Composition of Example 9 (containing silicone compound No. 9) 15.0 11. SS-3408 * 28) 2.6 12 Methyltrimethicone (M3T) 1.0 13.
- the powder before modification thus obtained is dispersed in chloroform, and further 8% of the composition of Production Example 11 (containing silicone compound No. 11) is added to the powder and stirred.
- Organopolysiloxane elastomer spherical powder composite powder with mica
- B Components 7 to 13 are mixed and added to A, followed by further stirring.
- C After pulverizing B with an atomizer, it is cast into a mold to obtain a foundation. (effect) While the powder feel is very light and smooth, a smooth and firm application feeling can be obtained. The unique squeakiness of the powder is also reduced. Because it is excellent in water resistance, water repellency, and sweat resistance, it has a long lasting makeup.
- Example 7 Composition of Example 7 (containing silicone compound No. 7) 2.0 15. Preservative 0.1 16. Fragrance 0.1 * 31) Organopolysiloxane elastomer spherical powder (silica coating type) (Production method)
- the foundation is strong against impact and hard to break. It also has good adhesion to the skin, and is excellent not only in water resistance, water repellency and sweat resistance, but also in sebum resistance, so that it has a very good makeup.
- a cream is obtained by gradually adding and mixing C to ingredients 7 to 11 while stirring. (effect) Lipid formation of lipid bilayer structure is expected in the cream based on the unique properties of soybean phospholipid. It has good skin fit and is not sticky, has a moist moisturizing feeling after use, and has good stability over time.
- Dextrin palmitate 0.5 17. Inulin stearate 0.5 18. Dimethyl distearyl ammonium hectorite 1.0 19. Silicone-treated titanium oxide 10.0 20. Silicone treated bengara 0.3 21. Silicone-treated yellow iron oxide 1.5 22. Silicone-treated black iron oxide 0.05 23. Silicone-treated fine particle titanium oxide 2.0 24. Nylon powder 2.0 25. Decamethylcyclopentasiloxane 18.0 * 32) Polyether-modified silicone (Production method) A: Heat components 1 to 5 to 75 ° C. B: Heat component 6 to 75 ° C. C: After adding and mixing B with A, cool to room temperature. D: Components 7 to 9 are added to C and mixed.
- E Components 10 to 25 are mixed with a roll mill.
- F E is added to D with stirring and mixed to obtain a foundation.
- effect Based on the unique properties of soybean phospholipids, the formation of liposomes with a lipid bilayer structure is expected during the emulsion foundation. Good adhesion to the skin and excellent makeup. There is no stickiness during use, and a plain, natural skin sensation and a moderate moisturizing feeling are maintained. Good product stability over time.
- Example 25 Water-in-oil emulsified sunscreen] (Ingredient) (Wt%) 1. Silicone-treated iron oxide-containing zinc oxide 30.0 2. Composition of Example 10 (containing silicone compound No. 10) 6.0 3. Decamethylcyclopentasiloxane 25.0 4). Methyltrimethicone (M3T) 5.0 5. Isononyl isononanoate 2.0 6). Octyl methoxycinnamate 7.0 7). Polymethylsilsesquioxane powder 5.0 8). Purified water 13.9 9. Ethanol 2.0 10. Glycerin 3.0 11.
- Carboxyvinyl powder (1% aqueous solution) 1.0 12 Sodium chloride 0.1
- effect The transparency of the decorative film is high and there is no bluish white when applied. The sticky feeling peculiar to suncare products has been reduced, and the spreadability is also very good. The stability of the product over time is good, and it is difficult for the powder to aggregate.
- Example 26 Lipstick] (Ingredient) (Wt%) 1. Polyethylene-polypropylene copolymer 5.0 2. Candelilla wax 5.0 3. Carnauba wax 5.0 4). Vaseline 10.0 5. Cetyl 2-ethylhexanoate 10.0 6). Diglycerin diisostearate 14.5 7). Macadamia nut oil 7.0 8). Inulin stearate (Leopard ISK2 from Chiba Flour Mills) 23.0 9. Composition of Example 10 (containing silicone compound No. 10 2.0 10. Red No. 201 1.0 11. Red No. 202 3.0 12 Yellow No. 4 aluminum lake 3.0 13. Titanium oxide 1.0 14 Black iron oxide 0.5 15. Iron oxide mica titanium 10.0 16. Preservative appropriate amount17.
- Perfume appropriate amount (production method) A: Components 1 to 9 are dissolved by heating, and components 10 to 16 are added and mixed uniformly. B: Component 17 is added to A and filled into a container to obtain a lipstick. (effect) It can be applied smoothly with a moist feel, and there is no stickiness during use, preventing lips from drying. Beautiful color and luster are obtained, and the makeup lasting is also good.
- Example 27 Lipstick] (Ingredient) (Wt%) 1. Microcrystalline wax 10.0 2. Paraffin wax 15.0 3. Carnauba wax 5.0 4). Vaseline 5.0 5. Diisostearyl malate 7.0 6). Glyceryl triisostearate 11.5 7). Propylene glycol dicaprate 7.0 8). Inulin stearate (Leopard ISK2 from Chiba Flour Mills) 2.0 9. Composition of Example 8 (containing silicone compound No. 8) 3.0 10. Decamethylcyclopentasiloxane 10.0 11. FA 4001 CM * 33) 3.0 12 DC 593 * 34) 2.0 13. Red No. 201 1.0 14 Red No. 202 1.0 15. Yellow 4 2.0 16. Titanium oxide 4.0 17. Black iron oxide 0.5 18.
- Component 23 is added to B and filled into a container to obtain a lipstick. (effect) It can be applied smoothly with a moist feel, and there is no stickiness during use, preventing lips from drying. The emulsion stability of the product is also very good.
- B Components 1 to 5 (powder part) are mixed in the oil phase part and dispersed uniformly.
- C Component 12 (propellant) is filled to obtain an antiperspirant aerosol cosmetic. (effect) The adhesion of the powder is good, the whiteness after use is inconspicuous, and the safety is high. It has no stickiness after application, has an appropriate dry feeling, and has a smooth and natural skin feel.
- component 9 (propellant) is filled to obtain a non-water pressurized antiperspirant product.
- effect Since a transparent and uniform pressurized liquid is obtained, there is no separation of AP active ingredients and the product life is long. The antiperspirant effect is immediate and the whiteness after use is inconspicuous. After application, a natural skin sensation with a moisturizing feeling can be obtained.
- component 17 is filled to obtain an aerosol type antiperspirant composition.
- effect Since a transparent and uniform pressurized liquid is obtained, there is no separation of antiperspirant active ingredients and the life of the product is long. Antiperspirant action immediately appears immediately after application to the skin. After application, a natural skin sensation without stickiness and moisturizing feeling can be obtained.
- Phenyl trimethicone production method
- effect Since a transparent and uniform liquid agent is obtained, there is no separation of AP active components and the like, and the stability over time is good. Antiperspirant action immediately appears immediately after application to the skin. After application, it suppresses the tension caused by the evaporation of ethanol, resulting in a natural skin sensation that is not sticky and smooth.
- B is gradually added to A and emulsified to obtain an aftershave cream. (effect) Since it has an appropriate viscosity, it does not sag during use and spreads lightly and is not sticky. There is little irritation to the skin, and after application, it can provide a moist but continuous moisturizing feeling. The stability of the product is also very good.
- Octylsilylated fine particle titanium oxide 2.0 (Average primary particle size 10 nm) [Liquid part] Volatile silicone (25% by weight) 8). Decamethylcyclopentasiloxane 15.0 9. Methyltrimethicone 10.0 Polyol (6.5% by weight) 10.1,3-butylene glycol 5.0 11. Maltitol 1.0 12 Raffinose 0.5 Surfactant (2% by weight) 13. Silicone compound no. 15 1.0 14 Sorbitan isostearate 1.0 Solid or pasty oil (5% by weight) 15. Paraffin 5.0 Purified water (12.7% by weight) 16. Purified water 12.7 Oil (9.5% by weight) 17. Dimethylpolysiloxane (6cst) 3.0 18.
- aqueous liquid part (components 10 to 12, component 16, component 22) uniformly mixed and dissolved in advance at 80 ° C. is added here and emulsified and dispersed.
- D The obtained emulsion is deaerated, filled into a metal pan, and set in a hermetic container to obtain a solid foundation. (effect) There is no dryness on the skin when applied, and it is also excellent in skin familiarity. The oily feeling is suppressed, and the touch is good. Good makeup. The stability of the preparation is also good and separation / aggregation hardly occurs.
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Abstract
Description
R1 aL1 bQcSiO(4−a−b−c)/2 (1)
で表される、シロキサンデンドロン構造を有する基および親水性基を有する共変性オルガノポリシロキサン、該共変性オルガノポリシロキサンからなる界面活性剤、該共変性オルガノポリシロキサンからなる粉体処理剤及びそれらを含有してなる外用剤、特に化粧料により達成される。
{一般式(1)中、
R1は一価の有機基(ただし、L1またはQである基を除く)または水素原子である。
L1はi=1のときの下記一般式(2)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る。
一般式(2)
