WO2011049247A1 - 油性原料の増粘剤またはゲル化剤 - Google Patents
油性原料の増粘剤またはゲル化剤 Download PDFInfo
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- WO2011049247A1 WO2011049247A1 PCT/JP2010/069248 JP2010069248W WO2011049247A1 WO 2011049247 A1 WO2011049247 A1 WO 2011049247A1 JP 2010069248 W JP2010069248 W JP 2010069248W WO 2011049247 A1 WO2011049247 A1 WO 2011049247A1
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- 0 CC*N(C(C)(C(C)C)ON(*)*)NC Chemical compound CC*N(C(C)(C(C)C)ON(*)*)NC 0.000 description 5
- DAJQIHLUYCXGAB-DJRKXVOMSA-N CCCCO[C@H]1O[IH]([C@@H]2C)(NC)NC2C1C Chemical compound CCCCO[C@H]1O[IH]([C@@H]2C)(NC)NC2C1C DAJQIHLUYCXGAB-DJRKXVOMSA-N 0.000 description 1
Classifications
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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
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/14—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
- A61K47/34—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyesters, polyamino acids, polysiloxanes, polyphosphazines, copolymers of polyalkylene glycol or poloxamers
-
- 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
-
- 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
- A61K8/042—Gels
-
- 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
- A61K8/892—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone modified by a hydroxy group, e.g. dimethiconol
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/06—Ointments; Bases therefor; Other semi-solid forms, e.g. creams, sticks, gels
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/08—Solutions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/16—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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/48—Thickener, Thickening system
Definitions
- the present invention relates to a thickener or gelling agent of an oily raw material containing a novel hydrophilic silicone having a siloxane dendron structure, a gel composition, and a gel cosmetic or gel external preparation comprising the same.
- the present invention also relates to a thickener or gelling agent of an oily raw material containing a high molecular weight hydrophilic silicone having a siloxane dendron structure and a tetraglycerin structure, and a gel composition, a gel cosmetic composition or a gel composition comprising the same. It relates to an external preparation.
- the new hydrophilic silicone with siloxane dendron structure has various functional aspects, and it is incorporated into cosmetics based on oily raw materials to suppress oily feeling, and the natural and uncomfortable skin feeling after application And a cosmetic that imparts an excellent moisturizing feeling.
- a high molecular weight hydrophilic silicone having a group having a siloxane dendron structure and a tetraglycerin structure is excellent in compatibility with various oil systems, and the form and viscosity of oils and cosmetics can be freely controlled by the amount added. Functions as an excellent oil thickener.
- powders and colorants can be uniformly and stably dispersed and fixed in cosmetics based on oil-based raw materials, and excellent cosmetic effects can be obtained for about one day after application to the skin. It also functions as an excellent dispersing / fixing agent that can maintain a natural skin feeling without any discomfort.
- a gel-like composition can be obtained.
- a stable gel composition can be easily obtained by blending powder into this composition and further blending an ultraviolet absorber, a film-forming agent, salts and the like. Further, by blending and diluting water with these gel-like compositions, it is possible to obtain cosmetics of any form having a lower viscosity than paste, cream, emulsion and the like.
- the external preparation of arbitrary forms can be similarly obtained by further mix
- Oil thickening / gelation technology gives cosmetic manufacturers the freedom to control the cosmetic form from liquid to cream, paste, gel or solid, and is extremely important. High technology. Therefore, development of a modified silicone-based thickening / gelling agent that is advantageous in terms of feel and studies of applying it to cosmetics have been actively conducted.
- Patent Document 7 a technique related to a gel-like silicone composition in which silicone oil is gelled using polyether-modified silicone and water has also been developed, but this technique includes organic oil in the oil system. In this case, there is a problem that the thickening / gelling effect is insufficient. Also, there were problems such as a feeling of sliminess on the touch surface.
- Silicone branched polyhydric alcohol-modified silicone for example, alkyl / linear siloxane branched / polyglycerin co-polymer) Modified silicone
- organic modified viscosity minerals or fructooligosaccharide fatty acid esters known as oil thickening / gelling agents
- Patent Documents 12 and 13 organic modified viscosity minerals or fructooligosaccharide fatty acid esters known as oil thickening / gelling agents
- modified alkyl glyceryl ether having a specific structure
- a makeup cosmetic Patent Document 14
- silicone and silicic anhydride which is known as a thickening / gelling agent for oil, in a specific ratio.
- the (poly) glycerin-modified silicone used in these technologies lacks the ability to thicken and gel oil, so it is necessary to use another material that can effectively thicken and gel the oil. There was a problem that the effect of controlling the necessary viscosity and form was insufficient.
- organically modified viscosity minerals and silicic acid anhydride may cause aggregation due to the effects of oil type and moisture, and the proposed cosmetics have problems in terms of stability.
- the fructooligosaccharide fatty acid ester has a problem in that it has insufficient ability to thicken and gel silicone oil other than cyclic siloxane, and has a low degree of freedom in terms of cosmetic formulation.
- Patent Document 15 a novel organopolysiloxane / glycerin derivative alternating copolymer has been proposed in Patent Document 15, 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, the properties are completely different from conventionally used hydrophilic silicones such as polyether-modified silicones, and a considerable amount of technology is required to stably add them to delicate formulations such as cosmetics, and the fields of application are limited. It was. Furthermore, although compatibility with the oil agent which consists only of silicone type
- silicone modified with a polyhydric alcohol such as (poly) glycerin has a low degree of freedom in structural design, and it has been difficult to produce it with stable quality.
- 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. Since the compatibility with the copolymer, which is a product, is low and two-phase separation occurs within a short time after production, there is a great restriction on industrialization.
- 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 kinds of components having different properties are easily generated as a copolymer, and there are many problems in terms of quality and purification steps.
- powders such as mica and sericite, including basic cosmetics, lipsticks, suncuts, nail colors, nail coats, Widely used in the fields of cosmetics such as foundation, mascara, eyeliner.
- Examples of the purpose of blending these powders into cosmetics include adjustment of color tone and covering power and adjustment of touch, and examples of use in oily cosmetics in combination with conventional polyhydric alcohol-modified silicones have also been reported. Yes. (Patent Documents 1-6, 12-14)
- silicone-based powders such as organopolysiloxane elastomer spherical powder, polymethylsilsesquioxane powder, silicone resin powder, silicone rubber powder, silk powder, nylon powder, polymethylmethacrylate powder, polyethylene
- organic resin powders such as powders are excellent in oil-absorbing ability, they have an effect of relieving a strong oily feeling such as oily cosmetics and making the skin feeling and skin feeling after application closer to a natural impression.
- it was difficult to uniformly disperse during the formulation and there was a problem that the powdery feel became conspicuous when the blending amount was increased.
- Gel (gel) cosmetics have been interesting in terms of characteristics and effects based on their physical structure, and various studies have been made so far. Although it is related to oil thickening and gelation technology, cosmetics often have problems in usability in completely solidified forms and low-viscosity liquids, and use is limited. For this reason, among gel cosmetics, cosmetics having viscosity and elasticity in the middle region between liquid and solid, and materials and technology development that can control the cosmetics to these forms have been required.
- Patent Document 7 can widely thicken or gel silicone oil, which is an oil agent frequently incorporated into cosmetics. It is widely used as a base for gel-like cosmetics or as a base for emulsified compositions and emulsified cosmetics, because the stability of the composition is better than when a powder gelling agent is used. . (Patent Documents 21 to 26)
- the polyether-modified silicone used as a thickening / gelling agent in Patent Document 7 has a problem that water is essential for gelation, so that the preparation is limited. There was a problem of being concerned about the slimy feeling. Furthermore, when organic oil is contained in the oil system, there is a problem that the thickening / gelling effect is poor.
- various oils such as hydrocarbon oils and ester oils are used in addition to silicone oils, and these oils are used in cosmetic formulations in order to make use of each other's strengths such as the touch and make up for each other.
- various oils such as hydrocarbon oils and ester oils are used in cosmetic formulations in order to make use of each other's strengths such as the touch and make up for each other.
- gel cosmetics in which various oil systems composed of combinations of silicone oils and organic oils are held in a gel form having viscoelasticity in the middle region between liquid and solid.
- a gel cosmetic that can freely control the form and viscosity of the gel cosmetic by the amount of the thickening / gelling agent added.
- Japanese Patent No. 3389271 Japanese Patent Laid-Open No. 6-157236) Japanese Patent No. 3513682 (Japanese Patent Laid-Open No. 9-71504) Japanese Patent No. 3625471 (WO2003-075864) 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) Japanese Patent No. 3333782 (Japanese Patent Laid-Open No. 5-311076) JP 2004-182680 A US 5874409 US 5919441 US 6534072 Japanese Patent No. 3678420 (WO2003-041664) Japanese Patent Laid-Open No.
- the present invention has been made to solve the above-mentioned problems, and is excellent in oil thickening, which is excellent in compatibility with various oil systems, and can freely control the form and viscosity of oily raw materials and cosmetics depending on the amount added. It is to provide an agent or a gelling agent.
- the second problem of the present invention is that the powder and the colorant can be uniformly and stably dispersed and fixed in the cosmetic based on the oily raw material, and about 1 after applying it to the skin.
- the aim is to provide an excellent dispersing / fixing agent capable of sustaining an excellent cosmetic effect and a natural skin feeling without any sense of incongruity.
- the third object of the present invention is to provide a base for stably and easily producing cosmetics having various viscoelasticities and forms such as gel, paste, cream, and emulsion, and various oils can be used as liquids and solids.
- An object of the present invention is to provide a gel-like composition held in a gel form having viscoelasticity in the middle region. Furthermore, various functions that can be easily obtained by mixing powders with this composition, and further by mixing ingredients usually used in cosmetics such as UV absorbers, film forming agents, and salts. It is in providing the stable gel-like composition which has this.
- an object of the present invention is to provide a gel-like cosmetic that ensures optical transparency and is excellent in storage stability when blended in an emulsion-type gel-like cosmetic.
- the fourth object of the present invention is to provide a method for easily obtaining cosmetics of any form having a lower viscosity than paste, cream, milky liquid, etc. by mixing and diluting the composition with water. There is. Furthermore, it is providing the method of obtaining external preparations of arbitrary forms by mix
- the object of the present invention is to thicken or gelate an oily raw material having a group having a siloxane dendron structure in the molecule and a hydrophilic group such as polyether and containing a novel co-modified organopolysiloxane. It is achieved by agents, external preparations containing them, and cosmetics. Furthermore, it is achieved by a method for producing an external preparation or a cosmetic using the thickener or gelling agent or gel composition of the oily raw material.
- the above object is more preferably achieved by a thickener or gelling agent and a gel-like cosmetic material of an oily raw material containing a high molecular weight hydrophilic silicone having a siloxane dendron structure and a tetraglycerin structure as a hydrophilic group.
- the object is (B) powder or colorant, (C) silicone surfactant (excluding those corresponding to component (A)), crosslinkable organopolysiloxane, silicone resin, acrylic silicone dendrimer copolymer, It is suitably achieved by a thickener or gelling agent containing at least one selected from the group consisting of polyamide-modified silicones and alkyl-modified silicone resin waxes.
- 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
- the first object of the present invention is the following general formula (1).
- R 1 is a monovalent organic group (excluding a group that is L1 or Q) or a hydrogen atom
- a silylalkyl group having a siloxane dendron structure
- R 1 are the same groups as defined above, R 2 is an alkyl group or a phenyl group having 1 to 6 carbon atoms, Z is a divalent organic group .i is represented by L i
- R 1 is the same group as described above, In 2), it is preferably a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms.
- Q is selected from hydrophilic units bonded to a silicon atom via a divalent or higher linking group and represented by the following structural formulas (3-1) to (3-4).
- a hydrophilic group comprising at least one or more hydrophilic units. —C r H 2r —O— (3-1) (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.) (Wherein W is the same group as described above)
- 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. It is.
- the object is a co-modified organopolysiloxane having a silylalkyl group represented by the following structural formula (1-1) and having at least one siloxane dendron structure in one molecule,
- a group derived from polyglycene (particularly preferably, a group having a tetraglycerin structure) is selected as (Q), and the numbers represented by n1, n2 and n3, which are the degrees of polymerization of the following organosiloxane units, It is within the following range, and is achieved by a thickening agent or gelling agent and a gel cosmetic which are oily raw materials containing a high molecular weight co-modified organopolysiloxane.
- R 1 , L 1 and Q are the same groups as described above, and R is a group selected from R 1 , L 1 and Q.
- a thickener or gelling agent for an oily raw material comprising a co-modified organopolysiloxane having a group having a siloxane dendron structure and a hydrophilic group.
- Agent [1] (A) Thickener or gelation of oily raw material containing co-modified organopolysiloxane having a siloxane dendron structure and a hydrophilic group represented by the above general formula (1) Agent.
- the component (A) is a co-modified organopolysiloxane represented by the structural formula (1-1) and having a silylalkyl group having at least one siloxane dendron structure in one molecule.
- Z and R 1 are the same groups as described above, and R is a group selected from R 1 , the L 1 described above, and Q 1 described below.
- Q 1 each independently binds to a silicon atom via a divalent or higher valent linking group and is at least 1 selected from the hydrophilic units represented by the structural formulas (3-1) to (3-4). It binds to a silicon atom via a hydrophilic group formed by linearly connecting more than one kind of hydrophilic units or a divalent or higher valent linking group, and in the above structural formulas (3-1) to (3-4) Selected from groups represented by the following structural formulas (3-5) to (3-7), which contain at least one or more hydrophilic units selected from the hydrophilic units represented. It is a hydrophilic group having a branch unit.
- the hydrophilic group Q or Q 1 is a hydrophilic group represented by the following structural formula (4-1), (4-2), (4-3) or (4-4).
- the thickener or gelling agent for oily raw materials according to any one of [1] to [4], which is characterized in that ⁇ In the formula, R 3 is a (p + 1) -valent organic group, p is a number of 1 or more and 3 or less.
- X 1 is each independently represented by the following general formulas (3-2-1) to (3- 4-1) is at least one hydrophilic unit selected from the hydrophilic units represented by 4-1), and m is a number in the range of 3-5.
- X 2 is a hydrophilic unit represented by the following structural formula (3-1), and q is a number in the range of 0 to 50.
- the form of the bond of X 1 and X 2 is independently a block shape or a random shape.
- —C r H 2r —O— (3-1) (Wherein r is a number in the range of 1-6)
- 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. ) ⁇
- the hydrophilic group Q or Q 1 is independently a hydrophilic group derived from polyglycerin represented by the following structural formula (4-1-1), [1] The thickener or gelling agent of the oily raw material according to any one of [5].
- R 3 ′ is a divalent organic group, and each X 1 is independently selected from the hydrophilic units represented by the general formulas (3-2-1) to (3-4-1). Wherein m is a number in the range of 3 to 5.
- R 4 is 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. Selected group.
- silicone-based surfactant excluding those corresponding to component (A)
- crosslinkable organopolysiloxane silicone resin
- acrylic silicone dendrimer copolymer acrylic silicone dendrimer copolymer
- polyamide-modified silicone alkyl-modified silicone resin wax
- the component (B) is (B1) silicone resin powder, silicone rubber powder, organic resin powder (excluding silicone resin powder), organically modified viscosity mineral, titanium oxide, zinc oxide, titanium mica, metal soap,
- the object of the present invention is achieved by the invention of the gel composition containing the above-mentioned co-modified organopolysiloxane, “[12] (D) 30 to 80% by mass of the oily raw material, 10 to 70% by mass of the thickener or gelling agent of the oily raw material according to any one of [1] to [11],
- a gel composition comprising 0 to 20% by mass of at least one compound selected from the group consisting of a monohydric alcohol and an organic polyhydric alcohol compound and 0 to 20% by mass of water (E).
- the gel composition according to [12] further comprising (F) an ultraviolet absorber.
- the object of the present invention is to [17] After independently mixing the water phase and the oil phase containing the above component (A) and (D) oily raw material, the difference in refractive index between both phases at 25 ° C. is 0.0020 unit or less. It is achieved by the “transparency adjustment method of emulsion composition” characterized in that emulsification is performed.
- the object of the present invention is a cosmetic invention characterized by containing a thickener or gelling agent for the above oily raw material and the above gel composition, and further comprising a physiologically active substance. It is suitably achieved by the invention of the external preparation and the invention of these production methods, “[17] The cosmetic composition is mixed by mixing 100 parts by mass of the gel composition according to any one of [12] to [16] and (E) 0.1 to 4,000 parts by mass of water. How to manufacture. [18] A cosmetic obtained by mixing 100 parts by mass of the gel composition according to any one of [12] to [16] and (E) 0.1 to 4,000 parts by mass of water.
- the physiologically active substance is an anti-inflammatory agent, anti-aging agent, whitening agent, hair growth agent, hair growth agent, blood circulation promoter, antibacterial agent, bactericidal agent, vitamins, wound healing promoter, stimulation relieving agent, analgesic agent
- the cosmetic according to [18] or [19], wherein the product form is liquid, emulsion, cream, solid, paste, gel, powder, multilayer, mousse, or spray. .
- Any one of [21] to [23], wherein the form of the product is liquid, emulsion, cream, solid, paste, gel, powder, multilayer, mousse, or spray.
- the object of the present invention is suitably achieved by a method for producing the above thickener or gelling agent of an oily raw material by a hydrosilylation reaction between an organopolysiloxane having a silicon-bonded hydrogen atom and another raw material.
- the production method includes: “[26]
- the co-modified organopolysiloxane as the component (A) is composed of an organopolysiloxane having a silicon-bonded hydrogen atom and one carbon-carbon dioxygen at the molecular chain end represented by the following general formula (2 ′).
- 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 ′
- a j is a number in the range of 0 to 3.
- the first problem regarding the oil thickener related to the degree of freedom of form control of the oil, dispersion and immobilization of powder and colorant The second problem related to the third problem, the third problem related to the gel-like composition, and the fourth problem related to the method for producing cosmetics or external preparations can all be suitably solved.
- the cosmetic when blended in an emulsion-type gel cosmetic, it is possible to provide a cosmetic that ensures optical transparency and is excellent in storage stability, if desired.
- the thickener or gelling agent of the oily raw material according to the present invention is characterized by containing a co-modified organopolysiloxane having a group having a siloxane dendron structure and a hydrophilic group. Furthermore, the thickener or gelling agent of the oily raw material according to the present invention preferably has a group derived from polyglycene as the hydrophilic group (particularly preferably, a group having a tetraglycerin structure), And a co-modified organopolysiloxane having a high molecular weight.
- the co-modified organopolysiloxane has the following general formula (1): R 1 a L 1 b Q c SiO (4-abc) / 2 (1) And a co-modified organopolysiloxane having a group having a siloxane dendron structure (-L 1 ) and a hydrophilic group (-Q), and preferably having a degree of polymerization of 200 or more of the organosiloxane unit.
- a modified organopolysiloxane is exemplified.
- 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 (excluding a group that is L 1 or Q)
- 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 given an excellent thickening effect and gelling ability of the oil component. 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.
- 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.
- Q is preferably a group derived from polyglycene, and Q is particularly preferably a hydrophilic group having 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.
- 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 connecting more than one type of hydrophilic unit.
- Q is bonded to a silicon atom via a divalent or higher linking group and is at least one selected from hydrophilic units represented by the structural formulas (3-1) to (3-4).
- the two oxygen atoms are independently selected from hydrophilic units represented by the general formulas (3-1) to (3-4). At least one or more hydrophilic units are bonded.
- 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.
- the structure of the hydrophilic group Q having one branch unit represented by the structural formula (3-5) and two branch units represented by the structural formula (3-7) and branched in a tree shape is shown below.
- the dendritic polyether structure, polyglycerol structure or polyglycidyl ether structure is not limited thereto.
- m is a number in the range of 1 to 50.
- the divalent or higher valent linking group is a bonding site to a silicon atom contained in the hydrophilic group Q, and the structure thereof is not particularly limited, but an ethylene group, a propylene group, a 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 thereof include alkylenoxy benzylene groups such as a nonoxy benzylene group, an ethylenoxy benzylene group and 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 structural formulas (4-1) to (4-4), and these are generally hydrophilic groups derived from polyglycerin compounds. .
- 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.
- R 3 examples include groups selected from divalent organic groups represented by the following general formula.
- 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 hydrophilic units represented by the following general formulas (3-2-1) to (3-4-1), and m is The number is in the range of 3 to 5, particularly preferably 4.
- X 2 is an oxyalkylene unit represented by the following structural formula (3-1), and q is a number in the range of 0-50. —C r H 2r —O— (3-1) In the formula, r is a number in the range of 1 to 6, and X 2 is preferably an oxyethylene unit or an oxypropylene unit. Further, when X 2 is bound in succession, it can also be included Q 1 or more in the polyoxyalkylene unit of formula (3-1-1).
- t1 and t2 are each a number of 0 or more, and (t1 + t2) is a number in the range of 0 to 50, preferably a number in the range of 0 to 30.
- the form of the bond between X 1 and X 2 may be block or random. That is, the hydrophilic group represented by Q includes a hydrophilic segment formed by binding the hydrophilic units represented by the general formulas (3-2-1) to (3-4-1) in a block shape, and a polyoxyalkylene.
- bonds may be sufficient, and the hydrophilic group which the unit which comprises these couple
- - (X 2) m1 -X 1 - (X 2) m2 -X 1 - binding format like can be exemplified.
- 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.
- the particularly preferred hydrophilic group Q is from polyglycerin represented by the following structural formula (4-1-1). It is a hydrophilic group derived.
- R 3 ′ is a divalent organic group, and examples thereof are the same as those described above.
- X 1 and R 4 are the same groups as described above, and m is a number in the range of 3 to 5. Particularly preferably, m is 4 and preferably has a tetraglycerin structure.
- the hydrophilic group Q is preferably a hydrophilic group derived from a polyglycerol-based compound as described above. Most preferably, the hydrophilic group is derived from tetraglycerin. Specific examples include hydrophilic groups derived from polyglycerin compounds having a tetraglycerin structure, which are polyglyceryl monoallyl ether and polyglyceryl eugenol.
- the co-modified organopolysiloxane having the group (-L 1 ) having a siloxane dendron structure and the hydrophilic group (-Q) represented by the general formula (1) is a thickening effect on the oil component.
- the degree of polymerization of the organosiloxane unit is preferably 200 or more
- the co-modified organopolysiloxane having a linear polysiloxane structure represented by the following structural formula (1-1) Siloxane is preferably exemplified.
- R 1 , L 1 and Q are each independently the same group as described above, and the functional groups suitable as L 1 and Q are the same as in the previous period.
- 90 mol to 100% of all R 1 is preferably a group selected from a methyl group, an ethyl group, or a phenyl group. 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 preferably a number in the range of 200 to 2,000, particularly preferably in the range of 200 to 1,200. That is, from the viewpoint of the thickening effect of the co-modified organopolysiloxane according to the present invention on the oil component and the gelling ability, it is preferably a high molecular weight organopolysiloxane having a polymerization degree of 200 or more.
