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• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
  • A61K8/89—Polysiloxanes
  • A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
  • A61K8/892—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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  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
• • A—HUMAN NECESSITIES
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  • 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
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  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
  • A61K8/0241—Containing particulates characterized by their shape and/or structure
• • 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
  • A61K8/893—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone modified by an alkoxy or aryloxy group, e.g. behenoxy dimethicone or stearoxy dimethicone
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
  • A61K8/89—Polysiloxanes
  • A61K8/895—Polysiloxanes containing silicon bound to unsaturated aliphatic groups, e.g. vinyl dimethicone
• • A—HUMAN NECESSITIES
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  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K9/00—Medicinal preparations characterised by special physical form
  • A61K9/0012—Galenical forms characterised by the site of application
  • A61K9/0014—Skin, i.e. galenical aspects of topical compositions
• • A—HUMAN NECESSITIES
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  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K9/00—Medicinal preparations characterised by special physical form
  • A61K9/10—Dispersions; Emulsions
  • A61K9/107—Emulsions ; Emulsion preconcentrates; Micelles
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
  • A61Q1/12—Face or body powders for grooming, adorning or absorbing
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q15/00—Anti-perspirants or body deodorants
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
  • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q19/00—Preparations for care of the skin
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q19/00—Preparations for care of the skin
  • A61Q19/007—Preparations for dry skin
• • 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
  • A61Q19/08—Anti-ageing preparations
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q5/00—Preparations for care of the hair
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
  • C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
  • C08G77/50—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
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  • 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
  • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
  • C08L83/12—Block- or graft-copolymers containing polysiloxane sequences containing polyether sequences
• • 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
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
  • A61K2800/10—General cosmetic use
• • 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
  • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]

Definitions

• the present invention relates to a novel organopolysiloxane elastomer having a crosslinked structure and uses thereof.
• the applications and background art of the novel organopolysiloxane elastomer of the present invention are common to the corresponding disclosed content of another patent application claiming priority rights based on Japanese Patent Application No. 2011-121097 filed on the same day as this application (related to a modified organopolysiloxane elastomer having a siloxane dendron structure and a mono-diglycerin-modified organopolysiloxane elastomer).
• Patent Documents 1 and 2 As an organopolysiloxane elastomer having a hydrophilic group, a silicone polymer which is swellable with respect to silicone oil and a paste-like silicone composition which is produced using the silicone polymer and can stably and uniformly disperse water have been reported (Patent Documents 1 and 2). This is a material provided with enhanced adaptability with respect to formulations containing water in addition to stable viscosity-improving characteristics for silicone oils by introducing a polyoxyalkylene group into the gel skeleton of a silicone gel composition (Patent Document 3) or powder, paste-like, or grease-like silicone composition (Patent Document 4) reported prior to these patents.
• compositions proposed in Patent Documents 1 and 2 have excellent characteristics for emulsifying/dispersing water in silicone oils, the compositions cannot stably emulsify/disperse water in a system containing non-silicone oils such as a hydrocarbon oil or an ester oil, leading to the problem that the viscosity-improving effects are also limited. Further, there is the drawback that when the resulting emulsion is stored for a long period of time, the pH decreases and the emulsion develops an abnormal odor.
• Patent Documents 5 and 6 a polyoxyalkylene group-containing organopolysiloxane elastomer having a structure differing from that of the materials described above and a silicone paste containing this elastomer and a solvent have also been proposed.
• These technologies are characterized in that decamethylcyclopentasiloxane, which also has excellent compatibility with non-silicone oil agents as a solvent, is used, and the effect of this substance enables the stable emulsification/dispersion of water in silicone/non-silicone mixed oils.
• this organopolysiloxane elastomer uses a chain silicone oil or non-silicone oil other than a cyclic dimethylpolysiloxane such as decamethylcyclopentasiloxane as a solvent, there is a problem in that it becomes difficult to stably emulsify/disperse water in a silicone/non-silicone mixed oil or a non-silicone oil.
• known technologies which aim to demonstrate stable emulsification performance with a formulation containing organic oils by improving the compatibility of the organopolysiloxane elastomer itself with non-silicone oils include a technology using a composition containing a blend of a crosslinked elastomeric silicone polyether and a crosslinked elastomeric silicone containing an alkyl group having from 3 to 40 carbon atoms (Patent Document 7) and a technology using an elastomer silicone terpolymer composition containing a polyoxyalkylene group and a higher alkyl group having at least 10 carbon atoms (Patent Document 8).
• Patent Document 9 a technology which uses a silicone substance containing a polymer network structure formed by the polymerization of a polyfunctional organosilicone compound containing an alkenyl group and a hydride group in the same molecule
• Patent Document 10 a technology which uses a polyether siloxane elastomer compatible with polar solvents
• Patent Document 11 a technology which uses a crosslinked silicone polymer mesh-like composition expanded by alkyltrisiloxane
• Patent Document 9 Even if an attempt is made to introduce allyl polyether into the molecule, a self-polymerization reaction of the polyfunctional organosilicone occurs preferentially due to the problem of compatibility and the difference between the reactivities of the C ⁇ C bonding sites, which causes the substance to gelify quickly. Therefore, the polyether group serving as a hydrophilic portion cannot be introduced evenly, which leads to the problem that fluctuations in emulsification performance tend to occur.
• the technologies of Patent Documents 10 and 11 have problems in that the stability of W/O emulsions containing organic oils is insufficient.
• Patent Documents 14 to 17 several technologies related to emulsions or emulsion-type cosmetic compositions using the materials described above have also been reported (Patent Documents 14 to 17), but the respective materials serving as a foundation have the problems described above, so the degree of completion when used as a cosmetic composition is low.
• the issue that the resulting emulsion develops a strong abnormal odor when the emulsion is stored for a long period of time remains unresolved.
• Patent Document 20 recites that propionaldehyde originating from unreacted propenyl-etherified polyoxyalkylene is a cause of the odor.
• the polyether-modified polysiloxane composition is typically synthesized via a hydrosilylation reaction of an organohydrogenpolysiloxane having a silicon-bonded hydrogen group and a polyoxyalkylene having an allyl ether group at a terminal.
• Patent Document 20 recites that, in the production of the polyether-modified polysiloxane composition, a double bond of the allyl etherified polyoxyalkylene migrates inward due to the influence of a platinum catalyst and a portion of the allyl-etherified polyoxyalkylene becomes a propenyl-etherified polyoxyalkylene and remains in the polyether-modified polysiloxane composition as is without reacting with the organohydrogenpolysiloxane.
• Patent Document 12 also recites that the propenyl-etherified polyoxyalkylene degrades over time, thus producing ketones and aldehydes which results in the odorization. Moreover, hydrolysis in the presence of an acid is disclosed as a useful deodorization method.
• Patent Documents 21 to 24 methods for suppressing the production of propionaldehyde have been disclosed (Patent Documents 21 to 24).
• a hydrogenation treatment is performed as a deodorization method of the polyether-modified polysiloxane composition in order to alkylate the alkenyl groups (double bonds) included in the alkenyl group-containing polyoxyalkylene (including both propenyl-etherified polyoxyalkylene and allyl-etherified polyoxyalkylene) remaining in the composition.
• a hydrogenation treatment is performed as a deodorization method of the polyether-modified polysiloxane composition in order to alkylate the alkenyl groups (double bonds) included in the alkenyl group-containing polyoxyalkylene (including both propenyl-etherified polyoxyalkylene and allyl-etherified polyoxyalkylene) remaining in the composition.
• a polyether-modified polysiloxane composition deodorized using a hydrogenation reaction in cases where a formulation including water and
• a cause of the odorization is acetal and similar aldehyde condensation products that are free of unsaturated bonds that remain in the composition.
• Patent Document 25 technology in which treatment using the acid aqueous solution and hydrogenation treatment are combined
• Patent Documents 26 and 27 technologies in which hydrogenation treatment and treatment using a solid acid catalyst are combined. That is, it is acknowledged that performing at least hydrogenation treatment is preferable in the deodorization of polyether-modified polysiloxanes as a raw material suitable for use in cosmetic products.
• Patent Document 28 introduces a paste-like composition which is obtained by adding at least one type of acidic substance selected from the group consisting of organic acids, phosphoric acids, and phosphoric acid salts to a mixture consisting of a crosslinked organopolysiloxane polymer having a polyoxyalkylene chain and a liquid oil, adding a basic neutralizing salt so that the pH is from 5 to 8, and then removing volatile components by heating and/or decompression.
• Patent Document 29 introduces a composition obtained by adding at least one type of acidic substance selected from the group consisting of organic acids, inorganic acids, and inorganic acid salts to an organopolysiloxane polymer having a glycerin derivative and containing a liquid oil in an amount equal to or greater than its own weight so that the polymer is capable of swelling, and a paste-like composition prepared by adding a liquid oil agent to this polymer so that the polymer swells, adding a basic neutralizing salt so that the pH is from 5 to 8, and then removing volatile components by heating and/or decompression.
• an organopolysiloxane polymer having a glycerin derivative and containing a liquid oil in an amount equal to or greater than its own weight so that the polymer is capable of swelling
• a paste-like composition prepared by adding a liquid oil agent to this polymer so that the polymer swells, adding a basic neutralizing salt so that the pH is from 5 to 8, and then removing volatile components by
• This organopolysiloxane elastomer containing a glycerin derivative is assumed to have good solubility and emulsifiability in various oil agents in comparison to conventional polyoxyalkylene group-containing organopolysiloxane elastomers. Further, it has been reported that when comparing the sensation during use of W/O type creams using these substances as emulsifiers, elastomers having glycerin derivatives demonstrate better moisture and retention. However, this material has poor compatibility with oil agents other than silicone oils such as hydrocarbon oils or ester oils, for example, and there is a problem in that the viscosity-improving effect on these organic oils is insufficient. Further, there are cases in which the effect is also insufficient from the perspective of the capacity to stably emulsify/disperse water in an oil agent system containing large amounts of organic oils.
• Patent Document 30 an organopolysiloxane elastomer characterized by a branched structure based on a polydimethylsiloxyethyl group and further having a hydrophilic group.
• this elastomer demonstrates a high viscosity-improving effect on silicone oils and organic oils other than silicone oils and provides a paste free of stickiness.
• this paste demonstrates oily gooeyness and an unnatural warm sensation, so the paste is not necessarily satisfactory from the perspective of the tactile sensation.
• a first object of the present invention is to provide a novel organomodified organopolysiloxane elastomer and a production method thereof, wherein the novel organomodified organopolysiloxane elastomer has affinity with various oil agents, has excellent viscosity-improving characteristics, gelification characteristics, and emulsification characteristics, imparts excellent tactile sensation—in particular, an excellent tactile sensation characterized by smoothness with a velvet-like thickness—and imparts an excellent sensation during use.