(式中、R2は炭素原子数1~6のアルキル基またはフェニル基であり、Zは二価の有機基である。iはLiで示されるシリルアルキル基の階層を示し、該シリルアルキル基の繰り返し数である階層数がcのとき1~cの整数であり、階層数cは1~10の整数であり、Li+1はiがc未満のときは該シリルアルキル基であり、i=cのときはメチル基またはフェニル基である。aiは0~3の範囲の数である。)
Qは二価以上の連結基を介してケイ素原子に結合し、かつ下記構造式(3−1)~(3−4)で表される親水性単位から選択される少なくとも1種以上の親水性単位を含有してなる親水性基である。
−CrH2r−O− (3−1)
(rは1~6の範囲の数)
(式中、Wは水素原子または炭素原子数1~20のアルキル基。)
(式中、Wは前記同様の基)
a、b及びcは、1.0≦a≦2.5、0.001≦b≦1.5、及び0.001≦c≦1.5となる範囲の数である。}
「[1] 下記一般式(1)
R1 aL1 bQcSiO(4−a−b−c)/2 (1)
で表される、シロキサンデンドロン構造を有する基および親水性基を有する共変性オルガノポリシロキサン。
{一般式(1)中、
R1は一価の有機基(ただし、L1またはQである基を除く)または水素原子である。
L1はi=1のときの下記一般式(2)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る。
一般式(2):
(式中、R2は炭素原子数1~6のアルキル基またはフェニル基であり、Zは二価の有機基である。iはLiで示されるシリルアルキル基の階層を示し、該シリルアルキル基の繰り返し数である階層数がcのとき1~cの整数であり、階層数cは1~10の整数であり、Li+1はiがc未満のときは該シリルアルキル基であり、i=cのときはメチル基またはフェニル基である。aiは0~3の範囲の数である。R1は前記同様の基であり、一般式(2)においては、水素原子、置換もしくは非置換の炭素原子数1~30の一価炭化水素基であることが好ましい。)
Qは二価以上の連結基を介してケイ素原子に結合し、かつ下記構造式(3−1)~(3−4)で表される親水性単位から選択される少なくとも1種以上の親水性単位を含有してなる親水性基である。
−CrH2r−O− (3−1)
(rは1~6の範囲の数)
(式中、Wは水素原子または炭素原子数1~20のアルキル基。)
(式中、Wは前記同様の基)
a、b及びcは、1.0≦a≦2.5、0.001≦b≦1.5、及び0.001≦c≦1.5となる範囲の数である。}
一般式(2−1):
一般式(2−2):
(式中、R1,R2およびZは前記同様の基であり、a1およびa2は各々独立に0~3の範囲の数である。)
一般式(4−1):
−R3(−O−X1 m−R4)p (4−1)
(R3は(p+1)価の有機基であり、pは1以上3以下の数である。X1は各々独立に、上記一般式(3−1)~(3−4)で表される親水性単位から選択される少なくとも1種以上の親水性単位であり、mは1~100の範囲の数である。R4は水素原子、炭素原子数1~20のアルキル基、アシル基およびグリシジル基からなる群から選択される基である。)
一般式(4−2):
−R3(−O−X2)p (4−2)
{R3は前記同様の基であり、pは前記同様の数である。X2は下記構造式(4−2−1)で表される親水性基である、
(式中、2つの酸素原子には、各々独立に、上記一般式(3−1)~(3−4)で表される親水性単位から選択される少なくとも1種以上の親水性単位が結合する。)}
一般式(4−3):
−R3(−O−X3)p (4−3)
{R3は前記同様の基であり、pは前記同様の数である。X3は下記構造式(4−3−1)で表される親水性基である。
(式中、2つの酸素原子には、各々独立に、上記一般式(3−1)~(3−4)で表される親水性単位から選択される少なくとも1種以上の親水性単位が結合する。)}
一般式(4−4):
−R3(−O−X4)p (4−4)
{R3は前記同様の基であり、pは前記同様の数である。X4は下記構造式(4−4−1)で表される親水性基である。
(式中、2つの酸素原子には、各々独立に、上記一般式(3−1)~(3−4)で表される親水性単位から選択される少なくとも1種以上の親水性単位が結合する。)}
{式中、R1,L1およびQは前記同様の基であり、RはR1,L1およびQから選択される基である。ただし、n2=0のとき、Rの少なくとも一方はL1である。また、n3=0のとき、Rの少なくとも一方はQである。(n1+n2+n3)は3~2,000の範囲の数であり、n1,n2およびn3は0~2,000の範囲の数である。}
{式中、Z,R1は前記同様の基であり、Rは、R1,前記のL1、および以下に説明するQ1から選択される基である。n1は10~1,000の範囲の数であり、n2は0~250の範囲の数であり、n3は0~250の範囲の数である。ただし、n2=0のとき、Rの少なくとも一方はL1である。また、n3=0のとき、Rの少なくとも一方はQ1である。
Q1は、各々独立に、下記構造式(4−1−2),(4−2−2),(4−3−2)および(4−4−2)からなる群から選択される親水性基である。
(式中、R3は(p+1)価の有機基であり、pは1以上3以下の数である。X1は各々独立に、前記一般式(3−1)~(3−4)で表される親水性単位から選択される少なくとも1種以上の親水性単位であり、mは1~100の範囲の数である。R4は水素原子、炭素原子数1~20のアルキル基、アシル基およびグリシジル基からなる群から選択される基である。)
(式中、R6は、各々独立に、置換基を有していてもよい、炭素数2~22の直鎖状若しくは分岐鎖状のアルキレン基、アルケニレン基又は炭素数6~22のアリーレン基である。R7は、下記式で示される二価の有機基から選択される基である。
(式中、R6は、各々独立に、置換基を有していてもよい、炭素数2~22の直鎖状若しくは分岐鎖状のアルキレン基、アルケニレン基又は炭素数6~22のアリーレン基である。)」により達成される。
「[9] [1]~[8]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を含有する界面活性剤。
[10] (A)[1]~[8]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(A2)反応性官能基を有する親水性化合物を含有する界面活性剤。
[11] (A)[1]~[8]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、(B)水および(C)5~100℃で液状であるシリコーンオイル、炭化水素油またはエステル油から選択される1以上の油剤を含有するエマルジョン組成物。
[11−1] 上記の(B)成分を含む水相と、上記の(A)成分および(C)成分を含む油相とを、独立に混合した後、両相の25℃における屈折率の差を0.0020単位以下になるように調整して乳化することを特徴とする、請求項11に記載のエマルジョン組成物の透明性調整方法。」により達成される。
「[12] [1]~[8]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を含有する粉体処理剤。
[13] (A)[1]~[8]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(D)粉体又は粉状着色剤を含有してなる粉体組成物。
[14] (D)粉体又は粉状着色剤100質量部に対して、(A)[1]~[8]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1.0~30質量部を使用して前記の(D)成分を表面処理してなることを特徴とする、[13]に記載の粉体組成物。
[15] 前記の(D)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]または[14]に記載の粉体組成物。
[16] 前記の(D)成分が、無機体質顔料であることを特徴とする[13]または[14]に記載の粉体組成物。
[17] (A)[1]~[8]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、(D)粉体又は粉状着色剤および(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。」により達成される。
「[18] [1]~[8]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を含有する外用剤組成物。
[19] 化粧料または医薬である[18]に記載の外用剤組成物。
[20] [11]に記載のエマルジョン組成物を含有する化粧料。
[21] [13]~[16]のいずれか1項に記載の粉体組成物を含有する化粧料。
[22] [17]に記載の油中粉体分散物を含有する化粧料。
[23] [1]~[8]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油剤を含有してなる、実質的に水を含まない化粧料。
[25] 更に、(H)架橋性オルガノポリシロキサン、オルガノポリシロキサンエラストマー球状粉体、シリコーン樹脂、アクリルシリコーンデンドリマーコポリマー、シリコーン生ゴム、ポリアミド変性シリコーン、アルキル変性シリコーンワックス、アルキル変性シリコーンレジンワックスからなる群から選択される少なくとも1種を含有する、[18]~[24]のいずれか1項に記載の化粧料。
[26] 更に、(J)アニオン性界面活性剤、カチオン性界面活性剤、ノニオン性界面活性剤(シリコーン系界面活性剤を除く)、両性界面活性剤、半極性界面活性剤からなる群より選ばれる1種又は2種類以上を含有する[18]~[25]のいずれか1項に記載の化粧料。
[27] 更に、(K)水溶性高分子または(L)紫外線防御成分を含有する[18]~[26]のいずれか1項に記載の化粧料。
[29] 製品の形態が、液状、乳液状、クリーム状、固形状、ペースト状、ゲル状、粉末状、多層状、ムース状、スプレー状のいずれかである[18]~[28]のいずれか1項記載の化粧料。」により達成される。
「[30] ヒドロシリル化反応触媒の存在下において、下記一般式(1’)
R1 aHb+cSiO(4−a−b−c)/2 (1’)
(式中、R1、a、b及びcは前記と同じ)で表されるオルガノハイドロジェンシロキサン(a)と、反応性不飽和基を1分子中に1つ有する親水性誘導体(b)と、反応性不飽和基を1分子中に1つ有するシロキサンデンドロン(c)とを少なくとも反応させて得られることを特徴とする、[1]~[8]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の製造方法。
[31] 反応性不飽和基を1分子中に1つ有する親水性誘導体(b)および反応性不飽和基を1分子中に1つ有するシロキサンデンドロン(c)が少なくとも共存する状態として、前記(b)成分、前記(c)成分および上記一般式(1’)で表されるオルガノハイドロジェンシロキサン(a)を一緒に反応させる事を特徴とする、[30]に記載の共変性オルガノポリシロキサンの製造方法。
[32] 反応性不飽和基を1分子中に1つ有するシロキサンデンドロン(c)が、下記一般式(2’)で表される分子鎖末端に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である、[30]または[31]に記載の共変性オルガノポリシロキサンの製造方法。
一般式(2’):
{式中、L´1はメチル基またはj=1のときの下記一般式(2’’)で示されるシリルアルキル基である。Z´は二価の有機基である。
(式中、R2は炭素原子数1~6のアルキル基またはフェニル基であり、Zは二価の有機基である。jはLjで示されるシリルアルキル基の階層を示し、該シリルアルキル基の繰り返し数である階層数がc’のとき1~c’の整数であり、階層数c’は1~10の整数であり、Lj+1はjがc’未満のときは該シリルアルキル基であり、j=c’のときはメチル基またはフェニル基である。ajは0~3の範囲の数である。)}」により達成される。」により達成される。
R1 aL1 bQcSiO(4−a−b−c)/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)および親水性基(−Q)を有する共変性オルガノポリシロキサンである。(以下、一般式(1)におけるL1で示される基であり、i=1のときに下記一般式(2)で示されるシリルアルキル基を、「カルボシロキサンデンドリマー」または「シロキサンデンドロン構造を有するシリルアルキル基」と表現する場合がある。)。
−(C2H4O)t1(C3H6O)t2− (3−1−1)
式中、t1およびt2は各々0以上の数であり、(t1+t2)は4~50の範囲の数であり、好ましくは8~30の範囲の数である。
一般式(4−1):
−R3(−O−X1 m−R4)p (4−1)
(式中、R6は、各々独立に、置換基を有していてもよい、炭素数2~22の直鎖状若しくは分岐鎖状のアルキレン基、アルケニレン基又は炭素数6~22のアリーレン基である。)
−R3(−O−X2)p (4−2)
式中、2つの酸素原子には、各々独立に、上記一般式(3−1)~(3−4)で表される親水性単位から選択される少なくとも1種以上の親水性単位が結合する。当該親水性単位は、さらに、構造式(3−5)~(3−7)で表される基から選択される分岐単位に結合してもよく、親水性単位が多階層に分岐してなる樹状のポリエーテル構造、ポリグリセロール構造またはポリグリシジルエーテル構造を形成していても良い。
−R3(−O−X3)p (4−3)
式中、R3は前記同様の基であり、pは前記同様の数である。X3は下記構造式(4−3−1)で表される親水性基である。
式中、2つの酸素原子には、各々独立に、上記一般式(3−1)~(3−4)で表される親水性単位から選択される少なくとも1種以上の親水性単位が結合する。当該親水性単位は、さらに、構造式(3−5)~(3−7)で表される基から選択される分岐単位に結合してもよく、親水性単位が多階層に分岐してなる樹状のポリエーテル構造、ポリグリセロール構造またはポリグリシジルエーテル構造を形成していても良い。
−R3(−O−X4)p (4−4)
式中、R3は前記同様の基であり、pは前記同様の数である。X4は下記構造式(4−4−1)で表される親水性基である。
式中、2つの酸素原子には、各々独立に、上記一般式(3−1)~(3−4)で表される親水性単位から選択される少なくとも1種以上の親水性単位が結合する。当該親水性単位は、さらに、構造式(3−5)~(3−7)で表される基から選択される分岐単位に結合してもよく、親水性単位が多階層に分岐してなる樹状のポリエーテル構造、ポリグリセロール構造またはポリグリシジルエーテル構造を形成していても良い。
R1 aHb+cSiO(4−a−b−c)/2 (1’)
(式中、R1、a、b及びcは前記と同じ)で表されるオルガノハイドロジェンシロキサン(a)と、反応性不飽和基を1分子中に1つ有する親水性誘導体(b)と、反応性不飽和基を1分子中に1つ有するシロキサンデンドロン(c)とを少なくとも反応させて得ることができる。
一般式(2’):
{式中、L´1はメチル基またはj=1のときの下記一般式(2’’)で示されるシリルアルキル基である。Z´は二価の有機基である。
一般式(2’’):
(式中、R2は炭素原子数1~6のアルキル基またはフェニル基であり、Zは二価の有機基である。jはLjで示されるシリルアルキル基の階層を示し、該シリルアルキル基の繰り返し数である階層数がc’のとき1~c’の整数であり、階層数c’は1~10の整数であり、Lj+1はjがc’未満のときは該シリルアルキル基であり、j=c’のときはメチル基またはフェニル基である。ajは0~3の範囲の数である。R1は前記同様の基であり、一般式(2’’)においては、水素原子、置換もしくは非置換の炭素原子数1~30の一価炭化水素基であることが好ましい。特に好適には、メチル基または水素原子である。)
R1 4−rSi(OSiMe3)r (3)
(i)(A)共変性オルガノポリシロキサン、油剤である(C)成分である揮発性油剤、不揮発性油剤、可溶化剤などの油相成分を当該技術において既知の任意の方法によって混合する。同様に、水相成分も別の容器中で混合する。
(ii)室温(25℃)において、各相の屈折率(RI)を別々に測定する。
(iii)これら二相の屈折率の差が、少なくとも0.0020単位内にあるように、各相の屈折率の調整を行い、最終混合物の光学的透明性を確保する。
(iv)これらニ相を乳化する。乳化は、所望の乳化手段により行うことができるが、一般的には、剪断ミキサー等の機械的手段を用いて撹拌しつつ、該水相を該油相中に徐々に注入することによってこれら二相をエマルジョンとして合体させる。
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。
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、そのまま化粧料に配合することができる。
さらに詳しくは、アニオン性界面活性剤として、飽和または不飽和脂肪酸塩(例えば、ラウリン酸ナトリウム,ステアリン酸ナトリウム,オレイン酸ナトリウム,リノレン酸ナトリウム等),アルキル硫酸塩,アルキルベンゼンスルホン酸(例えば、ヘキシルベンゼンスルホン酸,トクチルベンゼンスルホン酸,ドデシルベンゼンスルホン酸等)およびその塩,ポリオキシアルキレンアルキルエーテル硫酸塩,ポリオキシアルキレンアルケニルエーテル硫酸塩,ポリオキシエチレンアルキル硫酸エステル塩,スルホコハク酸アルキルエステル塩,ポリオキシアルキレンスルホコハク酸アルキルエステル塩,ポリオキシアルキレンアルキルフェニルエーテル硫酸塩,アルカンスルホン酸塩,オクチルトリメチルアンモニウムヒドロキシド,ドデシルトリメチルアンモニウムヒドロキシド,アルキルスルホネート,ポリオキシエチレンアルキルフェニルエーテル硫酸塩,ポリオキシアルキレンアルキルエーテル酢酸塩,アルキルリン酸塩,ポリオキシアルキレンアルキルエーテルリン酸塩,アシルグルタミン酸塩,α−アシルスルホン酸塩、アルキルスルホン酸塩、アルキルアリルスルホン酸塩、α−オレフィンスルホン酸塩、アルキルナフタレンスルホン酸塩、アルカンスルホン酸塩、アルキルまたはアルケニル硫酸塩、アルキルアミド硫酸塩、アルキルまたはアルケニルリン酸塩、アルキルアミドリン酸塩、アルキロイルアルキルタウリン塩、N−アシルアミノ酸塩、スルホコハク酸塩、アルキルエーテルカルボン酸塩、アミドエーテルカルボン酸塩、α−スルホ脂肪酸エステル塩、アラニン誘導体、グリシン誘導体、アルギニン誘導体が例示される。塩としてはナトリウム塩等のアルカリ金属塩、マグネシウム塩等のアルカリ土類金属塩、トリエタノールアミン塩等のアルカノールアミン塩、さらにはアンモニウム塩が挙げられる。
以上のとおり、本発明に係る共変性オルガノポリシロキサンは汎用性に優れた化粧料原料であり、化粧料または医薬として人体に適用される組成物として、幅広く用いることができるものである。そこで、より具体的に、制汗剤組成物を例にとり説明する。本発明に係る制汗剤組成物は、油中水型エマルジョン(水系製剤)、スティック状の製剤およびスプレー等のエアゾール製剤のいずれであっても選択することができる。その配合成分は、製剤の種類に応じ、前記の化粧料成分を適宜選択して使用できる。特に、水相または油相に配合される制汗活性成分は、前記のとおりであり、所望により、前記のデオドラント成分を配合することが好ましい。
本発明の一実施態様である油中水エマルジョン型の制汗剤組成物においては、共変性オルガノポリシロキサンを含有する油相成分(共変性オルガノポリシロキサン、揮発性油剤、不揮発性油剤、可溶化剤など)、水相成分を任意の方法によって混合する。この際、透明性を確保するために、「本発明の共変性オルガノポリシロキサンを含有するエマルジョンの透明性調整方法」で述べた、各相の屈折率調整を行い、油中水エマルジョン型の制汗剤組成物の透明性および安定性を改善することが好ましい。
次に、本発明の一実施態様であるスティック状制汗剤組成物について説明する。本スティック状制汗剤組成物は固形状制汗剤組成物の一形態であり、固形W/Oエマルションなど水を含有させた形態としても良いし、実質的に水を含まない外用剤組成物とすることもできる。ここでは、実質的に水を含まない系を例にとって説明する。非水のスティック状制汗剤組成物は、安定性に優れておりドライな使用感を得たい場合に有利である。