- n1 is preferably a number in the range of 200 to 2,000, preferably in the range of 200 to 1,000, from the viewpoint of the thickening effect and gelling ability of the co-modified organopolysiloxane according to the present invention on the oil component. More preferably, it is more preferably in the range of 250 to 800. In view of the effect of the invention, the most preferable range of n1 is 300 to 750.
- n2 is a number in the range of 1 to 250, that is, having at least one group (-L 1 ) having a siloxane dendron structure in the side chain portion from the viewpoint of thickening effect on the oil component and gelling ability.
- N2 is preferably in the range of 1 to 50, more preferably in the range of 3 to 35, and particularly preferably in the range of 5 to 25.
- co-modified organopolysiloxane according to the present application is used as a thickener and a gelling agent for the oil component, particularly preferably, the following structural formula (1-1-1) or (1-1-2)
- Z, R 1 and Q are the same groups as described above, and R is a group selected from R 1 and the above L 1 and Q.
- 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), an organohydrogensiloxane (a) having a polymerization degree of 200 or more, and a hydrophilic property having one reactive unsaturated group in one molecule
- the derivative (b) 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.
- the (b) component, the (c) component and the organohydrogensiloxane (a) having a polymerization degree of 200 or more represented by the general formula (1 ′) are reacted together, Alternatively, after at least an addition reaction between the organohydrogensiloxane (a) and the component (c) ⁇ amount of 0.9 molar equivalent or less with respect to the silicon-bonded hydrogen atom of the (a) ⁇ , the (b It can be suitably produced by subjecting the component to an addition reaction.
- 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.
- the hydrophilic derivative (b) having one reactive unsaturated group in one molecule is an alkenyl group at the end of the molecular chain of terminal allyl etherified polyglycerol / polyether copolymer, allyl polyglycerol, allyl polyglycidyl ether, etc. It is a hydrophilic compound having a reactive functional group such as, and can be synthesized by a known method.
- Polyglycerin monoallyl ether and polyglyceryl eugenol are preferably exemplified from the viewpoint of the thickening effect on the oil component of the co-modified organopolysiloxane according to the present invention and the gelling ability, and from the triglycerin, tetraglycerin and pentaglycerin to the hydrophilic group portion. It is preferable to have a selected polyglycerin structure, and a hydrophilic compound having a tetraglycerin structure in the hydrophilic group portion is particularly preferable from the viewpoint of thickening effect and gelling ability.
- 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.
- Z ′ is a divalent organic group.
- R 2 is an alkyl group having 1 to 6 carbon atoms or a phenyl group, and Z is a divalent organic group.
- j represents the hierarchy of the silylalkyl group represented by L j , and when the hierarchy number that is the number of repetitions of the silylalkyl group is c ′, it is an integer from 1 to c ′, and the hierarchy number c ′ is an integer from 1 to 10
- a j is a number in the range of 0-3.
- R 1 is the same group as described above, and in the general formula (2 ′′), a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms is preferable. Particularly preferred is 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 has a silylalkyl group having a siloxane dendron structure exhibiting high water repellency and a hydrophilic group in the same molecule, and preferably the degree of polymerization of the organosiloxane unit. Is a polymer having 200 or more, it is extremely useful as a thickener or gelling agent for (D) oily raw materials.
- the co-modified organopolysiloxane according to the present invention is blended in a small amount with respect to the oil component, it functions as a thickener, and if blended in a large amount, the oil component can be gelled.
- thickening or gelling an oily raw material can bring about great effects and changes in its appearance, blending system, feeling of use and dosage form.
- Gelation technology is highly important.
- the cosmetics can be given a degree of freedom to control the form of the cosmetics from liquid to syrup, cream, paste, gel or solid, so that the thickener / gelation technology for oily raw materials can be given. Is an extremely important technology.
- the technical effect of increasing the viscosity of the oily raw material is particularly remarkable when the polymerization degree of the organosiloxane unit of the novel co-modified organopolysiloxane according to the present invention is a polymer having a molecular weight of 200 or more. Can be gelled.
- a co-modified organopolysiloxane having a degree of polymerization of an organosiloxane unit of about 30 to 150 can be used as a thickener for an oil component in a dosage form where gelation is not desired. It is useful as a thickener for oily raw materials used in cosmetics.
- the degree of gelation can be controlled by the amount of these components used.
- the novel co-modified organopolysiloxane according to the present application is remarkably excellent in compatibility with various oily raw materials, it has an advantage that it does not cause a phase separation problem even when mixed with an oil agent other than silicone.
- the oily raw material is a component that is thickened / gelled by a thickener or gelling agent comprising the novel co-modified organopolysiloxane according to the present invention, and is an oily raw material used for external preparations or cosmetics. There is no particular limitation as long as it is present.
- a particularly suitable oily raw material is an oil agent, and (D1) at least one oil agent selected from solid oil, pasty oil, silicone oil, hydrocarbon oil, and ester oil can be suitably exemplified.
- the oily raw material thickened / gelled by the thickener or gelling agent according to the present invention is more preferably (D1-1) silicone oil, hydrocarbon oil or ester oil which is liquid at 5 to 100 ° C.
- One or more oil agents selected from These oils are thickened or gelled by combining one or two or more kinds selected from known vegetable oils, animal fats, higher alcohols, liquid fatty acids, triglycerides, and artificial sebum. be able to.
- the silicone oil as component (D) 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 is a hydrogen atom, a hydroxyl group or a monovalent unsubstituted or fluorine-substituted alkyl group having 2 to 30 carbon atoms, an aryl group, an amino-substituted alkyl.
- m is an integer from 0 to 1000
- n is an integer from 0 to 1000
- m + n is an integer from 1 to 2000
- x is 0, 1, 2, or 3
- p and q are integers from 0 to 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 (D) 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.
- Component ester oils 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-ethylhexanoate, tri
- oils and fats include oils and fats, higher alcohols and higher fatty acids.
- Natural animal and vegetable oils and semi-synthetic oils include avocado oil, linseed oil, almond oil, ibotarou, eno oil, olive oil, cacao butter, kapok wax, kayak oil, carnauba wax, liver oil, candelilla wax, beef tallow, beef leg fat, beef bone Fat, hydrogenated beef tallow, Kyonin oil, whale wax, hydrogenated oil, wheat germ oil, sesame oil, rice germ oil, rice bran oil, sugarcane wax, sasanqua oil, saflower oil, shea butter, cinnamon oil, cinnamon oil, jojoballow, olive Squalane, shellac wax, turtle oil, soybean oil, tea seed oil, camellia oil, evening primrose oil, corn oil, lard, rapeseed oil, Japanese kiri oil, nukarou, germ oil, horse fat, persic oil, palm oil, palm kernel oil , Castor oil, hydrogenated castor oil, castor oil fatty acid methyl ester, sunflower oil, grape oil, bayberry wax
- higher alcohols examples 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.
- higher fatty acids examples 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.
- the thickener or gelling agent of the oily raw material of the present invention is mixed with the above oily raw material using a known means to thicken or gel these oily raw materials to form a gel composition.
- other components can be further blended, and as will be described later, a composition for producing a cosmetic composition (premix) for preparing an aqueous composition It can be used as a gel composition.
- the thickener or gelling agent of the oily raw material of the present invention is added or uniformly dispersed in a previously prepared external preparation or cosmetic, and the oily raw material contained in the external preparation is thickened or gelled. can do.
- thickening or gelling cosmetic oils it is possible to moderate the viscosity and hardness of cosmetics and to improve their appearance, blendability, and feeling of use, and to achieve desired dosage forms and cosmetic forms. Can be implemented.
- the amount used and the compounding ratio are not particularly limited, but it is preferably in the range of 1 to 99% by mass with respect to the total mass including the oily raw material, in particular. It is preferably in the range of 5 to 40% by mass.
- the degree of thickening changes according to the blending amount to the oily raw material, the total viscosity including the oily raw material, the hardness of the gel composition obtained (expressed as gel viscoelasticity, elastic texture) (Which is a characteristic of cosmetics that can be used) can be controlled within a desired range.
- the co-modified organopolysiloxane according to the present invention can be used alone as a thickener or gelling agent for oily raw materials, but when used together with (B) powder or a colorant, thickening / gelling of the oily agent is possible.
- these powders can be stably and uniformly dispersed in the resulting thickened oil or oily gel, and there is no agglomeration or sedimentation of the powder especially in mixed oil systems.
- a powder dispersion in oil having excellent stability can be provided. Furthermore, after applying the powder dispersion in oil to the skin, it can maintain an excellent cosmetic effect and a natural skin sensation without discomfort for about a day, and exhibits an excellent dispersion / fixation function. be able to.
- the component (B) is a powder or a colorant, and is a powder or a colorant mainly used for cosmetics. These powders or colorants are used for ordinary cosmetics. If there is any, its shape (spherical, rod-like, needle-like, plate-like, indeterminate shape, spindle shape, etc.), particle size (smoke-like, fine particles, pigment grade, etc.), particle structure (porous, non-porous, etc.) Any of these can be used, but when these powders and / or colorants are blended as pigments, inorganic pigment powders, organic 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 resin powders.
- the powder or colorant examples include inorganic powder, organic powder, surfactant metal salt powder (metal soap), colored pigment, pearl pigment, organic modified viscosity mineral, metal powder pigment, and the like.
- a composite of these 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, zeolite
- inorganic powders include 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 their composites.
- the inorganic ultraviolet protection component may be formulated with the above-mentioned inorganic powder pigment, metal powder pigment or the like as an ultraviolet dispersant, such as titanium oxide, zinc oxide, cerium oxide, Examples thereof include metal oxides such as titanium suboxide and iron-doped titanium oxide, metal hydroxides such as iron hydroxide, metal flakes such as plate-like iron oxide and aluminum flakes, and ceramics such as silicon carbide.
- 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.
- 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.
- silicone rubber spherical powder (sometimes referred to as silicone elastomer spherical powder), those having a primary particle diameter in the range of 0.1 to 50 ⁇ m are preferable.
- silicone rubber spherical powders include Trefill E-506S, Trefill E-508, 9701, Cosmetic Powder, 9702 Powder manufactured by Toray Dow Corning.
- Silicone rubber spherical powder can also be used in the cosmetic composition of the present invention in the form of an aqueous dispersion. Examples of such commercially available aqueous dispersions include BY29-129 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.
- these powders 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.
- Examples of such a water repellent treatment include those obtained by treating the powder and / or colorant with various water repellent surface treatment agents, such as methyl hydrogen polysiloxane treatment, silicone resin treatment, Silicone gum treatment, acrylic silicone treatment, organosiloxane treatment such as fluorinated silicone treatment, metal soap treatment such as zinc stearate treatment, silane coupling agent treatment, silane treatment such as alkylsilane treatment, perfluoroalkylsilane, perfluoroalkyl Fluorine compound treatment such as phosphate 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. Used in combination with one or more of Rukoto is possible.
- various water repellent surface treatment agents such as methyl hydrogen polysiloxane treatment, silicone resin treatment, Silicone gum treatment, acrylic silicone treatment, organosiloxane treatment such as fluorinated
- silicone-based powders such as silicone resin powder and silicone rubber powder, which have excellent oil-absorbing ability of oil components, and organic resin powders such as silk powder, nylon powder, polymethyl methacrylate powder, and polyethylene powder.
- silicone-based powders such as silicone resin powder and silicone rubber powder
- organic resin powders such as silk powder, nylon powder, polymethyl methacrylate powder, and polyethylene powder.
- the blending amount of component (B) can be selected according to the dosage form and the form of the cosmetic, but is 0.1 to 99% by mass of the entire gel composition comprising the oily raw material and the co-modified organopolysiloxane according to the present invention. This range is preferred.
- the gel-like composition containing these powders or colorants can also be used as a gel-like cosmetic as it is, and the blending amount in the case of the gel-like cosmetic is in the range of 10 to 50% by mass of the whole cosmetic. Is preferred.
- powder or colorant can be blended in the range of 50 to 80% by mass.
- the gelling agent containing the co-modified organopolysiloxane according to the present invention further includes (C) a silicone-based surfactant (excluding those corresponding to the component (A)), a crosslinkable organopolysiloxane, and a silicone. At least one selected from the group consisting of a resin, an acrylic silicone dendrimer copolymer, a polyamide-modified silicone, an alkyl-modified silicone wax, and an alkyl-modified silicone resin wax can be blended. These components (C) are excellent in compatibility with the mixture of the co-modified organopolysiloxane according to the present invention and the oily raw material, and can be stably blended in the gel composition.
- the silicone-based surfactant is a silicone-based surfactant other than the co-modified organopolysiloxane according to the present invention.
- Such silicone surfactants are emulsifying and cleaning components for oils, and are typically polyoxyalkylene-modified silicones, polyglyceryl-modified silicones, glyceryl-modified silicones, sugar-modified silicones, fluorine-based surfactants, polyoxyethylene poly Examples thereof include oxypropylene block polymers and alkylpolyoxyethylene / polyoxypropylene block polymer ethers.
- Preferred silicone surfactants include linear polyoxyalkylene-modified organopolysiloxane (polyether-modified silicone in which polyoxyalkylene groups are bonded to the side chain and / or terminal), block copolymer type polyoxy Alkylene / dimethylpolysiloxane copolymer, linear polyoxyalkylene / alkyl co-modified organopolysiloxane (alkyl / polyether-modified silicone with polyoxyalkylene group and alkyl group bonded to side chain and / or terminal) And the like.
- specific elastomer silicone polyethers described in Japanese Patent No. 4080597 Japanese Patent Laid-Open No. 11-49957
- Japanese Patent Laid-Open No. 2001-011281, etc. commercially available products include DC 9011 Silicone Elastomer Blend, Dow Corning, USA
- Mode is also preferably exemplified.
- the crosslinkable organopolysiloxane preferably has a structure in which the organopolysiloxane chain is three-dimensionally cross-linked by reaction with a crosslinkable component or the like and does not have a hydrophilic part such as a polyoxyalkylene unit and is non-emulsifiable. .
- 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 is used as a surfactant or a surfactant aid. Since it functions, 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.
- an MQ resin comprising any combination of trialkylsiloxy units (M units), dialkylsiloxy units (D units), monoalkylsiloxy units (T units), and tetrafunctional siloxy units (Q units).
- MDQ resin, MTQ resin, MDTQ resin, TD resin, TQ resin, and a solid silicone network compound that is a TDQ resin are preferable.
- 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
- acrylic silicone dendrimer copolymer examples include vinyl polymers having a carbosiloxane dendrimer structure in the side chain described in Japanese Patent No. 4009382 (Japanese Patent Laid-Open No. 2000-063225).
- the Examples of 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%.
- polyamide-modified silicone examples include siloxane-based polyamides described in US Pat. No. 5,981,680, and commercially available products include 2-8178 Gelrant, 2-8179 Gelrant, etc. (manufactured by Dow Corning, USA). .
- Such a polyamide-modified silicone is useful as a thickening / gelling agent for oily raw materials, particularly silicone oil, as well as an oil-soluble gelling agent.
- 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 organopolysiloxane 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 examples include silsesquioxane resin wax described in JP-T-2007-532754.
- 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 gel-like cosmetic is further selected from the group consisting of an arbitrary amount of (E) a lower monohydric alcohol and an organic polyhydric alcohol compound.
- the gel composition includes (F) an ultraviolet absorber, (G) at least one compound selected from sucrose fatty acid ester and polyglycerin fatty acid ester, (H) an organic film-forming agent, J) At least one compound selected from the group consisting of amino acids and / or salts thereof, inorganic salts, organic acids and / or salts thereof, and water-soluble polymers can be blended, and these components are contained. It is possible to easily and stably obtain a gel cosmetic composition.
- the gel composition according to the present invention is a cosmetic preparation composition (premix) for preparing a water-containing cosmetic, and is stable by a simple stirring device and mixing device without using a special high-pressure emulsification device.
- a water-containing cosmetic can be formed, and optimization studies of emulsification and dispersion conditions are almost unnecessary.
- the cosmetic produced using the gel composition according to the present invention is a water-containing cosmetic, particularly a water-in-oil emulsion cosmetic, which has excellent stability over time, feel, moisture retention, product appearance, and the like. And a water-containing cosmetic comprising the above-mentioned components in a stable and easy manner.
- the component (E) is at least one compound selected from the group consisting of lower monohydric alcohols and organic polyhydric alcohol compounds, and the gel composition containing the component further has a self-emulsifying property.
- 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.
- 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 a preferred embodiment of the present invention.
- Component (E) is preferably ethanol, isopropanol, 1,3-butylene glycol, sorbitol, dipropylene glycol, glycerin or polyethylene glycol, and can improve the stability of the emulsion.
- 1,3-butylene glycol, sorbitol, dipropylene glycol, glycerin, and polyethylene glycol are more preferable because they also have a moisturizing effect.
- the mass ratio of ethanol to a physiologically acceptable hydrophilic medium other than ethanol is preferably 6/4 or more from the viewpoint of the self-emulsifying property of the gel composition.
- 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.
- a water-soluble component such as a water-soluble ionic surfactant can be previously dispersed in water and blended in the gel composition.
- the cosmetic according to the present invention is a cosmetic produced by mixing the above gel composition with additional water, particularly a water-in-oil emulsion cosmetic, It contains both the water contained in the gel composition as the composition for preparing a cosmetic and the water added during the production of the cosmetic. Needless to say, these waters cannot be distinguished in cosmetics.
- the gel composition according to the present invention preferably comprises (A) 10 to 70% by mass of a thickener or gelling agent of the oily material according to the present invention, (D) 30 to 80% by mass of the oily material, E) A gel-like composition comprising 0 to 20% by mass of at least one compound selected from the group consisting of lower monohydric alcohols and organic polyhydric alcoholic compounds and 0 to 20% by mass of water.
- the gel composition according to the present invention is more preferably (A) 20 to 50% by mass of the thickener or gelling agent of the oily material according to the present invention, and (D) 40 to 60% by mass of the oily material. (E) A gel-like composition comprising 5 to 15% by mass of at least one compound selected from the group consisting of lower monohydric alcohols and organic polyhydric alcoholic compounds and 5 to 15% by mass of water. .
- the ultraviolet protection component includes an inorganic ultraviolet protection component and an organic ultraviolet protection component.
- the inorganic ultraviolet protection component is an ultraviolet dispersant containing the inorganic powder pigment, metal powder pigment, etc.
- the organic ultraviolet protection component is homomenthyl salicylate, Salicylic acid systems such as octyl salicylate, triethanolamine salicylate; paraaminobenzoic acid, ethyldihydroxypropylparaaminobenzoic acid, glycerylparaaminobenzoic acid, octyldimethylparaaminobenzoic acid, amyl paradimethylaminobenzoate, 2-ethylhexyl paradimethylaminobenzoate, etc.
- Salicylic acid systems such as octyl salicylate, triethanolamine salicylate
- paraaminobenzoic acid ethyldihydroxypropylparaaminobenzoic acid
- glycerylparaaminobenzoic acid octyldimethylparaaminobenzoic acid
- amyl paradimethylaminobenzoate 2-ethylhexyl paradimethylaminobenzoate, etc
- 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 a thickening / gelling agent having an emulsifying function, and a medium polar oil such as an ester oil.
- a binder to obtain a W / O gel emulsion cosmetic that is stable even when the oil phase contains a low-polar oil such as silicone oil or hydrocarbon oil. it can.
- 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.
- the polymer powder may or may not be hollow, the average primary particle diameter may be in the range of 0.1 to 50 ⁇ m, and the particle size distribution may be broad or sharp.
- the polymer include acrylic resin, methacrylic resin, styrene resin, polyurethane resin, polyethylene, polypropylene, polyethylene terephthalate, silicone resin, nylon, and acrylamide resin.
- a polymer powder containing an organic UV protection component in a range of 0.1 to 30% by mass is preferable, and a polymer powder containing 4-tert-butyl-4′-methoxydibenzoylmethane, which is a UV-A absorber, is particularly preferable. preferable.
- Sucrose fatty acid ester or polyglycerin fatty acid ester is a component that functions as a nonionic surfactant, and fatty acids preferably have 12 or more carbon atoms, more preferably 12 to 20 carbon atoms. These are useful for further improving the stability of the high internal aqueous phase W / O gel emulsion cosmetic.
- sucrose fatty acid esters include sucrose dioleate, sucrose distearate, sucrose dipalmitate, sucrose dimyristate, sucrose dilaurate, sucrose monooleate, Examples thereof include sucrose monostearate, sucrose monopalmitate, sucrose monomyristic ester, and sucrose monolaurate.
- the polyglycerin fatty acid ester includes polyglycerin having an average polymerization degree of 2 to 10 and fatty acids (for example, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, and linoleic acid). Esters with selected fatty acids).
- fatty acids for example, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, and linoleic acid.
- polyglycerol fatty acid esters include hexaglycerol monooleate, hexaglycerol monostearate, hexaglycerol monopalmitate, hexaglycerol monomyristate, hexaglycerol monolaurate, decaglycerol monooleate , Decaglycerin monostearate, decaglycerin monopalmitate, decaglycerin monomyristate, decaglycerin monolaurate, and the like. These fatty acid esters can be used alone or in combination.
- the organic film-forming agent is a component that forms a polymer film on the skin or hair, and examples include polyvinyl alcohol, polyvinyl pyrrolidone, polyalkyl acrylate copolymer, and silicone raw rubber (also referred to as silicone gum). Can do.
- the silicone raw rubber has a substituted or unsubstituted organopolysiloxane having a dialkylsiloxy unit (D unit), such as dimethylpolysiloxane, methylphenylpolysiloxane, methylfluoroalkylpolysiloxane, or the like, or a micro-crosslinked structure thereof.
- D unit dialkylsiloxy unit
- dimethylpolysiloxane raw rubber having a polymerization degree of 3,000 to 20,000 is preferable.
- 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.
- At least one compound selected from the group consisting of amino acids and / or salts thereof, inorganic salts, organic acids and / or salts thereof, and water-soluble polymers is an optional component for external preparations or cosmetics. Depending on the function of the cosmetic, it can be appropriately blended.
- amino acids examples include amino acids such as glycine, valine, leucine, isoleucine, serine, threonine, phenylalanine, arginine, lysine, aspartic acid, glutamic acid, cystine, cysteine, methionine, tryptophan, and / or salts thereof.
- 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.
- 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 acids are acids such as acetic acid, lactic acid, citric acid, ascorbic acid, malic acid, tartaric acid, and organic acid salts include sodium acetate, potassium acetate, sodium ascorbate, etc.