• a second object of the present invention is to provide a raw material for an external use preparation or a cosmetic composition such as a thickening agent, a gelling agent, a tactile sensation improver, a surfactant, an emulsifier, or a powder dispersion stabilizer containing the organomodified organopolysiloxane elastomer, and a cosmetic composition or an external use preparation containing the organomodified organopolysiloxane elastomer.
• a cosmetic composition such as a thickening agent, a gelling agent, a tactile sensation improver, a surfactant, an emulsifier, or a powder dispersion stabilizer containing the organomodified organopolysiloxane elastomer
• a third object of the present invention is to provide an organomodified organopolysiloxane elastomer with a reduced odor, a raw material for an external use preparation or a cosmetic composition containing the same, and an external use preparation or a cosmetic composition containing the raw material.
• the present inventors arrived at the present invention as a result of conducting dedicated research in order to achieve the objective described above.
• the first object of the present invention is achieved by an organopolysiloxane elastomer having a silicon-bonded sugar alcohol-modified group and having a crosslinked three-dimensional network structure comprising a carbon-silicon bond in the crosslinking portion.
• the sugar alcohol-modified group is preferably expressed by the following general formula (4-1):
• the divalent organic group represented by R is preferably a substituted or unsubstituted, straight-chain or branched divalent hydrocarbon group having from 3 to 5 carbon atoms.
• the organopolysiloxane elastomer described above can be obtained by reacting:
• the average number of silicon-bonded hydrogen atoms per molecule of the component (A), which reacts with reactive unsaturated groups of the component (C) constituting the crosslinking portion, is preferably at least 1.5.
• the component (A) is preferably expressed by the average composition formula (1):
• R 1 moieties are each independently monovalent organic groups, 1.0 ⁇ a ⁇ 3.0, and 0.001 ⁇ b ⁇ 1.5).
• the component (C) is preferably at least one organic compound selected from the following formulas (C1-1) to (C1-5) and (C2-1) to (C2-2):
• R 2 moieties may each be independent from one another but are monovalent organic groups that are different from R 3 ; R 3 moieties are each independently monovalent unsaturated aliphatic hydrocarbon groups having from 2 to 30 carbon atoms, 1.0 ⁇ p ⁇ 2.5, and 0.001 ⁇ q ⁇ 1.5);
• C2-1 an unsaturated epoxy compound expressed by the general formula (2-6):
• R 4 is a substituted or unsubstituted, straight-chain or branched monovalent hydrocarbon group having one reactive unsaturated group and from 2 to 20 carbon atoms
• C2-2 an unsaturated group-containing cycloaliphatic epoxy compound expressed by the general formula (2-7):
• C2-2 an unsaturated group-containing cycloaliphatic epoxy compound expressed by the general formula (2-7):
• R 5 is a substituted or unsubstituted, straight-chain or branched monovalent hydrocarbon group having one reactive unsaturated group and from 2 to 20 carbon atoms;
• R 6 is a hydrogen atom or a methyl group; and
• R 7 is a hydrogen atom or a methyl group).
• the monovalent organic group represented by R 1 is preferably selected from the following (D1) to (D10):
• (D1) a substituted or unsubstituted, straight-chain or branched monovalent hydrocarbon group having from 1 to 60 carbon atoms;
• (D2) a polyoxyalkylene group expressed by —R 8 O(AO) z R 9 (wherein AO is an oxyalkylene group having from 2 to 4 carbon atoms;
• R 8 is a substituted or unsubstituted, straight-chain or branched divalent hydrocarbon group having from 3 to 5 carbon atoms;
• (D3) a substituted or unsubstituted, straight-chain or branched alkoxy group having from 1 to 30 carbon atoms;
• R 12 is a substituted or unsubstituted, straight-chain or branched monovalent hydrocarbon group having from 1 to 30 carbon atoms;
• R 13 moieties each independently represents an alkyl group or a phenyl group having from 1 to 6 carbon atoms;
• Z is a divalent organic group;
• i represents a generation of the silylalkyl group represented by L i and is an integer of 1 to k when k is the number of generations, which is the number of repetitions of the silylalkyl group; the number of generations k is an integer from 1 to 10;
• h′ is a number in a range from 0 to 3
• D8 an alkyl group substituted by a chain polysiloxane structure expressed by the following general formula (4):
• R 14 moieties are each independently substituted or unsubstituted, straight-chain or branched monovalent hydrocarbon groups having from 1 to 30 carbon atoms, hydroxyl groups, or hydrogen atoms, and at least one of the R 14 moieties is the monovalent hydrocarbon group; t is a number in a range from 2 to 10; and r is a number in a range from 1 to 100);
• D9 an epoxy group expressed by the following general formula (5):
• R 15 is a substituted or unsubstituted, straight-chain or branched divalent hydrocarbon group having from 2 to 20 carbon atoms
• D10 a cycloaliphatic epoxy group expressed by the following general formula (6):
• R 16 is a substituted or unsubstituted, straight-chain or branched divalent hydrocarbon group having from 2 to 20 carbon atoms, and R 6 and R 7 are synonymous with those described above).
• the organopolysiloxane elastomer of the present invention is preferably in a particulate form and is more preferably in a particulate form with a volume average particle size in the range of from 20 to 1000 ⁇ m.
• the organopolysiloxane elastomer of the present invention is preferably swellable with an oil agent content of at least the weight of the elastomer itself.
• the first object of the present invention can be achieved by a production method for a liquid organopolysiloxane comprising a process of reacting:
• part or all of the reaction is preferable for part or all of the reaction to be performed in the presence of at least one solvent selected from the group indicated by (P-1) to (P-2) below.
• the component (A) and the component (B) are reacted first, and a crosslinking reaction is then performed by adding the component (C).
• a crosslinking reaction is then performed by adding the component (C).
• any component (Q) shown below may be reacted with the component (A) prior to the reaction between the component (A) and the component (B), further reacted after the reaction between the component (A) and the component (B), or further reacted after crosslinking with the component (C).
• a reaction between the component (A) and the component (C) is first performed to derive a crosslinked portion, and the component (B) is then added and reacted thereafter.
• any component (Q) shown below may be reacted with the component (A) prior to the reaction between the component (A) and the component (C), further reacted after the reaction between the component (A) and the component (C), or further reacted after the reaction of the component (B).
• the second object of the present invention can be achieved by a raw material for an external use preparation, a raw material for a cosmetic composition, an external use preparation, or a cosmetic composition containing the organopolysiloxane elastomer; a composition containing at least one type of oil agent in addition to the organopolysiloxane elastomer; and a raw material for an external use preparation or a cosmetic composition, an external use preparation, or a cosmetic composition containing the composition.
• composition described above can be obtained by mixing the organopolysiloxane elastomer of the present invention with at least one type of oil agent after grinding the elastomer using a mechanical force or grinding a mixture of the organopolysiloxane elastomer and at least one type of oil agent using a mechanical force.
• the composition may be in the form of an emulsion or a paste.
• the raw material for use in an external use preparation or a cosmetic composition can be a thickening agent, a gelling agent, a tactile sensation improver, a surfactant, an emulsifier, or a powder dispersion stabilizer.
• the third object of the present invention can be achieved by further performing an acidizing process of treating the organopolysiloxane elastomer obtained by the production method for the organopolysiloxane elastomer described above with at least one type of an acidic substance and a raw material for an external use preparation or a cosmetic composition, an external use preparation, or a cosmetic composition containing the composition described above.
• a process of heating and/or decompressing the composition is preferably performed after the acidizing process. Further, it is preferable to neutralize the composition by adding at least one type of a basic substance after the acidizing treatment process.
• the present invention it is possible to provide a novel organomodified organopolysiloxane elastomer, wherein the novel organomodified organopolysiloxane elastomer has affinity with various oil agents, has excellent viscosity-improving characteristics, gelification characteristics, and emulsification characteristics, imparts excellent tactile sensation—in particular, an excellent tactile sensation characterized by smoothness with a velvet-like thickness—and imparts an excellent sensation during use.
• the organomodified organopolysiloxane elastomer of the present invention has a thickening or gelling effect on various oil agents and can efficiently and stably thicken or gelate various oil agents.
• the organomodified organopolysiloxane elastomer of the present invention can demonstrate excellent emulsifying performance with respect to both nonpolar oil agents and polar oil agents in emulsions in which both water and an oil agent are present.
• the emulsion may also contain a polyhydroxy alcohol. Accordingly, it is possible to design an external use preparation or a cosmetic composition with various formulations by compounding the organomodified organopolysiloxane elastomer of the present invention in an external use preparation or a cosmetic composition. It is unnecessary for the preparation for external use or the cosmetic of the present invention to include a polyether-containing compound.
• a composition containing the organomodified organopolysiloxane elastomer of the present invention has the contradictory characteristics of having an extremely soft tactile sensation while being in a highly viscous form capable of guaranteeing stability. This effect is prominent when the organomodified organopolysiloxane elastomer is in a particulate form.
• the organomodified organopolysiloxane elastomer of the present invention has an excellent effect of maintaining the dispersion state of a powder dispersed in a medium, which makes it possible to enhance the storage stability of a composition containing the powder, in particular.
• the organomodified organopolysiloxane elastomer of the present invention can be advantageously used as a raw material for an external use preparation or a cosmetic composition such as a thickening agent, a gelling agent, a tactile sensation improver, a surfactant, an emulsifier, or a powder dispersion stabilizer and can be compounded in a cosmetic composition or an external use preparation as necessary.
• a cosmetic composition such as a thickening agent, a gelling agent, a tactile sensation improver, a surfactant, an emulsifier, or a powder dispersion stabilizer and can be compounded in a cosmetic composition or an external use preparation as necessary.
• the present invention can provide a nonaqueous emulsion composition with excellent stability that is usable as a drug delivery system.
• the present invention can provide a water-in-oil type or an oil-in-water type emulsion composition having excellent stability.
• organomodified organopolysiloxane elastomer of the present invention can be used as a composition with various oil agents because it can be uniformly mixed with a wide range of types of oil agents. Furthermore, a composition comprising an oil agent in conjunction with the organomodified organopolysiloxane elastomer of the present invention has superior storage stability.
• the odor of the organomodified organopolysiloxane elastomer can be reduced.
• the organomodified organopolysiloxane elastomer of the present invention having a reduced odor is particularly suitable as a raw material for an external use preparation or a cosmetic composition or as a component of an external use preparation or a cosmetic composition.
• the odor-reducing effect of the organomodified organopolysiloxane elastomer of the present invention is very high, and the odor-reducing effect achieved in the present invention cannot be achieved even by acidizing another modified organopolysiloxane elastomer in the same manner as in the present invention.
• the present invention is advantageous in industrial scale implementation and can provide an organomodified organopolysiloxane elastomer or a composition containing the same which is deodorized simply and at low cost.
• the odor of the organomodified organopolysiloxane elastomer of the present invention having a reduced odor does not need to be masked when compounded in an external use preparation or a cosmetic composition, and there is a high degree of flexibility in the design of the formulations of an external use preparation or a cosmetic composition.