好適には、硬化ヒマシ油、脂肪酸、ワックス状の変性シリコーン、グリセロールモノステアレート、2−8178 Gellant,2−8179 Gellant等(米国ダウコーニング社製)、AMS−C30 Cosmetic Wax,2503 Cosmetic Wax等(米国ダウコーニング社製)、アルキル変性シリコーンレジンワックスなどを例示することができ、得られるスティック状制汗剤組成物に、適度な硬度と安定性を与える。
次に、本発明に係る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の一つであり、本発明の一実施態様であるエアゾール制汗剤組成物について説明する。本エアゾール制汗剤組成物は水を含有させた形態としても良いし、実質的に水を含まない外用剤組成物とすることもできる。非水のエアゾール制汗剤組成物はドライ感のあるサラサラした使用感を得るのに有利であり、一方、水を含むエアゾール制汗剤組成物は制汗作用の効率が良く清涼感が得られやすいという利点がある。
反応器に平均組成式MD400DH 10Mで表されるメチルハイドロジェンポリシロキサン194.5g、平均組成式CH2=CH−Si(OSiMe3)3で表されるビニルトリストリメチルシロキシシラン18.8g、構造式CH2=CH−CH2−OCH2CH(OH)CH2OHで表されるグリセリンモノアリルエーテル3.3g、イソプロピルアルコール(IPA)90gを仕込み、窒素流通下で攪拌しながら50℃まで加温した。白金−1,3−ジビニル−1,1,3,3−テトラメチルジシロキサン錯体のIPA溶液(Pt濃度4.5wt%)を0.055g添加し、80℃で2.5時間反応を行なった。次いで反応液を2g採取し、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。反応液を減圧下で加熱して低沸分を溜去することによって、平均組成式MD400DR*31 7DR*21 3Mで表されるシロキサンデンドロン構造を有する新規なグリセリン共変性シリコーンを得た。
式中、R*21およびR*31は下記を示す。
R*21= −C3H6OCH2CH(OH)CH2OH
R*31= −C2H4Si(OSiMe3)3
この生成物は、淡黄色の半透明均一な粘稠液体であった。
反応器に平均組成式MD400DH 10Mで表されるメチルハイドロジェンポリシロキサン196.6g、平均組成式CH2=CH−Si(OSiMe3)3で表されるビニルトリストリメチルシロキシシラン13.6g、構造式CH2=CH−CH2−OCH2CH(OH)CH2OHで表されるグリセリンモノアリルエーテル5.5g、IPA90gを仕込み、窒素流通下で攪拌しながら70℃まで加温した。白金−1,3−ジビニル−1,1,3,3−テトラメチルジシロキサン錯体のIPA溶液(Pt濃度4.5wt%)を0.060g添加し、80℃で5時間反応を行なった。次いで反応液を2g採取し、アルカリ分解ガス発生法により反応が完結したことを確認した。反応液を減圧下で加熱して低沸分を溜去することによって、平均組成式MD400DR*31 5DR*21 5Mで表されるシロキサンデンドロン構造を有する新規なグリセリン変性シリコーンを得た。
式中、R*21およびR*31は上記と同様である。
この生成物は、淡黄色の半透明均一な粘稠液体であった。
反応器に平均組成式MD400DH 10Mで表されるメチルハイドロジェンポリシロキサン198.8g、平均組成式CH2=CH−Si(OSiMe3)3で表されるビニルトリストリメチルシロキシシラン8.2g、構造式CH2=CH−CH2−OCH2CH(OH)CH2OHで表されるグリセリンモノアリルエーテル7.9g、IPA90gを仕込み、窒素流通下で攪拌しながら70℃まで加温した。白金−1,3−ジビニル−1,1,3,3−テトラメチルジシロキサン錯体のIPA溶液(Pt濃度4.5wt%)を0.060g添加し、80℃で5時間反応を行なった。次いで反応液を2g採取し、アルカリ分解ガス発生法により反応が完結したことを確認した。反応液を減圧下で加熱して低沸分を溜去することによって、平均組成式MD400DR*31 3DR*21 7Mで表されるシロキサンデンドロン構造を有する新規なグリセリン変性シリコーンを得た。
式中、R*21およびR*31は上記と同様である。
この生成物は、褐色の半透明均一な粘稠液体であった。
反応器に平均組成式MD72DH 12Mで表されるメチルハイドロジェンポリシロキサン177.5g、平均組成式CH2=CH−Si(OSiMe3)3で表されるビニルトリストリメチルシロキシシラン107.6g、構造式CH2=CH−CH2−OCH2CH(OH)CH2OHで表されるグリセリンモノアリルエーテル14.7g、IPA90gを仕込み、窒素流通下で攪拌しながら40℃まで加温した。白金−1,3−ジビニル−1,1,3,3−テトラメチルジシロキサン錯体のIPA溶液(Pt濃度4.5wt%)を0.130g添加し、80℃で3時間反応を行なった。次いで反応液を2g採取し、アルカリ分解ガス発生法により反応が完結したことを確認した。反応液を減圧下で加熱して低沸分を溜去することによって、平均組成式MD72DR*31 9DR*21 3Mで表されるシロキサンデンドロン構造を有する新規なグリセリン変性シリコーンを得た。
式中、R*21およびR*31は上記と同様である。
この生成物は、ほぼ無色の半透明均一な液体であった。
反応器に平均組成式MD400DH 10Mで表されるメチルハイドロジェンポリシロキサン198.7g、平均組成式CH2=CH−Si(OSiMe3)3で表されるビニルトリストリメチルシロキシシラン8.2g、構造式CH2=CH−CH2−OCH2CH(OH)CH2OHで表されるグリセリンモノアリルエーテル5.6g、1−デセン2.4g、IPA90gを仕込み、窒素流通下で攪拌しながら70℃まで加温した。白金−1,3−ジビニル−1,1,3,3−テトラメチルジシロキサン錯体のIPA溶液(Pt濃度4.5wt%)を0.050g添加し、80℃で3時間反応を行なった。次いで反応液を2g採取し、アルカリ分解ガス発生法により反応が完結したことを確認した。反応液を減圧下で加熱して低沸分を溜去することによって、平均組成式MD400DR*11 2DR*31 3DR*21 5Mで表されるシロキサンデンドロン構造とアルキル基を有する新規なグリセリン変性シリコーンを得た。
式中、R*21およびR*31は上記と同様であり、R*11= −C10H21である。
この生成物は、淡黄褐色の半透明均一液体であった。
反応器に平均組成式MD72DH 12Mで表されるメチルハイドロジェンポリシロキサン109.3g、平均組成式CH2=CH−Si(OSiMe3)3で表されるビニルトリストリメチルシロキシシラン66.3g、ポリグリセリンモノアリルエーテル24.3g、IPA200g、2.3wt%酢酸ナトリウム/メタノール溶液0.23gを仕込み、窒素流通下で攪拌しながら50℃まで加温した。塩化白金酸の5wt%IPA溶液を0.160g添加し、80℃で7時間反応を行なった。次いで反応液を2g採取し、アルカリ分解ガス発生法により反応が完結したことを確認した。反応液を減圧下で加熱して低沸分を溜去することによって、平均組成式MD72DR*31 9DR*22 3Mで表されるシロキサンデンドロン構造を有する新規なポリグリセリン変性シリコーンを得た。
式中、R*31は上記と同様である。
R*22は、−C3H6O−Xで表される親水基であり、Xはテトラグリセリン部分である。
この生成物は、乳白色の均一なガム状であった。
反応器に平均組成式MD72DH 12Mで表されるメチルハイドロジェンポリシロキサン105.5g、平均組成式CH2=CH−Si(OSiMe3)3で表されるビニルトリストリメチルシロキシシラン64.0g、ポリグリセリルオイゲノール30.5g、IPA200gを仕込み、窒素流通下で攪拌しながら60℃まで加温した。白金−1,3−ジビニル−1,1,3,3−テトラメチルジシロキサン錯体のIPA溶液(Pt濃度4.5wt%)を0.130g添加し、80℃で3時間反応を行なった。次いで反応液を2g採取し、アルカリ分解ガス発生法により反応が完結したことを確認した。反応液を減圧下で加熱して低沸分を溜去することによって、平均組成式MD72DR*31 9DR*23 3Mで表されるシロキサンデンドロン構造を有する新規なポリグリセリン変性シリコーンを得た。
式中、R*31は上記と同様である。
この生成物は、乳白色の均一なガム状であった。
反応器に平均組成式MD72DH 12Mで表されるメチルハイドロジェンポリシロキサン112.3g、平均組成式CH2=CH−Si(OSiMe3)3で表されるビニルトリストリメチルシロキシシラン45.4g、ポリグリセリルオイゲノール32.5g、IPA200gを仕込み、窒素流通下で攪拌しながら55℃まで加温した。白金−1,3−ジビニル−1,1,3,3−テトラメチルジシロキサン錯体のIPA溶液(Pt濃度4.5wt%)を0.100g添加し、80℃で2時間反応を行なった。次いで反応液を2g採取し、アルカリ分解ガス発生法により反応率が75−80%に達している事を確認した。1−デセン9.9gを添加し80℃で1時間反応を継続した。再度反応液を採取して確認したところ、反応は完結していた。反応液を減圧下で加熱して低沸分を溜去することによって、平均組成式MD72DR*11 3DR*31 6DR*23 3Mで表されるシロキサンデンドロン構造とアルキル基を有する新規なポリグリセリン変性シリコーンを得た。
式中、R*31およびR*23は上記と同様であり、R*11= −C10H21である。
この生成物は、灰白色の均一なガム状であった。
反応器に平均組成式MD45DH 2Mで表されるメチルハイドロジェンポリシロキサン171.9g、平均組成式CH2=CH−Si(OSiMe3)3で表されるビニルトリストリメチルシロキシシラン19.9g、構造式CH2=CH−CH2−OCH2CH(OH)CH2OHで表されるグリセリンモノアリルエーテル8.2g、IPA60gを仕込み、窒素流通下で攪拌しながら60℃まで加温した。白金−1,3−ジビニル−1,1,3,3−テトラメチルジシロキサン錯体のIPA溶液(Pt濃度4.5wt%)を0.04g添加し、80℃で2時間反応を行なった。次いで反応液を2g採取し、アルカリ分解ガス発生法により反応が完結したことを確認した。反応液を減圧下で加熱して低沸分を溜去することによって、平均組成式MD45DR*31 1DR*21 1Mで表されるシロキサンデンドロン構造を有する新規なグリセリン変性シリコーンを得た。
R*21= −C3H6OCH2CH(OH)CH2OH
R*31= −C2H4Si(OSiMe3)3
この生成物は、ほぼ無色の半透明均一な液体であった。
反応器に平均組成式MD45DH 2Mで表されるメチルハイドロジェンポリシロキサン160.9g、平均組成式CH2=CH−Si(OSiMe3)3で表されるビニルトリストリメチルシロキシシラン18.6g、ポリグリセリンモノアリルエーテル20.5g、IPA200gを仕込み、窒素流通下で攪拌しながら65℃まで加温した。白金−1,3−ジビニル−1,1,3,3−テトラメチルジシロキサン錯体のIPA溶液(Pt濃度4.5wt%)を0.067g添加し、80℃で3時間反応を行なった。次いで反応液を2g採取し、アルカリ分解ガス発生法により反応が完結したことを確認した。反応液を減圧下で加熱して低沸分を溜去することによって、平均組成式MD45DR*31 1DR*22 1Mで表されるシロキサンデンドロン構造を有する新規なポリグリセリン変性シリコーンを得た。
式中、R*31は上記と同様である。
R*22は、−C3H6O−X,Xはテトラグリセリン部分
この生成物は、乳白色均一な粘稠液体であった。
反応器に平均組成式MD45DH 2Mで表されるメチルハイドロジェンポリシロキサン124.1g、下記平均組成式(10)で表される3−メタクリロキシプロピル(トリス(トリメチルシロキシ)シリルエチルジメチルシロキシ)シラン60.1g、ポリグリセリンモノアリルエーテル15.8g、IPA200g、および4−t−ブチルカテコール(重合禁止剤)0.08gを仕込み、窒素流通下で攪拌しながら30℃まで加温した。白金−1,3−ジビニル−1,1,3,3−テトラメチルジシロキサン錯体のIPA溶液(Pt濃度4.5wt%)を0.130g添加し、80℃で7時間反応を行なった。次いで反応液を2g採取し、アルカリ分解ガス発生法により反応が完結したことを確認した。反応液を減圧下で加熱して低沸分と重合禁止剤を溜去することによって、平均組成式MD45DR*32 1DR*22 1Mで表されるカルボシロキサンデンドリマー構造を有する新規なポリグリセリン変性シリコーンを得た。
組成式(10):
平均組成式MD45DR*32 1DR*22 1M中、R*22は上記と同様であり、R*32は下記官能基である。
得られた生成物は、乳白色均一な粘稠液体であった。
反応器に平均組成式MD45DH 2Mで表されるメチルハイドロジェンポリシロキサン156.1g、平均組成式CH2=CH−Si(OSiMe3)3で表されるビニルトリストリメチルシロキシシラン18.1g、ポリグリセリルオイゲノール25.9g、IPA200gを仕込み、窒素流通下で攪拌しながら70℃まで加温した。白金−1,3−ジビニル−1,1,3,3−テトラメチルジシロキサン錯体のIPA溶液(Pt濃度4.5wt%)を0.067g添加し、80℃で3時間反応を行なった。次いで反応液を2g採取し、アルカリ分解ガス発生法により反応が完結したことを確認した。反応液を減圧下で加熱して低沸分を溜去することによって、平均組成式MD45DR*31 1DR*23 1Mで表されるシロキサンデンドロン構造を有する新規なポリグリセリン変性シリコーンを得た。
R*31= −C2H4Si(OSiMe3)3
なお、前記のポリグリセリルオイゲノールは、オイゲノール1モルに対し4モル相当のグリシドールを開環重合する事により合成されたものである。ポリグリセリン部分は鎖状構造だけでなく分岐構造も含まれ得る。
この生成物は、乳白色均一な粘稠液体であった。
反応器に平均組成式MD150DH 10Mで表されるメチルハイドロジェンポリシロキサン151.3g、平均組成式CH2=CH−Si(OSiMe3)3で表されるビニルトリストリメチルシロキシシラン26.7g、ポリグリセリンモノアリルエーテル11.7g、ジグリセリンモノアリルエーテル10.2g、IPA200gを仕込み、窒素流通下で攪拌しながら65℃まで加温した。白金−1,3−ジビニル−1,1,3,3−テトラメチルジシロキサン錯体のIPA溶液(Pt濃度4.5wt%)を0.100g添加し、80℃で5時間反応を行なった。次いで反応液を2g採取し、アルカリ分解ガス発生法により反応が完結したことを確認した。反応液を減圧下で加熱して低沸分を溜去することによって、平均組成式MD150DR*31 5DR*22 2DR*28 3Mで表されるシロキサンデンドロン構造を有する新規なポリグリセリン変性シリコーンを得た。
式中、R*31は上記と同様である。
R*22も前記と同様で、−C3H6O−X,Xはテトラグリセリン部分
R*28= −C3H6O−X,Xはジグリセリン部分
この生成物は、乳白色均一な粘稠液体であった。
反応器に平均組成式MD43DH 7Mで表されるメチルハイドロジェンポリシロキサン100.0g、ポリオキシエチレン(10)モノアリルエーテル27.9g、天然ビタミンEを0.055g仕込み、窒素流通下で攪拌しながら65℃まで加温した。白金−1,3−ジビニル−1,1,3,3−テトラメチルジシロキサン錯体のトルエン溶液(Pt濃度2.2wt%)を0.018g添加し、80℃で3.5時間反応を行なった。次いで、平均組成式CH2=CH−Si(OSiMe3)3で表されるビニルトリストリメチルシロキシシラン54.7gを添加し、上記と同じ白金触媒溶液0.018g追加投入した。85℃で4時間の反応を行なった後、反応液を2g採取しアルカリ分解ガス発生法で確認したところ反応は完結していた。反応液を減圧下で加熱して低沸分を溜去することによって、平均組成式MD43DR*31 5DR*24 2Mで表されるシロキサンデンドロン構造を有する新規なポリエーテル変性シリコーンを得た。
式中、R*31は上記と同様である。
R*24= −C3H6O(C2H4O)10H
この生成物は、淡褐色のほぼ透明均一な液体であった。
反応器に平均組成式MD72DH 12Mで表されるメチルハイドロジェンポリシロキサン109.3g、平均組成式CH2=CH−Si(OSiMe3)3で表されるビニルトリストリメチルシロキシシラン66.3g、IPA200g、2.3wt%酢酸ナトリウム/メタノール溶液0.23gを仕込み、窒素流通下で攪拌しながら50℃まで加温した。塩化白金酸の5wt%IPA溶液を0.160g添加し、80℃で3時間反応を行なった。反応液を2g採取しアルカリ分解ガス発生法で確認したところ、反応率は目標の75%±5%を上回り85%に達していた。次いでポリグリセリンモノアリルエーテル24.3g添加し80℃で4時間反応を行なった。反応液を2g採取し、アルカリ分解ガス発生法により反応が完結したことを確認した。反応液を減圧下で加熱して低沸分を溜去することによって、平均組成式MD72DR*31 10DR*22 2Mで表されるシロキサンデンドロン構造を有する新規なポリグリセリン変性シリコーンを得た。
式中、R*31は前記と同じく−C2H4Si(OSiMe3)3
R*22も前記と同様で、−C3H6O−X,Xはテトラグリセリン部分
反応器に平均組成式MD72DH 12Mで表されるメチルハイドロジェンポリシロキサン109.3g、ポリグリセリンモノアリルエーテル24.3g、IPA200g、2.3wt%酢酸ナトリウム/メタノール溶液0.23gを仕込み、窒素流通下で攪拌しながら50℃まで加温した。塩化白金酸の5wt%IPA溶液を0.160g添加し、80℃で3時間反応を行なった。反応液を2g採取しアルカリ分解ガス発生法で確認したところ、反応率は目標の25%に達せず約20%であった。そこで塩化白金酸の5wt%IPA溶液を0.080g添加し、85~87℃まで加熱して更に4時間反応を継続した。その結果、反応液が攪拌捧に巻きつくゲル化現象が生じたため、予定していた平均組成式CH2=CH−Si(OSiMe3)3で表されるビニルトリストリメチルシロキシシラン66.3gの添加をやめ、製造を中断した。
反応器に平均組成式MHD40MHで表されるメチルハイドロジェンポリシロキサン241.0g、平均組成式CH2=C(CH3)CH2−O(C2H4O)10(C3H6O)7−CH2−C(CH3)=CH2で表されるビスメタリルポリエーテル100.0g、IPA102g、天然ビタミンE0.17g、5wt%酢酸ナトリウム/メタノール溶液0.89gを仕込み、窒素流通下で攪拌しながら50℃まで加温した。白金−2,4,6,8−テトラメチル−2,4,6,8−テトラビニルテトラシロキサン錯体のトルエン溶液(Pt濃度3.0wt%)を0.023g添加し、80℃で2.5時間反応を行なった。次いで反応液を2g採取し、アルカリ分解ガス発生法により反応が完結したことを確認した。反応液を減圧下で加熱して低沸分を溜去することによって、平均組成式[D40MR*25 2]3で表されるブロック型ポリエーテル変性シリコーンを得た。なお、平均組成式を簡易に表記したが、原料のC=C基とSi−H基のモル比はおよそ4:3であるため、実際には変性シリコーンの両末端はポリエーテルで封鎖された形となっている。
式中、R*25= −C4H8O(C2H4O)10(C3H6O)7−C4H8−であり、ポリエーテル部分はエチレンオキサイドとプロピレンオキサイドのランダム付加体である。
この生成物は、淡黄色の透明均一な液体であった。
反応器に平均組成式MD45DH 2Mで表されるメチルハイドロジェンポリシロキサン129.4g、ポリオキシエチレン(10)モノアリルエーテル40.0g、トルエン51gを仕込み、窒素流通下で攪拌しながら75℃まで加温した。塩化白金酸の10wt%IPA溶液を0.017g添加し、73~93℃で1.5時間反応を行なった。反応液を2g採取しアルカリ分解ガス発生法で確認したところ反応は完結していた。重曹を0.51g添加し、反応液を減圧下で加熱する事で低沸分を溜去した。更に濾過を行って平均組成式MD45DR*24 2Mで表されるポリエーテル変性シリコーンを得た。