- ⁇ -hydroxy acid salts such as sodium glycolate, sodium malate, sodium tartrate, sodium aspartate, potassium aspartate, magnesium aspartate, calcium aspartate, sodium glutamate, potassium glutamate, magnesium glutamate, calcium glutamate, arginine-glutamate
- amino acid salts such as ornithine-glutamate, lysine-glutamate, lysine-aspartate, ornithine-aspartate, sodium alginate, etc. It is.
- 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, hair, etc., improve the conditioning effect, etc. Any one of amphoteric, cationic, anionic, nonionic, and water-swelling clay minerals can be used as long as it is blended for the purpose of improving the viscosity and used in normal cosmetics. Alternatively, two or more types of water-soluble polymers can be used in combination. 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.
- amphoteric water-soluble polymers include amphoteric starch, dimethyldiallylammonium chloride derivatives (for example, acrylamide / acrylic acid / dimethyldiallylammonium chloride copolymer, acrylic acid / dimethyldiallylammonium chloride copolymer), and methacrylic acid derivatives (for example, And polymethacryloylethyldimethylbetaine, N-methacryloyloxyethyl N, N-dimethylammonium- ⁇ -methylcarboxybetaine / alkyl methacrylate copolymer, etc.).
- dimethyldiallylammonium chloride derivatives for example, acrylamide / acrylic acid / dimethyldiallylammonium chloride copolymer, acrylic acid / dimethyldiallylammonium chloride copolymer
- methacrylic acid derivatives for example, And polymethacryloylethyldimethylbetaine, N-methacryloyloxyethy
- cationic water-soluble polymers examples include quaternary nitrogen-modified polysaccharides (for example, cation-modified cellulose, cation-modified hydroxyethyl cellulose, cation-modified guar gum, cation-modified locust bean gum, cation-modified starch), dimethyldiallylammonium chloride derivatives ( For example, dimethyldiallylammonium chloride / acrylamide copolymer, polydimethylmethylenepiperidinium chloride, etc.), vinylpyrrolidone derivatives (for example, vinylpyrrolidone / dimethylaminoethyl methacrylate copolymer salt, vinylpyrrolidone / methacrylamidepropyltrimethylammonium chloride) Copolymer, vinylpyrrolidone / methylvinylimidazolium chloride copolymer, etc.), methacrylic acid derivatives (eg, methacryloylethyldimethyl)
- Anionic water-soluble polymers include polyacrylic acid or alkali metal salts thereof, polymethacrylic acid or alkali metal salts thereof, hyaluronic acid or alkali metal salts thereof, acetylated hyaluronic acid or alkali metal salts thereof, methyl vinyl ether / anhydrous Water-soluble polymer of aliphatic carboxylic acid or its metal salt such as hydrolyzate of maleic acid copolymer, carboxymethyl cellulose or its alkali metal salt, methyl vinyl ether-maleic acid half ester copolymer, acrylic resin alkanolamine liquid, Carboxyvinyl polymers are exemplified.
- Nonionic water-soluble polymers include polyvinyl pyrrolidone, highly polymerized polyethylene glycol, PEG / PPG-36 / 41 dimethyl ether, PEG / PPG-14 / 7 dimethyl ether, vinyl pyrrolidone / vinyl acetate copolymer, vinyl pyrrolidone / dimethylamino.
- the water-swellable clay mineral is an inorganic water-soluble polymer and is a kind of colloid-containing aluminum silicate having a three-layer structure, and is generally exemplified by the following formula (1).
- X is Al, Fe (III), Mn (III), or Cr (III)
- Y is Mg, Fe (II), Ni, Zn, or Li
- Z is K, Na or Ca
- Specific examples of such inorganic water-soluble polymers include bentonite, montmorillonite, piderite, nontronite, saponite, hectorite, aluminum magnesium silicate, and silicic anhydride, which are natural and synthetic products. Any of these may be used.
- the gel composition composed of each of the above components is a homomixer, paddle mixer, Henschel mixer, homodisper, colloid mill, propeller stirrer, homogenizer, in-line continuous emulsifier, ultrasonic emulsifier, vacuum kneader, etc.
- the device can be mixed with water using mechanical force.
- the amount of water used and the blending ratio are not limited, but 100 parts by weight of the gel composition containing each of the above components and 0.1 to 4000 parts by weight of water, preferably 5 to 2000 parts by mass can be mixed.
- the resulting gel composition can take the form of an oil-in-water emulsion, a water-in-oil emulsion, etc., but is particularly useful in that it can stably form a water-in-oil emulsion. .
- 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 said emulsion composition can mix
- the emulsion composition containing these cosmetic raw material components is included by this invention.
- each component constituting the water phase and each component constituting the oil phase are independently mixed, and then the refractive index of both phases at room temperature is mixed.
- the difference By adjusting the difference to 0.0020 unit or less and emulsifying, the transparency can be adjusted. That is, in the present invention, the aqueous phase and the oil phase containing the component (A) and the oily raw material (D) are mixed independently, and then the difference in refractive index between the two phases at 25 ° C. is 0.0020 unit.
- a method for adjusting the transparency of an emulsion composition which comprises emulsifying by adjusting to the following, is included.
- the method for adjusting the transparency of the emulsion composition of the present invention includes the following procedures (i) to (iv).
- (I) The components of the oil phase containing the co-modified organopolysiloxane according to the present application and (D) the oily raw material are mixed by any method known in the art. At this time, the entire oil phase may be gelled or thickened. That is, as long as the water phase component is not included, the oil phase may be a gel composition. Similarly, each component constituting the aqueous phase is also mixed in a separate container.
- the refractive index (RI) of each phase is measured separately at room temperature (25 ° C.).
- 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.
- these water phase refractive index modifiers may be used in combination. That is, the component which is a part of the cosmetic raw material component can be suitably used as a 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.
- oils and fats usually used in cosmetics, higher alcohols, higher fatty acids, organic lipophilic surfactants, 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.
- 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.
- a method for easily obtaining an emulsion cosmetic can be provided. Specifically, 100 parts by weight of the gel composition containing each of the above components, 0.1 to 4000 parts by weight of water, and (K) 0.001 to 1.0 parts by weight of a physiologically active substance are mixed. Thus, an external preparation can be obtained.
- an emulsion cosmetic having excellent transparency can be obtained by adjusting the refractive indexes of the oil phase component and the water phase component.
- physiologically active substance examples include substances that impart some physiological activity to the skin when applied to the skin.
- antiperspirant active ingredient deodorant agent, anti-inflammatory agent, anti-aging agent, whitening agent, tanning agent, antioxidant, hair growth agent, hair growth agent, blood circulation promoter, antibacterial agent, disinfectant, desiccant, cooling sensation Agents, warming agents, vitamins, amino acids, wound healing promoters, stimulation relieving agents, analgesics, cell activators, enzyme components, and the like.
- physiologically active substances are anti-inflammatory agents, anti-aging agents, whitening agents, hair growth agents, hair growth agents, blood circulation promoters, antibacterial agents, bactericidal agents, vitamins, wound healing promoters, stimulation relieving agents, analgesics.
- physiologically active substances selected from the group consisting of agents, cell activators and enzymes.
- the cosmetic according to the present invention is an antiperspirant, or depending on the purpose, it is preferable to blend an antiperspirant active ingredient and a deodorant agent.
- 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-lauroyl sarcosine potassium, trimethylammonium chloride, 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); dia
- 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. More specifically, including various extracts, fragrances extracted from flowers, seeds, leaves, roots, etc. of various plants, fragrances extracted from seaweeds, fragrances extracted from animal parts or secretions (eg, Potato, sperm), and artificially synthesized fragrances (eg, menthol, musk, acetate, vanilla).
- 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, for example, Ashitaba extract, Avocado extract, Achacha extract, Altea extract, Arnica extract, Aloe extract, Apricot extract, Apricot extract, Ginkgo biloba extract, Fennel extract, Turmeric extract, Oolong tea extract, Ages extract, Echinashi Leaf extract, Ogon extract, Oat extract, Oen extract, Barley extract, Hypericum extract, Odrianthus extract, Dutch mustard extract, Orange extract, Seawater extract, 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, Kumazasaeki , Clara extract, walnut extract, grapefruit extract, clematis extract, chlorella extract, mulberry extract, gentian extract, tea extract, yeast extract, burdock extract, rice bran extract, rice germ oil
- biopolymers such as deoxyribonucleic acid, mucopolysaccharide, sodium hyaluronate, sodium chondroitin sulfate, collagen, elastin, chitin, chitosan, hydrolyzed eggshell membrane, hormones such as estradiol and ethenylestradiol, sphingolipids, ceramide, cholesterol Derivatives, oil components such as phospholipids, ⁇ -aminocaproic acid, glycyrrhizic acid, ⁇ -glycyrrhetinic acid, lysozyme chloride, guaiazulene, hydrocortisone, allantoin, tranexamic acid, azulene and other anti-inflammatory agents, vitamins A, B2, B6, C, Vitamins such as D, E, calcium pantothenate, biotin, nicotinamide, vitamin C ester, allantoin, diisopropylamine dich
- 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
- surfactants can be further blended as necessary.
- it is selected from the group consisting of an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, and a semipolar surfactant. Species or two or more surfactants can be used in combination.
- a silicone-based nonionic surfactant since the stability as a whole preparation can be improved, it is preferable to use a 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 mass with respect to the entire cosmetic.
- the external preparation, gel cosmetic or cosmetic 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.
- the cosmetic according to the present invention is a cosmetic for washing skin or hair, it can be blended within the range of 0.1 to 90% by mass of the entire cosmetic for the purpose of improving cleaning properties, From the viewpoint of detergency, it is also preferable to blend a surfactant component of 25% by mass or more.
- saturated or unsaturated fatty acid salts for example, sodium laurate, sodium stearate, sodium oleate, sodium linolenate, etc.
- alkyl sulfates for example, 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 Alkylenesulfosuccinic acid alkyl ester salts, polyoxyalkylene alkylphenyl ether sulfates, alkane sulfonates, octyltrimethylammonium
- 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
- silicone surfactants that are polyoxyalkylene-modified silicone, polyglyceryl-modified silicone, and glyceryl-modified silicone are preferably those in which alkyl branching, linear silicone branching, etc. are applied simultaneously with hydrophilic groups as needed. Can be 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.
- the external preparation and cosmetics of the present invention include various components such as oil-soluble gelling agents, pH adjusters, antioxidants, chelating agents, moisturizing components, and perfumes. Can be used within a range not impairing the above.
- 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.
- 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.
- the chelating agent has an action of insolubilizing mineral ions in water, and examples thereof include EDTA, alanine, sodium edetate, sodium polyphosphate, sodium metaphosphate, and phosphoric acid.
- 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. .
- the moisturizing component examples include hyaluronic acid, chondroitin sulfate, pyrrolidone carboxylate, polyoxyethylene methyl glucoside, polyoxypropylene methyl glucoside and the like. Needless to say, the aforementioned polyhydric alcohols and the like exhibit a moisturizing 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 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 color products, hair nourishing products, hair rinse products, hair conditioner products, hair treatment products, etc .; hair cosmetic products; bath cosmetics.
- skin products such as skin cleanser products, skin care products, makeup products, antiperspirant products, UV protection products
- hair cleanser products hair styling products, Hair color products, hair nourishing products, hair rinse products, hair conditioner products, hair treatment products, etc .
- hair cosmetic products bath cosmetics.
- Examples of the external preparation of the present invention include, but are not limited to, hair growth agents, hair growth agents, analgesics, bactericides, anti-inflammatory agents, cooling 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.
- cleansing gels cleansing creams, cleansing foams, facial cleansing creams, eye makeup removers, facial cleansing foams, liquid soaps (body soaps), hand soaps, gel-like soaps, shaving creams, light removal liquids, acne prevention cosmetics, etc.
- Skin cleanser products skin cream, scalp treatment, skin milk, milk lotion, emulsion, facial pack, body powder, essence, shaving lotion, massage, etc .; skin care products; foundation, liquid foundation, oily foundation, make-up Makeup products such as up base, white powder, face powder, lip balm, rim cream, lip gloss, eye cream, eyebrows, eyelash cosmetics; antiperspirants such as deodorants; sunscreen Agents, ultraviolet protection products such as tanning agent (tanning agent) are exemplified.
- tanning agent tanning agent
- the above-mentioned cosmetics for hair include hair cleaning agents such as shampoos and rinse-in shampoos; hair-styling products such as hair waxes, hair curl retention agents, setting agents, hair creams, hair sprays and hair liquids; hair dyes and hair color sprays. Hair color rinses, hair color sticks and other hair coloring products; hair tonics, hair treatment essences, hair nourishing products such as hair packs; oil rinses, cream rinses, treatment rinses, hair conditioners, hair treatments, hair rinses or hair A conditioning product is illustrated.
- the bath cosmetic is exemplified by a foam bath.
- the form of the cosmetics and cosmetics 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, and paste. It can be preferably applied to gel, powder, multilayer, mousse, mist, granule, flake, and meteorite. Particularly preferred forms are W / O cream, solid, paste, gel, and powder, and cosmetics that make use of the viscous or gelled properties by the gelling agent and thickener of the present invention and Cosmetic forms are useful.
- the cosmetics and cosmetic containers according to the present invention are not particularly limited, and jars, pumps, tubes, bottles, pressure can discharge containers, pressure-resistant aerosol containers, light-shielding containers, compact containers, metal plates, stick containers, feeding An arbitrary container such as a container, a spray container, or a container with a partition provided with a mixed solution discharge port can be filled.
- An arbitrary container such as a 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 easily in ordinary silicone preparations
- the cosmetics and cosmetics according to the present invention are excellent in stability, so that they can be stably stored even when filled in such tube containers. There is a merit.
- the co-modified organopolysiloxane according to the present invention is a gelling agent or thickening agent having excellent versatility, and can be widely used as a composition applied to the human body as a cosmetic or a medicine. is there. 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 emulsion type gel antiperspirants, stick 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 gel antiperspirant composition In the water-in-oil emulsion type gel antiperspirant which is an embodiment of the present invention, an oil phase component containing a co-modified organopolysiloxane (co-modified organopolysiloxane, volatile oil, non-volatile oil, solubilizer)
- the oily cosmetic raw material) and the aqueous phase component are mixed by any method.
- the co-modified organopolysiloxane of the present invention can give a natural feeling of application without a moisturizing feeling and an uncomfortable feeling when blended with a water-in-oil emulsion type gel antiperspirant.
- 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 gel antiperspirant having excellent transparency can be obtained by using the above-described method for adjusting the transparency of the emulsion.
- the amount of the volatile oil that is the base oil of the water-in-oil emulsion type gel antiperspirant is 5 to 40 parts, preferably 10 to 30 parts, more preferably even when the total composition is 100 parts by mass. 15 to 20 parts.
- the volatile oil among those exemplified as the component (D) 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.
- non-volatile oil agent among those exemplified as the “oil-based raw material” in the present invention, those not corresponding to the above “volatile oil”, component (C) in the present invention, ether oil such as dioctyl ether, dioctyl carbonate and dioctadecyl Examples include carbonate ester oils such as carbonate, ester oils such as neopentyl glycol dicaprate, polyalkylene glycol and derivatives thereof. These have an emollient effect and an effect of adjusting the feel and form of the water-in-oil emulsion type gel antiperspirant.
- 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 gel antiperspirant of the present invention, a solubilizer can also be used.
- it is selected from an oil agent used as a base oil, an oil agent used as the refractive index adjusting agent, and an 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 that may be present in the water-in-oil emulsion type gel antiperspirant of the present invention may be the components (F), (G), (H), (J) 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.
- the surfactants already exemplified may be added to the water-in-oil emulsion type gel antiperspirant of the present invention.
- These include any hydrophilic emulsifier with an HLB greater 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 the solid antiperspirant composition. If the gel-like antiperspirant composition according to the present invention contains the gelling agent or thickener, water such as a solid W / O emulsion is contained.
- the composition may be in the form of an external preparation that does not substantially contain water.
- 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.
- these non-volatile oils can be used, and contained in the total composition in an amount of 1 to 30% by weight, preferably 5 to 15% by weight.
- the non-aqueous stick-like antiperspirant composition according to the present invention is preferable because it can further contain a wax and the high-temperature stability is improved.
- wax include the component (D), fats and oils, and higher fatty acids that are solid at room temperature.
- 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. can be exemplified, and 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.
- non-aqueous stick-type antiperspirant composition is the components (F), (G), (H), and (J) described above.
- the proportion is usually from about 0 to about 8 parts based on the total amount of the composition, 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 co-modified organopolysiloxane can be blended in the form of the gel composition described above.
- 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 (B) and (C) 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.
- Preferred polyhydric alcohols are the components exemplified as “the refractive index adjuster of the aqueous 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.
- Silicone Compound No. Synthesis of 1 Reactor is represented by 196.6 g of methyl hydrogen polysiloxane represented by the average structural formula MD 400 DH 10 M, represented by the average structural formula CH 2 ⁇ CH—Si (OSiMe 3 ) 3 13.6 g of vinyltristrimethylsiloxysilane, 5.5 g of glycerol monoallyl ether represented by the structural formula CH 2 ⁇ CH—CH 2 —OCH 2 CH (OH) CH 2 OH, 90 g of isopropyl alcohol (hereinafter abbreviated as IPA) Was heated to 70 ° C. with stirring under a nitrogen stream.
- IPA isopropyl alcohol
- a novel glycerin-modified silicone having a siloxane dendron structure represented by an average structural formula MD 400 D R * 31 5 D R * 21 5 M is obtained by heating the reaction solution under reduced pressure to distill off the low boiling point component ( A composition containing silicone compound No. 1) was obtained.
- 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
- This composition was a pale yellow translucent uniform viscous liquid.
- Silicone Compound No. Synthesis of 2 Reactor is represented by 198.7 g of methyl hydrogen polysiloxane represented by average structural formula MD 400 DH 10 M, and represented by average structural formula CH 2 ⁇ CH—Si (OSiMe 3 ) 3 8.2 g of vinyltristrimethylsiloxysilane, 5.6 g of glycerol monoallyl ether represented by the structural formula CH 2 ⁇ CH—CH 2 —OCH 2 CH (OH) CH 2 OH, 2.4 g of 1-decene, and 90 g of IPA are charged. The mixture was heated to 70 ° C. with stirring under a nitrogen stream.
- the polyglycerin monoallyl ether is synthesized by ring-opening polymerization of 3 moles of glycidol per mole of glycerin monoallyl ether, and has a structure in which glycerin is added in an average of 4 moles. . Since glycerin monoallyl ether has two hydroxyl groups and glycidol can react with both, the polyglycerin part 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 composition was a milky white uniform gum.
- reaction solution 2 g was sampled, and it was confirmed that the reaction rate reached 85% by the alkali decomposition gas generation method.
- 1.2 g of 1-decene and 0.06 g of 5 wt% IPA solution of chloroplatinic acid were added, and the reaction was continued at 80 ° C. for 3 hours. When the reaction solution was collected again and confirmed, the reaction was complete.
- reaction solution 2 g was sampled, and it was confirmed that the reaction rate reached 65% by the alkali decomposition gas generation method.
- 7.0 g of 1-decene and 0.06 g of 5 wt% IPA solution of chloroplatinic acid were added, and the reaction was continued at 80 ° C. for 3 hours.
- the reaction solution was collected again and confirmed, the reaction was complete.
- the polyglyceryl eugenol is synthesized by ring-opening polymerization of 4 moles of glycidol with respect to 1 mole of eugenol, and has a structure in which 4 moles of glycerin are added on average.
- the polyglycerin moiety can include not only a chain structure but also a branched structure.
- reaction solution was sampled, and it was confirmed that the reaction rate reached 65% by the alkali decomposition gas generation method. 6.8 g of 1-decene and 0.06 g of 5 wt% IPA solution of chloroplatinic acid were added and the reaction was continued at 80 ° C. for 4 hours. When the reaction solution was collected again and confirmed, the reaction was complete.
- Comparative Silicone Compound RE1 The reactor is represented by 89.9 g of methyl hydrogen polysiloxane represented by the average structural formula MD 63 DH 22 M, and represented by the average structural formula CH 2 ⁇ CH—CH 2 —O (C 2 H 4 O) 10 H. 36.4 g of allyl polyether, 73.7 g of 1-hexadecene and 60 g of toluene were charged, and the mixture was heated to 40 ° C. with stirring under a nitrogen flow.
- composition containing an alkyl / linear siloxane / polyglycerin co-modified silicone represented by an average structural formula MD 61 D R * 13 12 D R * 41 2 D R * 27 1 M I got a thing.
- R * 13 -C 12 H 25
- R * 41 -C 2 H 4 SiMe 2 (OSiMe 2) 6
- OSiMe 3 -C 3 H 6 O-X
- X is triglycerol partial
- This composition was a translucent uniform liquid substantially colorless.
- Comparative silicone compound RE7 A reactor was charged with 187.0 g of flaky ⁇ -olefin (average carbon number of 30 or more), and heated to 80 ° C. with stirring under a nitrogen stream to be dissolved. Platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of ligand solution (Pt concentration 22 wt%) was added 0.8 mg, expressed in average structural formula MD H 15 M under stirring 13.0 g of methyl hydrogen polysiloxane was added dropwise over 30 minutes. The reaction temperature was controlled at 120 ° C. and the reaction was continued for 3 hours. Sampling was performed, and it was confirmed that the residual Si—H group concentration was within specifications, and the reaction was terminated.
- composition containing an alkyl-modified silicone wax represented by an average structural formula MD R * 14 15 M was obtained.
- R * 14 -C 30 H 61 or more long-chain alkyl group.
- Comparative silicone compound RE8 (amino acid derivative-modified silicone) (Manufactured according to the method described in Patent Document 8, Production Example 1)
- 20.1 g of N ⁇ -lauroyl-L-lysine was suspended in 205 ml of ethanol. After cooling the reaction solution with ice, dry hydrogen chloride gas was introduced until saturation, and the mixture was stirred for 6 hours. Next, ethanol was distilled off, 250 ml of diisobutyl ether was added, and after suction filtration, 300 ml of purified water was added. To this solution, 55 g of morpholine dissolved in 70 ml of purified water was slowly added with stirring, and the precipitated white powder was filtered off.
- the obtained white powder was recrystallized from n-hexane to obtain 20.1 g of N ⁇ -lauroyl-L-lysine isobutyl ester.
- (2) 150 g of purified water was added to 45.5 g of sodium azide, and the mixture was stirred to obtain a completely homogeneous solution while cooling in ice water.
- a solution prepared by mixing 101.4 g of 10-undecenoyl chloride and 150 ml of acetone was added dropwise little by little so that the temperature of the solution was in the range of 10 to 15 ° C. After completion of the addition, the mixture was stirred at around 12 ° C. for 1 hour. The solution was then transferred to a separatory funnel and the aqueous and organic layers were separated.
- the organic layer was slowly added to 500 ml of toluene maintained at 60 ° C., and stirred at a temperature in the range of 50-60 ° C. for 3 hours. After distilling off toluene, 73.2 g of 10-undecenoyl isocyanate was obtained by distillation under reduced pressure.