• This is particularly advantageous in cosmetic compositions, in which functions that contain an odor are emphasized, and, therefore, design of a fragrance free cosmetic composition, a faintly scented cosmetic composition, or a cosmetic composition with a desired fragrance is easy.
• a first aspect of the present invention is an organopolysiloxane elastomer having a silicon-bonded sugar alcohol-modified group and having a crosslinked three-dimensional network structure comprising a carbon-silicon bond in the crosslinking portion.
• the organopolysiloxane elastomer of the present invention is an elastic substance with a relatively high crosslinking density and is a gel-like, rubber-like, or powder-like solid that is insoluble in solvents or the like.
• the organopolysiloxane elastomer of the present invention preferably does not have fluidity (non-liquid form) at 25° C. “Not having fluidity at 25° C.” means that after the organopolysiloxane elastomer is introduced into a prescribed container and the surface thereof is made horizontal using an instrument such as a trowel, the container is tilted, and the surface does not become horizontal once again after 24 hours.
• “horizontal” means to form a plane that intersects the direction of gravitational force at a right angle.
• the organopolysiloxane elastomer of the present invention has a crosslinked three-dimensional network structure having a crosslinking portion containing a carbon-silicon bond.
• the crosslinked three-dimensional network structure also contains a polysiloxane chain.
• the organopolysiloxane elastomer of the present invention has a high crosslinking molecular structure in which the polysiloxane chains are relatively densely crosslinked in a three-dimensional mesh. Accordingly, the organopolysiloxane is a gel-like, rubber-like, or powder-like solid that is insoluble in solvents or the like.
• the organopolysiloxane elastomer of the present invention is preferably swellable with an oil agent content of at least the weight of the elastomer itself (mass of the elastomer itself).
• the organopolysiloxane elastomer of the present invention containing an oil agent can exist in a paste form.
• the types and the like of the oil agents are as described below, and silicone oils are preferable.
• the organopolysiloxane elastomer of the present invention has a silicon-bonded sugar alcohol-modified group.
• the sugar alcohol-modified group constitutes a hydrophilic site of the organopolysiloxane elastomer of the present invention.
• the structure of the sugar alcohol-modified group is not limited as long as the structure has a sugar alcohol site, but the sugar alcohol residue is preferably bonded to a silicon atom via a divalent organic group.
• the sugar alcohol-modified group is preferably expressed by the following general formula (4-1):
• the organopolysiloxane elastomer of the present invention is characterized in that at least one type of a sugar alcohol-modified group expressed by the general formula (4-1) or (4-2) above is bonded to a silicon atom. Further, the organopolysiloxane may also have two or more types of sugar alcohol-modified groups selected from these sugar alcohol-modified groups in the molecule. Similarly, a mixture of organopolysiloxanes having different sugar alcohol-modified groups may also be used.
• the divalent organic group represented by R in the general formula (4-1) or (4-2) is not particularly limited, but examples include substituted or unsubstituted, straight-chain or branched divalent hydrocarbon groups having from 1 to 30 carbon atoms.
• a substituted or unsubstituted, straight-chain or branched divalent hydrocarbon group having from 3 to 5 carbon atoms is preferable.
• Examples of the substituted or unsubstituted, and straight-chain or branched divalent hydrocarbon group having from 1 to 30 carbon atoms include: straight-chain or branched alkylene groups having from 1 to 30 carbon atoms such as the methylene group, dimethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, or the like; alkenylene groups having from 2 to 30 carbon atoms such as the vinylene group, allylene group, butenylene group, hexenylene group, octenylene group, or the like; arylene groups having from 6 to 30 carbon atoms such as the phenylene group, diphenylene group, or the like; alkylenearylene groups having from 7 to 30 carbon atoms such as the dimethylenephenylene group or the like; and groups thereof in which hydrogen atoms bonded to carbon atoms of the groups are at least partially substituted by a
• the sugar alcohol-modified group in this case is a xylitol residue expressed by the structural formula: —C 3 H 6 —OCH 2 [CH(OH)] 3 CH 2 OH or the structural formula: —C 3 H 6 —OCH[CH(OH)CH 2 OH] 2 corresponding to the general formula (4-1) or (4-2) (hereinafter, simply referred to as a “xylitol residue” or a “xylitol modified group”).
• the bond position of the sugar alcohol-modified group may be either the side chain or the terminal of the polysiloxane, which is the main chain, and the organopolysiloxane of the present invention may have two or more sugar alcohol-modified groups. Further, these two or more sugar alcohol-modified groups may be the same or different sugar alcohol-modified groups. These two or more sugar alcohol-modified groups can be structured such that bonding occurs only in a side chain of polysiloxane, which is the main chain, only at a terminal, or in a side chain and at a terminal.
• the organopolysiloxane elastomer of the present invention can be produced by reacting:
• the (A) organohydrogenpolysiloxane is not particularly limited as long as it has silicon-bonded hydrogen atoms, but an organohydrogenpolysiloxane having more than one—preferably from 1.01 to 100, more preferably from 1.1 to 50, even more preferably from 1.2 to 25, and particularly preferably from 1.3 to 10-silicon-bonded hydrogen atoms in the molecule on average is preferable, and a straight-chain, branched, or reticulated organopolysiloxane may be used.
• the positions of the silicon-bonded hydrogen atoms in the organohydrogenpolysiloxane are not limited, and can be on the main chain or at the terminals. However, the atoms are preferably positioned at the terminals from the perspective of reducing the degree of crosslinking.
• One type or two or more types of organohydrogenpolysiloxanes may be used as the component (A).
• component (A) examples include 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, methylhydrogenpolysiloxane capped at both molecular terminals with trimethylsiloxy groups, dimethylsiloxane-methylhydrogensiloxane copolymers capped at both molecular terminals with trimethylsiloxy groups, dimethylsiloxane capped at both molecular terminals with dimethylhydrogensiloxy groups, dimethylpolysiloxane capped at both molecular terminals with dimethylhydrogensiloxy groups, dimethylsiloxane-methylhydrogensiloxane copolymers capped at both molecular terminals with dimethylhydrogensiloxy groups, methylhydrogensiloxane-diphenylsiloxane copolymers capped at both molecular terminals with trimethylsiloxy groups, methylhydrogensiloxane-diphenyl
• the component (A) is preferably expressed by the average composition formula (1):
• R 1 moieties are each independently monovalent organic groups, 1.0 ⁇ a ⁇ 3.0, and 0.001 ⁇ b ⁇ 1.5).
• the molecular structure of the (A) organohydrogenpolysiloxane is not limited, examples include straight-chain, partially branching straight-chain, branched-chain, cyclic, and dentric structures, and straight-chain is preferable.
• the molecular weight is not particularly limited, and products having a low molecular weight to products having a high molecular weight can be used.
• the number-average molecular weight is preferably in a range from 100 to 1,000,000 and more preferably in a range from 300 to 500,000.
• organohydrogenpolysiloxanes examples include those expressed by the following structural formulas:
• organohydrogenpolysiloxanes are straight-chain organohydrogenpolysiloxanes having a silicon-bonded hydrogen atom on (i) only the side chain, (ii) the side chain or one molecular terminal, or (iii) the side chain or both molecular terminals.
• the monovalent organic group is not particularly limited but is preferably selected from the following (D1) to (D10):
• (D1) a substituted or unsubstituted, straight-chain or branched monovalent hydrocarbon group having from 1 to 60 carbon atoms;
• (D2) a polyoxyalkylene group expressed by —R 8 O(AO) z R 9 (wherein AO is an oxyalkylene group having from 2 to 4 carbon atoms;
• R 8 is a substituted or unsubstituted, straight-chain or branched divalent hydrocarbon group having from 3 to 5 carbon atoms;
• (D3) a substituted or unsubstituted, straight-chain or branched alkoxy group having from 1 to 30 carbon atoms;
• R 12 is a substituted or unsubstituted, straight-chain or branched monovalent hydrocarbon group having from 1 to 30 carbon atoms;
• R 13 moieties each independently represents an alkyl group or a phenyl group having from 1 to 6 carbon atoms;
• Z is a divalent organic group;
• i represents a generation of the aforementioned silylalkyl group represented by L i and is an integer of 1 to k when k is the number of generations, which is the number of repetitions of the silylalkyl group; the number of generations k is an integer from 1 to 10;
• h′ is a number in a range from 0 to 3
• D8 an alkyl group substituted by a chain polysiloxane structure expressed by the following general formula (4):
• R 14 moieties are each independently substituted or unsubstituted, straight-chain or branched monovalent hydrocarbon groups having from 1 to 30 carbon atoms, hydroxyl groups, or hydrogen atoms, and at least one of the R 14 moieties is the monovalent hydrocarbon group; t is a number in a range from 2 to 10; and r is a number in a range from 1 to 100);
• D9 an epoxy group expressed by the following general formula (5):
• R 15 is a substituted or unsubstituted, straight-chain or branched divalent hydrocarbon group having from 2 to 20 carbon atoms
• D10 a cycloaliphatic epoxy group expressed by the following general formula (6):
• R 16 is a substituted or unsubstituted, straight-chain or branched divalent hydrocarbon group having from 2 to 20 carbon atoms, and R 6 and R 7 are synonymous with those described above).
• Examples of the substituted or unsubstituted, straight-chain or branched monovalent hydrocarbon group in (D1), (D2), and (D5) to (D8) include alkyl groups such as methyl groups, ethyl groups, propyl groups, butyl groups, pentyl groups, hexyl groups, heptyl groups, and octyl groups; cycloalkyl groups such as cyclopentyl groups and cyclohexyl groups; alkenyl groups such as vinyl groups, allyl groups, and butenyl groups; aryl groups such as phenyl groups and tolyl groups; aralkyl groups such as benzyl groups; and groups in which the hydrogen atoms bonded to the carbon atoms of these groups are substituted at least partially by halogen atoms such as fluorine atoms or organic groups such as epoxy groups, glycidyl groups, acyl groups, carboxyl groups, amino groups, methacryl groups, and
• the substituted or unsubstituted, straight-chain or branched divalent hydrocarbon group in (D2), (D5), (D6), (D9), and (D10) is as described above.
• Examples of the substituted or unsubstituted, straight-chain or branched alkoxy group in (D3) include lower alkoxy groups such as methoxy groups, ethoxy groups, isopropoxy groups, and butoxy groups and higher alkoxy groups such as lauryl alkoxy groups, myristyl alkoxy groups, palmityl alkoxy groups, oleyl alkoxy groups, stearyl alkoxy groups, and behenyl alkoxy groups.
• examples of the alkyl group having from 1 to 6 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, pentyl, neopentyl, cyclopentyl, hexyl, and similar straight, branched, or cyclic alkyl groups.
• R 4 is preferably a methyl group or a phenyl group.
• the number of generations k is preferably an integer from 1 to 3, and more preferably is 1 or 2.