R*24= −C3H6O(C2H4O)10H
この生成物は、ほぼ無色の透明均一な液体であった。
反応器に平均組成式MD63DH 22Mで表されるメチルハイドロジェンポリシロキサン89.9g、ポリオキシエチレン(10)モノアリルエーテル36.4g、1−ヘキサデセン73.7g、トルエン60gを仕込み、窒素流通下で攪拌しながら40℃まで加温した。白金−1,3−ジビニル−1,1,3,3−テトラメチルジシロキサン錯体のIPA溶液(Pt濃度4.5wt%)を0.06g添加し、80−110℃で2.5時間反応を行なった。次いで反応液を2g採取し、アルカリ分解ガス発生法により反応が完結したことを確認した。反応液を減圧下で加熱して低沸分を溜去することによって、平均組成式MD63DR*12 18DR*24 4Mで表されるアルキル/ポリエーテル共変性シリコーンを得た。
式中、R*12= −C16H33
R*24= −C3H6O(C2H4O)10H
この生成物は、淡褐色の半透明均一な液体であった。
反応器に平均組成式MD406DH 4Mで表されるメチルハイドロジェンポリシロキサン116.2g、平均組成式CH2=CH−CH2−O(C2H4O)19(C3H6O)19Hで表されるアリルポリエーテル34.0g、IPA45g、天然ビタミンE0.03g、1.5wt%酢酸ナトリウム/メタノール溶液0.15gを仕込み、窒素流通下で攪拌しながら50℃まで加温した。塩化白金酸の1wt%IPA溶液を0.39g添加し、80~85℃で4時間反応を行なった。反応液を2g採取しアルカリ分解ガス発生法で確認したところ、反応は完結していた。希釈剤のジメチルポリシロキサン(2cst)を230g添加して溶解させた後、減圧下で加熱してIPAとメタノールとを溜去した。これにより、平均組成式MD406DR*26 4Mで表されるポリエーテル変性シリコーンとジメチルポリシロキサン(2cst)との40:60(wt比)混合液が得られた。
式中、R*26= −C3H6O(C2H4O)19(C3H6O)19H
この生成物は、やや褐色味ある灰白色の粘稠液体であった。
反応器に平均組成式MD37DH 14Mで表されるメチルハイドロジェンポリシロキサン92.7gを仕込み、構造式CH2=CH−SiMe2(OSiMe2)6OSiMe3で表される片末端ビニル変性ジメチルポリシロキサン19.2gと白金−1,3−ジビニル−1,1,3,3−テトラメチルジシロキサン錯体のトルエン溶液(Pt濃度0.5wt%)0.10gの混合物を滴下して、室温下で攪拌しリニアシロキサン分岐型ポリシロキサン中間体を得た。
別の反応器にポリオキシエチレン(10)モノアリルエーテル30.9g、1−ドデセン57.3g、IPA100g、白金−1,3−ジビニル−1,1,3,3−テトラメチルジシロキサン錯体のIPA溶液(Pt濃度0.5wt%)0.30gを仕込み、窒素流通下で攪拌しながら先に合成したリニアシロキサン分岐型ポリシロキサンを溶剤の還流下に滴下を行った。滴下終了後に1時間の加熱攪拌を継続し、反応液を2g採取し、アルカリ分解ガス発生法により反応が完結したことを確認した。反応液を減圧下で加熱して低沸分を溜去した。更に濾過を行う事によって、平均組成式MD37DR*13 11DR*41 1DR*24 2Mで表されるアルキル/リニアシロキサン/ポリエーテル共変性シリコーンを得た。
式中、R*13= −C12H25
R*41= −C2H4SiMe2(OSiMe2)6OSiMe3
R*24= −C3H6O(C2H4O)10H
この生成物は、ほぼ無色の半透明均一液体であった。
反応器に平均組成式MD61DH 15Mで表されるメチルハイドロジェンポリシロキサン111.6gを仕込み、構造式CH2=CHSiMe2(OSiMe2)6OSiMe3で表される片末端ビニル変性ジメチルポリシロキサン30.9gと白金−1,3−ジビニル−1,1,3,3−テトラメチルジシロキサン錯体のトルエン溶液(Pt濃度0.5wt%)0.10gの混合物を滴下して、室温下で攪拌しリニアシロキサン分岐型ポリシロキサン中間体を得た。
式中、R*13= −C12H25
R*41= −C2H4SiMe2(OSiMe2)6OSiMe3
R*27= −C3H6O−X,Xはトリグリセリン部分
この生成物は、ほぼ無色の半透明均一な液体であった。
反応器に平均組成式MD406DH 4Mで表されるメチルハイドロジェンポリシロキサン212.5g、構造式CH2=CH−CH2−OCH2CH(OH)CH2OHで表されるグリセリンモノアリルエーテル4.9g、IPA90gを仕込み、窒素流通下で攪拌しながら70℃まで加温した。白金−1,3−ジビニル−1,1,3,3−テトラメチルジシロキサン錯体のIPA溶液(Pt濃度4.5wt%)を0.053g添加し、80℃で3時間反応を行なった。次いで反応液を2g採取し、アルカリ分解ガス発生法により反応が完結したことを確認した。反応液を減圧下で加熱して低沸分を溜去することによって、平均組成式MD406DR*21 4Mで表されるグリセリン変性シリコーンを得た。
式中、R*21= −C3H6OCH2CH(OH)CH2OH
この生成物は、淡黄褐色の半透明均一な粘稠液体であった。
反応器に平均組成式MD72DH 12Mで表されるメチルハイドロジェンポリシロキサン155.9g、構造式CH2=CH−CH2−OCH2CH(OH)CH2OHで表されるグリセリンモノアリルエーテル13.0g、1−デセン41.1g、IPA63gを仕込み、窒素流通下で攪拌しながら45℃まで加温した。白金−1,3−ジビニル−1,1,3,3−テトラメチルジシロキサン錯体のIPA溶液(Pt濃度4.5wt%)を0.055g添加し、80℃で1時間反応を行なった。次いで反応液を2g採取し、アルカリ分解ガス発生法により反応が完結したことを確認した。反応液を減圧下で加熱して低沸分を溜去することによって、平均組成式MD72DR*11 9DR*21 3Mで表されるアルキル/グリセリン共変性シリコーンを得た。
式中、R*11= −C10H21
R*21= −C3H6OCH2CH(OH)CH2OH、
この生成物は、淡褐色の半透明液体であった。
反応器に平均組成式MD72DH 12Mで表されるメチルハイドロジェンポリシロキサン134.6g、1−デセン36.2g、ポリグリセリンモノアリルエーテル29.9g、IPA200g、2.3wt%酢酸ナトリウム/メタノール溶液0.25gを仕込み、窒素流通下で攪拌しながら55℃まで加温した。塩化白金酸の5wt%IPA溶液を0.160g添加し、80℃で7時間反応を行なった。次いで反応液を2g採取し、アルカリ分解ガス発生法により確認したところ反応は完結していた。反応液を減圧下で加熱して低沸分を溜去することによって、平均組成式MD72DR*11 9DR*22 3Mで表されるアルキル/ポリグリセリン共変性シリコーンを得た。
式中、R*11は前記と同様、
R*22も前記と同様で、−C3H6O−X,Xはテトラグリセリン部分
この生成物は、全体としては灰白色のガム状であったが、均一ではなく部分的に相分離(ガム状の淡褐色相)を起こしていた。
<長鎖アルキル基:R*1>
R*11= −C10H21
R*12= −C16H33
R*13= −C12H25
<親水性基:R*2>
R*21= −C3H6OCH2CH(OH)CH2OH
R*22は、−C3H6O−Xで表される親水基(Xはテトラグリセリン部分)
R*24= −C3H6O(C2H4O)10H
R*25= −C4H8O(C2H4O)10(C3H6O)7−C4H8−であり、ポリエーテル部分はエチレンオキサイドとプロピレンオキサイドのランダム付加体である。
R*26= −C3H6O(C2H4O)19(C3H6O)19H
R*27= −C3H6O−Xで表される親水基(Xはトリグリセリン部分)
R*28= −C3H6O−Xで表される親水基(Xはジグリセリン部分)
<シロキサンデンドロン構造を有する基:R*3>
R*31= −C2H4Si(OSiMe3)3
<リニアポリシロキサン構造を有する基:R*4>
R*41= −C2H4SiMe2(OSiMe2)6OSiMe3
表2~表7に示す組成で各成分を以下の手順に従って混合・乳化する事により、W/(Si+O)及びW/Siの乳液を調製した。なお、乳化化粧料の説明において前記のW/(Si+O)やW/Siエマルションにおいて、Wは水相の略であり、Siはシリコーン系油剤の略であり、Oは他の有機油剤の略である。また、「Si+O」はシリコーンオイルおよび他の有機油剤の混合油からなる油相を表す。
1.200ml容器に、基油としてのジメチルポリシロキサン(2cst)、基油と組み合わせる油剤、および界面活性剤としての親水性シリコーン化合物を仕込んだ。
2.スパチュラによる混合を行い、界面活性剤を油剤中に分散・溶解させた。(油相A)
3.ホモディスパーの鋸歯を油相Aに浸し、容器を固定したのち攪拌を開始した。全体が均一な溶液状となるまで、攪拌を実施した。
4.別のカップに食塩とイオン交換水とを仕込み、スパチュラで混合して溶解させた。(水相B)
5.ホモディスパーの回転数を3000rpmまで上げ、攪拌下に水相Bをほぼ定速で約40秒かけて油相A中に注ぎ込んだ。
6.攪拌を更に2分間継続してから一旦止め、容器の内壁に付着した油分をスパチュラで掻き落とし、生成しているエマルションと混合した。
7.ホモディスパーの回転数3000rpmで3分間の攪拌を行い、乳化化粧料を得た。
[乳液処方についての説明]
基油であるジメチルポリシロキサン(2cst)は、ダウコーニング社製の200 FLUID 2 CSを使用した。(表中「2cst」と略記)
また、これと併用する油剤としては以下の6種類を用いた。(実施例、比較例1つ当たり6点の乳液を調製したので、評価した乳液サンプル数は合計で108個(9×6+9×6)であった。
[併用する油剤]
1)ジメチルポリシロキサン(6cst){東レ・ダウコーニング(株)製、製品名:SH200 C FLUID 6CS}
(表中、「6cst」と略記)
2)カプリリルメチコン{東レ・ダウコーニング(株)製 アルキル変性シリコーン、製品名:SS−3408}
(表中、「SS−3408」と略記)
3)トリ2−エチルヘキサン酸グリセリル{日本精化(株)製 エステル油、製品名:IOTG}
(表中、「IOTG」と略記)
4)2−エチルヘキサン酸セチル{高級アルコール工業(株)製 エステル油、製品名:CEH}(表中、「CEH」と略記)
5)イソドデカン{丸善石油化学(株)製 炭化水素油(ID)、製品名:マルカゾールR}
(表中、「ID」と略記)
6)イソパラフィン{日油(株)製 炭化水素油(IP)、製品名:パールリーム4}
(表中、「IP」と略記)
上記の組成、調製方法により得た乳液は、以下の方法で評価した。
1−1:乳液を手の甲から指先にかけて(0.1g×2回)と腕に(0.2g×1回。但し、油剤としてイソドデカンおよびイソパラフィンを使用した乳液の場合は0.2g×2回)塗布した時の感触や使用感について、4つの側面から官能評価を行い、各側面に対して0点(不良)~5点(良)までのスコアをつけて優劣を判定した。
側面1:塗布時の触感(みずみずしい=5点~0点=油性感が強く油っぽい)
側面2:塗布時の伸び拡がり性(抵抗なく伸び拡がる=5点~0点=伸び拡げるときに抵抗が大きい)
側面3:塗布時の滑らかさ(皮膚の皺や凹凸をほとんど感じずなめらか=5点~0点=皮膚の皺や凹凸を強く感じる)
側面4:塗布時の軽さ(軽くさらっとしている=5点~0点=重く濃厚すぎる塗布感)
1−2:乳液塗布から5分間経過後の肌感覚について、3つの側面から官能評価を行い0点(不良)~5点(良)までのスコアをつけて優劣を判定した。更に、油の指残り感については、乳液0.05gを人差し指にとり親指・中指と擦り合わせた時の残り感を評価して、同様のスコアで判定した。
側面5:塗布後の肌感覚(保湿感が大きい=5点~0点=油性感が強く油っぽい又はべとつきが有る)
側面6:塗布後の肌感覚(違和感なく自然=5点~0点=不自然な又は不快な残留感)
側面7:肌の状態(皮脂の溶解や乾燥がない=5点~0点=皮脂が溶解して肌が白くなり、乾燥によるツッパリ感やかゆみ、刺激を感じる程度がひどい)
側面8:油の指残り感(油の残り感がほとんど無い=5点~0点=しつこい油のぬるつきや不自然な滑りが続き、指残り感が無くならない)
1−3:各乳液サンプルの評価側面ごとのスコアと合計点を、油剤系ごとに一覧表にまとめた。(表12~表29)更に、油剤系と活性剤の違いによる、乳液の感触評価の合計得点(総合点)を一覧表にまとめた。(表9~表11)また、油剤系および評価側面ごとに、実施例9サンプルの合計得点と比較例9サンプルの合計得点を表にまとめ比較する事により、実施例で用いた新規な親水性シリコーンのもたらす感触面の特長を明らかにした。(表30~表32)
2−1:東京計器(株)製のE型粘度計:VISCOMIC EMDを用いて、調製後の乳液粘度を測定した。(コーンローター小:3°×R9.7、25℃、2.5rpm)
2−2:次いで、乳液25g×2つを35mlガラス瓶×2本に入れ、栓をして0℃及び40℃の高温槽に2週間静置した。その後、取り出して室温に戻し、同様に粘度測定を実施した。
2−3:初期の粘度値を100%としたときの相対値で経時後の粘度値を表示し、油剤系ごとに一覧表にまとめた。(表32~表37)
乳液の外観上の特長すなわち質感について目視で評価した。実施例サンプル群ごとに下記の2グループに分類し、比較例の市販シリコーン活性剤を使用したサンプル群との比較を行った。評価結果を◎、○、△、×で一覧表にまとめた。(表38~表41)
3−1:マット感の付与(外観に強い光沢やテカリの無いものを良とした。)
乳液の光沢や輝きが強すぎると、皮膚に塗布した時に油っぽいギラツキが出やすくなるため、乳液の光沢を抑えることに一つの価値がある。
◎ 光沢がなくマット感に優れる。
○ 少し光沢はあるがマット感が優勢である。
△ 少しマット感がある。
× 光沢が強くマット感がない。
3−2:パール光沢の付与(美しい高級感あるパール様光沢を有するものを良とした。)
乳液やクリームに美しいパール光沢を付与できれば、外観上の商品価値が高まることに加えて、塗布使用後にも上品で落ち着きのある輝きを皮膚にもたらす事ができる。
◎ 高級感あふれる美しいパール様の光沢がある。 ○ パール様の光沢がある。
△ パール様の光沢が少し認められる。 × パール様の光沢はない。
以下に、油剤系と活性剤の違いによる、乳液の感触評価の合計点一覧を示した。
以下の表33~表38に示したように、本発明のシロキサンデンドロン構造を有する新規な親水性シリコーンを乳化剤として使用して得た乳液は、どの油剤系であっても温度や経時による粘度変化が少なく初期値±8%以内の変動に収まっていた。一方で、既存のシリコーン系界面活性剤を乳化剤として使用して得た乳液は、油剤系の種類によっては粘度が初期値±10%以上まで変動することが分かった。
以下の表39~表42に示したとおり、本発明の新規な親水性シリコーンを乳化剤として使用して得た乳液は、比較例の乳液と比較して様々な油剤系に対してマット感を付与できる、又は高級感あふれるパール光沢を付与できる事が分かった。乳液の光沢が強すぎない事は、皮膚に塗布した後の油っぽいギラツキや過剰な油性感を抑える事にもつながり、有効である。即ち、本発明の新規な親水性シリコーンは、乳液に対して独特の優れた質感を与えるものであることが明らかになった。
表43~表51に示す組成を以下の手順に従って混合・乳化する事により、W/(Si+O)及びW/Siの乳液を調製した。
1.200ml容器に、基油としてのジメチルポリシロキサン(2cst)、基油と組み合わせる油剤、および界面活性剤としての親水性シリコーン化合物を仕込んだ。
2.スパチュラによる混合を行い、界面活性剤を油剤中に分散・溶解させた。(油相A)
3.ホモディスパーの鋸歯を油相Aに浸し、容器を固定したのち攪拌を開始した。全体が均一な溶液状となるまで、攪拌を実施した。
4.別のカップに塩類とイオン交換水とを仕込み、スパチュラで混合して溶解させた。処方によっては、更にグリセリン又はエタノールを添加して溶解した。(水相B)
5.ホモディスパーの回転数を3000rpmまで上げ、攪拌下に水相Bをほぼ定速で約40秒かけて油相A中に注ぎ込んだ。
6.攪拌を更に2分間継続してから一旦止め、容器の内壁に付着した油分をスパチュラで掻き落とし、生成しているエマルションと混合した。
7.ホモディスパーの回転数3000rpmで3分間の攪拌を行い、終了。
乳液処方:以下の表41~49に記載した数字の単位はgである。
1.感触評価
以下の表52、表53に油剤系と活性剤系の違いによる、乳液の感触評価の合計点一覧を示した。実施例は、本発明のシロキサンデンドロン構造を有する新規な親水性シリコーンと既存のシリコーン系界面活性剤とを組み合わせて乳化剤として使用した処方である。
外観
以下の表66~表67に示したとおり、本発明の新規な親水性シリコーンと油剤と水とを少なくとも含む乳液処方に、グリセリン、エタノール、クエン酸ナトリウム、食塩などの添加剤を1種以上更に配合した場合でも、乳液外観にマット感を付与できる、又は高級感あふれるパール光沢を付与できる事が分かった。
表68(実施例)/表69(比較例)に示す組成(処方)を以下の手順に従って混合・分散する事により、油中粉体分散物を調製した。なお、以下の表68、表69に記載した処方において、数字の単位は全てgである。
1.200mlガラス瓶に、デカメチルシクロペンタシロキサン(D5)とシリコーン化合物(分散剤)を仕込み、混合して溶解させた。
2.粉体と粉体の10倍の質量のジルコニアボール(YTZボール、直径0.8mm)を上のガラス瓶に仕込み、蓋をして軽く振り混ぜた。ここで、粉体は以下のものを用いた。
酸化チタン:MTY−100SAS(テイカ株式会社製)
酸化亜鉛 :MZY−505S(テイカ株式会社製)
3.ガラス瓶をペイントシェーカーにセットして、1時間振とうを行った。
4.得られた混合物を篩にとおしてジルコニアボールを取り除くことにより、油中粉体分散物を得た。
表70(実施例)/表71(比較例)に示す組成(処方)を以下の手順に従って処理することにより、本発明に係る粉体組成物および比較例となる粉体組成物を調製した。
ここで、粉体は以下のものを用いた。
酸化チタン:MTY−100SAS(テイカ株式会社製)
酸化亜鉛 :MZY−505S(テイカ株式会社製)
1.D5中での分散安定性
調製した油中粉体分散物および粉体組成物を、油剤と配合した場合の粉体の分散性について、該組成物のデカメチルシクロペンタシロキサン(D5)中での分散安定性により評価した。具体的には、粉体の濃度が5.1wt%になるように、実施例44~実施例53及び比較例21~比較例36の粉体分散物および粉体組成物をD5と混合して、この混合液を50ml沈降管にいれ、2日後の沈降性を目視にて観察し、以下の基準に従って評価した。その結果を表71に示した。
◎:沈降性0.2%以下
○:沈降性0.2%~2.0%
△:沈降性2.0%~2.8%
×:沈降性2.8%以上
××:サンプルの性状から、分散安定性試験を行うことができなかった
なお、本評価において、その配合量は粉体分散物5.0gに対しD5を35.0g、粉体組成物2.55gに対しD5を37.45gとした。
注 *)比較例24と比較例28では液状の粉体分散物を得ることができなかったため、分散安定性試験を行う事ができなかった。(ペイントシェーカーで振とう後に確認したところ、粉体分散物がジルコニアボールを抱え込む形でペースト状に固まっていたため、ジルコニアボールの除去不能であった。)
注 **)比較例32と比較例36では、溶媒を留去したあとの粉体組成物が強く凝集して固まっており、再分散が困難であったため分散安定性試験を行わなかった。
2.D5/IOTG溶液中での分散安定性
調製した油中粉体分散物および粉体組成物を、油剤と配合した場合の粉体の分散性について、該組成物のD5/トリ2−エチルヘキサン酸グリセリル(IOTG)混合油(配合比は70/30)中での分散安定性により評価した。
◎:沈降性0.2%以下
○:沈降性0.2%~2.0%
△:沈降性2.0%~2.8%
×:沈降性2.8%以上
××:サンプルの性状から、分散安定性試験を行うことができなかった。