- the obtained transparent rubber-like solid was dissolved by heating in 1000 g of hexane, followed by hot filtration. After removing hexane from the filtrate, a solid was obtained. Next, the obtained solid is finely pulverized, filtered with suction while thoroughly washing with hexane at 25 ° C., and then dried under reduced pressure to obtain a powdery lysine derivative-modified silicone (N ⁇ -lauroyl-L-) represented by the following formula. 20.3 g of lysine isobutyl ester derivative-modified silicone) was obtained.
- composition formulas of “silicone compound No. 1” to “silicone compound No. 12” according to the present invention synthesized by the above-described method and “comparative silicone compound RE1” to “comparative silicone compound RE7” according to comparative examples are as follows. Summarize as follows. The structure of “Comparative Silicone Compound RE8” is as described in the previous paragraph.
- Tables 2 to 12 show the evaluation results regarding the formulation and thickening / gelation.
- the “concentration” in the table represents wt% of the modified silicone compound.
- surfaces the kind of oil agent is shown using the following abbreviations on account of space.
- a ratio is shown in (). For example, an oil agent system in which oil agent A and oil agent B are blended at 70:30 is expressed as “A / B (70:30)”.
- FA 4002 ID is a 40 wt% isododecane solution of (acrylates / polytrimethylsiloxy methacrylate) copolymer
- DC 593 is a 33 wt% dimethyl polysiloxane (100 CST) solution of trimethylsiloxysilicate.
- Example 16 to 18, Comparative Example 14 Gel composition
- a gel composition was prepared by mixing the compositions shown in Table 18 using a homodisper mixer according to the following procedure. In the table, the numerical value indicates the number of added parts (parts by mass). Moreover, the obtained gel-like composition was evaluated using the following reference
- Preparation Procedure A Components 1 to 6 were put in a container, heated at 60 ° C., mixed and dissolved uniformly. B. The temperature was returned to room temperature, and component 7 was added to A and mixed and dispersed uniformly. C. While stirring B at a homodisper mixer of 1200 rpm, component 8 was added dropwise little by little, and the addition of water was stopped when the mixture changed from thickening to gel. D. Stirring is continued for 1 minute and the preparation is completed. The amount of water added until gelation (wt%) was recorded. Note) Since the required amount of water until gelation differs depending on the structure of the silicone compound used, the total amount of the gel composition was slightly different for each formulation.
- Test procedure The properties (whether gelation was possible) of the obtained composition were determined by visual observation and tactile sensation. 2. Tactile sensation and skin sensation were determined 5 minutes after 0.10 g of the gel composition was spread on the back of the hand. Furthermore, the appearance of the coated part was judged as good or bad.
- gel compositions were prepared by mixing the compositions shown in Tables 18 to 19 using a homodisper mixer according to the following procedure. In the table, the numerical value indicates the number of added parts (parts by mass). Moreover, the obtained gel-like composition was evaluated using the following reference
- Preparation Procedure A Ingredients 1 to 4 were placed in a container, heated at 60 ° C., mixed and dissolved uniformly. B. After returning to room temperature, Component 5 was added to A and mixed and dispersed uniformly. C. While stirring B at a homodisper mixer at 2500 rpm, component 6 was added dropwise little by little, and the addition of water was stopped when the mixture changed from thickening to gel. D. Continue stirring for 1 minute. E. While stirring at 500 rpm, components 7 to 10 were added to D in small portions. When all the components 7 to 10 were added, the mixture was stirred and mixed at 2500 rpm for 5 minutes so as to be uniform.
- Test procedure 0.15 g of the gel composition thus obtained was spread on the back of the hand, and the feel and feel during application to immediately after application were evaluated. Furthermore, the appearance (skin impression) of the application part was evaluated. 2. 20 minutes after application, “appearance of applied part (skin impression)”, “moisturizing feeling”, “powdered surface”, “wrinkle hiding effect”, “makeup satisfaction (overall evaluation)” Went.
- EP-9215 represents an organopolysiloxane elastomer spherical powder
- Benton 38 represents distearyldimethylammonium chloride-treated hectorite
- Aerosil 200 represents silica (anhydrous silicic acid).
- Examples 25 to 38 Gel composition
- a gel composition was prepared by mixing the compositions shown in Tables 21 to 24 using a homodisper mixer according to the following procedure. (The numbers in the table indicate the number of parts added (parts by mass).)
- Preparation Procedure A Components 1 to 6 were put in a container, heated at 60 ° C., mixed and dissolved uniformly. B. The temperature was returned to room temperature, and component 7 was added to A and mixed and dispersed uniformly. C. Ingredients 8 to 11 were placed in a separate container and stirred and mixed to dissolve. D. C was added little by little while stirring B at a homodisper mixer at 2500 rpm, and the addition was stopped when the mixture changed from thickening to gel. E. Continue stirring for 2 minutes. F. While stirring at 500 rpm, components 12 to 15 were added to E little by little. When the entire amount was charged, the mixture was stirred and mixed at 2500 rpm for 5 minutes so as to be uniform.
- D5 represents decamethylcyclopentasiloxane
- SS-3408 represents caprylyl methicone
- PEG represents polyethylene glycol
- Emulsified cosmetics were prepared by mixing the compositions shown in Table 25 and Table 26 using a homodisper mixer according to the following procedure.
- Preparation Procedure A Components 1 to 4 were put in a container, and stirring was started at 2500 rpm at room temperature with a homodisper mixer.
- B While stirring, Component 5 or a mixture of Component 5 and Component 6 was added over 10 minutes.
- C The deposits on the inner wall of the container were removed with a spatula, and the mixture was stirred and mixed again for 5 minutes so that the whole was uniform.
- Step 1 94.6 g of methylhydrogenpolysiloxane represented by an average composition formula MD 330 DH 80 M and vinyl tristrimethylsiloxy represented by an average composition formula CH 2 ⁇ CH—Si (OSiMe 3 ) 3 in a 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, it was heated under reduced pressure to distill off IPA and low boiling point.
- SS-3408 diluent caprylyl methicone
- Step 1 110.3 g of methylhydrogenpolysiloxane represented by average composition formula MD 330 DH 80 M and vinyl tristrimethylsiloxy represented by average composition formula CH 2 ⁇ CH—Si (OSiMe 3 ) 3 in the reactor 12.1 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 To the reaction solution, 8.0 g of polyglycerol monoallyl polyether, 0.02 g of natural vitamin E and 60 g of IPA were added, and 0.25 g of the same platinum catalyst solution as above was added.
- Step 3 15.1 g of 1-hexadecene was added to the reaction solution at about 65 ° C.
- 15.1 g of 1-hexadecene (second time) was added and reacted in the same manner.
- 15.2 g of 1-hexadecene (third time) and 0.25 g of a platinum catalyst solution were additionally charged, and the reaction was performed at 65 to 80 ° C. for 3 hours.
- Step 4 After adding 200 g of diluent caprylyl methicone (SS-3408) and dissolving it, it was heated under reduced pressure to distill off IPA and low boiling point. Further, after filtration, a novel polyglycerin-modified silicone having a siloxane dendron structure and a long-chain alkyl group represented by the average composition formula MD 330 D R * 12 45 D R * 31 30 D R * 22 5 M, and caprylyl A 50:50 (wt ratio) mixture with methicone was obtained.
- SS-3408 diluent caprylyl methicone
- R * 12 -C 16 H 33
- R * 31 -C 2 H 4 Si (OSiMe 3) 3
- R * 22 is —C 3 H 6 O—X
- X is a tetraglycerin moiety.
- the product was a milky white uniform gum.
- the polyglycerin monoallyl ether is synthesized by ring-opening polymerization of 3 moles of glycidol with respect to 1 mole of glycerin monoallyl ether, and has a structure in which glycerin is added in an average of 4 moles. . Since glycerin monoallyl ether has two hydroxyl groups and glycidol can react with both, the polyglycerin part includes not only a chain structure but also a branched structure.
- Examples 47 to 48 and Comparative Examples 15 to 16 show the results of preparing water-in-oil emulsion type transparent soft gel antiperspirants as examples of external preparations or cosmetics according to the present invention and evaluating their properties.
- a water-in-oil emulsion type transparent soft gel antiperspirant was prepared by mixing and emulsifying each component according to the following procedure with the formulation (composition) shown in Table 27.
- the co-modified organopolysiloxane (silicone compound) according to the present invention plays both a role as a thickening / gelling agent and a role as an emulsifier having a surfactant effect.
- “Stability” The appearance and form of the antiperspirant after the storage stability test were visually observed. ⁇ Translucent to transparent with no change in appearance or soft gel morphology. ⁇ Although the soft gel form was maintained, the transparency slightly decreased. ⁇ An opaque or non-uniform appearance was obtained. Or the form of the soft gel was not shown.
- Composition of Production Example 7 (containing silicone compound No. 7) 5.0 17.
- Red No. 104 (1) Aluminum Lake 1.0 18.
- Red No. 201 1.0 19.
- Red No. 202 1.0 20.
- Yellow No. 4 aluminum lake 1.0 21.
- B Fill a container to obtain a lipstick. (effect) The appearance color of lipstick is bright and the saturation is high.
- the color when actually applied to the lips is also a bright and vibrant color that is close to the appearance color of the lipstick itself. It can be applied naturally without a sense of incongruity, and a uniform finish is possible with no coating unevenness. It has good water resistance, water repellency, sweat resistance, long lasting makeup, and less color dullness.
- 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) There is no stickiness and a natural coating feel is obtained, and gloss on the lips is good. It has moderate occlusion and moisturizing properties and protects the lips from drying. It has good water resistance, water repellency, sweat resistance and good makeup.
- Component 23 is added to B and filled into a container to obtain a lipstick. (effect) Easy to apply when applied to lips. In addition, the feeling of use is not sticky and the gloss on the lips is also good. It has excellent water resistance, water repellency, and sweat resistance, and is excellent in long-lasting makeup because it does not easily cause color transfer, discoloration, or bleeding.
- Oil-based solid eye shadow (component) (Wt%) 1.
- Diisostearyl malate 6.0 Isotridecyl isononanoate 10.0 3. Liquid paraffin 10.0 4).
- Silicic anhydride (Aerosil 200) 1.2 7).
- Composition of Production Example 12 (containing silicone compound No. 12) 10.0 8).
- Ceresin 6.0 9. Polyethylene wax 6.0 10. Blue No. 1 0.8 11. Titanium oxide 1.0 12 Silicone-treated titanium oxide coated mica 1.0 13. Titanium oxide / silica / titanium oxide coated mica 3.0 14 Silicone-treated mica 10.0 15. Polymethyl methacrylate 5.0 16.
- Preservative appropriate amount15 Purified water 24.5 * 7) Phenyltrimethicone * 8) Decamethylcyclopentasiloxane solution of (acrylates / polytrimethylsiloxy methacrylate) copolymer (active ingredient 30 wt%) * 9) A 33 wt% dimethylpolysiloxane (100 cst) solution of trimethylsiloxysilicic acid (production method)
- C B is gradually added to A and emulsified to obtain an eyeliner.
- E F is added little by little while stirring E, and stirred and mixed so that the whole becomes uniform to obtain an eyeliner.
- effect The product has an appropriate viscosity and is easy to use. When applied, it is refreshing and refreshing, and a natural feeling without stickiness is obtained. Since it has excellent water resistance and sweat resistance, it has a very good makeup and has good temperature and stability over time.
- B Components 13 to 15 are mixed and then emulsified in addition to A to obtain a foundation. (effect) Even though it is light and well spreads, a smooth and thick cosmetic film can be obtained. After application, almost no dryness or skin tension is felt, adhesion to the skin is good, and makeup is excellent. Good product temperature and stability over time.
- Both A and B are returned to room temperature, and A is slowly added and emulsified while stirring B with a homodisper mixer to obtain a cream-like emulsified cosmetic.
- effect When applied, it spreads lightly and well, and is smooth and fresh without stickiness. After application, it is excellent in sustainability of natural skin sensation and moisturizing feeling, and since skin drying is suppressed, an effect of maintaining skin elasticity is expected. The stability over time of the product is also good.
- Caprylyl methicone (production method) A: Components 1 to 6, 11, and 15 are mixed and dissolved uniformly. B: While stirring A with a homodisper mixer, components 7 to 10 are added and uniformly dispersed. C: Components 12 to 14 are heated at 60 ° C., mixed and dissolved uniformly. D: Both B and C are returned to room temperature. While stirring B with a homodisper mixer, C is slowly added and emulsified to obtain a pasty emulsified cosmetic. (effect) When applied, it spreads smoothly and gives a natural, plain skin feel without stickiness. After application, the skin is smooth and natural and moderate moisturizing feeling is maintained. Excellent UV protection effect and good stability over time.
- Aerosol antiperspirant composition (component) (Wt%) 1.
- Aluminum chlorohydrate 12.00 2. Decamethylcyclopentasiloxane 15.67 3.
- Silicone compound no. 14 1.00 5. Quaterium-18 hectorite 1.00 6).
- Lectin 5.00 8.1,1-Difluoroethane (propellant) 60.00 (Production method)
- B Components 5 to 6 (powder suspending agent and clay activator) are mixed in the oil phase part and dispersed uniformly.
- C The dispersion of B is allowed to stand for 15 to 20 minutes to increase the viscosity.
- D While stirring C, Component 1 and Component 7 are added.
- E The mixture is homogenized with a mixing stirrer having a strong shearing force such as a homogenizer to obtain a soft gel composition.
- F E is transferred to an aerosol can treated with epoxy-phenol and further filled with a propellant to obtain an aerosol antiperspirant composition. (effect) Adhesiveness of the powder is good, there is little stickiness after application, it has an appropriate dry feeling, and a smooth and natural skin sensation is obtained.
- E Pour into a container and allow to cool and gel. (effect) It provides a smooth and smooth feel, a moderate moisturizing feeling despite being less sticky, and excellent appearance uniformity. Since it softens the skin, it is easy to rub into the skin during application. Sustained antiperspirant effect is also good.
- Oily Gel Cleansing Agent (Component) (Wt%) 1. Liquid paraffin 6.0 2. Dimethylpolysiloxane 6.0 3. Glycerol tri-2-ethylhexanoate 50.0 4). POE octyldodecyl alcohol ether 10.0 5. Silicone compound no. 14 0.5 6). Vitamin A Palmitate 2.0 7). Resorcin derivative 0.5 8). Lavender oil 0.001 9. Sorbitol 10.0 10. Polyethylene glycol (PEG400) 5.0 11. Acylmethyl taurine 5.0 12 Purified water residue (manufacturing method) A: Ingredients 1 to 7 are dissolved by heating and stirring at 70 ° C. and allowed to cool to obtain an oil phase.
- Formulation Example 17 Gel Cream (Ingredient) (Wt%) 1. Dimethylpolysiloxane (6 cst) 8.0 2. Decamethylcyclopentasiloxane 24.0 3. Silicone compound no. 6 10.0 4). Silicone rubber powder * 29) 6.0 5. Hydrophobized silica * 30) 2.0 6). Glucomannan 0.2 7). Pullulan 0.2 8). Agar powder (Japanese Pharmacopoeia) 0.1 9. Purified water 49.5 * 29) Polydimethylsiloxane cross-linked elastomer * 30) Dimethylsilylated silicic anhydride (Production method) A: Components 1 to 3 are dissolved by heating and stirring at 70 ° C.
- B Components 4 to 5 are added to this and mixed well to disperse uniformly.
- C Separately, components 6 to 9 are mixed to form a solution. This is heated to 70 ° C.
- D B is maintained at 70 ° C., and C is gradually added to emulsify while stirring uniformly with a homodisper. Further, the mixture is cooled to 30 ° C. with stirring to obtain a gel cream. (effect) It is smooth and easy to apply to the skin. It is expected that skin dryness is suppressed by the excellent moisturizing effect, and the elasticity of the skin is restored after application. A matte finish is obtained, and the effect of making fine lines and pores inconspicuous is also obtained.
- effect Can be applied lightly and smoothly, giving a fresh refreshing sensation to the lips.
- the film after application has moderate occlusion and moisture retention, and suppresses drying of the lips. As a result, an effect of maintaining the elasticity of the lips is expected.
- B is gradually added to A and emulsified to obtain a gel-like aftershave cream. (effect) It has an appropriate viscosity and does not sag at the time of use. When applied, it spreads lightly and can give a refreshing refreshing feeling. 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.
- 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. 14 0.3 14 Sorbitan isostearate 1.7 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. Methylphenylpolysiloxane 2.0 19. Octyl paramethoxycinnamate 2.0 20. Propylene glycol dicaprylate 2.0 21.
- effect There is no sense of incongruity such as dry feel at the time of application, and the spread is light and fresh. It has a long-lasting moisturizing effect and will not cause skin irritation after application. Easy to use as a makeup base. Good stability over time and temperature of the product.