• the group represented by L 1 is expressed as follows.
• R 12 , R 13 , and Z are the same groups as described above.
• L 1 is expressed by the following general formula (3-1).
• L 1 is expressed by the following general formula (3-2).
• L 1 is expressed by the following general formula (3-3).
• each of h 1 , h 2 and h 3 moieties is independently a number in a range from 0 to 3.
• These h′ moieties are preferably a number in a range from 0 to 1, and h′ is, in particular, preferably 0.
• Z are each independently a divalent organic group, and specific examples thereof include a divalent organic group formed by addition-reacting a silicon-bonded hydrogen atom and a functional group having an unsaturated hydrocarbon group such as an alkenyl group, an acryloxy group, a methacryloxy group, or the like at the terminal.
• the functional group can be appropriately selected and is not restricted to the functional groups described above.
• Z are each independently a group selected from divalent organic groups expressed by the following general formula.
• Z in L 1 is preferably a divalent organic group expressed by general formula —R 19 — that is introduced by a reaction between a silicon-bonded hydrogen atom and an alkenyl group.
• Z is preferably a divalent organic group expressed by general formula —R 19 —COO—R 20 — that is introduced by a reaction between a silicon-bonded hydrogen atom and an unsaturated carboxylic ester group.
• Z is preferably an alkylene group having from 2 to 10 carbon atoms and, in particular, is preferably a group selected from an ethylene group, a propylene group, a methylethylene group, and a hexylene group, and most preferably is an ethylene group.
• R 19 moieties are each independently a substituted or unsubstituted, straight or branched chain alkylene group or alkenylene group having from 2 to 22 carbon atoms or an arylene group having from 6 to 22 carbon atoms. More specifically, examples of R 19 include an ethylene group, a propylene group, a butylene group, a hexylene group, and similar straight alkylene groups; a methylmethylene group, a methylethylene group, a 1-methylpentylene group, a 1,4-dimethylbutylene group, and similar branched alkylene groups.
• R 7 is preferably a group selected from an ethylene group, a propylene group, a methylethylene group, and a hexylene group.
• R 2 ° is a group selected from divalent organic groups expressed by the following formula.
• the (B) sugar alcohol-modified group-containing compound having a reactive unsaturated group is not particularly limited as long as the compound has at least one reactive unsaturated group and one sugar alcohol-modified group in the molecule, but a monounsaturated ether compound of the sugar alcohol represented by the following general formula (4′-1):
• R′ is an unsaturated organic group, and e is 1 or 2 and more preferably 1) or the following general formula (4′-2):
• R′ is an unsaturated organic group, and e′ is 0 or 1 and more preferably 0
• e′ is 0 or 1 and more preferably 0
• the unsaturated organic groups are not particularly limited as long as it has an unsaturated group, but a substituted or unsubstituted, straight-chain or branched unsaturated hydrocarbon group having from 3 to 5 carbon atoms is preferable.
• the unsaturated hydrocarbon group having from 3 to 5 carbon atoms include vinyl groups, allyl groups, butenyl groups, methallyl groups and similar alkenyl groups. Among these, allyl groups are preferable.
• a monoallyl ether of a sugar alcohol is preferable, and a xylitol monoallyl ether expressed by the structural formula: CH 2 ⁇ CH—CH 2 —OCH 2 [CH(OH)] 3 CH 2 OH or the structural formula: CH 2 ⁇ CH—CH 2 —OCH[CH(OH)CH 2 OH] 2 (hereinafter, referred to as a “xylitol monoallyl ether”) is more preferable.
• the xylitol monoallyl ether can be synthesized with a conventionally known method, and a commercially available product may also be used.
• the xylitol monoallyl ether may be only one of the compounds represented by the structural formula: CH 2 ⁇ CH—CH 2 —OCH 2 [CH(OH)] 3 CH 2 OH and the structural formula: CH 2 ⁇ CH—CH 2 —OCH[CH(OH)CH 2 OH] 2 , or mixtures thereof can be used without any particularly restrictions.
• a xylitol monoallyl ether represented by the structural formula: CH 2 ⁇ CH—CH 2 —OCH 2 [CH(OH)] 3 CH 2 OH or the structural formula: CH 2 ⁇ CH—CH 2 —OCH[CH(OH)CH 2 OH] 2 and use the product as a raw material or to use a xylitol monoallyl ether containing xylitol monoallyl ethers represented by the structural formula: CH 2 ⁇ CH—CH 2 —OCH 2 [CH(OH)] 3 CH 2 OH and the structural formula: CH 2 ⁇ CH—CH 2 —OCH[CH(OH)CH 2 OH] 2 at a compositional ratio in a range from 5:5 to 10:0 as a raw material.
• a xylitol monoallyl ether containing the substances at a ratio in a range from 8:2 to 10:0.
• the raw material is essentially a refined product comprising only a xylitol monoallyl ether represented by the structural formula: CH 2 ⁇ CH—CH 2 —OCH 2 [CH(OH)] 3 CH 2 OH.
• a derivative (ketal derivative) of a sugar alcohol compound prepared by protecting a hydroxyl group of the sugar alcohol compound corresponding to the introduced sugar alcohol-modified group with a ketalizing agent such as 2,2-dimethoxypropane in the presence of an acid catalyst can be used as a raw material.
• a ketal derivative of a sugar alcohol having a carbon-carbon double bond in the molecule obtained by refining the reaction product of the ketal compound described above and an alkenyl halide is subjected to an addition reaction with an organohydrogenpolysiloxane instead of the monounsaturated ether compound of the sugar alcohol described above.
• the organopolysiloxane can be produced by performing a deketalation reaction by acid hydrolysis treatment to deprotect the hydroxyl group. Even with a production method using the ketal derivative described above, an organopolysiloxane elastomer having a sugar alcohol-modified group can be obtained after deprotection, but this method is typically inefficient. Either production method may be selected in accordance with conditions such as the desired yield, the production equipment, and the refinement of the raw material. Either production method may also be selected for the purpose of improving the quality such as the purity or the desired characteristics of the organopolysiloxane elastomer.
• (C1) the organic compound having an average number of reactive unsaturated groups in the molecule that is greater than 1 serving as the component (C) as long as the compound has more than 1—preferably from 1.01 to 10, more preferably from 1.2 to 8, even more preferably from 1.5 to 6, and particularly preferably from 2.0 to 4.5—reactive unsaturated groups and preferably carbon-carbon double bonds on average in the molecule, and straight-chain, branched, or reticulated organic compounds may be used.
• An organopolysiloxane or an unsaturated aliphatic hydrocarbon is preferable as an organic compound.
• the organic compound preferably the organopolysiloxane, the unsaturated aliphatic hydrocarbon, or the aforementioned reactive unsaturated group
• the component may be positioned on the main chain or on a terminal.
• a reactive unsaturated group is preferably present in an unsaturated aliphatic hydrocarbon group.
• the unsaturated aliphatic hydrocarbon group preferably has from 2 to 30 carbon atoms and more preferably has from 2 to 20 carbon atoms.
• Examples of the monovalent unsaturated aliphatic hydrocarbon group having from 2 to 30 carbon atoms include straight-chain or branched alkenyl groups such as vinyl groups, 1-propenyl groups, allyl groups, isopropenyl groups, 1-butenyl groups, 2-butenyl groups, pentenyl groups, and hexenyl groups; cycloalkenyl groups such as cyclopentenyl groups and cyclohexenyl groups; cycloalkenylalkyl groups such as cyclopentenylethyl groups, cyclohexenylethyl groups, and cyclohexenylpropyl groups; and alkynyl groups such as ethynyl groups and propargy
• the unsaturated aliphatic hydrocarbon group containing a reactive unsaturated group is preferably bonded to a silicon atom.
• the group bonding to silicon atoms other than the unsaturated aliphatic hydrocarbon may be a substituted or unsubstituted monovalent hydrocarbon group or a monovalent organic group having a reactive functional group.
• Substituted or unsubstituted monovalent hydrocarbon groups are typically substituted or unsubstituted, straight or branched monovalent saturated hydrocarbon groups having from 1 to 30 carbon atoms, preferably from 1 to 10 carbon atoms, and more preferably from 1 to 4 carbon atoms, and substituted or unsubstituted monovalent aromatic hydrocarbon groups having from 6 to 30 carbon atoms, and more preferably from 6 to 12 carbon atoms.
• component (C1) may contain, as a monovalent organic group, a hydroxyl group or an alkoxy group having from 1 to 12 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group or a butoxy group.
• Examples of the monovalent saturated hydrocarbon group having from 1 to 30 carbon atoms include straight chain or branched chain alkyl groups such as methyl groups, ethyl groups, n-propyl groups, isopropyl groups, n-butyl groups, isobutyl groups, sec-butyl groups, tert-butyl groups, pentyl groups, hexyl groups, heptyl groups, octyl groups, nonyl groups, decyl groups, and the like; and cycloalkyl groups such as cyclopentyl groups, cyclohexyl groups, cycloheptyl groups, cyclooctyl groups, and the like.
• Examples of the monovalent aromatic hydrocarbon group having from 6 to 30 carbon atoms include aryl groups such as phenyl groups, tolyl groups, xylyl groups, mesityl groups, and the like. Of these, a phenyl group is preferable.
• aromatic hydrocarbon group also includes groups in which an aromatic hydrocarbon and a saturated aliphatic hydrocarbon are conjugated in addition to groups formed only from an aromatic hydrocarbon. Examples of groups in which an aromatic hydrocarbon and a saturated hydrocarbon are conjugated include aralkyl groups such as benzyl groups, phenethyl groups, and the like.
• Hydrogen atoms in the above-mentioned monovalent hydrocarbon groups may be substituted by one or more substituted groups, and said substituted groups may be selected from the group consisting of, for example, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom), a hydroxyl group, an amide group, an ester group, a carboxyl group and an isocyanate group.
• a monovalent saturated or aromatic hydrocarbon group having at least one of the above-mentioned substituted groups is preferred.
• Examples of monovalent organic groups having reactive functional groups include monovalent saturated or aromatic hydrocarbon groups having reactive functional groups selected from the group consisting of, for example, hydroxyl groups, mercapto groups, epoxy groups, amino groups, amide groups, ester groups, carboxyl groups and isocyanate groups.
• One or a plurality of reactive functional groups may exist in the monovalent organic group.
• R 1 is preferably a monosaturated or aromatic hydrocarbon group having at least one of the reactive functional groups described above.
• the reactive functional group include 3-hydroxypropyl groups, 3-(2-hydroxyethoxy)propyl groups, 3-mercaptopropyl groups, 2,3-epoxypropyl groups, 3,4-epoxybutyl groups, 4,5-epoxypentyl groups, 2-glycidoxyethyl groups, 3-glycidoxypropyl groups, 4-glycidoxybutyl groups, 2-(3,4-epoxycyclohexyl)ethyl groups, 3-(3,4-epoxycyclohexyl)propyl groups, aminopropyl groups, N-methylaminopropyl groups, N-butylaminopropyl groups, N,N-dibutylaminopropyl groups, 3-(2-aminoethoxy)propyl groups, 3-(2-aminoethylamino)propyl groups, 3-(2-aminoethylamino)propyl groups, 3-carboxypropyl groups, 10-carboxydecyl groups
• a straight-chain or branched polysiloxane is preferable as the component (C1).