なお、本評価において、混合油のD5/IOTG配合比は70/30としたため、配合量は粉体分散物5.0gに対しD5を23.6g、IOTGを11.4gとした。また、粉体組成物2.55gに対しD5を26.2g、IOTGを11.2gとした。
注 *)比較例24と比較例28では液状の粉体分散物を得ることができなかったため、分散安定性試験を行う事ができなかった。(ペイントシェーカーで振とう後に確認したところ、粉体分散物がジルコニアボールを抱え込む形でペースト状に固まっていたため、ジルコニアボールの除去不能であった。)
注 **)比較例32と比較例36では、溶媒を留去したあとの粉体組成物が強く凝集して固まっており、再分散が困難であったため分散安定性試験を行わなかった。
本発明にかかる化粧料であり、実質的に水を含まない化粧料の一例として、リップグロスを調製し、その感触を評価した結果を実施例54~58及び比較例37~40に示す。
[調製手順]
1.成分1~15を40~50℃で加熱し、均一に混合分散した。
2.脱泡したのち充填し、室温に放置して成型した。
[試験手順]
(1)得られたリップグロスを0.05g、清浄な皮膚(手の甲)上1cm×3cmに均一に塗布した。
注)リップグロスは唇の皺に入りそこから滲みやすくなる傾向にあるため、同様に皺が多く触覚神経も集中しており、目視観察も行い易い手の甲を試験面に使用した。
(2)塗布1時間後、以下の5項目について評価した。
「滲みにくさ」:目視判定
「違和感ない自然な肌感覚」、「保湿感の持続性」:塗布部の皮膚感覚により判定
「油性感の抑制効果」: 触感により判定
「満足度」: 総合評価
各項目について、以下の基準により評価した。
「滲みにくさ」: 初期1cm×3cmの塗膜が、経時で膨張し周囲に広がる程度を目視にて観察した。
◎ 色や油の滲みは無かった。 ○目立たないが僅かに色や油の滲みがあった。
△ 少し色や油の滲み出しが認められた。 × 色と油の滲みが気になった。
「違和感のない自然な肌感覚」: 塗布部の皮膚感覚によって判定した。
◎ 違和感の無い自然な皮膚感覚であった。
○ 皮膚感覚に僅かの違和感があった。
△ 少し不自然な皮膚感覚があった。
「保湿感の持続性」: 塗布部の皮膚感覚によって判定した。
◎ 肌表面の適度で快適なうるおいを持続していた。
○ 肌表面のうるおいが残っていた。 △ 肌にドライ感が感じられた。
「油性感の抑制効果」: 油っぽいべたつきの程度を触感により判定した。
◎ 油っぽいべたつきは無かった。
○ 油っぽいべたつきをほとんど感じなかった。
△ 油っぽいべたつきが少しあった。 × 油っぽいべたつきが気になった。
「満足度」: リップグロスとしての総合的な満足度を判定した。
◎ 大いに満足 ○ 満足 △ 許容 × 不満
本発明にかかる化粧料であり、実質的に水を含まない化粧料の一例として、油性ファンデーションを調製し、その特性を評価した結果を実施例59~63及び比較例41~44に示す。
[調製手順]
1.成分1~14を90℃で加熱し、溶解した。
2.これに成分15~18を加え、均一に混合及び脱気を行った。
3.金型に流し込み、冷却して成型した。
[試験手順]
1.得られた油性ファンデーション0.15gを、予め産毛を剃り落とした清浄な皮膚上(前腕部)に、パフを用いて直径約5cmの円形に均一に塗布し、肌への伸び広がり性を評価した。
2.塗布10分後(初期)、4時間後、9時間後のそれそれの時点で、以下の3項目について評価した。
「仕上がりの美しさ」:目視判定
「密着感」、「違和感のない自然な肌感覚」:塗布部の皮膚感覚により判定
各項目について、以下の基準により評価した。
「伸び広がり性」: パフを用いて塗布した時の伸び広げやすさを判定した。
◎ 滑らかによく伸び広がった。 ○ 普通に伸び広がった。
△ 伸び広げるのに通常よりも力を要した。
「仕上がりの美しさ」: 目視で判定した。
◎ 緊密にカバーされ、非常に美しい仕上がりであった。
○ 緊密にカバーされてはいるが、小皺による溝が僅かにあった。
× 塗布表面の均一感がやや不足し、きめの粗さが目立ってきた。
「密着感」: 塗膜が皮膚に密着してある感覚を、塗布部の皮膚感覚によって判定した。
◎ 密着感をはっきりと感じた。
○ 密着感はあるが、意識しないと気づかないレベルだった。
× 密着感を全く感じなかった。
「違和感のない自然な肌感覚」: 塗布部の皮膚感覚によって判定した。
◎ 違和感の無い自然な皮膚感覚であった。
○ 皮膚感覚に僅かの違和感があった。
△ 少し不自然な皮膚感覚があった。
ステップ1:反応器に平均組成式MD37DH 13Mで表されるメチルハイドロジェンポリシロキサン94.5g、平均組成式CH2=CH−Si(OSiMe3)3で表されるビニルトリストリメチルシロキシシラン8.3gを仕込み、窒素流通下で攪拌しながら室温で白金−1,3−ジビニル−1,1,3,3−テトラメチルジシロキサン錯体のIPA溶液(Pt濃度0.4wt%)を0.25g添加した。65℃にセットしたオイルバスで加温しながら1時間反応を行なった。反応液を2g採取し、アルカリ分解ガス発生法により反応率に問題がないことを確認した。
ステップ2:反応液に1−ヘキサデセン34.5gを添加したところ、発熱により35℃→60℃まで温度上昇した。65℃にセットしたオイルバスで加温しながら1.5時間反応を行なった後、上記と同様の方法で反応率に問題ないことを確認した。
ステップ3:反応液にポリオキシエチレン(10)モノアリルエーテル28.1g、天然ビタミンEを0.02g、IPAを60g添加し、上記と同じ白金触媒溶液を0.25g追加投入した。発熱により約5℃の温度上昇があった。上記と同様の条件で1時間反応を行った後、同様の方法で反応率に問題ないことを確認した。
ステップ4:1−ヘキサデセン34.5gを添加したところ、発熱により約10℃の温度上昇があった。85℃にセットしたオイルバスで加温しながら3時間反応を行なった後に確認したところ、反応は完結していた。反応液を減圧下で加熱して低沸分を溜去し、更にろ過を行うことによって、平均組成式MD37DR*12 10DR*31 1DR*24 2Mで表されるシロキサンデンドロン構造と長鎖アルキル基とを有する新規なポリエーテル変性シリコーンを得た。式中、R*12= −C16H33
R*31= −C2H4Si(OSiMe3)3
R*24= −C3H6O(C2H4O)10H
この生成物は、淡褐色のほぼ透明均一な液体であった。
ステップ1:反応器に平均組成式MD330DH 80Mで表されるメチルハイドロジェンポリシロキサン94.6g、平均組成式CH2=CH−Si(OSiMe3)3で表されるビニルトリストリメチルシロキシシラン10.4gを仕込み、窒素流通下で攪拌しながら35℃で白金−1,3−ジビニル−1,1,3,3−テトラメチルジシロキサン錯体のIPA溶液(Pt濃度0.4wt%)を0.25g添加した。発熱による温度上昇が収まったところで、ビニルトリストリメチルシロキシシラン(2回目)10.4gを添加して同様に反応させた。発熱による温度上昇が収まったところで、ビニルトリストリメチルシロキシシラン(3回目)10.4gを添加して同様に反応させた。反応液を2g採取し、アルカリ分解ガス発生法により反応率に問題がないことを確認した。
ステップ2:反応液に平均組成式CH2=CH−CH2−O(C2H4O)19(C3H6O)19Hで表されるアリルポリエーテル35.3g、天然ビタミンEを0.02g、IPAを60g添加し、上記と同じ白金触媒溶液を0.25g追加投入した。発熱による温度上昇が収まった後、65~80℃で2時間反応を行ない、同様の方法で反応率に問題ないことを確認した。
ステップ3:約65℃の反応液に1−ヘキサデセン13.0gを添加した。発熱による温度上昇が収まったところで、1−ヘキサデセン(2回目)13.0gを添加して同様に反応させた。発熱による温度上昇が収まったところで、1−ヘキサデセン(3回目)13.0g及び白金触媒溶液0.25gを追加投入し、65~80℃で3時間反応を行なった。反応液を2g採取し、アルカリ分解ガス発生法により確認したところ、反応は完結していた。
ステップ4:希釈剤のカプリリルメチコン(SS−3408)を200g添加して溶解させた後、減圧下で加熱してIPA及び低沸分を溜去した。さらにろ過を行い、平均組成式MD330DR*12 45DR*31 30DR*26 5Mで表されるシロキサンデンドロン構造と長鎖アルキル基とを有する新規なポリエーテル変性シリコーンと、カプリリルメチコンとの50:50(wt比)混合液が得られた。
式中、R*12= −C16H33
R*31= −C2H4Si(OSiMe3)3
R*26= −C3H6O(C2H4O)19(C3H6O)19H
この生成物は、灰褐色の半透明感ある均一な粘稠液体であった。
本発明にかかる化粧料の一例として、油中水型透明制汗剤組成物を調製し、その特性を評価した結果を実施例66~67及び比較例45~46に示す。
1.200mlの容器に油相成分を秤量し、表80に示された順序で仕込んだ。
2.スパチュラによる混合を行い、界面活性剤(シリコーン化合物)を油剤中に分散・溶解させた。(油相A)
3.ホモディスパーの鋸歯を油相Aに浸し、容器を固定したのち攪拌を開始した。全体が均一な液状となるまで、攪拌を実施した。
4.別のカップに水相成分(ただし最後に示したイオン交換水No.14を除く)の指定量を仕込み、スパチュラで混合して溶解させた。(水相B)
5.これらの相の各々の2、3滴を取り、25℃における屈折率(RI)を測定した。
6.最後の~1.0部のイオン交換水(No.14)は、水相のRI値を<0.0001単位内で油相のRIに合致させるため、少しずつ分割して添加した。この工程を所望のRI値の合致に達するまで反復した。
7.ホモディスパーの回転数を3000rpmとして、攪拌下に水相Bをほぼ定速で約2分かけて油相A中に注ぎ込んだ。
8.攪拌を更に2分間継続してから一旦止め、容器の内壁に付着した油分をスパチュラで掻き落とし、生成しているエマルションと混合した。
9.ホモディスパーの回転数3000rpmで3分間の攪拌を行い、終了。
1. 外観の透明性を目視観察した。
2. 25℃における屈折率(RI)を測定した。
3. 制汗剤組成物を、ハンドリング性、触感及び非白化性能の評価のために皮膚に塗布した。ハンドリング性と皮膚の触感は主観的比較を用いて測定し、そして非白化性もまた主観的比較により判定した。
4. 制汗剤組成物25gを35mlガラス瓶に入れて密栓したものを2つ準備し、50℃恒温槽内及び−5℃恒温槽内ににそれぞれを静置した。2週間後に取り出して室温に戻した後、外観変化の有無を確認した。
各項目について、以下の基準により評価した。
「外観」: 制汗剤組成物の透明性を100mlガラス瓶を通して目視により判定した。
「RI」: 株式会社ATAGO製 デジタル屈折率計 RX−7000αを使用して、得られた制汗剤組成物の25.0℃における屈折率を測定した。
「ハンドリング性」: 制汗剤組成物0.3gを指に取ろうとした時に、直ぐに流れ落ちることなく、容易に希望の量が取れるかどうかを確認した。
○ 直ぐに流れ落ちることなく、容易に希望の量が取れた。
× 指で取ろうとしたらすぐに流れ落ち、希望の量が取れなかった。
「触感」: 前腕部に制汗剤組成物を0.2g×1回塗布した時の感触について、塗布後のべたつき感の少なさの観点から、優劣を判定した。
○ べたつきが少なく、気にならなかった。
× べたつきが気になった。
「非白化性能」: 前腕部に制汗剤組成物を0.2g×1回塗布し、15分おいて乾燥後、見た目の白さを目視で判定した。
○ 白さが分からなかった。
△ やや白っぽく見えた。
× 白っぽく見えた。
「安定性」: 保存安定性試験後の制汗剤組成物の外観を目視観察した。
○ 半透明~透明であり、初期と比べ外観上の変化がほとんど無かった。
△ 若干透明性が低下した。
× 不透明になった、又は不均一な外観となった。
本発明にかかる化粧料の一例として、非水のスティック状制汗剤組成物を調製し、その特性を評価した結果を実施例68~69及び比較例47~48に示す。
1.200mlの容器に表82の成分No1~No8を秤量し、高級アルコールとワックスが融解する温度(約80℃)で加熱及び撹拌を行い、単一の液体相を形成させた。
2.系の凝固点より少し高い温度(約65℃)に保ち、撹拌を行いながら、成分No9~No11を加えて溶解させた。
3.系の凝固点より少し高い温度(約65℃)に保ち、成分No12を加え、よく撹拌して均一に分散させた。
4.容器に流し込み、室温で固化させた。
1.非水のスティック状制汗剤組成物を、使用感及び非白化性能の評価のために皮膚に塗布した。塗布時の使用感として「なめらかさ」と「適度なドライ感」、塗布直後の使用感として「べたつきの無さ」、乾燥後の非白化性として「白残りの無さ」を主観的比較により判定した。
各項目について、以下の基準により評価した。
「なめらかさ」: 手の甲に制汗剤組成物を0.2g×1回塗布した時の感触について、塗布時のなめらかさの観点から、優劣を判定した。
◎ 皮膚の凹凸をほとんど感じず、なめらかに塗布できた。
○ ややなめらかであった。
△ どちらともいえない。
× 抵抗感があり、なめらかに塗布できなかった。
「適度なドライ感」: 手の甲に制汗剤組成物を0.2g×1回塗布した時の皮膚感触について、塗布時のドライ感の観点から、優劣を判定した。
○ 違和感なく自然で適度なドライ感があった。
△ 違和感なく自然であるが、ややドライ感が不足していた。
× 違和感があった。
「べたつきの無さ」: 手の甲に制汗剤組成物を0.2g×1回塗布した後、塗布部を指で触った時のべたつき感の無さの観点から、優劣を判定した。
◎ 全くべたつかなかった。
○ ほとんどべたつかなかった。
△ ややべたついた。
× べたつきが気になった。
「非白化性能」: 前腕部に制汗剤組成物を0.2g×1回塗布し、5分おいて乾燥後、見た目の白さを目視で判定した。
○ 白さがほとんど目立たなかった。
△ やや白っぼく見えた。
× 白っぽく見えた。
(成分) (Wt%)
1.デカメチルシクロペンタシロキサン 27.0
2.ジメチルポリシロキサン(6cst) 2.0
3.メチルトリメチコン(M3T) 2.0
4.実施例7の組成物(シリコーン化合物No.7を含有) 2.0
5.プロピレングリコール 10.0
6.イオン交換水 30.0
7.L−アスパラギン酸ナトリウム 2.0
8.パルミチン酸デキストリン処理二酸化チタン 10.0
9.パルミチン酸デキストリン処理マイカ 12.0
10.パルミチン酸デキストリン処理タルク 2.0
11.パルミチン酸デキストリン処理酸化鉄 1.0
12.パラベン 適 量
13.酸化防止剤 適 量
14.香料 適 量
(製造方法)
A: 成分1~4及び成分12、13を50℃で加熱溶解し、成分8~11を加え攪拌分散する。
B: 一方、成分5~7および成分14を70℃で攪拌混合し、溶解させる。
C: A,Bとも室温に戻し、先に調製したAをホモミキサーで攪拌しながらBを添加し、充分に攪拌する。その後、脱気、充填し乳化ファンデーションを得る。
(効果)
塗布時には非常にさらっとして伸びが軽く、しっとりした感触を有しながら、塗布後のべたつきはなく適度な保湿感が持続する独特の使用感がえられる。製品の経時安定性も良好である。
(成分) (Wt%)
1.デカメチルシクロペンタシロキサン 25.0
2.ジメチルポリシロキサン(2cst) 18.0
3.ジメチルポリシロキサン(6cst) 2.0
4.2−エチルヘキサン酸セチル 5.0
5.実施例8の組成物(シリコーン化合物No.8を含有) 7.0
6.エタノール 8.0
7.イオン交換水 2.0
8.ポリメチルシルセスキオキサン末 13.0
9.二酸化チタン 13.0
10.マイカ 2.0
11.酸化鉄 1.0
12.ポリエチレン粉末 1.0
13.ポリスチレン粉末 1.0
14.セルロース粉末 1.0
15.ポリアミド樹脂粉末 1.0
16.パラベン 適 量
17.酸化防止剤 適 量
18.香料 適 量
(製造方法)
A:成分1~5および成分16~18を室温で混合溶解した後、ホモミキサーで撹拌しながら成分6を加えて完全に混合する。
B:その後、ホモミキサーで撹拌を続けながら成分7を添加する。
C:これに成分8~15を加え、ホモミキサーで混合分散後、脱気、充填して液状ファンデーションを得る。
(効果)
塗布時にはべたつきがなく軽く伸び、すべり感が非常に優れている。塗布後は適度な保湿感とプレーンで自然な使用感が持続する。製品の経時安定性も優れており、化粧持ちも良好である。
(成分) (Wt%)
1.デカメチルシクロペンタシロキサン 24.0
2.SS−3408 *1 5.0
3.軽質流動イソパラフィン 15.0
4.ジカプリン酸ネオペンチルグリコール 3.0
5.実施例6の組成物(シリコーン化合物No.6を含有) 1.5
6.SS−2910 *2 0.5
7.オクタデシルジメチルベンジルアンモニウム塩変性モンモリロナイト 4.0
8.疎水化処理酸化チタン*3 10.0
9.疎水化処理タルク*3 6.0
10.疎水化処理マイカ*3 6.0
11.疎水化処理ベンガラ*3 1.6
12.疎水化処理黄酸化鉄*3 0.7
13.疎水化処理黒酸化鉄*3 0.2
14.ジプロピレングリコール 5.0
15.パラオキシ安息香酸メチルエステル 0.3
16.香料 適 量
17.精製水 17.2
注 *1)カプリリルメチコン
注 *2)ポリエーテル変性シリコーン
注 *3)疎水化処理; 粉体に対して2%のメチルハイドロジェンポリシロキサン添加後、加熱
処理したもの
(製造方法)
A : 成分1~7を加熱混合し、成分8~13を添加して均一に分散させる。
B : 成分14~15及び17を加熱溶解する。
C : 攪拌下、AにBを徐添して乳化し、冷却して成分16を添加しファンデーションを得る。
(効果)
ファンデーションのキメが細かく、伸び広がりが軽い。塗布後のべたつきや油性感がなく、しっとりしてみずみずしく、違和感のない自然な使用感が持続する。化粧持ちも良好で、温度や経時的な変化が少なく安定性にも優れている。
(成分) (Wt%)
1.ジメチルジステアリルアンモニウムヘクトライト 1.0
2.ジオクタデシルメチルアンモニウム塩変性モンモリロナイト 1.0
3.ジメチルポリシロキサン(6cst) 5.0
4.パラメトキシ桂皮酸2−エチルヘキシル 2.0
5.ジネオペンタン酸ジエチルペンタンジオール 3.0
6.DC 9011 Silicone Elastomer Blend *4) 6.0
7.実施例2の組成物(シリコーン化合物No.2を含有) 1.0
8.ジプロピレングリコール 10.0
9.クエン酸ナトリウム 0.2
10.エタノール 3.0
11.防腐剤 適 量
12.香料 適 量
13.精製水 67.8
注 *4)架橋型ポリエーテル変性シリコーンをデカメチルシクロペンタシロキサンで希釈したもの(エラストマー成分15%)
(製造方法)
A :成分1~7を混合する。
B :成分8~13を混合溶解し、上記Aに加えて攪拌乳化を行い、油中水型クリームを得る。
(効果)
油っぽさやべたつきがほとんど無く、のび広がりも軽く、みずみずしいさっぱりとした使用感が得られる。肌へのなじみが良く、しっとりとした保湿感が持続する。また自然なマット感のある仕上がりが得られる。製品の経時安定性も良好である。
(成分) (Wt%)
1.デカメチルシクロペンタシロキサン 4.2
2.ジメチルポリシロキサン(6cst) 3.0
3.ジメチルポリシロキサン(2cst) 2.0
4.メチルトリメチコン(M3T) 2.0
5.SH 556 *5) 3.0
6.ジネオペンタン酸メチルペンタンジオール 3.0
7.9040 Silicone Elastomer Blend *6) 5.0
8.スクワラン 5.8
9.パラフィンワックス 0.3
10.パルミチン酸 0.2
11.実施例13の組成物(シリコーン化合物No.13を含有) 4.0
12.擬似型スフィンゴシン 0.2
13.擬似型セラミド 5.0
14.ステアリン酸マグネシウム 1.0
15.硫酸マグネシウム 1.0
16.パラオキシ安息香酸メチル 0.2
17.グリセリン 16.0
18.ジプロピレングリコール 0.5
19.精製水 43.6
注 *5)フェニルトリメチコン
注 *6)架橋型オルガノポリシロキサン(ジメチコンクロスポリマー)をデカメチルシクロペンタシロキサンで希釈したもの(エラストマー成分12%)