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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し、好適には重合度200以上の共変性オルガノポリシロキサンを含有してなる油性原料の増粘剤またはゲル化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。
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を含有してなる油性原料の増粘剤またはゲル化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(2):
(式中、R1は前記と同様の基であり、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。)
−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)
「[1] (A)上記一般式(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を含有してなる、油性原料の増粘剤またはゲル化剤。
[2] 前記成分(A)が、上記構造式(1−1)で表され、1分子中に少なくとも1つのシロキサンデンドロン構造を有するシリルアルキル基を有する共変性オルガノポリシロキサンである、[1]に記載の油性原料の増粘剤またはゲル化剤。
[3] 前記成分(A)が、一般式(1)または構造式(1−1)において、L1が下記一般式(2−1)または一般式(2−2)で表される官能基であることを特徴とする共変性オルガノポリシロキサンである、[1]または[2]に記載の油性原料の増
粘剤またはゲル化剤。
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。)
{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,n2およびn3は、200≦n1≦1000,1≦n2≦50,0≦n3≦20となる範囲の数であり、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、二価以上の連結基を介してケイ素原子に結合し、上記構造式(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が直鎖状に連結してなる親水性基または二価以上の連結基を介してケイ素原子に結合し、かつ上記構造式(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2以上含有してなり、かつ下記構造式(3−5)~(3−7)で表される基から選択される分岐単位を有する親水性基である。
{(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、下記一般式(3−2−1)~(3−4−1)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3~5の範囲の数である。
X2は下記構造式(3−1)で表される親水性単位であり、qは0~50の範囲の数である。X1およびX2の結合の形式は、各々独立にブロック状またはランダム状である。
−CrH2r−O− (3−1)
(式中、rは1~6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、R3’は2価の有機基であり、X1は各々独立に、上記一般式(3−2−1)~(3−4−1)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3~5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。)
[8] さらに、(B)粉体または着色剤を含有してなる、[1]~[7]のいずれか1項に記載の油性原料の増粘剤またはゲル化剤。
[9] さらに、(C)シリコーン系界面活性剤(成分(A)に該当するものを除く)、架橋性オルガノポリシロキサン、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、ポリアミド変性シリコーン、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種を含有してなる、[1]~[8]のいずれか1項に記載の油性原料の増粘剤またはゲル化剤。
[10] 油性原料が、(D1)固形油、ペースト状油、シリコーン油、炭化水素油、エステル油から選択される少なくとも1種の油剤である、[1]~[9]のいずれか1項に記載の油性原料の増粘剤またはゲル化剤。
[11] 前記の成分(B)が、(B1)シリコーン樹脂粉末、シリコーンゴム粉末、有機樹脂粉末(シリコーン樹脂粉末を除く)、有機変性粘度鉱物、酸化チタン、酸化亜鉛、雲母チタン、金属石鹸、無機体質顔料および無機着色顔料からなる群から選択される少なくとも1種の粉体または着色剤である、[8]に記載の油性原料の増粘剤またはゲル化剤。」により達成される。
「[12] (D)油性原料30~80質量%と、[1]~[11]のいずれか1項に記載の油性原料の増粘剤またはゲル化剤10~70質量%と、低級一価アルコール及び有機系多価アルコール性化合物からなる群から選択される少なくとも1種の化合物0~20質量%および(E)水0~20質量%を含有してなるゲル状組成物。
[13] (F)紫外線吸収剤を更に含有する、[12]に記載のゲル状組成物。
[14] (G)ショ糖脂肪酸エステル、ポリグリセリン脂肪酸エステルから選択される少なくとも1種の化合物を更に含有する、[12]または[13]に記載のゲル状組成物。
[15] (H)有機系の皮膜形成剤を更に含有する、[12]~[14]のいずれか1項に記載のゲル状組成物。
[16] (J)アミノ酸及び/又はその塩、無機塩、有機酸及び/又はその塩、水溶性高分子、からなる群から選択される少なくとも1種の化合物を更に含有する、[12]~[15]のいずれか1項に記載のゲル状組成物。」により達成される。
[17] 水相と、上記の(A)成分および(D)油性原料を含む油相とを、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、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。
「[17] [12]~[16]のいずれか1項に記載のゲル状組成物100質量部と(E)水0.1~4,000質量部とを混合する事により、化粧料を製造する方法。
[18] [12]~[16]のいずれか1項に記載のゲル状組成物100質量部と(E)水0.1~4,000質量部とを混合する事により得られる化粧料。
[19] (D)油性原料30~80質量%と、[8]または[11]に記載の油性原料の増粘剤またはゲル化剤20~60質量%と、(E)水0~20質量%を含有してなるゲル状化粧料。
[20] [12]~[16]のいずれか1項に記載のゲル状組成物100質量部と(E)水0.1~4,000質量部と生理活性物質0.001~1.0質量部とを混合する事により、外用剤を製造する方法。
[21] [12]~[16]のいずれか1項に記載のゲル状組成物100質量部と(E)水0.1~4,000質量部と生理活性物質0.001~1.0質量部とを混合する事により得られる外用剤。
[22] (D)油性原料30~80質量%と、[8]または[11]に記載の油性原料の増粘剤またはゲル化剤20~60質量%と、D)低級一価アルコール及び有機系多価アルコール性化合物からなる群から選択される少なくとも1種の化合物0~20質量%と(E)水0~20質量%と生理活性物質0.001~1.0質量部を含有してなるゲル状外用剤。
[23] 生理活性物質が、抗炎症剤、老化防止剤、美白剤、発毛剤、育毛剤、血行促進剤、抗菌剤、殺菌剤、ビタミン類、創傷治癒促進剤、刺激緩和剤、鎮痛剤、細胞賦活剤および酵素からなる群から選択される1種類以上の生理活性物質である、[21]または[22]に記載の外用剤。
[24] 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、スプレー状である[18]または[19]に記載の化粧料。
[25] 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、スプレー状である[21]~[23]のいずれか一項に記載の外用剤。」により達成される。
「[26] 成分(A)である共変性オルガノポリシロキサンが、珪素結合水素原子を有するオルガノポリシロキサンと、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{成分(A)の珪素結合水素原子に対して0.9モル当量以下となる量}を(C)ヒドロシリル化反応触媒の存在下において付加反応させた後、(D)分子鎖末端に1個のアルケニル基を有する親水性化合物をさらに付加反応させることを特徴とする、[1]~[7]のいずれか1項に記載の油性原料の増粘剤またはゲル化剤の製造方法。
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。
該共変性オルガノポリシロキサンは、具体的には、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(−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り、好適にはそのオルガノシロキサン単位の重合度が200以上である共変性オルガノポリシロキサンが例示される。(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。)。
一般式(2):
(式中、R1は一価の有機基または水素原子(ただし、L1またはQである基を除く)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。)
(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。)
−CrH2r−O− (3−1)
式中、rは1~6の範囲の数であり、X2がオキシエチレン単位またはオキシプロピレン単位であることが好ましい。また、X2が連続して結合しているしている場合には、式(3−1−1)で示されるポリオキシアルキレン単位としてQに1種以上含まれることもできる。
−(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0~50の範囲の数であり、好ましくは0~30の範囲の数である。
R1 aHb+cSiO(4−a−b−c)/2 (1’)
(式中、R1、a、b及びcは前記と同じ)で表される重合度200以上の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、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)
(X,Y)2−3(Si,Al)4O10(OH)2Z1/3・nH2O
(1)
(ただし、Xは、Al、Fe(III)、Mn(III)、または、Cr(III)であり、Y は、Mg、Fe(II)、Ni、Zn、または、Liであり、Zは、K、Na、または、Caである)
このような無機系水溶性高分子として、具体的には、ベントナイト、モンモリロナイト、パイデライト、ノントロナイト、サポナイト、ヘクトライト、ケイ酸アルミニウムマグネシウム、無水ケイ酸が例示され、これらは天然物および合成物のいずれであってもよい。
(i)本願に係る共変性オルガノポリシロキサン、(D)油性原料を含有する油相の構成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。この際に、油相全体がゲル化あるいは増粘していても良い。すなわち、水相成分を含まない限り、油相はゲル状組成物であってよい。同様に、水相を構成する各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。
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ゲル化剤または増粘剤であり、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、油中水エマルジョン型ゲル状制汗剤、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ゲル状制汗剤においては、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、可溶化剤などの油性化粧料原料)、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、先に述べた、各相の屈折率調整を行い、油中水エマルジョン型ゲル状制汗剤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、本発明に係るゲル化剤または増粘剤を含有していれば、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。
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。
反応器に平均構造式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、平均構造式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、イソプロピルアルコール(以下、IPAと略)90g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(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、平均構造式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(シリコーン化合物No.1)を含有する組成物を得た。
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
この組成物は、淡黄色の半透明均一な粘稠液体であった。
反応器に平均構造式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、平均構造式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、平均構造式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(シリコーン化合物No.2)を含有する組成物を得た。
式中、R*21およびR*31は上記と同様であり、R*11= −C10H21である。
この組成物は、淡黄褐色の半透明均一液体であった。
反応器に平均構造式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、平均構造式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、平均構造式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(シリコーン化合物No.3)を含有する組成物を得た。
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
この組成物は、乳白色の均一なガム状であった。
反応器に平均構造式MD72DH 12Mで表されるメチルハイドロジェンポリシロキサン116.6g、平均構造式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47.3g、ポリグリセリンモノアリルエーテル26.0g、IPA200g、2.3wt%酢酸ナトリウム/メタノール溶液0.20gを仕込み、窒素流通下で攪拌しながら60℃まで加温した。塩化白金酸の5wt%IPA溶液を0.08g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80%に達している事を確認した。1−デセン10.2gと塩化白金酸の5wt%IPA溶液0.08gを添加し80℃で3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、平均構造式MD72DR*11 3DR*31 6DR*22 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(シリコーン化合物No.4)を含有する組成物を得た。
式中、R*22およびR*31は上記と同様であり、R*11= −C10H21である。
この組成物は、やや褐色味のある灰白色ガム状であった。
反応器に平均構造式MD400DH 10Mで表されるメチルハイドロジェンポリシロキサン96.3g、平均構造式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4.0g、ポリグリセリンモノアリルエーテル7.3g、IPA150g、2.3wt%酢酸ナトリウム/メタノール溶液0.16g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5wt%IPA溶液を0.06g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85%に達している事を確認した。1−デセン1.2gと塩化白金酸の5wt%IPA溶液0.06gを添加し80℃で3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。
式中、R*11およびR*22およびR*31は上記と同様である。
この混合物は乳白色均一であり、濃度50%に希釈されているにもかかわらずガム状であった。
反応器に平均構造式MD360DH 18Mで表されるメチルハイドロジェンポリシロキサン158.4g、平均構造式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28.5g、ポリグリセリンモノアリルエーテル13.1g、IPA200g、2.3wt%酢酸ナトリウム/メタノール溶液0.20gを仕込み、窒素流通下で攪拌しながら70℃まで加温した。塩化白金酸の5wt%IPA溶液を0.15g添加し、80℃で4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。
式中、R*22およびR*31は上記と同様である。
この混合物は乳白色均一であり、濃度50%に希釈されているにもかかわらずガム状であった。
反応器に平均構造式MD360DH 18Mで表されるメチルハイドロジェンポリシロキサン165.6g、平均構造式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13.8g、ポリグリセリンモノアリルエーテル13.7g、IPA200g、2.3wt%酢酸ナトリウム/メタノール溶液0.20gを仕込み、窒素流通下で攪拌しながら70℃まで加温した。塩化白金酸の5wt%IPA溶液を0.06g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率が65%に達している事を確認した。1−デセン7.0gと塩化白金酸の5wt%IPA溶液0.06gを添加し80℃で3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。
式中、R*22およびR*31は上記と同様であり、R*11= −C10H21である。
この混合物はやや淡褐色味のある乳白色均一であり、濃度50%に希釈されているにもかかわらずガム状であった。
反応器に平均構造式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、平均構造式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11.8g、ジグリセリンモノアリルエーテル10.4g、IPA 200g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0.125g添加し、80℃で5.5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低沸分を溜去することによって、平均構造式MD150DR*31 5DR*22 2DR*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(シリコーン化合物No.8)を含有する組成物を得た。
式中、R*22およびR*31は上記と同様であり、
R*23= −C3H6O−X,Xはジグリセリン部分である。
この組成物は、乳白色均一の極めて粘稠な液体であった。
反応器に平均構造式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、平均構造式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30.6g、IPA190g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0.117g添加し、80℃で9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り、MD72DR*31 9DR*24 3Mの平均構造式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(シリコーン化合物No.9)を含有する組成物を得た。この組成物は、半透明感ある微黄色の生ゴム状であった。
式中、R*31は上記と同様である。
反応器に平均構造式MD72DH 12Mで表されるメチルハイドロジェンポリシロキサン112.8g、平均構造式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、IPA195g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0.067g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率が80%に達している事を確認した。1−デセン9.9gと上記の白金触媒0.050gを添加し80℃で6時間反応後、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、平均構造式MD72DR*11 3DR*31 6DR*24 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(シリコーン化合物No.10)を含有する組成物を得た。
式中、R*31およびR*24は上記と同様であり、R*11= −C10H21である。
この組成物は、半透明感ある淡褐色の生ゴム状であった。
反応器に平均構造式MD360DH 18Mで表されるメチルハイドロジェンポリシロキサン155.3g、平均構造式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28.0g、ポリグリセリルオイゲノール16.7g、IPA200g、2.3wt%酢酸ナトリウム/メタノール溶液0.20gを仕込み、窒素流通下で攪拌しながら70℃まで加温した。塩化白金酸の5wt%IPA溶液を0.12g添加し、80℃で6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。
この混合物は半透明感ある微黄白色であり、濃度50%に希釈されているにもかかわらず生ゴム状であった。
反応器に平均構造式MD360DH 18Mで表されるメチルハイドロジェンポリシロキサン162.3g、平均構造式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13.5g、ポリグリセリルオイゲノール17.4g、IPA200g、2.3wt%酢酸ナトリウム/メタノール溶液0.20gを仕込み、窒素流通下で攪拌しながら70℃まで加温した。塩化白金酸の5wt%IPA溶液を0.06g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率が65%に達している事を確認した。1−デセン6.8gと塩化白金酸の5wt%IPA溶液0.06gを添加し80℃で4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。
式中、R*24およびR*31は上記と同様であり、R*11= −C10H21である。
この混合物は半透明感ある灰白色であり、濃度50%に希釈されているにもかかわらず生ゴム状であった。
反応器に平均構造式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、平均構造式CH2=CH−CH2−O(C2H4O)10Hで表されるアリルポリエーテル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、平均構造式MD63DR*12 18DR*25 4Mで表されるアルキル/ポリエーテル共変性シリコーン(シリコーン化合物RE1)を含有する組成物を得た。
式中、R*12= −C16H33
R*25= −C3H6O(C2H4O)10H
この組成物は、淡褐色の半透明均一な液体であった。
反応器に平均構造式MD400DH 10Mで表されるメチルハイドロジェンポリシロキサン206.1g、平均構造式CH2=CH−CH2−O(C2H4O)19(C3H6O)19Hで表されるアリルポリエーテル105.6g、IPA90g、天然ビタミンE0.12g、2.0wt%酢酸ナトリウム/メタノール溶液0.46g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0.04g添加し、90℃で5時間反応を行なった。サンプリングを行い、残存Si−H基濃度が規格内であることを確認し、反応を終了した。
式中、R*26= −C3H6O(C2H4O)19(C3H6O)19H
この混合物は、ほぼ無色透明の粘稠液体であった。
反応器に平均構造式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、平均構造式MD406DR*21 4Mで表されるグリセリン変性シリコーン(シリコーン化合物RE3)を含有する組成物を得た。
式中、R*21= −C3H6OCH2CH(OH)CH2OH
この組成物は、淡黄褐色の半透明均一な粘稠液体であった。
反応器に平均構造式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、平均構造式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(シリコーン化合物RE4)を含有する組成物を得た。
式中、R*11= −C10H21
R*21= −C3H6OCH2CH(OH)CH2OH、
この組成物は、淡褐色の半透明液体であった。
反応器に平均構造式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、平均構造式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(シリコーン化合物RE5)を含有する組成物を得た。
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
この組成物は、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。
反応器に平均構造式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
この組成物は、ほぼ無色の半透明均一な液体であった。
反応器にフレーク状のα−オレフィン(平均炭素数30以上)187.0gを仕込み、窒素流通下で攪拌しながら80℃まで加温し溶解させた。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リガンド溶液(Pt濃度22wt%)を0.8mg添加し、攪拌下に平均構造式MDH 15Mで表されるメチルハイドロジェンポリシロキサン13.0gを30分かけて滴下した。反応温度を120℃にコントロールし3時間反応を継続した。サンプリングを行い、残存Si−H基濃度が規格内であることを確認し、反応を終了した。これにより、平均構造式MDR*14 15Mで表されるアルキル変性シリコーンワックス(シリコーン化合物RE7)を含有する組成物を得た。
式中、R*14= −C30H61以上の長鎖アルキル基。
(特許文献8、製造例1記載の方法に準じて製造を行なった。)
(1)20.1gのNε−ラウロイル−L−リジンを205mlのエタノ−ルに懸濁させた。反応溶液を氷冷後、乾燥塩化水素ガスを飽和になるまで導入し、6時間撹拌した。次にエタノ−ルを留去後、250mlのジイソブチルエーテルを加え、吸引濾過後、精製水300mlを加えた。この溶液に精製水70mlに溶かしたモルホリン55gを撹拌しながらゆっくりと加え、析出した白色粉末をろ別した。得られた白色粉末は、n−ヘキサンから再結晶を行い、Nε−ラウロイル−L−リジンイソブチルエステル20.1gを得た。
(2)アジ化ナトリウム45.5gに精製水150gを加え、氷水中で冷却しながら、撹拌して完全に均一な溶液とした。ここに10−ウンデセノイルクロライド101.4gとアセトン150mlを混合した溶液を少しずつ、溶液の温度が10~15℃の範囲になるように滴下した。添加終了後、12℃付近で1時間撹拌した。次に溶液を分液ロートに移し、水層と有機層を分けた。有機層を60℃に維持した500mlのトルエンにゆっくりと加え、温度50~60℃の範囲で3時間撹拌を行った。トルエンを留去後、減圧蒸留することで10−ウンデセノイルイソシアネート73.2gを得た。
(3)MHD100MHの平均構造式表されるメチルハイドロジェンポリシロキサン92.6gと10−ウンデセノイルイソシアネート7.4gをトルエン100gに加え、85℃に加温した後、白金−1,3−ジビニル−1,1,3,3−テトラメチルジシロキサンのトルエン溶液(Pt濃度0.3wt%)0.33gを加え、3時間撹拌した。トルエンと余剰のイソシアネート化合物を減圧留去した後、新たにトルエン1000gとNε−ラウロイル−L−リジンイソブチルエステル10.5gを加え、90℃で6時間撹拌した。トルエンを留去後、得られた透明ゴム状固体をヘキサン1000gに加熱溶解させ、熱ろ過した。ろ液からヘキサンを留去後、固体を得た。次に得られた固体を細かく砕き、25℃のヘキサンでよく洗いながら吸引ろ過を行った後、減圧乾燥することにより下記式で表される粉末状のリジン誘導体変性シリコーン(Nε−ラウロイル−L−リジンイソブチルエステル誘導体変性シリコーン)20.3gを得た。
リコーン化合物No.12」、比較例に係る「比較用シリコーン化合物RE1」~「比較用シリコーン化合物RE7」の平均組成式を、以下の通りまとめる。なお、「比較用シリコーン化合物RE8」の構造は前段落に記載の通りである。
<長鎖アルキル基:R*1>
R*11= −C10H21
R*12= −C16H33
R*13= −C12H25
R*14= −C30H61以上の長鎖アルキル基
<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*23= −C3H6O−X,Xはジグリセリン部分
R*25= −C3H6O(C2H4O)10H
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)
<シロキサンデンドロン構造を有する基:R*3>
R*31= −C2H4Si(OSiMe3)
<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12に示す処方に従い、以下の手順に従って油剤系と上記の変性シリコーン化合物(組成物として得られ、製造例によっては、希釈形態のものもあり)との混合物を調製した。
1.油剤系と、先の製造例で示した変性シリコーン化合物とを容器に仕込み、80℃で加熱し、均一に混合分散した。(なお、比較例3では、比較用シリコーン化合物RE1およびRE4を配合比1:1で併用した)
2.室温に戻し、1週間静置した後の外観・性状を記録した。
1.外観(相溶性)○:均一な外観を維持していた。
△:ほぼ均一に近いが、僅かに析出物が観察された。
×:不均一であり分離していた。
2.性状(増粘効果):粘性の低い順に、「低粘性」、「粘稠」、「水飴状」、「ガム状」、「ゴム状」という表現を用い、記録した。ここでガム状とは、高重合シリコーンガムに近い性状を指す。なお、ワックス化など完全に固体状になった場合は、×を記入した。
処方および増粘/ゲル化に関する評価結果を表2~表12に示す。
なお、表中の「濃度」は、変性シリコーン化合物のwt%を表す。
なお、以下の表中において、スペースの都合上、油剤の種類は以下の略号を用いて示す。また、二種類以上の油剤を特定の比率で混合した混合油剤を使用した場合、各々の油剤の種類を「/」で区切った後、比率を()内に示す。例えば、油剤Aおよび油剤Bを70:30で配合した油剤系は、「A/B(70:30)」のように表す。