• a straight-chain component (C1) is preferably a polymer having a diorganosiloxane unit and a triorganosiloxane unit, examples of which include dimethylpolysiloxanes capped at both molecular terminals with dimethylvinylsiloxy groups, copolymers of dimethylsiloxane and methylphenylsiloxane capped at both molecular terminals with dimethylvinylsiloxy groups, copolymers of dimethylsiloxane and methylvinylsiloxane capped at both molecular terminals with dimethylvinylsiloxy groups, copolymers of dimethylsiloxane and methylvinylsiloxane capped at both molecular terminals with trimethylsiloxy groups, copolymers of dimethylsiloxane, methylvinylsiloxane and methylphenyls
• a branched chain polysiloxane of component (C1) is particularly preferable for a branched chain polysiloxane of component (C1) to be a polymer that contains a diorganosiloxane unit, an organosilsesquioxane unit and a triorganosiloxy unit.
• Silicon-bonded organic groups in these units are preferably monovalent hydrocarbon groups including alkyl groups such as methyl groups, ethyl groups and propyl groups; alkenyl groups such as vinyl groups, allyl groups, butenyl groups and hexenyl groups; aryl groups such as phenyl groups and tolyl groups; and halogenated alkyl groups such as 3,3,3-trifluoropropyl groups, and the like, and may contain extremely small quantities of hydroxyl groups and alkoxy groups such as methoxy groups, but at least two silicon-bonded organic groups in this polymer must be unsaturated aliphatic hydrocarbon groups, and especially alkenyl groups.
• alkyl groups such as methyl groups, ethyl groups and propyl groups
• alkenyl groups such as vinyl groups, allyl groups, butenyl groups and hexenyl groups
• aryl groups such as phenyl groups and tolyl groups
• halogenated alkyl groups such as 3,
• the proportions of these units are not limited, but in this polymer, it is preferable for diorganosiloxane units to account for in the range of 80.00 to 99.65 mol % and organosilsesquioxane units to account for in the range of 0.10 to 10.00 mol %, with the balance comprising triorganosiloxy units.
• component (C1) examples include (C1-5) unsaturated group-containing silicone compounds expressed by the average composition formula (2-5):
• R 2 moieties may each be independent from one another but are monovalent organic groups that are different from R 3 ;
• R 3 moieties are each independently monovalent unsaturated aliphatic hydrocarbon groups having from 2 to 30 carbon atoms, 1 ⁇ p ⁇ 2.5, and 0.001 ⁇ q ⁇ 1.5).
• the monovalent unsaturated aliphatic hydrocarbon group having from 2 to 30 carbon atoms is as described above.
• the monovalent organic group represented by R 2 is not particularly limited, but is preferably selected from the following (E1) to (E6):
• (E1) a substituted or unsubstituted, straight-chain or branched monovalent hydrocarbon group having from 1 to 60 carbon atoms (excluding monovalent hydrocarbon groups having from 2 to 20 carbon atoms and an aliphatic unsaturated group); (E2) a hydroxyl group; (E3) an ester group expressed by —R 10 —COOR 11 (wherein R 13 and R 11 are as defined above); (E4) an ester group expressed by —R 17 —OCOR 18 (wherein R 17 and R 18 are as defined above); (E5) an amide group expressed by —R 21 —NR 22 COR 23 (wherein R 21 is a substituted or unsubstituted, straight-chain or branched divalent hydrocarbon group having from 2 to 20 carbon atoms, R 22 is a hydrogen atom, or a substituted or unsubstituted, straight-chain or branched monovalent hydrocarbon group having from 1 to 20 carbon atoms, and R 23 is a substituted or unsubstituted
• the component (C1) may be an unsaturated aliphatic hydrocarbon.
• unsaturated aliphatic hydrocarbons include various dienes, diynes, enynes and similar products having two or more reactive unsaturated groups. In view of crosslinking, dienes, diynes, and enynes are preferable. Dienes, diynes, and enynes are compounds having a structure in which at least two reactive unsaturated groups are separated by one or more, and preferably two or more single bonds in a molecule.
• the unsaturated aliphatic hydrocarbon group may be present at the terminal of the molecular chain, or as a pendant group in the molecular chain.
• Examples of unsaturated aliphatic hydrocarbons serving as the component (C1) include ⁇ , ⁇ -unsaturated alkenes and alkynes having from 2 to 30 carbon atoms.
• Examples of the component (C1) include (C1-1) an ⁇ , ⁇ -diene expressed by the general formula (2-1):
• unsaturated aliphatic hydrocarbons serving as the component (C1) include 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,11-dodecadiene, 1,13-tetradecadiene, 1,19-eicosadiene, 1,3-butadiene, 1,5-hexadiyne, and 1-hexene-5-yne.
• the component (C1) may be a single component, but may also be a mixture of two or more components having different structures. That is, the component (C1) may be a mixture of one or more types of organopolysiloxanes and one or more types of unsaturated aliphatic hydrocarbons. Therefore, “having a number of reactive unsaturated groups greater than 1 on average” means having more than one reactive unsaturated group on average per molecule when two or more types of organopolysiloxanes and/or unsaturated aliphatic hydrocarbons are used.
• the (C2) organic compound having at least one reactive unsaturated group and at least one epoxy group in the molecule serving as the component (C) is not structurally limited as long as the compound has a total of two or more—preferably from 2 to 10, more preferably from 2 to 7, even more preferably from 2 to 5, and particularly preferably from 2 to 4-reactive unsaturated groups and epoxy groups in the molecule, and straight-chain, branched, or reticulated organic compounds can be used.
• An organopolysiloxane or an unsaturated aliphatic hydrocarbon is preferable as an organic compound.
• the organic compound preferably, the organopolysiloxane, the unsaturated aliphatic hydrocarbon, or the aforementioned reactive unsaturated group
• the component may be positioned on the main chain or on a terminal.
• a reactive unsaturated group is preferably present in an unsaturated aliphatic hydrocarbon group.
• unsaturated aliphatic hydrocarbon groups are as described above.
• the unsaturated aliphatic hydrocarbon group containing a reactive unsaturated group and/or the epoxy group is preferably bonded to the silicon atom.
• the group bonding to silicon atoms other than the unsaturated aliphatic hydrocarbon or the epoxy group may be a substituted or unsubstituted monovalent hydrocarbon group or a monovalent organic group having a reactive functional group as described above.
• the component (C2) is preferably an epoxy group-containing unsaturated aliphatic hydrocarbon having at least one epoxy group.
• unsaturated aliphatic hydrocarbon include compounds having the unsaturated aliphatic hydrocarbon groups described above.
• a compound having a monovalent unsaturated aliphatic hydrocarbon group is preferable.
• component (C1) examples include: (C2-1) an unsaturated epoxy compound expressed by the general formula (2-6):
• R 4 is a substituted or unsubstituted, straight-chain or branched monovalent hydrocarbon group having one reactive unsaturated group and from 2 to 20 carbon atoms
• C2-2 an unsaturated group-containing cycloaliphatic epoxy compound expressed by the general formula (2-7):
• R 5 is a substituted or unsubstituted, straight-chain or branched monovalent hydrocarbon group having one reactive unsaturated group and from 2 to 20 carbon atoms;
• R 6 is a hydrogen atom or a methyl group
• R 7 is a hydrogen atom or a methyl group
• Specific epoxy group-containing unsaturated aliphatic hydrocarbons serving as the component (C2) include an allylglycidylether, methallylglycidylether, 1-methyl-4-isopropenylcyclohexene oxide, 1,4-dimethylcyclohexene oxide, 4-vinylcyclohexene oxide, vinylnorbornene monooxide, dicyclopentadiene monooxide, butadiene monooxide, 1,2-epoxy-5-hexene, 1,2-epoxy-9-decene, and 2,6-dimethyl-2,3-epoxy-7-octene.
• 4-vinyl cyclohexane oxide is preferable.
• the component (C2) may be a single component, but may also be a mixture of two or more components having different structures.
• the reaction for producing the organopolysiloxane elastomer of the present invention may be performed in the presence or in the absence of a reaction solvent in accordance with a known method.
• the reaction between the unsaturated group and the Si—H group in the present invention is a hydrosilylation reaction.
• crosslinking is performed using an epoxide of (C2) the organic compound having one or more reactive unsaturated groups and one or more epoxy groups in the molecule, bonding caused by the reaction of the unsaturated group and the Si—H group and ether bond generation caused by the self ring-opening polymerization of the epoxy groups (cationic polymerization reaction that occurs in the presence of a SiH group and a platinum catalyst) both occur, resulting in crosslinking.
• irradiation using high energy beams such as ultraviolet light can be applied, or a common cation polymerization catalyst can be further added.
• the reaction solvent is not particularly limited as long as the solvent is nonreactive, and examples thereof include alcohol-based solvents such as ethanol and isopropyl alcohol; aromatic hydrocarbon-based solvents such as toluene and xylene; ether-based solvents such as dioxane and THF; aliphatic hydrocarbon-based solvents such as n-hexane, cyclohexane, n-heptane, cycloheptane, and methylcyclohexane; and chlorinated hydrocarbon-based organic solvents such as carbon tetrachloride.
• An oil agent described below may also be used as a reaction solvent.
• a composition consisting of an organopolysiloxane elastomer and an oil agent can be obtained directly after the crosslinking reaction, and a composition consisting of a particulate organopolysiloxane elastomer and an oil agent—preferably a paste-like composition—can be easily obtained by grinding the composition using a mechanical force.
• the hydrosilylation reaction may be performed in the presence or absence of a catalyst, but preferably is performed in the presence of a catalyst because the reaction can be carried out at a low temperature and in a shorter period of time.
• the hydrosilylation reaction catalyst include platinum, ruthenium, rhodium, palladium, osmium, iridium, and similar compounds, and platinum compounds are particularly effective due to their high catalytic activity.
• platinum compound examples include chloroplatinic acid; platinum metal; platinum metal supported on a carrier such as platinum supported on alumina, platinum supported on silica, platinum supported on carbon black, or the like; and a platinum complex such as platinum-vinylsiloxane complex, platinum-phosphine complex, platinum-phosphite complex, platinum alcoholate catalyst, or the like.
• a usage amount of the catalyst is about 0.5 to 1000 ppm in terms of platinum metal, when using a platinum catalyst.
• a reaction temperature of the hydrosilylation reaction is typically from 30 to 150° C., and a reaction time is typically from 10 minutes to 24 hours and preferably from 1 to 10 hours.