(製造方法)
A: 成分1~13、成分16を80~90℃で加熱撹拌して溶解させる。
B: 成分14をAに添加して攪拌混合し、均一に分散させる。
C: 別に、成分15と成分17~19を混合して溶液とする。
C: Bを80℃に保持し均一に撹拌しながら、Cを徐添する。更に撹拌しながら室温まで冷却して、油中水型乳化組成物を得る。
(効果)
スキンケア、特にフェイスケアに好適であり、サラッとした塗布感と違和感のない自然な肌感覚を得ることが出来る。ややマット感のある仕上がりとなり、皮膚の小皺を目立たなくする効果がある。更にシリコーン化合物No.13の配合により、セラミド類の経皮吸収性促進も期待できる。また、経皮吸収されることによりセラミド類それ自体の効能も高まると期待される。
(成分) (Wt%)
1.FA 4001 CM *7) 20.0
2.BY 11−018 *8) 25.0
3.煙霧状無水ケイ酸 0.1
4.球状ウレタン粉末 5.0
5.実施例5の組成物(シリコーン化合物No.5を含有) 5.0
6.オクチルメトキシシンナメート 1.0
7.赤色202号 0.5
8.酸化チタン 0.5
9.雲母チタン 3.0
10.香料 0.1
11.エタノール 10.0
12.防腐剤 0.2
13.塩化ナトリウム 0.1
14.精製水 29.5
注 *7) (アクリレーツ/メタクリル酸ポリトリメチルシロキシ)コポリマーの、デカメチルシクロペンタシロキサン溶液(有効成分30%)
注 *8) トリメチルシロキシケイ酸のデカメチルシクロペンタシロキサン溶液(有効成分30%)
(製造方法)
A : 成分1~10を分散混合する。
B : 別に、成分11~14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。
(効果)
伸びが軽くべたつきのない使用感が得られる。使用中も唇に突っ張り感が生じにくく、保湿効果の持続性がある。耐水性、撥水性に優れるため口紅の色移りがほとんど無く、製品の経時安定性も良好である。
(成分) (Wt%)
1.実施例14の組成物(シリコーン化合物No.14を含有) 10.0
2.無水ケイ酸(平均一次粒子径10nm) 1.5
3.リンゴ酸ジイソステアリル 15.0
4.オクチルドデカノール 4.0
5.メチルトリメチコン(M3T) 1.0
6.重質流動イソパラフィン 35.0
7.スクワラン 9.0
8.ヒマワリ油 5.0
9.トリオクタノイン 5.0
10.ワセリン 5.0
11.マイクロクリスタリンワックス 2.0
12.赤色202号 0.8
13.酸化チタン 0.7
14.酸化チタン被覆ガラス末 2.0
15.酸化チタン被覆シリカ末 2.0
16.Nε − ラウロイル− L− リジン 2.0
(製造法)
上記成分3~9を混合し、90℃に加熱した後、成分2を加え、ホモミキサーを用いて均一に分散し、さらに成分1を加える。90℃に温度を保持したまま、成分10~16を加え、ホモミキサーにかけ、容器に充填した後、冷却し、液状口紅を得る。
(効果)
口唇に塗布するときになめらかにのびて塗りやすく、その使用感はべたつきがなく、口唇上でのつやも良好。
(成分) (Wt%)
1.カルナバロウ 0.5
2.キャンデリラロウ 5.0
3.セレシン 10.0
4.スクワラン 29.0
5.メチルトリメチコン(M3T) 1.0
6.グリセリントリイソステアレート 10.0
7.グリセリンジイソステアレート 20.0
8.ヒドロキシプロピル−β−シクロデキストリン 1.0
9.コレステロールステアレート 3.5
10.実施例9の組成物(Si化合物No.9を含有)で被覆したベンガラ*9)0.2
11.グリセリン 0.5
12.精製水 2.0
13.色材 適 量
14.香料 適 量
15.防腐剤 適 量
注 *9)ベンガラに対して3%のシリコーン化合物を添加後、加熱処理したもの
(製造方法)
A: 成分9を60℃に加温し成分10を添加し混合して、均一に分散させる。
B: 別に、成分8と成分12の0.5%相当を混合して加温溶融させたものを準備する。
C: Aを攪拌しながらBを添加して混合し、均一に分散させる。
D: 次に、成分12の残部(1.5%相当)と成分11とをCに添加して混合し、抱水組成物を得る。
E: 成分1~7を80℃にて溶融し、攪拌しながらDを添加し均一に分散させる。
F: 成分13~15をEに添加して分散撹拌し、その後、成型して口紅を得る。
(効果)
ヒドロキシプロピル化βシクロデキストリンと水とコレステロールエステル、シリコーン化合物No.9で被覆した粉体からなる抱水組成物が口紅中に安定に配合される。そのため、製品は高い水分保持力を示し、潤い持続性に優れ、保湿効果が高い。
(成分) (Wt%)
1.デカメチルシクロペンタシロキサン 20.0
2.メチルフェニルポリシロキサン 3.0
3.モノイソステアリン酸ソルビタン 1.0
4.SS−2910 *10) 0.3
5.実施例10の組成物(シリコーン化合物No.10を含有) 0.3
6.ジオクタデシルメチルアンモニウム塩変性モンモリロナイト 0.2
7.BY 11−018 *11) 1.0
8.パラメトキシケイ皮酸オクチル 4.0
9.脂肪酸石鹸処理微粒子二酸化チタン 8.0
10.ソルビトール 2.0
11.塩化ナトリウム 1.0
12.防腐剤 適 量
13.香料 適 量
14.精製水 59.2
注 *10) ポリエーテル変性シリコーン
注 *11) トリメチルシロキシケイ酸のデカメチルシクロペンタシロキサン溶液
(製造方法)
A : 成分1~8を加熱混合し、成分9を均一分散する。
B : 別に、成分10~12及び14を加熱混合する。
C : 攪拌下でAにBを徐添して乳化し、冷却したあと成分13を添加し、日焼け止め乳液を得る。
(効果)
塗布時には、サンケア製品特有のべたつきやきしみがほとんど感じられず、キメ細かくのび広がりの軽い乳液である。しっとりとしてみずみずしい保湿感が持続し、化粧持ちも良いため、紫外線防止効果も持続する。製品の経時安定性も良好であり粉の凝集などが起こり難い。
(成分) (Wt%)
1. デカメチルシクロペンタシロキサン 15.0
2. メチルフェニルポリシロキサン 5.0
3. スクワレン 5.0
4. テトラ−2−エチルヘキサン酸ペンタエリスリトール 5.0
5. 実施例8の組成物(シリコーン化合物No.8を含有) 1.0
6. BY 22−008M *12) 2.0
7. 9701 Cosmetic Powder *13) 2.0
8. 疎水化シリカ 0.5
9. アスコルビン酸リン酸マグネシウム 1.0
10. 塩化ナトリウム 1.0
11. ポリエチレングリコール11000 1.0
12. プロピレングリコール 8.0
13. 防腐剤 適 量
14. 香料 適 量
15. 精製水 残 量
注 *12)ポリエーテル変性シリコーンのデカメチルシクロペンタシロキサン溶液(有効成分12%)
注 *13)オルガノポリシロキサンエラストマー球状粉体(シリカ被覆タイプ)
(製造方法)
A : 成分1~6を均一に混合し、成分7~8を加えて均一に分散する。
B : 成分15に成分9~11を加えて溶解し、更に成分12、13を均一にした後添加する。
C : BをAに徐添して乳化した後冷却し、成分14を加えて乳液を得る。
(効果)
ふわっとした柔らかいテクスチャーの乳液が得られ、軽く伸び広がりべたつきも無い。塗布後は、プレーンで違和感のない自然な皮膚感覚と適度な保湿感が持続する。温度や経時による変化が少なく、安定性も良好である。
(成分) (Wt%)
1.デカメチルシクロペンタシロキサン 17.5
2.FA 4002 ID *14) 12.0
3.トリイソオクタン酸グリセリル 5.0
4.パラメトキシケイ皮酸オクチル 6.0
5.SS−2910 *15) 1.0
6.実施例12の組成物(シリコーン化合物No.12を含有) 0.5
7.有機変性ベントナイト 0.2
8.シリコーン処理酸化亜鉛 20.0
9.9702 Powder *16) 3.0
10.塩化ナトリウム 0.5
11.1,3−ブチレングリコール 2.0
12.防腐剤 適 量
13.香料 適 量
14.精製水 32.3
注*14) (アクリレーツ/メタクリル酸ポリトリメチルシロキシ)コポリマーの、イソドデカン溶液(有効成分40%)
注*15)ポリエーテル変性シリコーン
注*16)オルガノポリシロキサンエラストマー球状粉体(マイカとの複合パウダー)
(製造方法)
A : 成分1の一部に成分2を加えて均一にし、成分8を添加してビーズミルにて分散する。
B : 成分1の残部及び成分3~7を混合し、均一に混合する。
C : 成分9~11及び13を混合して溶解する。
D : BにCを加えて乳化し、A及び成分12を添加してサンカットクリームを得る。
(効果)
べたつきがほとんどなく、非常に軽く良く伸び広がる。また、密着感に優れるにもかかわらず、違和感のない自然な皮膚感覚が得られる。つやのある仕上がりで化粧持ちも非常に良好。温度や経時に対しても安定である。
(成分) (Wt%)
1. ジメチルポリシロキサン(6cst) 5.0
2. DC 9011 Silicone Elastomer Blend *17) 5.0
3. トリオクタン酸グリセリル 2.0
4. ジメチルジステアリルアンモニウムヘクトライト 0.5
5. オクタデシルジメチルベンジルアンモニウム塩変性モンモリロナイト 0.5
6. SS−2910 *18) 1.0
7. 実施例45の油中粉体分散物 30.0
8. 実施例48の油中粉体分散物 30.0
9. ジプロピレングリコール 3.0
10. クエン酸ナトリウム 0.2
11. 防腐剤 適 量
12. 香料 適 量
13. 精製水 22.8
注 *17)架橋型ポリエーテル変性シリコーンをデカメチルシクロペンタシロキサンで希釈したもの(エラストマー成分15%)
注 *18)ポリエーテル変性シリコーン
(製造方法)
A : 成分1~6を混合する。
B : 成分9~11、13を混合溶解し、上記A に加えて攪拌乳化する。
C : 成分7、8、12を上記Bに加えて均一にする。
(効果)
のびが軽くさっぱりとして、べたつきや油感がなく、透明感があり化粧持ちが良好である。また温度や経時による変化もほとんど無く、使用性も安定性も非常に優れている。
(成分) (Wt%)
1.ジメチルポリシロキサン(6cst) 5.0
2.9040 Silicone Elastomer Blend*19) 5.0
3.トリイソオクタン酸グリセリル 3.0
4.メチルトリメチコン 2.5
5.SS−3408 *20) 1.5
6.SS−2910 *21) 1.0
7.オクチルメトキシシンナメート 6.0
8.デカメチルシクロペンタシロキサン 24.0
9.実施例53の粉体組成物 25.0
10.塩化ナトリウム 0.5
11.1,3−ブチレングリコール 2.0
12.精製水 24.5
13.香料 適 量
注 *19)架橋型オルガノポリシロキサン(ジメチコンクロスポリマー)をデカメチルシクロペンタシロキサンで希釈したもの(エラストマー成分12%)
注 *20)カプリリルメチコン
注 *21)ポリエーテル変性シリコーン
(製造方法)
A : 成分1~6を均一に混合したのち、成分8,9を添加する。
B : 成分10~12を混合溶解し、上記A に加えて攪拌乳化する。
C : 成分7を上記Bに加えて混合均一化し、サンスクリーン剤を得る。
(効果)
粉体の分散安定性が良好であり、温度変化や経時によっても凝集などが起こり難い。塗布時にはサラッとした感触で軽くよく伸び広がり、べたつきのない透明感ある化粧膜が得られる。化粧持ちが良好であるため、日焼け止め効果の持続性にも優れる。
(成分) (Wt%)
1.SH 556 *22) 5.0
2.オクチルメトキシシンナメート 5.0
3.実施例49の油中粉体分散物 25.0
4.実施例10の組成物(シリコーン化合物No.10を含有) 1.0
5.ジプロピレングリコール 5.0
6.PEG(10)/PPG(14)ジメチルエーテル 1.5
7.カルボキシメチルセルロースナトリウム 0.1
8.サクシノグリカン 0.3
9.キレート剤 適 量
10.防腐剤 適 量
11.緩衝剤 適 量
12.精製水 57.1
注 *22)フェニルトリメチコン
(製造方法)
A : 成分1,2,4を均一に混合したのち、成分3を添加する。
B : 成分5~12を混合溶解し、上記Aに加えて攪拌乳化してサンスクリーン剤を得る。
(効果)
透明感のある自然な仕上がり感が得られ、しっとりとした保湿感が持続する。且つUVA領域とUV B領域の両域おいて優れた紫外線防御効果を有する。
(成分) (Wt%)
1.2503 Cosmetic Wax *23) 5.0
2.セタノール 1.0
3.流動パラフィン 10.0
4.ジメチルポリシロキサン(20cst) 5.0
5.ワセリン 2.0
6.キャンデリラワックス 2.0
7.トリイソステアリン酸グリセリル 5.0
8.ステアリン酸 3.0
9.モノステアリン酸グリセリル 1.5
10.実施例5の組成物(シリコーン化合物No.5を含有) 10.0
11.セスキオレイン酸ソルビタン 0.5
12.モノオレイン酸ポリオキシエチレンソルビタン 1.0
13.水酸化ナトリウム(1%水溶液) 10.0
14.1,3−ブチレングリコール 5.0
15.グリセリン 5.0
16.防腐剤 適 量
17.香料 適 量
18.BY 29−129 *24) 5.0
19.精製水 51.0
注 *23)ステアリルジメチコン
注 *24)オルガノポリシロキサンエラストマー球状粉体の水分散液(有効成分63%)
(製造方法)
A : 成分1~12を混合、加熱溶解する。
B : 成分13~16及び19を混合、加熱溶解する。
C : AにBを加えて乳化し、40℃まで冷却して成分18、17を添加し、混合均一化する。D :さらに室温まで冷却し、O/Wハンドクリームを得る。
(効果)
伸び広がりが軽く、肌への密着性に優れ、しっとりした肌触りでありながらべたつかず、さらっとした感触を有する。皮膚表面の油性テカリがなく、マットで自然な仕上がりとなる。小じわを目立たせなくする効果もある。製品自体の経時安定性も良好である。
(成分) (Wt%)
1. デカメチルシクロペンタシロキサン 13.0
2. ジメチルポリシロキサン(6cst) 10.0
3. メチルトリメチコン(M3T) 2.0
4. 実施例1の組成物(シリコーン化合物No.1を含有) 2.0
5. PEG(10)ラウリルエ−テル 0.5
6. シリコーン処理酸化クロム *25) 6.2
7. シリコーン処理群青 *25) 4.0
8. シリコーン処理チタン被覆マイカ *25) 6.0
9. 塩化ナトリウム 2.0
10. プロピレングリコール 8.0
11. 防腐剤 適 量
12. 香料 適 量
13. 精製水 46.3
注 *25)シリコーン処理; 粉体に対して3%のメチルハイドロジェンポリシロキサン添加後、
加熱処理したもの
(製造方法)
A : 成分1~5を混合し、成分6~8を添加して均一に分散する。
B : 成分9~11及び13を均一溶解する。
C : 攪拌下、AにBを徐添して乳化し、成分12を添加してアイシャドウを得る。
(効果)
伸び広がりが軽くて油っぽさや粉っぽさが無く、みずみずしく、さっぱりとした使用感が持続する。肌へのなじみが良く、耐水性や撥水性、耐汗性が良好なため化粧崩れを起こし難い。製品は温度や経時的な変化が少なく安定性にも優れている。
(成分) (Wt%)
1.イソドデカン 23.0
2.メチルトリメチコン(M3T) 1.0
3.ジメチルパルミチルポリシロキサン 1.0
4.ジメチルポリシロキサン(10万cst) 1.0
5.マイクロクリスタリンワックス 5.0
6.ミツロウ 3.0
7.実施例4の組成物(シリコーン化合物No.4を含有) 3.0
8.シリコーン被覆処理黒酸化鉄 14.0
9.ベントナイト 2.0
10.ナイロン繊維(平均長さ2μm) 2.0
11.パラオキシ安息香酸エステル 0.5
12.無水エタノール 2.5
13.ポリビニルアルコール 0.5
14.アクリル酸アルキル共重合体エマルション(50%分散液) 19.5
15.アクリル酸アルキル・スチレン共重合体エマルション(50%分散液) 8.0
16.精製水 14.0
(製造方法)
A: 成分1~7を混合し溶解させたのち、ホモディスパーミキサーで攪拌下に成分8~10を
添加し均一に分散させる。
B: 成分11を成分12に溶かしたものを成分16に添加して混合均一化する。
C: Bを成分14、15と混合均一化したのち、成分13を加えて混合均一化する。
D: Aをホモディスパーミキサーで攪拌しながらCを徐添し、マスカラを得る。
(効果)
伸び広がりが軽く、べたつきや油っぽさの少ない使用感が得られる。耐水性、撥水性、耐汗性に加え、軽い衝撃等によっても落ちにくい耐久性に優れたマスカラが得られる。製品自体の温度や経時による安定性も良好である。
(成分) (Wt%)
1.デカメチルシクロペンタシロキサン 19.4
2.軽質流動イソパラフィン 14.6
3.メチルトリメチコン(M3T) 1.5
4.FA 4001 CM *26) 31.0
5.デキストリン脂肪酸エステル 15.0
6.実施例3の組成物(シリコーン化合物No.3を含有) 3.0
7.有機変性ベントナイト 1.5
8.疎水化無水ケイ酸 2.0
9.ナイロン繊維(平均長さ2μm) 2.0
10.カーボンブラック 10.0
注 *26)(アクリレーツ/メタクリル酸ポリトリメチルシロキシ)コポリマーの、デカメチルシクロペンタシロキサン溶液(有効成分30%)
(製造方法)
A:成分1~10を混合して均一化し、容器に充填してマスカラを得る。
(効果)
伸び広がりが軽く、べたつきや油っぽさが無い。耐水性、撥水性、耐汗性に優れているため、化粧持ちも良い。製品も、温度や経時による変化がほとんど無く、安定性に優れている。
(成分) (Wt%)
1.タルク(疎水化処理) 16.0
2.セリサイト(疎水化処理) 30.0
3.雲母チタン(疎水化処理) 35.0
4.群青(疎水化処理) 4.0
5.酸化鉄(疎水化処理) 2.0
6.SS−2910 *27) 5.0
7.実施例11の組成物(シリコーン化合物No.11を含有) 5.0
8.テトラキストリメチルシロキシシラン(M4Q) 2.0
9.流動パラフィン 0.5
10.パラフィン 0.5
注*27)ポリエーテル変性シリコーン
(製造方法)
A: 成分1~5をブレンダーで攪拌混合する。
B: 成分6~10を加熱溶解する。
C: BをAに吹きつけ、更に攪拌する。その後、粉砕して成型機で圧縮成型し、固形パウダーアイシャドウを得る。
(効果)
使用感や仕上がりに優れる。パウダーの密着性が良好で、耐水性、撥水性、耐汗性に優れるため、化粧持ちがよい。
(成分) (Wt%)
1.シリコーン処理酸化チタン 10.0
2.シリコーン処理雲母 50.8
3.シリコーン処理タルク 10.0
4.シリコーン処理黄酸化鉄 1.5
5.シリコーン処理ベンガラ 0.5
6.シリコーン処理黒酸化鉄 0.2
7.パラフィンワックス 2.0
8.スクワラン 1.4
9.2−エチルヘキシルパルミテート 2.0
10.実施例9の組成物(シリコーン化合物No.9を含有) 15.0
11.SS−3408 *28) 2.6
12.メチルトリメチコン(M3T) 1.0
13.ジメチルポリシロキサン 3.0
14.香料 適 量
注 *28)カプリリルメチコン
(製造方法)
A:成分1~6を混合する。
B:成分7~13を混合し、Aを加える。
C:Bに成分14を加えて金皿にプレス成型する。
(効果)
パウダーの感触がサラッとしていて使用感も良好である。自然な塗布感覚が得られ、肌へのなじみも良い。耐水性、撥水性、耐汗性も良好である。
(成分) (Wt%)
1.処理セリサイト *29) 42.0
2.処理酸化チタン *29) 12.0
3.処理タルク *29) 24.0
4.処理黄酸化鉄 *29) 2.4
5.処理ベンガラ *29) 0.8
6.処理黒酸化鉄 *29) 0.3
7.ジメチルポリシロキサン 1.8
8.メチルトリメチコン(M3T) 0.5
9.流動パラフィン 6.2
10.オクチルドデカノール 2.0
11.9702 Powder*30) 8.0
12.香料 適 量
13.防腐剤 適 量