20cst:ジメチルポリシロキサン(20cst)
SH 556:フェニルトリメチコン
SS−3408:カプリリルメチコン
CEH:2−エチルヘキサン酸セチル
IOTG:トリ2−エチルヘキサン酸グリセリル
IP:イソパラフィン
K−230:流動パラフィン
先の表3~表8までの結果から、液状油剤の形態コントロール能力を顕著に有していた変性シリコーン化合物について、各種油剤との濃度20wt%混合物表面における傷回復効果を試験した。
1.先に調製した混合物の表面に、スパチュラで長さ1cm、深さ5mmの傷を付け、その傷が自然に消え滑らかな表面に回復するまでの時間を観察し、記録した。
[評価]
1.表面の傷回復効果 ◎◎:瞬時に傷が消え、滑らかな表面になった。
◎:1時間以内に傷が消え、滑らかな表面に回復した。
○:12時間以内に傷が消え、滑らかな表面に回復した。
×:24時間以上経っても、全く傷が消える様子は無かった。
上記の実施例、比較例について、評価結果を表13に示す。
表15~表17に示す組成(処方)を、以下の手順に従って加熱混合・冷却成型する事により、リップスティックを調製した。また、得られたリップスティックは、以下に述べる試験手順に従い、下記の基準を用いて評価した。
A.成分1~成分15を50℃で加熱し、混合して均一に溶解した。
B.成分16をAに加えて均一に混合分散した。
C.成型用型に流し込み、冷却固化して口紅とした。
1.得られたリップスティックを0.05g、清浄な皮膚(手の甲)上1cm×3cmに均一に塗布した。なお、口紅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唇の代わりの試験面として使用した。
2.塗布10分後(初期)、4時間後、7時間後、9時間後のそれそれの時点で、以下の5項目について評価した。
「色移りのしにくさ」、「色落ちのしにくさ」、「滲みにくさ」:目視判定
「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
「仕上がり」:目視と化粧効果の総合的な満足度を判定
1.「色移りのしにくさ」: 塗布面を陶器製の白いカップに軽く押し付け、離したときのカップへの色移りを判定した。
◎ 色移りが全く無かった。 ○ 目立たないが僅かに色がついた。
△ 少し色移りが気になった。 × 色移りが目立っていた。
2.「色落ちのしにくさ」: 塗布色の変化(退色やくすみなど)を目視で観察した。4、7、9時間の夫々の時点で、塗布面付近の別の場所(手の甲)にリップスティックで初期と同様の塗布を行い、この新鮮な塗布面との比較により色変化を判定した。
◎ 色の変化は無かった。○ 目立たないが僅かに色の変化があった。
△ 少し色落ちが認められた。 × 色のくすみが気になった。
3.「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。
4.「違和感のない自然な肌感覚」: 塗布部の皮膚感覚と、塗布面を指で触った時の触感によって総合的に判定した。
◎違和感の無い自然な皮膚感覚であり、触感も滑らかでべとつきは無かった。
○ 皮膚感覚に僅かの違和感があった、又は僅かにべとつきを感じた。
△ 少し不自然な皮膚感覚があった、又は感触の滑らかさが少し不足していた。
× 皮膚のツッパリや刺激を感じた、又は触感に滑らかさが無くべとついた。
5.「仕上がり」: 目視と化粧効果の総合的な満足度を判定した。
◎ 大いに満足。 ○ 満足。 △ 許容。 × 不満。
下表23~表25を参照。(数値の単位は全てwt%を示す)
また、表中のFA 4002 IDは、(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40wt%イソドデカン溶液であり、DC 593は、トリメチルシロキシケイ酸の33wt%ジメチルポリシロキサン(100CST)溶液である。
表18に示す組成を、以下の手順に従ってホモディスパーミキサーを用いて混合することにより、ゲル状組成物を調製した。表中、数値は添加部数(質量部)を示す。また、得られたゲル状組成物は、以下に述べる試験手順に従い、下記の基準を用いて評価した。
A.成分1~成分6を容器に入れて60℃で加熱し、混合して均一に溶解した。
B.室温に戻し、成分7をAに加えて均一に混合分散した。
C.Bをホモディスパーミキサー1200rpmで攪拌しながら、成分8を少量ずつ滴下してゆき、混合物が増粘⇒ゲル状に変化したところで水の投入を止めた。
D.そのまま攪拌を1分間継続して調製を終了。ゲル化までの水の添加量(wt%)を記録した。
注)ゲル化までの水の必要量は、使用するシリコーン化合物の構造等により異なるため、ゲル状組成物の合計量は処方ごとに若干異なる結果となった。
1.目視と触感とにより、得られた組成物の性状(ゲル化の可否)を判定した。
2.ゲル状組成物の0.10gを手の甲に塗り伸ばしてから5分後の、触感及び肌感覚を判定した。更に、塗布部の外観の良し悪しを判定した。
1.ゲル化の可否(ゲルの性状)
◎ 完全にゲル化していた。 ○ 水飴状~柔らかいゲル状であった。
2.触感および肌感覚
○ 自然な肌感覚でタッチも軽く、不快なべとつき感が無かった。
× しつこいぬるつき感又はべとつき感があった。
3.塗布部の外観
◎ 自然でマットな外観を有していた。 × 油っぽいギラツキが目立った。
表18~19に示す組成を、以下の手順に従ってホモディスパーミキサーを用いて混合することにより、ゲル状組成物を調製した。表中、数値は添加部数(質量部)を示す。また、得られたゲル状組成物は、以下に述べる試験手順に従い、下記の基準を用いて評価した。
A.成分1~成分4を容器に入れて60℃で加熱し、混合して均一に溶解した。
B.室温に戻し、成分5をAに加えて均一に混合分散した。
C.Bをホモディスパーミキサー2500rpmで攪拌しながら、成分6を少量ずつ滴下してゆき、混合物が増粘⇒ゲル状に変化したところで水の投入を止めた。
D.そのまま攪拌を1分間継続。
E.500rpmで攪拌しながら、Dに成分7~成分10を少量ずつ添加した。全量の成分7~成分10を投入し終わったら、2500rpmで5分間全体が均一になるよう攪拌混合した。
1.得られたゲル状組成物0.15gを手の甲に塗り広げ、塗布時~塗布直後の感触・使用感を評価した。更に、塗布部の外観(肌の印象)を評価した。
2.塗布から20分経過後、「塗布部の外観(肌の印象)」、「保湿感」、「塗布表面の粉っぽさ」、「しわ隠し効果」、「化粧の満足度(総合評価)」を行った。
1. 感触および使用感:
◎ 厚みのある滑らかな感触に優れており、心地の良い使用感であった。
○ 厚みのある滑らかな感触を有し、使用感も問題なかった。
△ 滑らかさ、使用感ともにやや不足していた。
2. 塗布部の外観および肌感覚:
◎ マットでテカリが無く、外観、肌感覚ともに自然な印象であった。
○ マットでテカリが無い外観であったが、肌に少し不自然な違和感があった。
3. 保湿感:
◎ 肌表面に適度で快適なうるおいを感じた。
○ 肌表面のうるおいを維持できていた。 △ 肌にドライ感が感じられた。
4. 塗布部表面の粉っぽさ:
◎ 粉の転がり感やドライ感は全く感じられなかった。
○ 僅かに粉の転がり感が感じられた。
× 粉の転がり感とドライ感を強く感じた。
5. しわ隠し効果:
◎ 塗りむらも無く密着感も良好で、皮膚表面のしわが全く目立たなかった。
○ 塗りむらが無く、皮膚表面のしわがほとんど目立たなかった。
△ 皮膚表面のしわの溝に粉が入り込み、部分的にしわを目立たせていた。
6. 化粧の総合的な満足度:
◎ 大いに満足。 ○ 満足。 △ 許容。
表21~24に示す組成を、以下の手順に従ってホモディスパーミキサーを用いて混合することにより、ゲル状組成物を調製した。(表中の数値は添加部数(質量部)を示す。)
A.成分1~成分6を容器に入れて60℃で加熱し、混合して均一に溶解した。
B.室温に戻し、成分7をAに加えて均一に混合分散した。
C.成分8~成分11を別の容器にいれ、攪拌混合して溶解させた。
D.Bをホモディスパーミキサー2500rpmで攪拌しながら、Cを少量ずつ添加してゆき、混合物が増粘⇒ゲル状に変化したところで投入を止めた。
E.そのまま攪拌を2分間継続。
F.500rpmで攪拌しながら、Eに成分12~成分15を少量ずつ添加した。全量を投入し終わったら、2500rpmで5分間全体が均一になるよう攪拌混合した。
上記の実施例25~38で得られたゲル状組成物は均一なゲル形態を有しており、室温1ヶ月保管後も外観や形態の変化なく安定であった。従って、これらのゲル状組成物は、ゲル状化粧料としても利用価値の高いものであることが分かった。
表25、表26に示す組成を、以下の手順に従ってホモディスパーミキサーを用いて混合することにより、乳化化粧料を調製した。
調製手順
A.成分1~成分4を容器に入れて、室温下ホモディスパーミキサー2500rpmで攪拌を開始した。
B.攪拌しながら、成分5、または成分5と成分6の混合物を10分かけて添加した。
C.容器の内壁への付着物などをへらで落とし、全体が均一になるよう再度攪拌混合を5分間行った。
実施例39~42で得られた乳化化粧料は、均一なクリーム状~乳液状の外観を有しており、室温1ヶ月保管後も変化はなく安定であった。
実施例43~46で得られた乳化化粧料は、均一なペースト状~クリーム状の外観を有しており、室温1ヶ月保管後も変化はなく安定であった。
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。
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110.3g、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12.1g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)12.1g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)12.1g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:反応液にポリグリセリンモノアリルポリエーテル8.0g、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15.1g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)15.1g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)15.2g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*22 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グリセリン変性シリコーンと、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*22は、−C3H6O−X,Xはテトラグリセリン部分
この生成物は、乳白色均一なガム状であった。
なお、前記のポリグリセリンモノアリルエーテルは、グリセリンモノアリルエーテル1モルに対し3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り、グリセリンが平均4モル付加した形の構造を有する。なお、グリセリンモノアリルエーテルには2つの水酸基がありグリシドールはその両方と反応しえるため、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る。
本発明にかかる外用剤ないしは化粧料の一例として、油中水エマルジョン型透明ソフトゲル制汗剤を調製し、その特性を評価した結果を実施例47~48及び比較例15~16に示す。
1.200mlの容器に油相成分を秤量し、表27に示された順序で仕込んだ。
2.60℃で加熱を行い、時々、振り混ぜて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。放冷しながら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、攪拌下に室温で水相Bを約10分かけて少量ずつ油相A中に投入した。途中で、内容物がゲル状組成物の形態を示すかどうかを観察した。
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や水分をスパチュラで掻き落とし、生成しているW/Oエマルション型組成物と混合した。
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. 調製手順7において、水相Bの添加途中ないしは最後までにゲル状組成物の生成があったかどうかを目視および触覚により判断した。
2. 得られた制汗剤の外観(透明性)と形態を目視観察した。
3. 更に、25℃における屈折率(RI)と粘度を測定した。
4. 得られた制汗剤を、触感及び非白化性能の評価のために皮膚に塗布した。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。
5. 得られた制汗剤25gを、35mlガラス瓶に入れて密栓したもの2つを準備し、50℃恒温槽内及び−5℃恒温槽内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、外観及び形態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。
「ゲル生成」: 調製途中ないしは最後までにゲル化が起こったか(ゲル状組成物が生成したか)どうか、目視及び触覚で判定した。
「外観」: 制汗剤の透明性を、100mlガラス瓶を通して目視判定した。
「形態」: 制汗剤の形態がゲル状であるかどうか、触覚にて判定した。
「RI」: 株式会社ATAGO製 デジタル屈折率計 RX−7000αを使用して、得られた制汗剤の25.0℃における屈折率を測定した。
「粘度」: TOKIMEC.INC製 E型粘度計 VISCOMIC EMD、中型コーンローター(3°×R14)を使用して、25.0℃における粘度を測定した。なお、ローターの回転数は0.5rpmとした。
「触感」: 前腕部に制汗剤を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の外観と形態を目視観察した。
○ 半透明~透明であり、外観およびソフトゲル形態の変化が認められない。
△ ソフトゲルの形態が維持されているが、若干透明性が低下した。
× 不透明又は不均一な外観となった。又はソフトゲルの形態を示していなかった。
(成分) (Wt%)
1.ポリエチレンワックス(融点88℃) 2.0
2.ポリエチレンワックス(融点107℃) 2.0
3.ポリエチレンーポリプロピレンコポリマー 2.0
4.マイクロクリスタリンワックス 2.0
5.キャンデリラロウ 3.0
6.カルナウバロウ 3.0
7.セレシン 3.0
8.イソノナン酸イソトリデシル 9.0
9.2−オクチルドデカノール 10.0
10.ジカプリン酸ネオペンチルグリコール 10.0
11.リンゴ酸ジイソステアリル 10.0
12.ジイソステアリン酸ポリグリセリル 10.0
13.ひまし油 10.0
14.SH 556 *1) 2.0
15.DC 5200 Formulation Aid *2) 5.0
16.製造例7の組成物(シリコーン化合物No.7を含有) 5.0
17.赤色104号(1)アルミニウムレーキ 1.0
18.赤色201号 1.0
19.赤色202号 1.0
20.黄色4号アルミニウムレーキ 1.0
21.青色1号アルミニウムレーキ 1.0
22.雲母チタン 1.0
23.酸化チタン内包シリカ 2.0
24.酸化チタン内包ナイロン 2.0
25.酸化ジルコニア含有シリカ 2.0
注 *1)フェニルトリメチコン
注 *2)アルキル変性シリコーン
(製造方法)
A:成分1~16を加温溶解し、成分17~25を加え均一に混合する。
B:容器に充填し、口紅を得る。
(効果)
口紅の外観色が明るく彩度も高い。実際に唇に塗布したときの色も、口紅自体の外観色に近い明るく鮮やかな色合いである。違和感なく自然に塗布ができ、塗りムラが生じず均一な仕上がりが可能である。耐水性、撥水性、耐汗性が良好で化粧持ちに優れるほか、色のくすみも少ない。
(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.製造例5の組成物(シリコーン化合物No.5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)
べたつきがなく自然な塗布感が得られ、口唇上でのつやが良好。適度な閉塞性と保湿性を有し、唇を乾燥などから保護する。耐水性、撥水性、耐汗性が良好であり化粧持ちもよい。
(成分) (Wt%)
1.セレシン 6.0
2.パラフィンワックス 6.0
3.キャンデリラワックス 4.0
4.1−イソステアロイルー3−ミリストイルグリセロール 22.5
5.2−エチルヘキサン酸トリグリセライド 11.0
6.パルミチン酸イソプロピル 22.5
7.ホホバ油 10.0
8.SH 3775 M *3) 4.0
9.製造例12の組成物(シリコーン化合物No.12を含有) 4.0
10.酸化チタン 3.0
11.赤色201号 3.0
12.赤色202号 2.0
13.黄色4号アルミニウムレーキ 2.0
14.酸化防止剤 適 量
15.香料 適 量
注 *3)ポリエーテル変性シリコーン
(製造方法)
A:成分1~9を加温溶解し、成分10~14を加え均一に混合する。
B:Aに成分15を加えて容器に充填し、口紅を得る。
(効果)
違和感なく自然に塗布ができ、塗りムラを生じず均一な仕上がりが可能である。色移りや色落ち、滲みなどを起こしにくく化粧持ちに優れている。適度な閉塞性と保湿性を有し、唇を乾燥などから保護する。
(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.製造例10の組成物(シリコーン化合物No.10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 *4) 3.0
12.DC 593 *5) 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 *4)(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)*5)トリメチルシロキシケイ酸の33wt%ジメチルポリシロキサン
(100cst)溶液
(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)
口唇に塗布するときになめらかにのびて塗りやすい。また、その使用感はべたつきがなく、口唇上でのつやも良好である。耐水性、撥水性、耐汗性が良好であり、色移りや色落ち、滲みなどを起こしにくく化粧持ちに優れている。
(成分) (Wt%)
1.リンゴ酸ジイソステアリル 6.0
2.イソノナン酸イソトリデシル 10.0
3.流動パラフィン 10.0
4.ジメチルポリシロキサン(6cst) 8.0
5.SS−3408 *6) 10.0
6.無水ケイ酸(アエロジル200) 1.2
7.製造例12の組成物(シリコーン化合物No.12を含有) 10.0
8.セレシン 6.0
9.ポリエチレンワックス 6.0
10.青色1号 0.8
11.酸化チタン 1.0
12.シリコーン処理酸化チタン被覆雲母 1.0
13.酸化チタン・シリカ・酸化チタン被覆雲母 3.0
14.シリコーン処理マイカ 10.0
15.ポリメタクリル酸メチル 5.0
16.シリコーン処理セリサイト 12.0
注 *6)カプリリルメチコン
(製造方法)
A: 成分1~5を混合し、90℃に加熱した後、成分6を加え均一に混合分散する。
B: Aに成分7~9を添加して溶解させる。
C: Bに10~16を加えて均一混合する。
D: 金型に充填したのち冷却し、油性固形アイシャドウを得る。
(効果)
使用感や仕上がりに優れる。密着性が良好でありながら、違和感の少ない自然な塗布感が得られる。耐水性、撥水性、耐汗性が良好で色滲みなどを起こしにくく、化粧持ちがよい。また、固形アイシャドウが割れにくい。
(成分) (Wt%)
1.デカメチルシクロペンタシロキサン 17.0
2.イソパラフィン 10.0
3.ジメチルポリシロキサン(2cst) 5.0
4.SH 556 *7) 5.0
5.トリ2−エチルヘキサン酸グリセリル 2.0
6.製造例6の組成物(シロキサン化合物No.6を含有) 3.5
7.FA 4001 CM *8) 7.5
8.DC 593 *9) 7.5
9.エタノール 1.0
10.ジオクタデシルジメチルアンモニウム塩変性モンモリロナイト 2.0
11.シリコーン処理黒酸化鉄 10.0
12.1,3−ブチレングリコール 5.0
13.デヒドロ酢酸ナトリウム 適 量
14.防腐剤 適 量
15.精製水 24.5
注 *7)フェニルトリメチコン
注 *8)(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 *9)トリメチルシロキシケイ酸の33wt%ジメチルポリシロキサン
(100cst)溶液
(製造方法)
A : 成分1~10を混合し、成分11を加えて均一に混合分散する。(ゲル状化粧料)
B : 別に、成分12~15を混合する。
C : BをAに徐添して乳化し、アイライナーを得る。
(製造方法の別法)
A : 成分1~8を60℃で加熱し、混合して均一に溶解する。
B : 室温に戻し、成分9をAに加えて均一に混合分散する。
C : Bを攪拌混合しながら、成分15の1.5Wt%相当を少量ずつ滴下し、混合物をゲル状に変化させる。(ゲル状組成物)
D : Cに成分10を加えて均一に混合分散する。(ゲル状化粧料)
E : 更に成分11を加えて均一に混合分散する。
F : 成分12~14と15の残部(23.0Wt%相当)との混合液を別に調製する。
E : Eを攪拌しながらFを少量ずつ添加し、全体が均一になるよう攪拌混合し、アイライナーを得る。
(効果)
製品に適度な粘度があって使いやすく、伸びも軽くて描きやすい。塗布時には、清涼感があってさっぱりとし、べたつきのない自然な使用感が得られる。耐水性、耐汗性に優れるため化粧持ちが非常に良く、製品の温度や経時での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 27.0
2.SH 556 *10) 3.0
3.トリオクタン酸グリセリル 10.0
4.製造例11の組成物(シロキサン化合物No.11を含有) 4.0
5.ベントン27 *11) 0.5
6.疎水化処理混合粉体 *12) 18.0
7.ベンガラ 1.2
8.黄酸化鉄 2.6
9.群青 0.1
10.黒酸化鉄 0.1
11.1,3−ブチレングリコール 7.0
12.塩化ナトリウム 0.5
13.防腐剤 適 量
14.香料 適 量
15.精製水 26.0
注 *10)フェニルトリメチコン
注 *11)ベンジルジメチルステアリルアンモニウムクロライド処理ヘクトライト(ナショナルレッド社製)
注 *12)以下の組成の混合粉体に対して、1wt%相当のジメチルメチルハイドロジェンポリシロキサンで加熱処理して得られるもの。
a . 微粒子酸化チタン 8.0
b . 微粒子酸化亜鉛 4.0
c . タルク 3.0
d . マイカ 3.0
(製造方法)
A : 成分1~6を混合し、成分7~10を均一に分散する。(ゲル状化粧料)
B : 成分11~13及び15を混合した後、Aに加えて乳化する。
C : Cに、成分14を加えてファンデーションを得る。
(効果)
べたつきがなく、伸び広がりも軽いうえ密着感に優れ、自然な使用感である。また、つやのある仕上がりで化粧持ちも非常に優れている。製品の温度や経時での安定性も良好である。
(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 *13) 1.2
5.製造例10の組成物(シロキサン化合物No.10を含有) 0.6
6.BY 25−320 *14) 1.5
7.FZ−2250 *15) 1.5
8.FA 4002 ID *16) 2.0
9.DC 593 *17) 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 *13)ポリエーテル変性シリコーン
注 *14)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 *15)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 *16)(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 *17)トリメチルシロキシケイ酸の33wt%ジメチルポリシロキサン
(100cst)溶液
(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)
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。製品の温度や経時での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 12.0
2.SS−3408 *18) 13.0
3.ショ糖オレイン酸エステル 1.3
4.デカグリセリンオレイン酸エステル 1.3
5.製造例6の組成物(シロキサン化合物No.6を含有) 16.0
6.製造例3の組成物(シロキサン化合物No.3を含有) 12.0
7.SS−2910 *19) 4.0
8.エタノール 8.0
9.精製水 5.9
10.L−グルタミン酸ナトリウム 0.1
11.EP−9215 *20) 26.4
注 *18)カプリリルメチコン
注 *19)ポリエーテル変性シリコーン
注 *20)シリコーンエラストマー球状粉体
(製造方法)
A : 成分1~7を60℃で加熱し、混合して均一に溶解する。
B : 室温に戻し、成分8をAに加えて均一に混合分散する。
C : Bを攪拌混合しながら、成分10を成分9に溶解させたものを少量ずつ滴下し、混合物をゲル状に変化させる。(ゲル状組成物)
D : Cに成分11を少量ずつ加えていき均一に混合分散させて、ゲル状化粧料を得る。
(効果)
厚みのある滑らかな感触に優れており、油っぽくないさっぱりとした使用感が心地よい。塗布後の乾燥感や肌の突っ張りなどもなく、皮膚に保湿感がもたらされる。マットでテカリが無く、外観、肌感覚ともに自然な印象の仕上がりとなる。塗りむらも無く密着感も良好で、皮膚表面のしわが目立たない。製品の温度や経時での安定性も良好である。
(成分) (Wt%)
1.ジメチルポリシロキサン(6cst) 10.0
2.SS−3408 *21) 10.0
3.2−エチルヘキサン酸セチル 10.0
4.製造例11の組成物(シロキサン化合物No.11を含有) 4.0
5.ジプロピレングリコール 6.0
6.精製水 58.0
7.L−グルタミン酸ナトリウム 2.0
注 *21)カプリリルメチコン
(製造方法)
A :成分5~7を70℃で加熱し、混合して均一に溶解する。
B :成分1~4を60℃で加熱し、混合して均一に溶解する。
C :A、Bとも室温に戻し、ホモディスパーミキサーでBを攪拌しながらAをゆっくり添加して乳化して、クリーム状乳化化粧料を得る。
(効果)
塗布時には軽くよく伸び広がり、べとつかず滑らかで瑞々しい使用感が得られる。塗布後は、自然な皮膚感覚と保湿感の持続性に優れており、皮膚の乾燥が抑制される事から、肌の弾力性を保持する効果が期待される。製品の経時安定性も良好である。
(成分) (Wt%)
1.ジメチルポリシロキサン(6cst) 20.0
2.SS−3408 *22) 20.0
3.トリ2−エチルヘキサン酸グリセリル 20.0
4.オクチルメトキシシンナメート 8.0
5.製造例7の組成物(シロキサン化合物No.7を含有) 4.0
6.トリメチルシロキシシリケート 1.0
7.低密度ポリエチレン粉末 1.0
8.球状ポリエチレン 1.0
9.ポリスチレン粉末 1.0
10.ポリメチルシルセスキオキサン末 3.0
11.エタノール 2.0
12.ジプロピレングリコール 6.0
13.精製水 12.0
14.L−グルタミン酸ナトリウム 1.0
15.パラベン 適 量
注 *22)カプリリルメチコン
(製造方法)
A :成分1~6、11、15を混合して均一に溶解する。
B :ホモディスパーミキサーでAを攪拌しながら、成分7~10を添加して均一分散させる。
C :成分12~14を60℃で加熱し、混合して均一に溶解する。
D :B、Cとも室温に戻す。ホモディスパーミキサーでBを攪拌しながら、Cをゆっくり添加して乳化し、ペースト状乳化化粧料を得る。
(効果)
塗布時には滑らかに伸び広がり、べとつかず自然でプレーンな皮膚感覚が得られる。塗布後は、肌がすべすべとして自然で適度な保湿感が持続する。紫外線防御効果にも優れ、製品の経時安定性も良好である。
(成分) (Wt%)
1.アルミニウムクロロハイドレート 12.00
2.デカメチルシクロペンタシロキサン 15.67
3.イソプロピルミリステート 5.00
4.シリコーン化合物No.14 1.00
5.クォータ二ウム−18ヘクトライト 1.00
6.プロピレンカーボネート 0.33
7.レクチン 5.00
8.1,1−ジフルオロエタン(噴射剤) 60.00
(製造方法)
A:成分2~4(油相部)を混合し、均一液体とする。
B:油相部に、成分5~6(粉末懸濁剤及び粘土活性剤)を混合し、均一に分散させる。
C:Bの分散液を15~20分間静置し、増粘させる。
D:Cを撹拌しながら、成分1と成分7を添加する。
E:ホモジナイザーなど強いせん断力を有する混合撹拌機により均質化して、ソフトなゲル状組成物を得る。
F:Eをエポキシ−フェノール処理を施したエアゾール缶に移し、更に噴射剤を充填して、エアゾール制汗剤組成物を得る。
(効果)
粉末の付着性が良好で、塗布後にべたつき感が少なく適度なドライ感を有し、なめらかで自然な皮膚感覚が得られる。
(成分) (Wt%)
1.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 24.0
2.ジメチルポリシロキサン(2cst) 12.3
3.SS−3408 *23) 12.0
4.シリコーン化合物No.14 2.0
5.XX 3006 Alkyl Sugar Siloxane *24) 1.0
6.ステアリルアルコール 14.0
7.イソプロピルミリステート 1.0
8.トウゴマロウ 4.0
9.ポリデセン 13.0
10.DC 9041 Silicone Elastomer Blend *25) 12.5
11.タルク 3.2
12.芳香剤 1.0
(製造方法)
注*23) カプリリルメチコン
注*24) 糖/長鎖アルキル共変性シリコーン
注*25) 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)をジメチルシロキサン(5cst)で希釈したもの(エラストマー成分16%)
(製造方法)
A: 成分2~8を、80℃で加熱撹拌を行って溶解させる。
B: 80℃に保ち、よく撹拌を行いながら成分9~11をゆっくりと加え、均一に分散させる。
C: 65℃に保ち、成分1をゆっくりと加え、よく撹拌して均一に分散させる。
D:撹拌しながら成分12を添加する。
E: 容器に流し込み、放冷してゲル化させる。
(効果)
すべすべとした滑らかな感触、べとつきが少ないにもかかわらず適度な保湿感を付与し、外観上の均一性にも優れている。皮膚を柔軟化するので、塗布時に肌にすり込むのが容易である。制汗効果の持続性も良好である。
(成分) (Wt%)
1.流動パラフィン 6.0
2.ジメチルポリシロキサン 6.0
3.グリセロールトリ− 2 エチルヘキサン酸エステル 50.0
4.POEオクチルドデシルアルコールエーテル 10.0
5.シリコーン化合物No.14 0.5
6.ビタミンAパルミテート 2.0
7.レゾルシン誘導体 0.5
8.ラベンダー油 0.001
9.ソルビトール 10.0
10.ポリエチレングリコール(PEG400) 5.0
11.アシルメチルタウリン 5.0
12.精製水 残余
(製造方法)
A: 成分1~7を70℃で加熱撹拌して溶解させ、放冷して油相とする。
B: 別に、成分9~12を混合して溶解させ、水相とする。
C: Bをホモミキサーにより攪拌しながら、Aをゆっくり添加して乳化し、油性ジェルを得る。
(効果)
ゲル形態でありながら肌へのなじみが良いため、肌に必要な油分は残しながら、メイク汚れ等をしっかりと取り除くことができる。使用後の皮膚の乾燥も防ぐことができる。製品の経時での安定性も良好である。
(成分) (Wt%)
1.オクチルドデカノール 25.0
2.12−ヒドロキシステアリン酸 7.0
3.N−ラウリル−グルタミン酸−ジ−n−ブチルアミド 0.5
4.Unilin 425 *26) 0.5
5.Unithox 450 *27) 1.0
6.Unithox 480 *27) 1.0
7.ドデカメチルシクロヘキサシロキサン 46.3
8.シリコーン化合物No.14 2.0
9.Al/Zrトリクロロハイドレックスグリシネート 25.0
10.EDTA−2Na 0.2