• the component (A) is crosslinked by the component (C) as a result of the hydrosilylation reaction or the cationic polymerization reaction of the epoxy groups, and the polysiloxane chains originating from the component (A) are linked by the crosslinking portion having a carbon-silicon bond originating from the component (C).
• the component (A) also comprises a sugar alcohol-modified group originating from the component (B). In this way, the organopolysiloxane elastomer of the present invention can be obtained.
• the organopolysiloxane elastomer of the present invention typically has a structure that is linked by the crosslinking portion having a carbon-silicon bond originating from the component (C), it may also have a portion crosslinked by the Si—O—C bond.
• the structure has a condensation-reactable functional group such as a silanol group or an alkoxy group in the components (A) to (C)
• links can not only be formed between polysiloxane chains but can also be formed intermittently as a result of a partial reaction between the hydroxyl groups in the sugar alcohol-modified group originating from the component (B) and the Si—H groups of (A) when the crosslinking conditions are severe.
• the component (C) may be further reacted with the component (A) after the reaction between the component (A) and the component (B), or the component (B) can be further reacted with the component (A) after the reaction between the component (A) and the component (C).
• the average value of the number of silicon-bonded hydrogen atoms per molecule of the component (A) reacting with the reactive unsaturated groups of the component (C) is preferably 1.5 or greater. That is, the number of silicon-bonded hydrogen atoms per molecule of the component (A) which constitute the crosslinking portion and react with the unsaturated bonds of the component (C) is, on average, at least 1.5, preferably in a range from 2.0 to 5.0, and particularly preferably in a range from 2.5 to 3.5.
• the organopolysiloxane elastomer may be subjected to hydrogenation treatment for the purpose of improving the odor after the reaction caused by the remaining unsaturated compound.
• Methods of hydrogenation treatment include a method using a pressurized hydrogen gas and a method using a hydrogenation agent such as a metal hydride, and hydrogenation treatment may also entail homogeneous reactions and heterogeneous reactions. One of these methods may be performed alone, or multiple methods may be performed in combination. However, taking into consideration the advantage that the catalyst that is used will not remain in the finished product, a heterogeneous catalytic hydrogenation reaction using a solid catalyst is most preferable.
• solid catalysts hydrogenation catalyst
• noble metal-based catalysts such as common platinum-based catalysts and palladium-based catalysts as well as nickel-based catalysts. More specific examples include single substances such as nickel, palladium, platinum, rhodium, and cobalt and catalysts combining a plurality of metals such as platinum-palladium, nickel-copper-chromium, nickel-copper-zinc, nickel-tungsten, and nickel-molybdenum.
• an optional catalyst carrier include activated carbon, silica, silica alumina, alumina, and zeolite.
• copper-containing hydrogenation catalysts such as Cu—Cr, Cu—Zn, Cu—Si, Cu—Fe—Al, and Cu—Zn—Ti may be used.
• the form of the hydrogenation catalyst differs depending on the type of the reaction vessel and therefore cannot be determined generally, but the form is typically selected appropriately from forms such as a powder, granules, or pellets.
• the platinum catalyst used in the synthesis process hydrosilylation reaction
• These hydrogenation catalysts may be used alone or as a combination of two or more types of catalysts.
• the hydrogenation treatment can also be used to refine a crude product of the organopolysiloxane elastomer obtained by the hydrosilylation reaction described above.
• a crude product can be refined by deodorization resulting from the hydrogenation treatment in a solvent or without a solvent in the presence of a hydrogenation catalyst, and such a refined product can be used much more preferably when applied to an external use preparation or a cosmetic composition in which the reduction of odor and compatibility with other components are desired.
• the deodorizing treatment preferably has, as a pre-process or a post-process, a stripping treatment in which nitrogen gas is brought into contact with the crude organopolysiloxane elastomer or the hydrogenated product to remove light matter under reduced pressure.
• an organic compound having one reactive unsaturated group in the molecule may be further reacted in addition to the components (A), (B), and (C).
• One type of the component (Q) may be used, or two or more types of the component (Q) may be used in combination.
• the reactions are preferably performed sequentially in the presence of a hydrosilylation reaction catalyst.
• the definitions, types, and the like of the reactive unsaturated groups in the component (Q) are as described above.
• the component (Q) when the component (C) is further reacted with the component (A) after the reaction between the component (A) and the component (B), the component (Q) may be reacted with the component (A) prior to the reaction between the component (A) and the component (B), the component (Q) may be reacted with the component (A) after the reaction between the component (A) and the component (B), or the component (Q) may be further reacted with the component (A) after the reaction of the component (C).
• the component (Q) when the component (B) is further reacted with the component (A) after the reaction between the component (A) and the component (C), the component (Q) may be reacted with the component (A) prior to the reaction between the component (A) and the component (C), the component (Q) may be reacted with the component (A) after the reaction between the component (A) and the component (C), or the component (Q) may be further reacted with the component (A) after the reaction of the component (B).
• component (Q) examples include (Q1) a siloxane dendron compound having one reactive unsaturated group in the molecule and (Q2) a hydrocarbon compound having one reactive unsaturated group in the molecule, a chain organopolysiloxane having one reactive unsaturated group in the molecule, or the like.
• the siloxane dendron compound having one reactive unsaturated group in the molecule include compounds having a siloxane dendron structure that have one carbon-carbon double bond at a molecular terminal, the compounds being expressed by the following general formula (3′):
• R 12 and R 13 are synonymous with those described above;
• Z′ is a divalent organic group;
• h 1 is a number in a range from 0 to 3;
• R 12 and R 13 are synonymous with those described above;
• Z is a divalent organic group;
• j indicates the number of generations of the silylalkyl group represented by L j , when the number of generations (the number of repetitions) of the silylalkyl group is k′, j is an integer of 1 to k′, and the number of generations k′ is an integer from 1 to 9;
• h1 is a number in a range from 0 to 3).
• the divalent organic groups in the general formulas (3′) and (3′′) are as described above.
• hydrocarbon compound having one reactive unsaturated group in the molecule or the chain organopolysiloxane having one reactive unsaturated group in the molecule include monounsaturated hydrocarbon compounds expressed by the following general formula:
• R′ is synonymous with that described above; and R2′ is a substituted or unsubstituted, straight or branched monovalent hydrocarbon group having from 7 to 58 carbon atoms, or the chain organosiloxane group represented by the following general formula (4-1):
• the hydrocarbon compound having one reactive unsaturated group in the molecule (Q2) is preferably a monounsaturated hydrocarbons having from 9 to 30 carbon atoms and is more preferably a 1-alkene.
• the 1-alkene include 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, and the like.
• the chain organopolysiloxane having one reactive unsaturated group in the molecule include a dimethylpolysiloxane capped at one molecular terminal with a vinyl group, a methylphenylpolysiloxane capped at one molecular terminal with a vinyl group, and the like.
• the organopolysiloxane elastomer of the present invention it is preferable to further perform an acidizing process of treating the organopolysiloxane elastomer of the present invention obtained by the hydrosilylation reaction of the component (A), the component (B), the component (C), and the optional component (C) using at least one type of acidic substance.
• an acidizing process of treating the organopolysiloxane elastomer of the present invention obtained by the hydrosilylation reaction of the component (A), the component (B), the component (C), and the optional component (C) using at least one type of acidic substance As a result, the odor of the organopolysiloxane elastomer can be reduced.
• Odor attenuating treating may also be performed with a method of performing an acidization process at the stage prior to the formation of the organopolysiloxane elastomer (prior to crosslinking), but since acid, water, and alcoholic hydroxyl groups are present, the Si—H groups are consumed by the dehydrogenation reaction, which makes it difficult to perform subsequent crosslinking as designed, even if odor reduction is achieved. Accordingly, it is more preferable to perform acidization after forming the elastomer.
• the acidic substance is not particularly limited and may be any acid that matches the definition of a Lewis-acid, a Bronsted acid, or an Arrhenius acid.
• the acidic substance used in the present invention is preferably a water soluble acid. Therefore, the acidic substance used in the present invention is preferably an Arrheinius acid which releases protons in an aqueous solution.
• One type of the acidic substance may be used alone, or two or more types of acidic substances may be used in combination.
• the organopolysiloxane elastomer can be essentially deodorized and the generation of odor over time can be completely suppressed without severing the carbon-oxygen bonds or the silicon-oxygen bonds.
• the acidic substance can be selected from the group consisting of inorganic acids, organic acids, acidic inorganic salts, solid acids, and acidic platinum catalysts.
• the inorganic acid is not particularly limited, and examples thereof include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, carbonic acid, boric acid, sulfonic acid, sulfinic acid, and the like. Note that substances containing organic groups such as benzene sulfonic acid are not preferable as inorganic acids.
• the organic acid is not particularly limited, and can be a monocarboxylic acid (including monohydroxy monocarboxylic acid and dihydroxy monocarboxylic acid), a dicarboxylic acid (including monohydroxy dicarboxylic acid and dihydroxy dicarboxylic acid), a polycarboxylic acid, or the like. Examples thereof include:
• Straight saturated aliphatic monocarboxylic acids such as formic acid, acetic acid, trifluoroacetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, and the like;
• Branched saturated aliphatic monocarboxylic acids such as 2-methylpropanoic acid, 2-methylbutanoic acid, trimethylpropanoic acid, 2-methylpentanoic acid, trimethyl acetic acid, and the like
• Unsaturated aliphatic monocarboxylic acids alkenoic acids
• Unsaturated aliphatic monocarboxylic acids alkenoic acids
• alkyl sulfuric acid alkyl phosphoric acid, phenol, and the like can be used as the organic acid.
• higher fatty acids or salts thereof are not preferable as organic acids.
• the acidic inorganic salt is not limited, but a water soluble salt is preferable. Particularly preferable is a water soluble acidic inorganic salt that is solid at 25° C. and, when 50 g thereof is dissolved in 1 L of ion exchanged water, the solution has a pH at 25° C. of not more than 4, preferably not more than 3.5, and more preferably not more than 2.0.
• the acidic inorganic salt is solid at room temperature (25° C.)
• the acidic inorganic salt can be easily removed by filtration as necessary.
• the acidic inorganic salt is water soluble, the acidic inorganic salt can be easily rinsed off with water as necessary.
• the pH values in the present invention are values measured using a pH meter having a glass electrode in a sample aqueous solution at room temperature (25° C.).
• Examples that can be used as the acidic inorganic salt include acidic inorganic salts in which at least a monovalent hydrogen atom of the inorganic acid that is at least divalent is neutralized by a base.
• Examples of the inorganic acid that is at least divalent include sulfuric acid, sulfurous acid, and the like.
• Examples of the base include an alkali metal, ammonia, and the like.
• the acidic inorganic salt is preferably at least one type of acidic inorganic salt comprising a hydrogensulfate ion (HSO 4 ⁇ ) or a hydrogensulfite ion (HSO 3 ⁇ ) and a monovalent cation (M + ).