注 *29)3%メチルハイドロジェンポリシロキサン処理されたセリサイト、酸化チタン、タルク、黄酸化鉄、ベンガラ、黒酸化鉄を予め処方例21に示す配合比で混合しておく。こうして得た改質前の粉体をクロロホルムに分散させ、更に、粉体に対して8%の製造例11の組成物(シリコーン化合物No.11を含有)を加えて攪拌する。クロロホルムを減圧留去し、粉砕して得られる改質粉体。
注 *30)オルガノポリシロキサンエラストマー球状粉体(マイカとの複合パウダー)
(製造方法)
A: 成分1~6をヘンシェルミキサーで混合する。
B: 成分7~13を混合してAに加え、更に攪拌する。
C: Bをアトマイザーにて粉砕を行ったのち、金型に打型してファンデーションを得る。
(効果)
パウダーの感触が非常に軽くサラッとしていながら、滑らかでしっかりした塗布感が得られる。粉体独特のきしみ感も低減されている。耐水性、撥水性、耐汗性に優れているため、化粧持ちがよい。
(成分) (Wt%)
1.パーフルオロポリエーテル処理酸化チタン 9.0
2.パーフルオロポリエーテル処理酸化亜鉛 3.0
3.パーフルオロポリエーテル処理ベンガラ 0.4
4.パーフルオロポリエーテル処理黄酸化鉄 4.0
5.パーフルオロポリエーテル処理黒酸化鉄 0.2
6.パーフルオロポリエーテル処理タルク 15.0
7.パーフルオロポリエーテル処理マイカ 48.2
8.パーフルオロポリエーテル処理雲母チタン 2.0
9.9701 Cosmetic Powder *31) 2.0
10.スクワラン 4.0
11.ジメチルポリシロキサン 6.0
12.ワセリン 2.0
13.トリイソオクタン酸グリセリル 2.0
14.実施例7の組成物(シリコーン化合物No.7を含有) 2.0
15.防腐剤 0.1
16.香料 0.1
注 *31)オルガノポリシロキサンエラストマー球状粉体(シリカ被覆タイプ)
(製造方法)
A: 成分1~9を分散混合する。
B: 成分10~14を加温して均一に混合する。
C: AにBを添加して混合、粉砕後に金皿に圧縮成型してプレスドファンデーションを得る。
(効果)
ファンデーションが衝撃に強く、割れにくい。皮膚への密着性も良好であり、耐水性、撥水性、耐汗性だけでなく耐皮脂性にも優れているため、非常に化粧持ちがよい。
(成分) (Wt%)
1. 水素添加大豆リン脂質 1.0
2. コレステロール 0.5
3. ジプロピレングリコール 10.0
4. グリセリン 10.0
5. 精製水 56.5
6. 乳酸ナトリウム 1.0
7. 実施例6の組成物(シリコーン化合物No.6を含有) 3.0
8. デカメチルシクロペンタシロキサン 8.5
9. メチルトリメチコン(M3T) 1.5
10. トリ2 − エチルヘキサン酸グリセリル 5.0
11. メドゥフォーム油 3.0
(製造方法)
A : 成分1~4を75℃に加熱する。
B : 成分5、6を75℃に加熱する。
C : AにBを添加して混合した後、室温に冷却する。
D : 成分7~11にCを攪拌しながら徐々に添加混合してクリームを得る。
(効果)
大豆リン脂質固有の性質に基づき、クリーム中に脂質二重膜構造のリポソーム形成が期待される。肌なじみが良くべたつきもなく、使用後のしっとりとした保湿感に優れ、且つ、経時安定性も良好である。
(成分) (Wt%)
1. 水素添加大豆リン脂質 0.5
2. フィトステロール 0.1
3. スクワラン 1.0
4. グリセリン 2.0
5. 1,3−ブチレングリコール 2.0
6. 精製水 残 量
7. 塩化ナトリウム 1.0
8. パラオキシ安息香酸メチル 0.3
9. エタノール 3.0
10.実施例8の組成物(シリコーン化合物No.8を含有) 2.0
11.SS−2910 *32) 1.0
12. ジイソステアリン酸ジグリセリル 1.0
13. パラメトキシケイ皮酸2 − エチルヘキシル 3.0
14. トリ2 − エチルヘキサンサングリセリル 5.0
15. ロジン酸ペンタエリスリット 0.1
16. パルミチン酸デキストリン 0.5
17. イヌリンステアレート 0.5
18. ジメチルジステアリルアンモニウムヘクトライト 1.0
19. シリコーン処理酸化チタン 10.0
20. シリコーン処理ベンガラ 0.3
21. シリコーン処理黄酸化鉄 1.5
22. シリコーン処理黒酸化鉄 0.05
23. シリコーン処理微粒子酸化チタン 2.0
24. ナイロン末 2.0
25. デカメチルシクロペンタシロキサン 18.0
注 *32) ポリエーテル変性シリコーン
(製造方法)
A : 成分1~5を75℃に加熱する。
B : 成分6を75℃に加熱する。
C : AにBを添加混合した後、室温に冷却する。
D : Cに成分7~9を添加混合する。
E : 成分10~25をロールミルで混合する。
F : DにEを撹拌しながら添加混合し、ファンデーションを得る。
(効果)
大豆リン脂質固有の性質に基づき、乳化ファンデーション中に脂質二重膜構造のリポソーム形成が期待される。肌への密着性が良好であり、化粧持ちに優れる。使用中はべたつきがなく、プレーンで自然な皮膚感覚と適度な保湿感が持続する。製品の経時安定性が良好である。
(成分) (Wt%)
1. シリコーン処理酸化鉄含有酸化亜鉛 30.0
2. 実施例10の組成物(シリコーン化合物No.10を含有) 6.0
3. デカメチルシクロペンタシロキサン 25.0
4. メチルトリメチコン(M3T) 5.0
5. イソノナン酸イソノニル 2.0
6. メトキシ桂皮酸オクチル 7.0
7. ポリメチルシルセスキオキサン粉末 5.0
8. 精製水 13.9
9. エタノール 2.0
10. グリセリン 3.0
11. カルボキシビニルパウダー(1%水溶液) 1.0
12. 塩化ナトリウム 0.1
(製造方法)
A : 成分1~4を3本ローラーにて均一に混合する。
B : 成分5~7にAを加え、均一に混合する。
C : Bに成分8~12を添加して均一に乳化混合する。
D : Cを脱泡し、日焼け止め料を得る。
(効果)
化粧膜の透明性が高く、塗布時の青白さがない。サンケア製品特有のべたつき感が低減されており、伸び広がり性も非常に優れている。製品の経時安定性も良好であり粉の凝集などが起こり難い。
(成分) (Wt%)
1. ポリエチレンーポリプロピレンコポリマー 5.0
2. キャンデリラワックス 5.0
3.カルナウバワックス 5.0
4.ワセリン 10.0
5.2−エチルヘキサン酸セチル 10.0
6.ジグリセリンジイソステアレート 14.5
7.マカデミアナッツ油 7.0
8.ステアリン酸イヌリン(千葉製粉社製レオパールISK2) 23.0
9.実施例10の組成物(シリコーン化合物No.10を含有 2.0
10.赤色201号 1.0
11.赤色202号 3.0
12.黄色4号アルミニウムレーキ 3.0
13.酸化チタン 1.0
14.黒酸化鉄 0.5
15.酸化鉄雲母チタン 10.0
16.防腐剤 適 量
17.香料 適 量
(製造方法)
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。
(効果)
しっとりとした感触で滑らかに塗布ができ、使用時にはべたつきがなく唇の乾燥を抑制する。美しい発色と艶が得られ、化粧持ちも良好である。
(成分) (Wt%)
1.マイクロクリスタリンワックス 10.0
2.パラフィンワックス 15.0
3.カルナウバワックス 5.0
4.ワセリン 5.0
5.リンゴ酸ジイソステアリル 7.0
6.トリイソステアリン酸グリセリル 11.5
7.ジカプリン酸プロピレングリコール 7.0
8.ステアリン酸イヌリン(千葉製粉社製レオパールISK2) 2.0
9.実施例8の組成物(シリコーン化合物No.8を含有) 3.0
10.デカメチルシクロペンタシロキサン 10.0
11.FA 4001 CM *33) 3.0
12.DC 593 *34) 2.0
13.赤色201号 1.0
14.赤色202号 1.0
15.黄色4号 2.0
16.酸化チタン 4.0
17.黒酸化鉄 0.5
18.酸化鉄雲母チタン 3.0
19.雲母チタン 2.0
20.精製水 5.0
21.1,3−ブチレングリコール 1.0
22.防腐剤 適 量
23.香料 適 量
注 *33)(アクリレーツ/メタクリル酸ポリトリメチルシロキシ)コポリマーの、デカメチルシクロペンタシロキサン溶液(有効成分30wt%)
注 *34)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%)
(製造方法)
A : 成分1~12を加熱溶解し、成分13~19を加え均一に混合する。
B : 成分20~22を均一混合した後、Aに加えて混合する。
C : Bに成分23を加えて容器に充填し、口紅を得る。
(効果)
しっとりとした感触で滑らかに塗布ができ、使用時にはべたつきがなく唇の乾燥を抑制する。製品の乳化安定性も非常に優れている。
(成分) (Wt%)
1.ジメチルポリシロキサン(2cst) 10.0
2.イソドデカン 21.6
3.イソステアリルジグリセリルスクシナート 0.6
4.SS−2910 *35) 1.2
5.製造例13の組成物(シロキサン化合物No.13を含有) 0.6
6.BY 25−320 *36) 1.5
7.FZ−2250 *37) 1.5
8.FA 4002 ID *38) 2.0
9.DC 593 *39) 2.0
10.被覆酸化鉄 3.5
11.被覆二酸化チタン 6.8
12.ナイロン12 8.0
13.イオン交換水 40.0
14.硫酸マグネシウム 0.7
15.防腐剤 適 量
注 *35) ポリエーテル変性シリコーン
注 *36) ジメチルポリシロキサンガムのイソパラフィン溶液(20wt%)
注 *37) ポリエーテル−シリコーンブロック共重合体のイソパラフィン溶液(35wt%)
注 *38)(アクリレーツ/メタクリル酸ポリトリメチルシロキシ)コポリマーの、イソドデカン溶液(有効成分40wt%)
注 *39) 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%)
(製造方法)
A : 成分1~9を混合し、成分10~12を均一に分散する。
B : 成分13~15を混合した後、Aに加えて乳化してファンデーションを得る。
(効果)
なめらかに軽く良く伸び広がるにもかかわらず、滑らかで厚みの感じられる化粧膜が得られる。塗布後には乾燥感や肌の突っ張りなどはほとんど感じられず、肌への密着性が良好で、化粧持ちにも優れている。
(成分) (Wt%)
1.アルミニウムヒドロキシクロライド 3.0
2.酸化亜鉛 2.0
3.シリカ 3.0
4.銀イオン、亜鉛イオン、アンモニウムイオン担持ゼオライト 1.0
5.ステアリン酸カルシウム 0.1
6.ジメチルポリシロキサン 2.0
7.オクタン酸セチル 1.0
8.流動パラフィン 1.0
9.シリコーン化合物No.16 10.0
10.オレイン酸ソルビタン 1.0
11.酸化防止剤 適量
12.香料 適量
13.液化石油ガス 残余
(製造方法)
A:成分6~11(油相部)を混合し、均一液体とする。
B:油相部に、成分1~5(粉末部)を混合し、均一に分散させる。
C:成分12(噴射剤)を充填して、制汗エアゾール化粧料を得る。
(効果)
粉末の付着性が良好で、使用後の白さが目立たず、且つ安全性も高い。塗布後にべたつき感がなく適度なドライ感を有し、なめらかさで自然な皮膚感覚が得られる。
(成分) (Wt%)
1.アルミニウムクロロハイドレートの15wt%1,2−ヘキサンジオール溶液 12.0
2.ジメチルポリシロキサン(10cst) 3.0
3.デカメチルシクロペンタシロキサン 3.0
4.シリコーン化合物No.15 3.0
5.香料 1.0
6.ブタン 25.0
7.イソブタン 30.0
8.プロパン 3.0
9.ジメチルエーテル 20.0
(製造方法)
A:成分1~5を混合し、均一液体とする。
B:成分6~8(噴射剤)を充填する。
C:最後に、成分9(噴射剤)を充填して、非水加圧制汗剤製品を得る。
(効果)
透明均一な加圧液体が得られるため、AP活性成分などの分離がなく製品のライフが長い。制汗効果に即効性があり、使用後の白さも目立たない。塗布後には、保湿感のある自然な皮膚感覚が得られる。
(成分) (Wt%)
1.アルミニウムヒドロキシクロライド *40) 5.0
2.アルミニウムヒドロキシクロライド *41) 1.5
3.精製水 10.0
4.POE(10)POP(5)セチルエーテルリン酸 1.5
5.マグネシアシリカ 1.0
6.多孔質シリカ 0.5
7.ポリメチルシルセスキオキサン粉末 1.0
8.デカメチルシクロペンタシロキサン 2.0
9.シリコーン化合物No.13 0.5
10.イソプロピルメチルフェノール 0.05
11.ユーカリエキス 0.5
12.大豆エキス 0.1
13.メリッサエキス 0.1
14.リンゴエキス 0.1
15.香料M *42) 0.15
16.エタノール 26.0
17.LPG(0.15MPa/20℃) 50.0
注 *40)REACH 101 MICRO−DRY (商品名、リハイス社製)
注 *41)REACH 501 MICRO−DRY (商品名、リハイス社製)
注 *42)表82に記載の香料組成例に従って調合した。
(製造方法)
A:成分1~4を混合して溶解させ、均一液体とする。(水相)
B:別に、成分8~16を混合して溶解させ、均一液体とする。(エタノール相)
C:水相をエタノール相とよく混合し、均一液体とする。(原液)
D:原液に成分5~7を混合し、均一分散させる。
E:最後に成分17を充填して、エアゾール型制汗剤組成物を得る。
(効果)
透明均一な加圧液体が得られるため、制汗活性成分などの分離がなく製品のライフが長い。皮膚に塗布直後から速やかに制汗作用が発現する。塗布後には、べたつかず保湿感のある自然な皮膚感覚が得られる。
(成分) (Wt%)
1.アルミニウムヒドロキシクロライド 5.0
2.POE(15)POP(5)セチルエーテルリン酸 5.0
3.精製水 5.0
4.タルク 0.4
5.真球状シリカ 0.4
6.スメクタイト 0.4
7.ナイロン末 0.4
8.ポリエチレン末 0.4
9.デカメチルシクロペンタシロキサン 1.0
10.SH 556 *43) 1.0
11.シリコーン化合物No.13 1.0
12.トリクロサン 0.1
13.シラカバエキス 0.1
14.ローズマリーエキス 0.1
15.香料 1.0
16.エタノール 残部
注 *43)フェニルトリメチコン
(製造方法)
A:成分9~16を混合して溶解させ、均一液体とする。
B:これに、成分1~3を混合して溶解させる。
C:更に、成分4~8をよく混合して均一分散させる。
(効果)
透明均一な液状剤が得られるため、AP活性成分などの分離がなく経時安定性が良好である。皮膚に塗布直後から速やかに制汗作用が発現する。塗布後には、エタノールの蒸発による突っ張り感を抑制し、べたつかずサラサラ感のある自然な皮膚感覚をもたらす。
(成分) (Wt%)
1.ジメチルポリシロキサン(20cst) 10.0
2.ジメチルポリシロキサン(2cst) 20.0
3.シリコーン化合物No.13 2.0
4.エタノール 20.0
5.ジクロロ酢酸ジイソプロピルアミン 0.2
6.精製水 47.8
(製造方法)
A: 成分1~3を70℃で加熱撹拌して溶解させる。
B: 別に、成分4~6を混合して溶液とする。これを70℃に加熱する。
C:Aを70℃に保持し均一に撹拌しながら、Cを徐添して乳化する。更に撹拌しながら30℃まで冷却して、W/Oエマルション型皮膚外用剤を得る。
(効果)
シリコーン化合物No.13の配合により、生理活性物質であるジクロロ酢酸ジイソプロピルアミンの経皮吸収率の促進を期待できる。また、経皮吸収されることにより生理活性成分それ自体の薬効も高まると期待される。
(成分) (Wt%)
1.ステアリルアルコール 25.0
2.ベヘニルアルコール 0.5
3.硬化ヒマシ油 4.0
4.ポリプロピレングリコール(平均分子量1000) 7.0
5.PPG−14ブチルエーテル 1.0
6.デカメチルシクロペンタシロキサン 33.0
7.シリコーン化合物No.15 4.5
8.アルミニウム・ジルコニウム・テトラクロロハイドレート・グリシン 25.0
(製造方法)
A: 成分1~3及び成分6~7を、80℃で加熱撹拌を行って溶解させる。
B: 65℃に保ち、撹拌を行いながら成分4~5を加えて溶解させる。
C: 65℃に保ち、成分8を加え、よく撹拌して均一に分散させる。
D: 容器に流し込み、室温で固化させる。
(効果)
皮膚に対して抵抗感なく滑らかに塗布することができ、その皮膜はべたつかず適度な保湿感を有するため、快適で自然な使用感が得られる。乾燥後の白残りもほとんど見えないレベルである。制汗効果の持続性も良好である。
(成分) (Wt%)
1.ジメチルポリシロキサン(2cst) 22.5
2.安息香酸C12−15アルキル 12.5
3.ポリデセン 11.3
4.シリコーン化合物No.15 1.9
5.β−シトステロール 2.4
6.γ−オリザノール 2.4
7.アルミニウム・ジルコニウム・ペンタクロロハイドレート 18.8
8.精製水 18.8
9.グリセリン 9.4
(製造方法)
A: 成分1~4を、80℃で加熱撹拌を行って溶解させる。
B: 80℃に保ち、撹拌を行いながら成分5~6を順次加えて溶解させる。
C: 別に、成分7~9を混合し溶解させたのち、65℃に加熱する。
D: Bを65℃に保ち、撹拌しながらCを徐添して乳化する。
E: 静置して脱気した後、容器に流し込み室温で固化させる。
(効果)
半透明感のある上品な外観と適度なスティック硬度を有す。なめらかで潤いのある塗布感に優れており、制汗効果の持続性も良好である。塗布後の白残りもない。
(成分) (Wt%)
1.ミネラルオイル 4.0
2.セテアリルアルコール 4.7
3.ステアリン酸グリセリル 2.0
4.PEG−20ステアレート 1.2
5.シリコーン化合物No.15 1.5
6.フェノキシエタノール 0.4
7.酸化チタン 0.2
8.グリセリン 6.0
9.アルミニウム−ジルコニウムテトラクロルハイドレックスグリシン 15.0
10.精製水 65.0
(製造方法)
A: 成分1~6を、80℃で加熱撹拌を行って溶解させる。
B: 80℃に保ち、撹拌を行いながら成分7を加えて均一分散させる。
C: 別に、成分8~10を混合し溶解させたのち、65℃に加熱する。
D: Bを65℃に保ち、撹拌しながらCを徐添して乳化する。
(効果)
なめらかで違和感のない自然な塗布感の得られるクリームであり、制汗および保湿効果の即効性と持続性のバランスが良好である。皮膚に潤いを与え、弾力性を回復する。塗布後の白残りはほとんどない。
(成分) (Wt%)
1.FA 4002 ID *44) 19.0
2.パルミチン酸/エチルヘキサン酸デキストリン 8.0
3.ポリエチレンワックス 3.5
4.ミツロウ 6.5
5.レシチン 0.5
6.SS−3408 *45) 21.0
7.C11−12流動イソパラフィン 19.0
8.シリコーン化合物No.15 4.0
9.酸化鉄 5.0
10.アエロジルRY200 *46) 3.5
11.タルク 10.0
注*44) (アクリレーツ/メタクリル酸ポリトリメチルシロキシ)コポリマーの、イソドデカン溶液(有効成分40%)
注*45)カプリリルメチコン
注*46)アエロジルRY200(日本アエロジル社製):疎水化シリカ
(製造方法)
A:成分1~8をよく混合し溶解する。必要なら40℃に加温する。
B:成分9~11をAに加えローラーにて分散する。
(効果)
のび広がりが軽くてべたつきや油っぽさがなく、耐水性、撥水性、耐汗性があり化粧持ちも良い。温度や経時的に変化がなく安定性にも優れている。
(成分) (Wt%)
1.SS−3408 *47) 35.0
2.SS−2910 *48) 2.9
3.シリコーン化合物No.8 5.0
4.ポリエチレングリコール(分子量:400) 5.0
5.L−グルタミン酸ナトリウム 2.0
6.アラントイン 0.1
7.アロエ抽出物 0.1
8.防腐剤 0.1
9.酸化防止剤 0.1
10.香料 0.7
11.精製水 49.0
注*47)カプリリルメチコン
注*48)ポリエーテル変性シリコーン
(製造方法)
A:成分1~4及び成分10を加熱混合する。
B:成分5~9及び成分11を加熱混合する。