11.香料 1.0
注*26)C20−C40アルコール(BAKER PETROLITE社製)
注*27)C20−C40アルコールのEO付加物(BAKER PETROLITE社製)
(製造方法)
A: 成分1~8を、90℃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9~10を加え、均一に分散させる。
C:成分11を加えてよく混合したのち、容器に流し込み、放冷してゲル化させる。
(効果)
肌へのなじみが良く皮膚を柔軟化し、塗布時に肌にすり込むのが容易である。軽く滑らかに塗布することができ、その皮膜は適度な閉塞性と適度に乾いた皮膚感触を有する。制汗効果の持続性および製品の経時安定性も良好である。
(成分) (Wt%)
1.オクチルメトキシシンナメート 25.0
2.イソヘキサデカン 40.0
3.ドデカメチルシクロヘキサシロキサン 25.0
4.12−ヒドロキシステアリン酸 7.0
5.シリコーン化合物No.14 1.0
6.香料M’ *28) 2.0
注*28)下表28に示すブレンドの香料組成例を参照のこと。
(製造方法)
A: 成分1~5を、80℃で加熱撹拌を行って溶解させる。
B: 65~70℃に保ち、撹拌を行いながら成分6を加え、均一に分散させる。
C: 容器に流し込み、放冷してゲル化させる。
(効果)
塗布時および塗布後に、適度に乾いた皮膚感触を示し残留感が少ない。制汗効果の持続性、紫外線防御効果および製品の経時安定性も良好である。
(成分) (Wt%)
1.ジメチルポリシロキサン(6cst) 8.0
2.デカメチルシクロペンタシロキサン 24.0
3.シリコーン化合物No.6 10.0
4.シリコーンゴム粉末 *29) 6.0
5.疎水化シリカ *30) 2.0
6.グルコマンナン 0.2
7.プルラン 0.2
8.寒天末(日本薬局方) 0.1
9.精製水 49.5
注*29)ポリジメチルシロキサン架橋弾性体
注*30)ジメチルシリル化無水ケイ酸
(製造方法)
A: 成分1~3を70℃で加熱撹拌して溶解させる。
B: これに成分4~5を添加して良く混合し、均一に分散させる。
C: 別に、成分6~9を混合して溶液とする。これを70℃に加熱する。
D: Bを70℃に保持し、ホモディスパーで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℃まで冷却してゲル状クリームを得る。
(効果)
滑らかで肌に塗りやすく、塗布時にべたつきがなく瑞々しい清涼感が得られる。優れた保湿効果により皮膚の乾燥が抑制され、塗布後には肌の弾力性が回復すると期待される。マット感のある仕上がりが得られ、小じわや毛穴を目立たなくする効果も得られる。
(成分) (Wt%)
1.ジメチルポリシロキサン(6cst) 20.0
2.ジメチルポリシロキサン(2cst) 18.0
3.SS−3408 *31) 18.3
4.DC 2503 Cosmetic Wax *32) 19.0
5.シリコーン化合物No.14 1.0
6.疎水化シリカ(トリメチルシリル化無水ケイ酸) 1.5
7.シリコーンゴム粉末(ポリジメチルシロキサン架橋弾性体) 6.0
8.グルコマンナン 0.5
9.プルラン 1.0
10.グリセリン 2.7
11.イオン交換水 10.0
12.パラメトキシケイ皮酸オクチル 2.0
13.メントール 適量
14.カンファー 適量
注*31)カプリリルメチコン
注*32)ステアリルジメチコン
(製造方法)
A: 成分1~5を70℃で加熱撹拌して溶解させる。
B: これに成分6~7を添加してホモディスパーで良く混合し、均一分散させる。
C: Bを撹拌しながら、成分12~14を加えて溶解させる
D: 別に、成分8~11を混合して溶液とする。これを70℃に加熱する。
E: Cを70℃に保持し、ホモディスパーで均一に撹拌しながら、Dを徐添して乳化する。更に撹拌しながら30℃まで冷却してゲル状リップクリームを得る。
(効果)
軽く滑らかに塗布でき、唇にみずみずしい清涼感を与えることができる。塗布後の皮膜は適度な閉塞性と保湿性を有し、唇の乾燥を抑制する。その結果、唇の弾力性を保持す効果が期待される。
(成分) (Wt%)
1.FA 4002 ID *33) 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 *34) 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.14 4.0
9.酸化鉄 5.0
10.アエロジルRY200 *35) 3.5
11.タルク 10.0
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、イソドデカン溶液(有効成分40%)
注*34)カプリリルメチコン
注*35)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)
製品が適度な粘性を持つため使いやすい。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 *36) 35.0
2.SS−2910 *37) 2.9
3.シリコーン化合物No.7 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*36)カプリリルメチコン
注*37)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、ゲル状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、べたつかず滑らかな感触で使いやすい。塗布時にはのび広がりが軽く、瑞々しい清涼感を与えることができる。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)*38) 18.0
2.処理酸化鉄(黒酸化鉄、ベンガラ、黄酸化鉄の混合物)*38) 1.7
3.処理タルク *38) 6.0
4.処理マイカ *38) 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.14 0.3
14.イソステアリン酸ソルビタン 1.7
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*38) 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少なく、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く、またファンデーションが割れにくい。
(成分) (Wt%)
1.SS−2910 *39) 1.0
2.シリコーン化合物No.6 2.0
3.SH 556 *40) 5.0
4.SS−3408 *41) 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*39)ポリエーテル変性シリコーン
注*40)フェニルトリメチコン
注*41)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、のびが軽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。製品の温度や経時による安定性も良好である。
(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.7 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型非水ゲルエマルション皮膚外用剤を得る。
(効果)
非水系の安定なゲル状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.7 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型非水ゲルエマルション皮膚外用剤を得る。
(効果)
非水系の安定なゲル状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 (20)
- (A)下記一般式(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を含有してなる、油性原料の増粘剤またはゲル化剤。
R1 aL1 bQcSiO(4−a−b−c)/2 (1)
{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は前記と同様の基であり、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。} - 前記成分(A)が、下記構造式(1−1−1)または(1−1−2)で表される共変性オルガノポリシロキサンである、請求項1~請求項3のいずれか1項に記載の油性原料の増粘剤またはゲル化剤。
{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,n2およびn3は、200≦n1≦1000,1≦n2≦50,0≦n3≦20となる範囲の数であり、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、二価以上の連結基を介してケイ素原子に結合し、上記構造式(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が直鎖状に連結してなる親水性基または二価以上の連結基を介してケイ素原子に結合し、かつ上記構造式(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2以上含有してなり、かつ下記構造式(3−5)~(3−7)で表される基から選択される分岐単位を有する親水性基である。
- 前記の親水性基QまたはQ1が、下記構造式(4−1),(4−2),(4−3)または(4−4)で示される親水性基であることを特徴とする、請求項1~請求項4のいずれか1項に記載の油性原料の増粘剤またはゲル化剤。
{(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、下記一般式(3−2−1)~(3−4−1)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3~5の範囲の数である。
X2は下記構造式(3−1)で表される親水性単位であり、qは0~50の範囲の数である。X1およびX2の結合の形式は、各々独立にブロック状またはランダム状である。
−CrH2r−O− (3−1)
(式中、rは1~6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。)} - 前記の親水性基QまたはQ1が、テトラグリセリンから誘導されてなる親水性基であることを特徴とする、請求項1~6のいずれか1項に記載の油性原料の増粘剤またはゲル化剤。
- さらに、(B)粉体または着色剤を含有してなる、請求項1~7のいずれか1項に記載の油性原料の増粘剤またはゲル化剤。
- さらに、(C)シリコーン系界面活性剤(成分(A)に該当するものを除く)、架橋性オルガノポリシロキサン、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、ポリアミド変性シリコーン、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種を含有してなる、請求項1~8のいずれか1項に記載の油性原料の増粘剤またはゲル化剤。
- 油性原料が、(D1)固形油、ペースト状油、シリコーン油、炭化水素油、エステル油から選択される少なくとも1種の油剤である、請求項1~9のいずれか1項に記載の油性原料の増粘剤またはゲル化剤。
- 前記の成分(B)が、(B1)シリコーン樹脂粉末、シリコーンゴム粉末、有機樹脂粉末(シリコーン樹脂粉末を除く)、有機変性粘度鉱物、酸化チタン、酸化亜鉛、雲母チタン、金属石鹸、無機体質顔料および無機着色顔料からなる群から選択される少なくとも1種の粉体または着色剤である、請求項8に記載の油性原料の増粘剤またはゲル化剤。
- (D)油性原料30~80質量%と、請求項1~11のいずれか1項に記載の油性原料の増粘剤またはゲル化剤10~70質量%と、(D)低級一価アルコール及び有機系多価アルコール性化合物からなる群から選択される少なくとも1種の化合物0~20質量%および(E)水0~20質量%を含有してなるゲル状組成物。
- (F)紫外線吸収剤を更に含有する、請求項12に記載のゲル状組成物。
- (G)ショ糖脂肪酸エステル、ポリグリセリン脂肪酸エステルから選択される少なくとも1種の化合物を更に含有する、請求項12または請求項13に記載のゲル状組成物。
- (H)有機系の皮膜形成剤を更に含有する、請求項12~請求項14のいずれか1項に記載のゲル状組成物。
- (J)アミノ酸及び/又はその塩、無機塩、有機酸及び/又はその塩、水溶性高分子、からなる群から選択される少なくとも1種の化合物を更に含有する、請求項12~請求項15のいずれか1項に記載のゲル状組成物。
- 請求項12~請求項16のいずれか1項に記載のゲル状組成物100質量部と(E)水0.1~4,000質量部とを混合する事により、化粧料を製造する方法。
- 請求項12~請求項16のいずれか1項に記載のゲル状組成物100質量部と(E)水0.1~4,000質量部とを混合する事により得られる化粧料。
- (D)油性原料30~80質量%と、請求項8または11に記載の油性原料の増粘剤またはゲル化剤20~60質量%と、(E)水0~20質量%を含有してなるゲル状化粧料。
- 水相と、上記の(A)成分および(D)油性原料を含む油相とを、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1に記載の油性原料の増粘剤またはゲル化剤を含有するエマルジョン組成物の透明性調整方法。
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| CN201080056071.3A CN102648264B (zh) | 2009-10-23 | 2010-10-25 | 用于基于油的原料的增稠剂或胶凝剂 |
| JP2011537338A JP5878760B2 (ja) | 2009-10-23 | 2010-10-25 | 油性原料の増粘剤またはゲル化剤 |
| KR1020127013359A KR101833959B1 (ko) | 2009-10-23 | 2010-10-25 | 오일-기반 원료 물질을 위한 증점제 또는 겔화제 |
| EP10825093.7A EP2492333B1 (en) | 2009-10-23 | 2010-10-25 | Thickening or gelling agent for oily raw materials |
| US13/503,623 US9580600B2 (en) | 2009-10-23 | 2010-10-25 | Thickening or gelling agent for oily raw materials |
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| JP2009244977 | 2009-10-23 | ||
| JP2009-244977 | 2009-10-23 |
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| WO2011049247A1 true WO2011049247A1 (ja) | 2011-04-28 |
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| KR (1) | KR101833959B1 (ja) |
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| WO2014069400A1 (ja) * | 2012-10-30 | 2014-05-08 | 株式会社 資生堂 | オルガノシロキサン誘導体組成物 |
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| WO2014104256A1 (ja) | 2012-12-28 | 2014-07-03 | 東レ・ダウコーニング株式会社 | 高純度グリセリン誘導体変性シリコーンの製造法 |
| WO2014104255A1 (ja) | 2012-12-28 | 2014-07-03 | 東レ・ダウコーニング株式会社 | 高純度モノアルケニル含有グリセリン誘導体及びその製造方法 |
| WO2014104257A1 (ja) | 2012-12-28 | 2014-07-03 | 東レ・ダウコーニング株式会社 | 高純度有機ケイ素化合物の製造方法 |
| JP2014139145A (ja) * | 2013-01-21 | 2014-07-31 | Nippon Shikizai Inc | 油性固形化粧料 |
| EP2716685A4 (en) * | 2011-05-30 | 2014-10-29 | Dow Corning Toray Co Ltd | NOVEL LIQUID POLYSILOXANE ORGANO AND USE THEREOF |
| WO2014200111A1 (ja) | 2013-06-13 | 2014-12-18 | 東レ・ダウコーニング株式会社 | 長鎖炭化水素基含有ジグリセリン誘導体変性シリコーン及びその利用 |
| JP2015509488A (ja) * | 2012-02-10 | 2015-03-30 | ステパン カンパニー | 組織化された界面活性剤懸濁系 |
| JP2016510807A (ja) * | 2013-03-10 | 2016-04-11 | ペリテック・ファーマ・リミテッドPeritech Pharma Ltd. | 局所組成物および局所障害の処置方法 |
| JP2017043567A (ja) * | 2015-08-27 | 2017-03-02 | ロート製薬株式会社 | イソ吉草酸アルデヒドの消臭剤および消臭方法 |
| US10174170B2 (en) | 2014-04-21 | 2019-01-08 | Dow Corning Toray Co., Ltd. | Method for producing liquid high-purity polyhydric alcohol derivative-modified silicone or composition thereof |
| KR20190003601A (ko) | 2016-04-27 | 2019-01-09 | 다우 실리콘즈 코포레이션 | 신규 오가노폴리실록산 또는 그의 산 중화 염, 및 그것들의 용도 |
| JP2019514947A (ja) * | 2016-05-12 | 2019-06-06 | ユニリーバー・ナームローゼ・ベンノートシヤープ | レチノイン酸前駆体を安定化させるための方法および安定化レチノイン酸前駆体を含む皮膚有益組成物 |
| US10406092B2 (en) | 2012-12-28 | 2019-09-10 | Dow Silicones Corporation | Method for producing transparent or semi-transparent liquid glycerin-derivative-modified silicone composition |
| KR102064130B1 (ko) * | 2019-08-13 | 2020-01-09 | 성백연 | 피부 친화적 조소 조성물 |
| CN113831062A (zh) * | 2021-11-12 | 2021-12-24 | 深圳市华厦环境科技有限公司 | 无机固废固化剂专用粘合剂及其制备方法 |
| CN113876598A (zh) * | 2021-11-17 | 2022-01-04 | 中山中研化妆品有限公司 | O/w纳米乳及其制备方法、护肤品 |
| JP2022056928A (ja) * | 2020-09-30 | 2022-04-11 | 阪本薬品工業株式会社 | ポイントメイク化粧料 |
| CN116209481A (zh) * | 2020-07-30 | 2023-06-02 | 汉高股份有限及两合公司 | 湿态指示剂用组合物和湿态指示剂 |
| CN118126260A (zh) * | 2024-05-06 | 2024-06-04 | 西南石油大学 | 一种poss基杂化超临界co2增稠剂及其制备方法 |
Families Citing this family (38)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102666663A (zh) | 2009-10-23 | 2012-09-12 | 道康宁东丽株式会社 | 新的有机聚硅氧烷共聚物 |
| KR101925354B1 (ko) | 2009-10-23 | 2018-12-05 | 다우 코닝 도레이 캄파니 리미티드 | 공동-개질된 오가노폴리실록산 |
| EP2563844A1 (en) * | 2010-04-30 | 2013-03-06 | Dow Corning Toray Co., Ltd. | Organopolysiloxane and use thereof as surfactant, powder treatment agent, thickening agent of oil -based raw material or gelling agent. gel and emulsion compositions, as well as, preparations for external use and cosmetics comprising the same |
| WO2011136397A1 (en) | 2010-04-30 | 2011-11-03 | Dow Corning Toray Co., Ltd. | Novel organopolysiloxane, surfactant, emulsion composition, powder treatment agent, thickening agent of oil-based raw material, gelling agent, gel composition, and cosmetic raw material comprising novel organopolysiloxane, as well as, preparation for external use and cosmetic comprising the same |
| EP2766445A1 (en) * | 2011-10-12 | 2014-08-20 | Dow Corning Corporation | High-viscosity silicone adhesive |
| US20140243727A1 (en) * | 2011-10-12 | 2014-08-28 | Dow Corning Corporation | High-viscosity silicone gel adhesive compositions |
| US9668474B2 (en) | 2012-02-10 | 2017-06-06 | Stepan Company | Structured surfactant suspending systems |
| FR3002444B1 (fr) | 2013-02-25 | 2015-03-13 | Oreal | Composition cosmetique de type gel |
| FR3002449B1 (fr) | 2013-02-25 | 2015-04-03 | Oreal | Composition cosmetique de type gel |
| JP5834037B2 (ja) * | 2013-03-08 | 2015-12-16 | 株式会社 資生堂 | 油中水型乳化化粧料 |
| KR101598194B1 (ko) * | 2014-02-18 | 2016-02-26 | 주식회사 세화피앤씨 | 헤어 및 바디용 다기능 소취 화장료 조성물 |
| FR3021533B1 (fr) * | 2014-05-28 | 2017-09-15 | Oreal | Composition cosmetique de type gel |
| FR3025100B1 (fr) | 2014-08-28 | 2016-12-09 | Oreal | Composition cosmetique de type gel a tenue amelioree |
| DE102014217790A1 (de) | 2014-09-05 | 2016-03-10 | Evonik Degussa Gmbh | Verfahren zur Herstellung von hydrosilylierbaren Eugenol-Polyethern und Eugenol-Polyethersiloxanen sowie deren Verwendung |
| JP7046472B2 (ja) * | 2015-03-27 | 2022-04-04 | ロレアル | 油中水型エマルション組成物 |
| EP3173064B1 (en) * | 2015-11-30 | 2018-09-12 | Fujifilm Corporation | Oil-in-water emulsion gel composition, external preparation for skin and producing method of oil-in-water emulsion composition |
| KR101812877B1 (ko) | 2016-04-04 | 2017-12-28 | 주식회사 엘지생활건강 | 주름 은폐용 화장료 조성물 |
| CN107262291A (zh) * | 2016-04-08 | 2017-10-20 | 新疆科力新技术发展股份有限公司 | 水润型油砂气浮剂 |
| US11058626B2 (en) | 2017-01-31 | 2021-07-13 | L'oreal | Long-wear compositions containing silicone acrylate copolymer, silicone elastomer resin and surface-treated pigment |
| US11058625B2 (en) | 2017-01-31 | 2021-07-13 | L'oreal | Long-wear compositions containing silicone acrylate copolymer and silicone elastomer resin |
| US11058627B2 (en) | 2017-01-31 | 2021-07-13 | L'oreal | Long-wear compositions containing silicone acrylate copolymer and surface-treated pigment |
| JP6927739B2 (ja) * | 2017-04-28 | 2021-09-01 | 株式会社 資生堂 | 油中水型乳化メーキャップ化粧料 |
| KR102154565B1 (ko) * | 2018-11-13 | 2020-09-10 | 한국화학연구원 | 천연 오일을 함유하는 미세캡슐 및 이의 제조방법 |
| WO2020101461A1 (ko) | 2018-11-13 | 2020-05-22 | 한국화학연구원 | 세포 배양용 캐리어를 이용하여 제조된 오가노이드 및 이를 이용한 약물 독성 평가방법 |
| CN109735116B (zh) * | 2019-01-04 | 2021-03-30 | 山西大学 | 一种油污清洁棉及其制备方法 |
| US10842758B1 (en) * | 2019-06-18 | 2020-11-24 | Ampersand Biopharmaceuticals, Inc. | Transdermal penetrant formulations containing cannabidiol |
| DE102019211138A1 (de) * | 2019-07-26 | 2021-01-28 | Beiersdorf Ag | Kosmetische Zusammensetzung |
| US12409118B2 (en) | 2020-01-31 | 2025-09-09 | Kao Corporation | External skin preparation |
| JP7738397B2 (ja) * | 2020-04-01 | 2025-09-12 | 花王株式会社 | 化粧方法 |
| KR102340546B1 (ko) | 2020-04-21 | 2021-12-20 | 주식회사 케이씨씨실리콘 | 폴리실록산 조성물 및 이로부터 제조된 친수성 실리콘 |
| CN114762661B (zh) * | 2021-01-12 | 2024-02-02 | 万华化学集团股份有限公司 | 一种低温稳定的核壳结构柔珠及其制备方法 |
| CN114732758A (zh) * | 2021-04-28 | 2022-07-12 | 上海雪代日用化学有限公司 | 一种抗皱化妆品及其制备方法 |
| KR102793228B1 (ko) * | 2022-04-06 | 2025-04-08 | 주식회사 케이씨씨실리콘 | 폴리실록산 조성물 및 이로부터 제조된 친수성 실리콘 |
| CN115160451A (zh) * | 2022-08-09 | 2022-10-11 | 山东共聚有机硅技术研究院有限公司 | 疏水改性普鲁兰多糖的制备方法 |
| DE102022127154A1 (de) * | 2022-10-17 | 2024-04-18 | Viawa Gmbh | Stabiles oleogel |
| CN115974449B (zh) * | 2022-12-29 | 2024-02-23 | 中铁上海工程局集团有限公司 | 用于铁尾矿机制砂石混凝土的调节剂及其制备方法、使用方法 |
| KR20250109160A (ko) | 2024-01-09 | 2025-07-16 | 주식회사 케이씨씨실리콘 | 가교형 오르가노폴리실록산 공중합체 블렌드 및 이를 포함하는 겔 조성물 |
| CN118002585B (zh) * | 2024-03-12 | 2024-08-27 | 广西中玻新材料科技集团有限公司 | 一种固危废资源环保化处理工艺 |
Citations (37)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH049382B2 (ja) | 1982-06-22 | 1992-02-20 | ||
| JPH0480597B2 (ja) | 1983-11-30 | 1992-12-18 | Hitachi Ltd | |
| JPH05311076A (ja) | 1992-05-01 | 1993-11-22 | Toray Dow Corning Silicone Co Ltd | ゲル状シリコーン組成物 |
| JPH0689147A (ja) | 1992-09-09 | 1994-03-29 | Kobe Nippon Denki Software Kk | ディスク型外部記憶装置の書き込み抑制方法 |
| JPH06157236A (ja) | 1992-11-13 | 1994-06-03 | Kose Corp | 化粧料 |
| JPH06234039A (ja) | 1992-11-16 | 1994-08-23 | American Colloid Co | 非孔質カーボン鋳型製造用砂および鋳造方法 |
| JPH06305933A (ja) | 1993-04-21 | 1994-11-01 | Kao Corp | 油性固型化粧料 |
| JPH0725728A (ja) | 1993-07-09 | 1995-01-27 | Kao Corp | 油性化粧料 |
| JPH0733622A (ja) | 1993-07-27 | 1995-02-03 | Kao Corp | 油性化粧料 |
| JPH07100358A (ja) | 1993-09-30 | 1995-04-18 | Shiseido Co Ltd | ゲル状化粧料 |
| JPH08217626A (ja) | 1995-02-09 | 1996-08-27 | Shiseido Co Ltd | ゲル状化粧料 |
| JPH08268831A (ja) | 1995-03-31 | 1996-10-15 | Shiseido Co Ltd | 乳化化粧料 |
| JPH08268832A (ja) | 1995-03-31 | 1996-10-15 | Shiseido Co Ltd | 乳化化粧料 |