• the monovalent cation (M + ) include alkali metal ions or an ammonium ion.
• the monovalent cation is preferably at least one type selected from the group consisting of a sodium ion, a potassium ion, and an ammonium ion.
• the acidic inorganic salt include lithium hydrogensulfate, sodium hydrogensulfate, potassium hydrogensulfate, rubidium hydrogensulfate, cesium hydrogensulfate, ammonium hydrogensulfate, sodium hydrogensulfite, or hydrates thereof, and Lewis-acids such as AlCl 3 , FeCl 3 , TiCl 4 , and BF 3 -Et 2 O.
• Lewis-acids such as AlCl 3 , FeCl 3 , TiCl 4 , and BF 3 -Et 2 O.
• the water soluble acidic inorganic salt having a pH of not higher than 2.0 is most preferably at least one type of acidic inorganic salt selected from the group consisting of sodium hydrogensulfate, potassium hydrogensulfate, and ammonium hydrogensulfate.
• solid acids examples include acidic solid substances such as activated clay, acidic clay, solid acidic zirconium dioxide, strong acidic cation exchange resins, fluorinated sulfonic acid resins, alumina, silica alumina, and zeolite. Of these, a solid acidic zirconium dioxide is preferable. Examples of the solid acidic zirconium dioxide include products prepared at a temperature of at least 300° C.
• zirconium hydroxide after treating zirconium hydroxide with sulfuric acid; more specifically, aluminum hydroxides or hydrous oxides, zirconium hydroxides or hydrous oxides, a solid acidic zirconium—specifically zirconia sulfate—prepared by first obtaining a molded product by mixing and molding a sulfuric acid-containing compound and then baking the molded product at a temperature at which a tetragonal-structured zirconia is formed—specifically at a temperature of at least 300° C.
• a commercially available product of the solid zirconium dioxide is SZA-60 (manufactured by Japan Energy Corporation).
• the strong acidic cation exchange resin is, for example, a cation exchange resin in which a functional group is a sulfonic acid group (—SO 3 H), and examples of commercially available products thereof include Amberlyst 15, Amberlyst 16, Amberlyst 31, and Amberlyst 35 (manufactured by Organo Corporation).
• the fluorinated sulfonic acid resin is a perfluorinated polymer having a suspended sulfonic acid group bonded to the polymer chain, and specific examples thereof include the product described in Japanese Examined Patent Application Publication No. S59-4446 and the like.
• the acidic platinum catalyst examples include chloroplatinic acids, alcohol-modified chloroplatinic acids, olefin complexes of chloroplatinic acids, ketone complexes of chloroplatinic acids, vinylsiloxane complexes of chloroplatinic acids, and platinum tetrachlorides. Of these, chloroplatinic acid is preferable.
• the acidizing process described above can be performed by bringing the organopolysiloxane elastomer into contact with the acidic substance in a desired manner.
• the acidizing process can be performed by means of operations such as adding at least one type of the acidic substance described above and, optionally, an organic solvent such as water or alcohol to a reaction system containing the organopolysiloxane elastomer (for example, in a reaction vessel such as a flask, a kneading/grinding container, an emulsifier, or the like), mixing by stirring, kneading, and grinding or repeating these operations.
• a reaction vessel such as a flask, a kneading/grinding container, an emulsifier, or the like
• the process can be more advantageously performed by first grinding the organopolysiloxane elastomer or a composition containing the elastomer and an oil agent in advance, adding at least one type of acidic substance and, optionally, an organic solvent such as water or alcohol, and performing an operation such as stirring while heating.
• the acidic substance and water it is preferable to add at least one type of the acidic substance and water to a reaction system containing the organopolysiloxane elastomer and to then agitate or knead and pulverize the mixture using a mechanical force while heating.
• this treatment is preferably performed in the presence of a solvent such as a lower monohydric alcohol.
• the acid treatment can be carried out at any temperature and treatment time, and can be carried out at a temperature from 0 to 200° C. and more preferably from 50 to 100° C. for a reaction time of from 0.5 to 24 hours and more preferably from about 1 to 10 hours.
• the amount of the acidic substance that is used can be appropriately selected in accordance with the acid strength, the treatment apparatus, the treatment time, and the treatment temperature.
• the acidic substance is one with moderate acid strength such as sodium hydrogensulfate, potassium hydrogensulfate, ammonium hydrogensulfate, citric acid, glycolic acid, or phosphoric acid
• the content is preferably in a range from 10 to 500 ppm and more preferably in a range from 20 to 200 ppm in the organopolysiloxane elastomer of the present invention.
• the content is preferably in a range from 0.1 to 50 ppm in the organopolysiloxane elastomer, and when the acidic substance is a substance with weak acid strength or a solid acid exemplified by activated clay, acidic clay, solid acidic zirconium dioxide, strong acidic cation exchange resin, fluorinated sulfonic acid resin, zeolite, or the like, the content is preferably in a range from 500 to 10,000 ppm in the organopolysiloxane elastomer.
• a process of heating and/or decompressing the composition is preferably included after the acidizing process.
• Low-boiling-point components which are odor-causing substances, can be removed (stripped) by the heating and/or decompression described above.
• a large amount of the odor-causing substances can be removed by performing the acidizing process once again after stripping.
• the acidizing process and the stripping process can be respectively repeated two or more times for the purpose of increasing the degree of reduction in odor.
• the “low-boiling-point components” removed by the stripping process include, in addition to carbonyl compounds such as propionaldehyde, which are thought to be odor-causing substances, volatile compounds such as the reaction solvent used in the synthesis and the like of the organopolysiloxane elastomer.
• stripping process may be performed before the acidizing process.
• reaction conditions may be used in the stripping method, but stripping under normal pressure or under reduced pressure is preferable, and stripping is preferably performed at a temperature of 120° C. or lower.
• the stripping is preferably performed under reduced pressure or, for example, performed under a nitrogen gas or similar inert gas stream.
• a specific example of the low-boiling-point component removal operation is one in which the organopolysiloxane elastomer or composition thereof or a hydrogenated product thereof comprising a low boiling point component is placed in a flask having a refluxing cooler, a nitrogen injection port, or the like.
• a pressure reduction parameter is from 0.1 to 10.0 kPa
• a heating temperature is from 50 to 170° C.
• a treatment time is from 10 minutes to 24 hours.
• a basic substance may be used to neutralize the organopolysiloxane elastomer.
• One type of the basic substance may be used alone, or two or more types of substances may be used in combination.
• the basic substance include organic bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, ammonia water, and sodium hydrogen carbonate; basic buffers such as trisodium phosphate, tripotassium phosphate, trisodium citrate, and sodium acetate; and organic bases such as basic amino acids, amines and pyridines.
• An amount of the basic substance is preferably an amount needed to neutralize a reaction system comprising the organopolysiloxane elastomer but, as necessary, the amount of the basic substance may be adjusted to an amount by which weak acidity or weak alkalinity is obtained.
• the organopolysiloxane elastomer of the present invention is preferably in a particulate form and is more preferably in the form of solid particles.
• the particulate organopolysiloxane can be simply obtained by grinding the cured organopolysiloxane elastomer using a mechanical force, and solid particles of the organopolysiloxane elastomer with a desired particle size can be obtained by adjusting the grinding conditions using a publicly known method.
• grinding after the organopolysiloxane elastomer prior to or following primary grinding is mixed with an oil agent, the organopolysiloxane elastomer in a state in which the elastomer is swelled or dispersed in the oil agent is subjected to primary grinding or finer secondary grinding using a mechanical force.
• the mechanical means for grinding the organopolysiloxane elastomer or the composition is not particularly limited, but the substance is preferably ground by at least one method selected from the group consisting of shearing, kneading, and a means of passing the substance through an orifice under pressure.
• an aqueous dispersion of organopolysiloxane elastomer particles by emulsifying/dispersing the raw material composition of the organopolysiloxane elastomer prior to curing in water and then performing a crosslinking reaction and to obtain dried organopolysiloxane elastomer particles by removing the water from the aqueous dispersion.
• the particle size of the organopolysiloxane elastomer particles can be selected in accordance with the application or tactile sensation and is not particularly limited, but from the perspective of the preparation of a composition with the oil agent described below, the volume average particle size measured by microscopic observation or using a particle size distribution measurement device is preferably in a range from 20 to 1000 ⁇ m and more preferably in a range from 25 to 300 ⁇ m.
• the present invention relates to a composition
• a composition comprising the organopolysiloxane elastomer described above.
• the compounded amount of the organopolysiloxane elastomer in the composition is not particularly limited but can be set in a range from 1 to 99 wt. % (mass %), for example, preferably from 5 to 95 wt. % (mass %), more preferably from 10 to 90 wt. % (mass %), even more preferably from 20 to 80 wt. % (mass %), and even more preferably from 30 to 70 wt. % (mass %) based on the total weight (mass) of the composition.
• the composition of the present invention may contain at least one type of oil agent in addition to the organopolysiloxane elastomer.
• the oil agent is not particularly limited, and a solid, semi-solid, or liquid oil agent may be used.
• Specific examples of oil agent include one type or two or more types of oil agent selected from the group consisting of include silicone oils, hydrocarbon oils, ester oils, vegetable oils and fats, animal oils and fats, fatty acids, higher alcohols, triglycerides, artificial sebums, and fluorine-based oil agents.
• silicone oil examples include straight organopolysiloxanes expressed by the following general formula (7), cyclic organopolysiloxanes expressed by the general formula (8), and branched organopolysiloxanes expressed by the general formula (9).
• R 27 is a hydrogen atom, hydroxyl group or a group selected from a monovalent unsubstituted or fluorine substituted alkyl group having from 2 to 30 carbon atoms, an aryl group, an amino substituted alkyl group, an alkoxy group, and a group expressed by (CH 3 ) 3 SiO[(CH 3 ) 2 SiO] u Si(CH 3 ) 2 CH 2 CH 2 —.