C:AにBを徐添して乳化し、アフターシェーブクリームを得る。
(効果)
適度な粘度を有するため使用時にたれることがなく、のび広がりが軽くてべたつかない。皮膚に対する刺激が少なく、塗布後は、さらっとしているが持続的な保湿感を付与できる。製品の安定性にも非常に優れている。
(成分) (Wt%)
[顔料部]
(38.2重量%)
1.処理球状酸化チタン(平均一次粒子径0.4μm)*49) 18.0
2.処理酸化鉄(黒酸化鉄、ベンガラ、黄酸化鉄の混合物)*49) 1.7
3.処理タルク *49) 6.0
4.処理マイカ *49) 2.0
5.Nε−ラウロイル−L−リジン 3.5
6.ポリアルキル・メチルシルセスキオキサン 5.0
(平均一次粒子径4μm)
7.オクチルシリル化微粒子酸化チタン 2.0
(平均一次粒子径10nm)
[液状部]
揮発性シリコーン(25重量%)
8.デカメチルシクロペンタシロキサン 15.0
9.メチルトリメチコン 10.0
ポリオール(6.5重量%)
10.1,3−ブチレングリコール 5.0
11.マルチトール 1.0
12.ラフィノース 0.5
界面活性剤(2重量%)
13.シリコーン化合物No.15 1.0
14.イソステアリン酸ソルビタン 1.0
固形又はペースト状の油剤(5重量%)
15.パラフィン 5.0
精製水(12.7重量%)
16.精製水 12.7
油剤(9.5重量%)
17.ジメチルポリシロキサン(6cst) 3.0
18.メチルフェニルポリシロキサン 2.0
19.パラメトキシケイ皮酸オクチル 2.0
20.ジカプリル酸プロピレングリコール 2.0
21.ヘキサヒドロキシステアリン酸ジペンタエリスリチル 0.5
生理活性成分
22.クランベリーエキス 1.0
防腐剤
23.パラベン 0.1——
注*49) Nε−ラウロイル−L−リジン5重量%処理顔料
(製造方法)
A:油性液状部(成分8~9、成分13~15、成分17~21、成分23)を80℃にて均一に混合溶解する。
B:あらかじめ混合、粉砕した顔料部(成分1~7)をこれに加え、80℃で均一に分散する。
C:ここにあらかじめ80℃にて均一に混合、溶解した水性液状部(成分10~12、成分16、成分22)を投入し、乳化分散を行う。
D:得られた乳化物を脱気し、金皿に充填し、密閉性容器にセットして固形状ファンデーションを得る。
(効果)
塗布時に肌に乾燥感が無く、肌なじみにも優れている。油性感が抑えられており、つけた感触が良い。化粧持ちも良い。製剤の安定性も良好で、分離凝集などが起こり難い。
(成分) (Wt%)
1.SS−2910 *50) 1.0
2.シリコーン化合物No.6 2.0
3.SH 556 *51) 5.0
4.SS−3408 *52) 6.0
5.ジメチルポリシロキサン(2cst) 6.0
6.グリセリン 5.0
7.ジプロピレングリコール 10.0
8.パラオキシ安息香酸メチル 0.2
9.アスコルビン酸硫酸エステルナトリウム 0.1
10.アスコルビン酸リン酸エステルナトリウム 0.1
11.γ−アミノ酪酸 0.1
12.リンゴ種子核抽出物(抗酸化剤) 0.1
13.塩化ナトリウム 0.9
14.香料 0.1
15.精製水 63.4
注*50)ポリエーテル変性シリコーン
注*51)フェニルトリメチコン
注*52)カプリリルメチコン
(製造方法)
A:成分1~5を60℃で加熱溶解する。
B:成分6~15を60℃で加熱溶解する。
C:成分Bに成分Aを撹拌しながら添加して乳化混合する。
D:ついで、撹拌しながら30℃まで冷却し、容器に充填して製品とする。
(効果)
塗布時にドライフィールなどの違和感が無く、のびがよくみずみずしい使用感に優れる。保湿効果の持続性があり、塗布後に肌がきしまない。化粧下地としても使いやすい。
(成分) (Wt%)
1.SS−3408 12.0
2.ジメチルポリシロキサン(2cst) 3.0
3.ジメチルポリシロキサン(100cst) 5.0
4.アルキル変性シリコーンレジンワックス 0.5
5.シリコーン化合物No.10 2.2
6.シリコーン化合物No.16 6.0
7.パルミチン酸 0.2
8.ジメチルオクチルパラアミノ安息香酸 0.5
9.4−t−ブチル−4’−メトキシ−ジベンゾイルメタン 0.5
10.カオリン 0.5
11.ベンガラ 0.2
12.黄酸化鉄 0.3
13.黒酸化鉄 0.1
14.酸化チタンコーテッドマイカ 1.0
15.L−グルタミン酸ナトリウム 3.0
16.1,3−ブチレングリコール 5.0
17.ジオクタデシルジメチルアンモニウムクロライド 0.1
18.酸化防止剤 適量
19.防腐剤 適量
20.香料 適量
21.精製水 残量
(製造方法)
A:成分1~9及び成分18~19を加熱溶解する。
B:成分17及び21の一部を加熱攪拌後、成分10~14を添加し分散処理する。
C:成分15~16及び21の残部を均一溶解し、Bと混合する。
D:攪拌下、AにCを徐添して乳化し、冷却して成分20を添加しサンタンクリームを得る。
(効果)
温度や経時的に分離や粉体の凝集などの変化がなく安定性に優れるだけでなく、のびが良く、優れた保湿感がある。
(成分) (Wt%)
1.ジメチルポリシロキサン(20cst) 5.0
2.ジメチルポリシロキサン(2cst) 15.0
3.流動パラフィン 10.0
4.2−エチルヘキサン酸セチル 5.0
5.シリコーン化合物No.16 3.0
6.ビタミンE 0.1
7.リン酸アスコルビルMg 0.2
8.塩化ナトリウム 1.0
9.グリセリン 25.0
10.1,3−ブチレングリコール 10.7
11.ジプロピレングリコール 25.0
(製造方法)
A:成分1~6を50℃で加熱撹拌して溶解させる。
B:別に、成分7~11を50℃で撹拌混合して溶解させる。
C:Aを50℃に保持し均一に撹拌しながら、Bを徐添して乳化する。
D:更に撹拌しながら30℃まで冷却して、ポリオール/O型非水エマルション皮膚外用剤を得る。
(効果)
非水系の安定な乳化物が得られるため、アスコルビン酸誘導体の安定性も良好に保持される結果、生理活性物質であるビタミンC固有の効果が皮膚上または皮内にて温和かつ持続的に発揮されると期待される。
(成分) (Wt%)
1.ジメチルポリシロキサン(20cst) 5.0
2.ジメチルポリシロキサン(2cst) 15.0
3.流動パラフィン 10.0
4.2−エチルヘキサン酸セチル 5.0
5.シリコーン化合物No.16 3.0
6.パルミチン酸アスコルビルリン酸3Na 0.2
7.ビタミンE 0.1
8.塩化ナトリウム 1.0
9.グリセリン 25.0
10.1,3−ブチレングリコール 10.7
11.ジプロピレングリコール 25.0
(製造方法)
A:成分1~7を50℃で加熱撹拌して溶解させる。
B:別に、成分8~11を50℃で撹拌混合して溶解させる。
C:Aを50℃に保持し均一に撹拌しながら、Bを徐添して乳化する。
D:更に撹拌しながら30℃まで冷却して、ポリオール/O型非水エマルション皮膚外用剤を得る。
(効果)
非水系の安定な乳化物が得られるため、パルミチン酸アスコルビルリン酸3Naの安定性が良好に保持される結果、当該物質に固有の性質により効果的な経皮吸収が生じ、生理活性物質であるビタミンC固有の効果が皮内にて温和かつ持続的に発揮されると期待される。
Claims (33)
- 下記一般式(1)
R1 aL1 bQcSiO(4−a−b−c)/2 (1)
で表される、シロキサンデンドロン構造を有する基および親水性基を有する共変性オルガノポリシロキサン。
{一般式(1)中、
R1は一価の有機基(ただし、L1またはQに該当する基を除く)または水素原子である。
L1はi=1のときの下記一般式(2)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る。
一般式(2):
(式中、R1は前記同様の基であり、R2は炭素原子数1~6のアルキル基またはフェニル基であり、Zは二価の有機基である。iはL1で示されるシリルアルキル基の階層を示し、該シリルアルキル基の繰り返し数である階層数がcのとき1~cの整数であり、階層数cは1~10の整数であり、Li+1はiがc未満のときは該シリルアルキル基であり、i=cのときはメチル基またはフェニル基である。aiは0~3の範囲の数である。)
Qは二価以上の連結基を介してケイ素原子に結合し、かつ下記構造式(3−1)~(3−4)で表される親水性単位から選択される少なくとも1種以上の親水性単位を含有してなる親水性基である。
−CrH2r−O− (3−1)
(rは1~6の範囲の数)
(式中、Wは水素原子または炭素原子数1~20のアルキル基。)
(式中、Wは前記同様の基)
a、b及びcは、1.0≦a≦2.5、0.001≦b≦1.5、及び0.001≦c≦1.5となる範囲の数である。} - Qが下記一般式(4−1)~(4−4)で示される親水性基である、請求項1~3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。
一般式(4−1):
−R3(−O−X1 m−R4)p (4−1)
(R3は(p+1)価の有機基であり、pは1以上3以下の数である。X1は各々独立に、上記一般式(3−1)~(3−4)で表される親水性単位から選択される少なくとも1種以上の親水性単位であり、mは1~100の範囲の数である。R4は水素原子、炭素原子数1~20のアルキル基、アシル基およびグリシジル基からなる群から選択される基である。)
一般式(4−2):
−R3(−O−X2)p (4−2)
{R3は前記同様の基であり、pは前記同様の数である。X2は下記構造式(4−2−1)で表される親水性基である。
(式中、2つの酸素原子には、各々独立に、上記一般式(3−1)~(3−4)で表される親水性単位から選択される少なくとも1種以上の親水性単位が結合する。)}
一般式(4−3):
−R3(−O−X3)p (4−3)
{R3は前記同様の基であり、pは前記同様の数である。X3は下記構造式(4−3−1)で表される親水性基である。
(式中、2つの酸素原子には、各々独立に、上記一般式(3−1)~(3−4)で表される親水性単位から選択される少なくとも1種以上の親水性単位が結合する。)}
一般式(4−4):
−R3(−O−X4)p (4−4)
{R3は前記同様の基であり、pは前記同様の数である。X4は下記構造式(4−4−1)で表される親水性基である。
(式中、2つの酸素原子には、各々独立に、上記一般式(3−1)~(3−4)で表される親水性単位から選択される少なくとも1種以上の親水性単位が結合する。)} - 下記構造式(1−1−1)または(1−1−2)で表される請求項1~5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。
{式中、Z,R1は前記同様の基であり、Rは、R1,前記のL1、および以下に説明するQ1から選択される基である。n1は10~1,000の範囲の数であり、n2は0~250の範囲の数であり、n3は0~250の範囲の数である。ただし、n2=0のとき、Rの少なくとも一方はL1である。また、n3=0のとき、Rの少なくとも一方はQ1である。
Q1は、各々独立に、下記構造式(4−1−2),(4−2−2),(4−3−2)および(4−4−2)からなる群から選択される親水性基である。
(式中、R3は(p+1)価の有機基であり、pは1以上3以下の数である。X1は各々独立に、前記一般式(3−1)~(3−4)で表される親水性単位から選択される少なくとも1種以上の親水性単位であり、mは1~100の範囲の数である。R4は水素原子、炭素原子数1~20のアルキル基、アシル基およびグリシジル基からなる群から選択される基である。) - 請求項1~8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を含有する界面活性剤。
- (A)請求項1~8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(A2)反応性官能基を有する親水性化合物を含有する界面活性剤。
- (A)請求項1~8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、(B)水および(C)5~100℃で液状であるシリコーンオイル、炭化水素油またはエステル油から選択される1以上の油剤を含有するエマルジョン組成物。
- 上記の(B)成分を含む水相と、上記の(A)成分および(C)成分を含む油相とを、独立に混合した後、両相の25℃における屈折率の差を0.0020単位以下になるように調整して乳化することを特徴とする、請求項11に記載のエマルジョン組成物の透明性調整方法。
- 請求項1~8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を含有する粉体処理剤。
- (A)請求項1~8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(D)粉体又は粉状着色剤を含有してなる粉体組成物。
- (D)粉体又は粉状着色剤100質量部に対して、(A)請求項1~8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1.0~30質量部を使用して前記の(D)成分を表面処理してなることを特徴とする、請求項14に記載の粉体組成物。
- 前記の(D)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14または請求項15に記載の粉体組成物。
- 前記の(D)成分が、無機体質顔料であることを特徴とする請求項14または請求項15に記載の粉体組成物。
- (A)請求項1~8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、(D)粉体又は粉状着色剤および(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1~8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19に記載の外用剤組成物。
- 請求項11に記載のエマルジョン組成物を含有する化粧料。
- 請求項14~17のいずれか1項に記載の粉体組成物を含有する化粧料。
- 請求項18に記載の油中粉体分散物を含有する化粧料。
- 請求項1~8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油剤を含有してなる、実質的に水を含まない化粧料。
- 更に、(E)多価アルコールまたは低級一価アルコール、(F)無機塩類または有機酸塩、(G)シリコーン系界面活性剤(ただし(A)成分である共変性オルガノポリシロキサンであるものを除く)からなる群から選択される少なくとも1種を含有する、請求項20~請求項24のいずれか1項に記載の化粧料。
- 更に、(H)架橋性オルガノポリシロキサン、オルガノポリシロキサンエラストマー球状粉体、シリコーン樹脂、アクリルシリコーンデンドリマーコポリマー、シリコーン生ゴム、ポリアミド変性シリコーン、アルキル変性シリコーンワックス、アルキル変性シリコーンレジンワックスからなる群から選択される少なくとも1種を含有する、請求項20~請求項25のいずれか1項に記載の化粧料。
- 更に、(J)アニオン性界面活性剤、カチオン性界面活性剤、ノニオン性界面活性剤(シリコーン系界面活性剤を除く)、両性界面活性剤、半極性界面活性剤からなる群より選ばれる1種又は2種類以上を含有する請求項20~請求項26のいずれか1項に記載の化粧料。
- 更に、(K)水溶性高分子または(L)紫外線防御成分を含有する請求項20~請求項27のいずれか1項に記載の化粧料。
- 化粧料が、スキンケア製品、毛髪用化粧料製品、制汗剤製品、メイクアップ製品、又は紫外線防御製品である請求項20~請求項28のいずれか1項記載の化粧料。
- 製品の形態が、液状、乳液状、クリーム状、固形状、ペースト状、ゲル状、粉末状、多層状、ムース状、スプレー状のいずれかである請求項20~請求項29のいずれか1項記載の化粧料。
- ヒドロシリル化反応触媒の存在下において、下記一般式(1’)
R1 aHb+cSiO(4−a−b−c)/2 (1’)
(式中、R1、a、b及びcは前記と同じ)で表されるオルガノハイドロジェンシロキサン(a)と、反応性不飽和基を1分子中に1つ有する親水性誘導体(b)と、反応性不飽和基を1分子中に1つ有するシロキサンデンドロン(c)とを少なくとも反応させて得られることを特徴とする、請求項1~請求項8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の製造方法。 - 反応性不飽和基を1分子中に1つ有する親水性誘導体(b)および反応性不飽和基を1分子中に1つ有するシロキサンデンドロン(c)が少なくとも共存する状態として、前記(b)成分、前記(c)成分および上記一般式(1’)で表されるオルガノハイドロジェンシロキサン(a)を一緒に反応させる事を特徴とする、請求項31に記載の共変性オルガノポリシロキサンの製造方法。
- 反応性不飽和基を1分子中に1つ有するシロキサンデンドロン(c)が、下記一般式(2’)で表される分子鎖末端に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である、請求項31または請求項32に記載の共変性オルガノポリシロキサンの製造方法。
一般式(2’):
{式中、R1は前記同様の基であり、L´1はメチル基またはj=1のときの下記一般式(2’’)で示されるシリルアルキル基である。Z´は二価の有機基である。
(式中、R1は前記同様の基であり、R2は炭素原子数1~6のアルキル基またはフェニル基であり、Zは二価の有機基である。jはLjで示されるシリルアルキル基の階層を示し、該シリルアルキル基の繰り返し数である階層数がc’のとき1~c’の整数であり、階層数c’は1~10の整数であり、Lj+1はjがc’未満のときは該シリルアルキル基であり、j=c’のときはメチル基またはフェニル基である。ajは0~3の範囲の数である。)}
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| CN201080059088.4A CN102666664B (zh) | 2009-10-23 | 2010-10-25 | 共改性的有机聚硅氧烷 |
| US13/503,455 US8784787B2 (en) | 2009-10-23 | 2010-10-25 | Co-modified organopolysiloxane |
| JP2011537339A JP5770095B2 (ja) | 2009-10-23 | 2010-10-25 | 新規な共変性オルガノポリシロキサン |
| EP10825094.5A EP2492301B1 (en) | 2009-10-23 | 2010-10-25 | Novel co-modified organopolysiloxane |
| KR1020127013363A KR101925354B1 (ko) | 2009-10-23 | 2010-10-25 | 공동-개질된 오가노폴리실록산 |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN102666664A (zh) | 2012-09-12 |
| EP2492301A1 (en) | 2012-08-29 |
| US20120269875A1 (en) | 2012-10-25 |
| KR101925354B1 (ko) | 2018-12-05 |
| CN102666664B (zh) | 2015-09-23 |
| EP2492301A4 (en) | 2014-01-22 |
| JPWO2011049248A1 (ja) | 2013-03-14 |
| EP2492301B1 (en) | 2023-03-29 |
| JP5770095B2 (ja) | 2015-08-26 |
| US8784787B2 (en) | 2014-07-22 |
| KR20120093979A (ko) | 2012-08-23 |
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