| JPH0971504A (ja) | 1995-09-08 | 1997-03-18 | Kose Corp | 油性化粧料 |
| JPH09194323A (ja) | 1996-01-12 | 1997-07-29 | Shiseido Co Ltd | ゲル状化粧料 |
| US5654362A (en) | 1996-03-20 | 1997-08-05 | Dow Corning Corporation | Silicone oils and solvents thickened by silicone elastomers |
| JPH10245317A (ja) | 1997-03-05 | 1998-09-14 | Shiseido Co Ltd | 油中水型乳化組成物 |
| JPH1149957A (ja) | 1997-06-02 | 1999-02-23 | Dow Corning Corp | シリコーンエラストマーの製造方法 |
| US5874069A (en) | 1997-01-24 | 1999-02-23 | Colgate-Palmolive Company | Cosmetic composition containing silicon-modified amides as thickening agents and method of forming same |
| US5919441A (en) | 1996-04-01 | 1999-07-06 | Colgate-Palmolive Company | Cosmetic composition containing thickening agent of siloxane polymer with hydrogen-bonding groups |
| US5981680A (en) | 1998-07-13 | 1999-11-09 | Dow Corning Corporation | Method of making siloxane-based polyamides |
| JP2000063225A (ja) | 1998-06-12 | 2000-02-29 | Dow Corning Toray Silicone Co Ltd | 化粧品原料、化粧品および化粧品の製造方法 |
| JP2001011281A (ja) | 1999-05-24 | 2001-01-16 | Dow Corning Corp | エラストマーシリコーンポリエーテルを含む組成物 |
| JP2001316473A (ja) * | 2000-04-28 | 2001-11-13 | Dow Corning Toray Silicone Co Ltd | デンドリマー構造含有重合体 |
| JP2002179798A (ja) | 2000-12-08 | 2002-06-26 | Shin Etsu Chem Co Ltd | 多価アルコール変性シリコーン及びそれを含有する化粧料 |
| US6534072B2 (en) | 2000-05-09 | 2003-03-18 | L'oreal | Process for increasing the persistence of at least one cosmetic effect and/or care effect of a cosmetic composition, cosmetic composition and use thereof |
| WO2003041664A1 (fr) | 2001-11-15 | 2003-05-22 | Shin-Etsu Chemical Co., Ltd. | Cosmetiques contenant un mineral argileux |
| WO2003075864A1 (en) | 2002-03-11 | 2003-09-18 | Shin-Etsu Chemical Co., Ltd. | Oily cosmetics |
| JP2004169015A (ja) * | 2002-11-01 | 2004-06-17 | Shin Etsu Chem Co Ltd | 粉体組成物及び油中粉体分散物.並びにそれらを有する化粧料 |
| JP2004182680A (ja) | 2002-12-05 | 2004-07-02 | Nippon Unicar Co Ltd | アミノ酸誘導体変性シリコーンを含有する油性化粧料 |
| JP2004231608A (ja) | 2003-01-31 | 2004-08-19 | Kose Corp | 化粧料 |
| JP2004339244A (ja) | 2002-03-25 | 2004-12-02 | Kao Corp | 分岐ポリグリセロール変性シリコーン |
| JP2005042097A (ja) | 2003-07-07 | 2005-02-17 | Shin Etsu Chem Co Ltd | 新規なオルガノポリシロキサン・グリセリン誘導体交互共重合体およびそれを含有する化粧料 |
| JP2005089494A (ja) | 2003-09-12 | 2005-04-07 | Kao Corp | 分岐ポリグリセロール変性シリコーンの製法 |
| JP2005194523A (ja) | 2003-12-10 | 2005-07-21 | Kao Corp | 変性ポリシロキサン及び該変性ポリシロキサンを用いた化粧料 |
| JP2007532754A (ja) | 2004-04-12 | 2007-11-15 | ダウ・コーニング・コーポレイション | シルセスキオキサン樹脂ワックス |
| WO2009025146A1 (ja) * | 2007-07-26 | 2009-02-26 | Shiseido Company Ltd. | ゲル組成物及び化粧料 |
Family Cites Families (63)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5133840B2 (ja) | 1973-05-17 | 1976-09-22 | ||
| JPS57139123A (en) | 1981-01-30 | 1982-08-27 | Union Carbide Corp | Organosilicone ternary copolymers and use for fiber treatment |
| JPS57149290A (en) | 1981-03-13 | 1982-09-14 | Shin Etsu Chem Co Ltd | Production of glycerol-modified silicone |
| DE3436177A1 (de) | 1984-10-03 | 1986-04-03 | Goldschmidt Ag Th | Verwendung von polyoxyalkylen-polysiloxan-copolymerisaten mit an siliciumatomen gebundenen langkettigen alkylresten als emulgatoren zur herstellung von w/o-emulsionen |
| GB8428401D0 (en) | 1984-11-09 | 1984-12-19 | Dow Corning Ltd | Organosiloxane-oxy-alkylene copolymers |
| JPS61127733A (ja) | 1984-11-27 | 1986-06-16 | Toray Silicone Co Ltd | 新規なオルガノポリシロキサン化合物 |
| JPS61293903A (ja) | 1985-05-20 | 1986-12-24 | Shiseido Co Ltd | 油中水型乳化化粧料 |
| JPS61293904A (ja) | 1985-05-20 | 1986-12-24 | Shiseido Co Ltd | 油中水型乳化メーキャップ化粧料 |
| JPS62187406A (ja) | 1986-02-13 | 1987-08-15 | Shiseido Co Ltd | 油中水型乳化化粧料 |
| JP2583412B2 (ja) | 1986-02-24 | 1997-02-19 | チッソ株式会社 | ヒドロキシル基含有シロキサン化合物 |
| JPH0662385B2 (ja) | 1986-03-18 | 1994-08-17 | 株式会社資生堂 | 乳化組成物 |
| JPS62216635A (ja) | 1986-03-18 | 1987-09-24 | Shiseido Co Ltd | 油中水および多価アルコ−ル型乳化組成物 |
| JP3061434B2 (ja) | 1990-05-07 | 2000-07-10 | 日本ユニカー株式会社 | 毛髪化粧料 |
| US5472686A (en) | 1990-12-28 | 1995-12-05 | Nippon Unicar Company Limited | Cosmetic formulations |
| JPH0689147B2 (ja) | 1990-05-15 | 1994-11-09 | 信越化学工業株式会社 | 変性シリコーン化合物及びその製造方法 |
| JPH0822811B2 (ja) | 1990-09-26 | 1996-03-06 | 花王株式会社 | 皮膚外用剤 |
| EP0475130B1 (en) | 1990-08-30 | 1997-12-03 | Kao Corporation | Siloxane derivative, its use as emulsifier and cosmetic preparations |
| JP2613124B2 (ja) | 1990-08-30 | 1997-05-21 | 花王株式会社 | 新規シロキサン誘導体、その製造方法及びこれを含有する化粧料 |
| JP3071222B2 (ja) | 1990-12-28 | 2000-07-31 | 日本ユニカー株式会社 | 皮膚化粧料 |
| JP2601738B2 (ja) | 1991-10-22 | 1997-04-16 | 花王株式会社 | 化粧料 |
| JP3283277B2 (ja) | 1991-12-16 | 2002-05-20 | 日本ユニカー株式会社 | オルガノポリシロキサン組成物 |
| JP3172787B2 (ja) | 1992-01-14 | 2001-06-04 | 日本精化株式会社 | 糖残基を有するオルガノシロキサン誘導体およびその製造方法 |
| US5484950A (en) | 1992-12-21 | 1996-01-16 | Polyset Company, Inc. | Process for selective monoaddition to silanes containing two silicon-hydrogen bonds and products thereof |
| JP2719303B2 (ja) | 1993-08-12 | 1998-02-25 | 鐘紡株式会社 | メイクアップ化粧料 |
| JP2587797B2 (ja) | 1994-12-21 | 1997-03-05 | 花王株式会社 | 化粧料 |
| JP2844453B2 (ja) | 1996-10-02 | 1999-01-06 | 花王株式会社 | 新規シロキサン誘導体 |
| JPH10167946A (ja) | 1996-12-09 | 1998-06-23 | Fuji Shikiso Kk | 分散性良好な組成物およびその組成物含有皮膚保護剤 |
| JP3496133B2 (ja) | 1997-05-09 | 2004-02-09 | 株式会社コーセー | 改質粉体及びそれを含有する化粧料 |
| JPH10310509A (ja) | 1997-05-09 | 1998-11-24 | Kose Corp | 頭髪化粧料 |
| JPH10310507A (ja) | 1997-05-09 | 1998-11-24 | Kose Corp | 油性化粧料 |
| JP3533554B2 (ja) | 1997-05-09 | 2004-05-31 | 株式会社コーセー | 粉末化粧料 |
| JP3533553B2 (ja) | 1997-05-09 | 2004-05-31 | 株式会社コーセー | 乳化化粧料 |
| JPH10310506A (ja) | 1997-05-09 | 1998-11-24 | Kose Corp | 低刺激性化粧料 |
| JPH10316536A (ja) | 1997-05-19 | 1998-12-02 | Kose Corp | 改質粉体及びそれを配合した化粧料 |
| US6184407B1 (en) | 1998-05-29 | 2001-02-06 | Dow Corning Toray Silicone Co., Ltd. | Carbosiloxane dendrimers |
| JP4270607B2 (ja) | 1998-08-27 | 2009-06-03 | 東レ・ダウコーニング株式会社 | カルボシロキサンデンドリマー |
| US6280748B1 (en) * | 1998-06-12 | 2001-08-28 | Dow Corning Toray Silicone, Ltd. | Cosmetic raw material cosmetic product and method for manufacturing cosmetic products |
| FR2779641B1 (fr) * | 1998-06-16 | 2000-07-21 | Oreal | Compositions cosmetiques detergentes et utilisation |
| JP2000239390A (ja) | 1999-02-25 | 2000-09-05 | Dow Corning Toray Silicone Co Ltd | カルボシロキサンデンドリマー |
| JP3912961B2 (ja) | 1999-06-30 | 2007-05-09 | 信越化学工業株式会社 | 新規なシリコーン粉体処理剤及びそれを用いて表面処理された粉体、並びにこの粉体を含有する化粧料 |
| JP3724988B2 (ja) | 1999-07-30 | 2005-12-07 | 信越化学工業株式会社 | 新規シリコーン化合物及びそれを含有してなる化粧料 |
| JP2002038013A (ja) | 2000-07-21 | 2002-02-06 | Shin Etsu Chem Co Ltd | 粉体組成物、その油中粉体分散物及びそれらを含有する化粧料 |
| US7001971B2 (en) | 2000-12-08 | 2006-02-21 | Shin-Etsu Chemical Co., Ltd. | Polyhydric alcohol-modified silicone and cosmetic material containing same |
| JP4723083B2 (ja) | 2000-12-08 | 2011-07-13 | 信越化学工業株式会社 | シリコーン分岐型ポリエーテル変性シリコーン化合物の製造方法及びこの方法によって得られた化合物を含有する化粧料 |
| US7655744B2 (en) | 2002-03-25 | 2010-02-02 | Kao Corporation | Branched polyglycerol-modified silicone |
| US7998903B2 (en) | 2004-05-19 | 2011-08-16 | Shin-Etsu Chemical Co., Ltd. | Glycerol-modified silicone spreading agent and a composition comprising the same |
| JP4429812B2 (ja) | 2004-06-07 | 2010-03-10 | 信越化学工業株式会社 | Aba型グリセリン変性シリコーン |
| US20060013843A1 (en) * | 2004-07-16 | 2006-01-19 | L'oreal | Cosmetic composition comprising a defined silicone polymer and a surfactant |
| US8080239B2 (en) | 2005-01-17 | 2011-12-20 | Shiseido Co., Ltd. | Cosmetic |
| JP4567584B2 (ja) | 2005-01-17 | 2010-10-20 | 株式会社資生堂 | 粉体分散安定剤及びこれを配合した粉体分散組成物 |
| US7652072B2 (en) | 2005-10-13 | 2010-01-26 | Momentive Performance Materials Inc. | Hydrolysis resistant organomodified disiloxane surfactants |
| US7507775B2 (en) | 2005-10-13 | 2009-03-24 | Momentive Performance Materials Inc. | Hydrolysis resistant organomodified disiloxane surfactants |
| US7601680B2 (en) | 2005-12-13 | 2009-10-13 | Momentive Performance Materials | Gemini silicone surfactant compositions and associated methods |
| JP5239122B2 (ja) * | 2006-03-03 | 2013-07-17 | 信越化学工業株式会社 | オルガノポリシロキサン粉体処理剤及び該処理剤により処理された粉体並びに該粉体を含有する化粧料 |
| JP5005936B2 (ja) * | 2006-03-22 | 2012-08-22 | 東レ・ダウコーニング株式会社 | ゲル化剤、ゲル状組成物および化粧料 |
| EP2022812B1 (en) | 2006-05-19 | 2014-04-23 | Dow Corning Toray Co., Ltd. | Polyether-modified organopolysiloxane, diorganopolysiloxane-polyether block copolymer, their production methods, and cosmetic preparation |
| JP2008115358A (ja) | 2007-06-18 | 2008-05-22 | Shin Etsu Chem Co Ltd | オルガノポリシロキサン及びその製法ならびに該オルガノポリシロキサンを含む化粧料組成物 |
| US20110182846A1 (en) | 2007-08-10 | 2011-07-28 | Shiseido Company Ltd. | Surface Treating Agent, Surface-Treated Powder, And Cosmetic |
| JP5305677B2 (ja) | 2008-02-05 | 2013-10-02 | 株式会社 資生堂 | 洗浄料 |
| KR101925354B1 (ko) | 2009-10-23 | 2018-12-05 | 다우 코닝 도레이 캄파니 리미티드 | 공동-개질된 오가노폴리실록산 |
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| EP2598113B1 (en) * | 2010-07-30 | 2016-04-20 | Dow Corning Toray Co., Ltd. | Cosmetic for hair containing co-modified organopolysiloxane |
-
2010
- 2010-10-25 WO PCT/JP2010/069248 patent/WO2011049247A1/ja not_active Ceased
- 2010-10-25 JP JP2011537338A patent/JP5878760B2/ja active Active
- 2010-10-25 EP EP10825093.7A patent/EP2492333B1/en not_active Not-in-force
- 2010-10-25 US US13/503,623 patent/US9580600B2/en active Active
- 2010-10-25 CN CN201080056071.3A patent/CN102648264B/zh not_active Expired - Fee Related
- 2010-10-25 KR KR1020127013359A patent/KR101833959B1/ko not_active Expired - Fee Related
Patent Citations (52)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH049382B2 (ja) | 1982-06-22 | 1992-02-20 | ||
| JPH0480597B2 (ja) | 1983-11-30 | 1992-12-18 | Hitachi Ltd | |
| JP3333782B2 (ja) | 1992-05-01 | 2002-10-15 | 東レ・ダウコーニング・シリコーン株式会社 | ゲル状シリコーン組成物 |
| JPH05311076A (ja) | 1992-05-01 | 1993-11-22 | Toray Dow Corning Silicone Co Ltd | ゲル状シリコーン組成物 |
| JPH0689147A (ja) | 1992-09-09 | 1994-03-29 | Kobe Nippon Denki Software Kk | ディスク型外部記憶装置の書き込み抑制方法 |
| JPH06157236A (ja) | 1992-11-13 | 1994-06-03 | Kose Corp | 化粧料 |
| JP3389271B2 (ja) | 1992-11-13 | 2003-03-24 | 株式会社コーセー | 化粧料 |
| JPH06234039A (ja) | 1992-11-16 | 1994-08-23 | American Colloid Co | 非孔質カーボン鋳型製造用砂および鋳造方法 |
| JPH06305933A (ja) | 1993-04-21 | 1994-11-01 | Kao Corp | 油性固型化粧料 |
| JP3477222B2 (ja) | 1993-04-21 | 2003-12-10 | 花王株式会社 | 油性固型化粧料 |
| JPH0725728A (ja) | 1993-07-09 | 1995-01-27 | Kao Corp | 油性化粧料 |
| JP3160427B2 (ja) | 1993-07-09 | 2001-04-25 | 花王株式会社 | 油性化粧料 |
| JPH0733622A (ja) | 1993-07-27 | 1995-02-03 | Kao Corp | 油性化粧料 |
| JP3200247B2 (ja) | 1993-07-27 | 2001-08-20 | 花王株式会社 | 油性化粧料 |
| JPH07100358A (ja) | 1993-09-30 | 1995-04-18 | Shiseido Co Ltd | ゲル状化粧料 |
| JP3639315B2 (ja) | 1993-09-30 | 2005-04-20 | 株式会社資生堂 | ゲル状化粧料 |
| JPH08217626A (ja) | 1995-02-09 | 1996-08-27 | Shiseido Co Ltd | ゲル状化粧料 |
| JP3407770B2 (ja) | 1995-02-09 | 2003-05-19 | 株式会社資生堂 | ゲル状化粧料 |
| JP3580384B2 (ja) | 1995-03-31 | 2004-10-20 | 株式会社資生堂 | 乳化化粧料 |
| JP3580385B2 (ja) | 1995-03-31 | 2004-10-20 | 株式会社資生堂 | 乳化化粧料 |
| JPH08268832A (ja) | 1995-03-31 | 1996-10-15 | Shiseido Co Ltd | 乳化化粧料 |
| JPH08268831A (ja) | 1995-03-31 | 1996-10-15 | Shiseido Co Ltd | 乳化化粧料 |
| JPH0971504A (ja) | 1995-09-08 | 1997-03-18 | Kose Corp | 油性化粧料 |
| JP3513682B2 (ja) | 1995-09-08 | 2004-03-31 | 株式会社コーセー | 油性化粧料 |
| JP3719540B2 (ja) | 1996-01-12 | 2005-11-24 | 株式会社資生堂 | ゲル状化粧料 |
| JPH09194323A (ja) | 1996-01-12 | 1997-07-29 | Shiseido Co Ltd | ゲル状化粧料 |
| US5654362A (en) | 1996-03-20 | 1997-08-05 | Dow Corning Corporation | Silicone oils and solvents thickened by silicone elastomers |
| US5919441A (en) | 1996-04-01 | 1999-07-06 | Colgate-Palmolive Company | Cosmetic composition containing thickening agent of siloxane polymer with hydrogen-bonding groups |
| US5874069A (en) | 1997-01-24 | 1999-02-23 | Colgate-Palmolive Company | Cosmetic composition containing silicon-modified amides as thickening agents and method of forming same |
| JP3313043B2 (ja) | 1997-03-05 | 2002-08-12 | 株式会社資生堂 | 油中水型乳化組成物 |
| JPH10245317A (ja) | 1997-03-05 | 1998-09-14 | Shiseido Co Ltd | 油中水型乳化組成物 |
| JPH1149957A (ja) | 1997-06-02 | 1999-02-23 | Dow Corning Corp | シリコーンエラストマーの製造方法 |
| JP2000063225A (ja) | 1998-06-12 | 2000-02-29 | Dow Corning Toray Silicone Co Ltd | 化粧品原料、化粧品および化粧品の製造方法 |
| US5981680A (en) | 1998-07-13 | 1999-11-09 | Dow Corning Corporation | Method of making siloxane-based polyamides |
| JP2001011281A (ja) | 1999-05-24 | 2001-01-16 | Dow Corning Corp | エラストマーシリコーンポリエーテルを含む組成物 |
| JP2001316473A (ja) * | 2000-04-28 | 2001-11-13 | Dow Corning Toray Silicone Co Ltd | デンドリマー構造含有重合体 |
| US6534072B2 (en) | 2000-05-09 | 2003-03-18 | L'oreal | Process for increasing the persistence of at least one cosmetic effect and/or care effect of a cosmetic composition, cosmetic composition and use thereof |
| JP3976226B2 (ja) | 2000-12-08 | 2007-09-12 | 信越化学工業株式会社 | 多価アルコール変性シリコーン及びそれを含有する化粧料 |
| JP2002179798A (ja) | 2000-12-08 | 2002-06-26 | Shin Etsu Chem Co Ltd | 多価アルコール変性シリコーン及びそれを含有する化粧料 |
| WO2003041664A1 (fr) | 2001-11-15 | 2003-05-22 | Shin-Etsu Chemical Co., Ltd. | Cosmetiques contenant un mineral argileux |
| JP3678420B2 (ja) | 2001-11-15 | 2005-08-03 | 信越化学工業株式会社 | 粘度鉱物を有する化粧料 |
| WO2003075864A1 (en) | 2002-03-11 | 2003-09-18 | Shin-Etsu Chemical Co., Ltd. | Oily cosmetics |
| JP3625471B2 (ja) | 2002-03-11 | 2005-03-02 | 信越化学工業株式会社 | 油性化粧料 |
| JP2004339244A (ja) | 2002-03-25 | 2004-12-02 | Kao Corp | 分岐ポリグリセロール変性シリコーン |
| JP2004169015A (ja) * | 2002-11-01 | 2004-06-17 | Shin Etsu Chem Co Ltd | 粉体組成物及び油中粉体分散物.並びにそれらを有する化粧料 |
| JP2004182680A (ja) | 2002-12-05 | 2004-07-02 | Nippon Unicar Co Ltd | アミノ酸誘導体変性シリコーンを含有する油性化粧料 |
| JP2004231608A (ja) | 2003-01-31 | 2004-08-19 | Kose Corp | 化粧料 |
| JP2005042097A (ja) | 2003-07-07 | 2005-02-17 | Shin Etsu Chem Co Ltd | 新規なオルガノポリシロキサン・グリセリン誘導体交互共重合体およびそれを含有する化粧料 |
| JP2005089494A (ja) | 2003-09-12 | 2005-04-07 | Kao Corp | 分岐ポリグリセロール変性シリコーンの製法 |
| JP2005194523A (ja) | 2003-12-10 | 2005-07-21 | Kao Corp | 変性ポリシロキサン及び該変性ポリシロキサンを用いた化粧料 |
| JP2007532754A (ja) | 2004-04-12 | 2007-11-15 | ダウ・コーニング・コーポレイション | シルセスキオキサン樹脂ワックス |
| WO2009025146A1 (ja) * | 2007-07-26 | 2009-02-26 | Shiseido Company Ltd. | ゲル組成物及び化粧料 |
Non-Patent Citations (1)
| Title |
|---|
| See also references of EP2492333A4 |
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Also Published As
| Publication number | Publication date |
|---|---|
| KR20120089329A (ko) | 2012-08-09 |
| EP2492333A4 (en) | 2013-07-24 |
| EP2492333B1 (en) | 2014-04-30 |
| CN102648264A (zh) | 2012-08-22 |
| EP2492333A1 (en) | 2012-08-29 |
| KR101833959B1 (ko) | 2018-03-02 |
| JPWO2011049247A1 (ja) | 2013-03-14 |
| CN102648264B (zh) | 2015-08-19 |
| JP5878760B2 (ja) | 2016-03-08 |
| US9580600B2 (en) | 2017-02-28 |
| US20120269748A1 (en) | 2012-10-25 |
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