• saturated aliphatic hydrocarbon groups such as ethyl groups, propyl groups, butyl groups, pentyl groups, hexyl groups, heptyl groups, octyl groups, decyl groups, and dodecyl groups
• unsaturated aliphatic hydrocarbon groups such as vinyl groups, allyl groups, and hexenyl groups
• saturated cycloaliphatic hydrocarbon groups such as cyclopentyl groups and cyclohexyl groups
• aromatic hydrocarbon groups such as phenyl groups, tolyl groups, and naphthyl groups
• groups in which the hydrogen atoms bonded to the carbon atoms of these groups are substituted partially by an organic group having a halogen atom, an epoxy group, a carboxyl group, an amino group, a methacryl group, a mercapto group, or the like or a group substituted by a trimethylsiloxy group bonded via a divalent hydrocarbon group and/or
• silicone oils having the structure described above include cyclic organopolysiloxanes such as hexamethyl cyclotrisiloxane (D3), octamethyl cyclotetrasiloxane (D4), decamethyl cyclopentasiloxane (D5), dodecamethyl-cyclohexasiloxane (D6), 1,1-diethylhexamethyl cyclotetrasiloxane, phenylheptamethyl cyclotetrasiloxane, 1,1-diphenylhexamethyl cyclotetrasiloxane, 1,3,5,7-tetravinyltetramethyl cyclotetrasiloxane, 1,3,5,7-tetramethyl cyclotetrasiloxane, 1,3,5,7-tetracyclohexyltetramethyl cyclotetrasiloxane, tris(3,3,3-trifluoropropyl) trimethylcyclo
• Examples of straight organopolysiloxanes include dimethylpolysiloxane in which both molecular terminals are capped with trimethylsiloxy groups (dimethylsilicone with a low viscosity such as 2 cst or 6 cst to dimethylsilicone with a high viscosity such as 1,000,000 cst), organohydrogenpolysiloxane, methylphenylpolysiloxane in which both molecular terminals are capped with trimethylsiloxy groups, a copolymer of methylphenylsiloxane and dimethylsiloxane in which both molecular terminals are capped with trimethylsiloxy groups, diphenylpolysiloxane in which both molecular terminals are capped with trimethylsiloxy groups, a copolymer of diphenylsiloxane and dimethylsiloxane in which both molecular terminals are capped with trimethylsiloxy groups, trimethylp
• the organopolysiloxane elastomer of the present invention is able to stably maintain various powders dispersed in an oil phase containing these silicone oils and to stably emulsify/disperse an aqueous phase in an oil phase containing these silicone oils.
• hydrocarbon oil examples include liquid paraffin, light liquid isoparaffin, heavy liquid isoparaffin, vaseline, n-paraffin, isoparaffin, isododecane, isohexadecane, polyisobutylene, hydrogenated polyisobutylene, polybutene, ozokerite, ceresin, microcrystalline wax, paraffin wax, polyethylene wax, polyethylene/polypropylene wax, squalane, squalene, pristane, polyisoprene, wax, and the like.
• the organopolysiloxane elastomer of the present invention is able to stably maintain various powders dispersed in an oil phase containing these hydrocarbon oils and to stably emulsify/disperse an aqueous phase in an oil phase containing these hydrocarbon oils.
• ester oil examples include hexyldecyl octanoate, cetyl octanoate, isopropyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, oleyl oleate, decyl oleate, octyldodecyl myristate, hexyldecyl dimethyloctanoate, cetyl lactate, myristyl lactate, diethyl phthalate, dibutyl phthalate, lanolin acetate, ethylene glycol monostearate, propylene glycol monostearate, propylene glycol dioleate, glyceryl monostearate, glyceryl monooleate, glyceryl tri(2-ethylhexanoate), trimethylolpropane tri(2-ethylhexanoate
• the organopolysiloxane elastomer of the present invention is able to stably maintain various powders dispersed in an oil phase containing these ester oils and to stably emulsify/disperse an aqueous phase in an oil phase containing these ester oils.
• oils and fats such as avocado oil, linseed oil, almond oil, ibota wax, perilla oil, olive oil, cacao butter, kapok wax, kaya oil, carnauba wax, liver oil, candelilla wax, beef tallow, neatsfoot oil, beef bone fat, hydrogenated beef tallow, apricot kernel oil, spermaceti wax, hydrogenated oil, wheat germ oil, sesame oil, rice germ oil, rice bran oil, sugar cane wax, sasanqua oil, safflower oil, shea butter, Chinese tung oil, cinnamon oil, jojoba wax, olive squalane, shellac wax, turtle oil, soybean oil, tea seed oil, camellia oil, evening primrose oil, corn oil, lard, rapeseed oil, Japanese tung oil, rice bran wax, germ oil, horse fat, persic oil, palm oil, palm kernel oil, castor oil,
• oils and fats such as avocado oil, linseed oil, almond oil,
• higher fatty acids examples include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, undecylenic acid, oleic acid, linolic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA), isostearic acid, 12-hydroxystearic acid, and the like.
• higher alcohols examples include lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, behenyl alcohol, hexadecyl alcohol, oleyl alcohol, isostearyl alcohol, hexyldodecanol, octyldodecanol, cetostearyl alcohol, 2-decyltetradecinol, cholesterol, sitosterol, phytosterol, lanosterol, POE cholesterol ether, monostearyl glycerol ether (batyl alcohol), monooleyl glycerol ether (selachyl alcohol), and the like.
• fluorine-based oil agent examples include perfluoropolyether, perfluorodecalin, perfluorooctane, and the like, and one or two or more types of these oil agents can be used as necessary.
• the compounded amount of the oil agent in the composition of the present invention is not particularly limited but can be set in a range from 0.1 to 95 wt. % (mass %), for example, preferably from 1 to 90 wt. % (mass %), more preferably from 2 to 80 wt. % (mass %), even more preferably from 3 to 70 wt. % (mass %), and even more preferably from 5 to 60 wt. % (mass %) based on the total weight (mass) of the composition.
• composition of the present invention containing at least one type of oil agent in addition to the organopolysiloxane elastomer may be in the form of a paste.
• the organopolysiloxane elastomer compounded in the composition of the present invention is preferably in a particulate form.
• the mixing ratio with the oil agent is arbitrary, but from the perspective of obtaining a paste-like composition consisting of uniform, fine particles without a foreign body sensation, the ratio is preferably in a range from 5/95 to 95/5, particularly preferably from 20/80 to 80/20, and most preferably from 25/75 to 50/50.
• organopolysiloxane elastomer when the organopolysiloxane elastomer can be swelled with an oil agent in an amount equal to or greater than the weight (mass) of the elastomer itself, a composition which is swelled using an oil agent in an amount equal to or greater than the weight of the elastomer itself—preferably a paste-like composition—can be easily prepared.
• composition containing the particulate organopolysiloxane elastomer and an oil agent can be obtained by mixing the organopolysiloxane elastomer with an oil agent after grinding the elastomer using a mechanical force or grinding a mixture of the organopolysiloxane elastomer and an oil agent using a mechanical force.
• the composition of the present invention can contain water.
• the compounded amount of the water in the composition of the present invention is not particularly limited but can be set in a range from 1 to 90 wt. % (mass %), for example, preferably from 5 to 80 wt. % (mass %), more preferably from 10 to 70 wt. % (mass %), even more preferably from 20 to 60 wt. % (mass %), and even more preferably from 30 to 50 wt. % (mass %) based on the total weight (mass) of the composition.
• the organopolysiloxane elastomer of the present invention since the organopolysiloxane elastomer of the present invention has a hydrophobic silicone chain and a hydrophilic sugar alcohol-modified group, the organopolysiloxane elastomer functions as a surfactant or an emulsifier. That is, by mixing the organopolysiloxane elastomer of the present invention and water (or water and a hydrophilic medium), each component can be uniformly dispersed, so the present invention can be advantageously used as a hydrous composition.
• the hydrous composition described above is a composition containing the organopolysiloxane elastomer of the present invention and water and can be in the form of a hydrous gel composition or an emulsion composition.
• the emulsion form is not particularly limited and can be a water-based-oil-based oil composition such as an oil-in-water emulsion or a water-in-oil emulsion; or an arbitrary form of emulsion such as an oil-in-alcohol (polyol, for example) emulsion or an alcohol(polyol, for example)-in-oil emulsion.
• a water-in-oil emulsion composition or an alcohol(polyol, for example)-in-oil emulsion is preferable.
• the average particle size of the emulsion particle formed by emulsification using the organopolysiloxane elastomer of the present invention can be measured by a conventional measurement device using a laser diffraction/scattering method or the like.
• the emulsion composition according to the present invention is preferably a polar solvent-in-oil emulsion but may also be an oil-in-polar solvent emulsion.
• the emulsion composition of the present invention may be a transparent micro-emulsion in which the measured average particle size is not more than 0.1 ⁇ m or may be a large particulate white turbid emulsion in which the average particle size is more than 10.0 ⁇ m.
• the emulsion particles may be micronized for the purpose of improving the stability and transparency of the appearance of the emulsion.
• An emulsion having a particle diameter from 0.5 to 20 ⁇ m can be selected for the purpose of improving sensation during use and adhesion characteristics to hair and skin.
• the emulsion and the like described above may be produced by blending the organopolysiloxane elastomer of the present invention or composition comprising the same and water by means of a mechanical force using an apparatus such as a homomixer, a paddle mixer, a Henschel mixer, a homo-disper, a colloid mill, a propeller stirrer, a homogenizer, an in-line continuous emulsifier, an ultrasonic emulsifier, or a vacuum kneader.
• the content and compounding ratio of the water is as described above and is preferably appropriately selected within a range from 1 to 99 wt. % (mass %) of the entire emulsion composition in accordance with the form and use of the emulsion.
• composition of the present invention can contain at least one type of alcohol.
• the alcohol preferably has water miscibility and more preferably is a lower alcohol or a polyhydric alcohol.
• lower alcohols include ethanol, isopropanol, n-propanol, t-butanol, s-butanol, and the like.
• polyhydric alcohols include divalent alcohols such as 1,3-butylene glycol, 1,2-butylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, 2,3-butylene glycol, pentamethylene glycol, 2-buten-1,4-diol, dibutylene glycol, pentyl glycol, hexylene glycol, octylene glycol, and the like; trivalent alcohols such as glycerol, trimethylol propane, 1,2,6-hexanetriol, and the like; polyhydric alcohols having 4 or more valences such as pentaerythritol, xylitol, and the like; and sugar alcohols such as sorbitol, mannitol, maltitol, maltotriose
• examples other than these low-molecule polyhydric alcohols include polyhydric alcohol polymers such as diethylene glycol, dipropylene glycol, triethylene glycol, polypropylene glycol, tetraethylene glycol, diglycerol, polyethylene glycol, triglycerol, tetraglycerol, polyglycerol, and the like.
• the compounded amount of the alcohol in the composition of the present invention is not particularly limited but can be set in a range from 0.1 to 50 wt. % (mass %), for example, preferably from 1 to 40 wt. % (mass %), more preferably from 2 to 30 wt. % (mass %), even more preferably from 3 to 20 wt. % (mass %), and even more preferably from 4 to 10 wt. % (mass %) based on the total weight (mass) of the composition.
• the degree of odor of the organopolysiloxane elastomer of the present invention or the composition containing the same can be determined by the carbonyl value measured from the absorbance of a reaction solution obtained by reacting the organopolysiloxane elastomer or the composition containing the same and 2,4-dinitrophenylhydrazine (2,4-DNPH) in a reaction medium containing at least one type of monovalent lower alcohol having from 1 to 4 carbon atoms.
• the “carbonyl compound” also includes a potential carbonyl compound such as an acetal, propenyl ether, or a similar compound that does not comprise a carbonyl group but generates a carbonyl group by decomposing under certain conditions.
• the carbonyl value of the organopolysiloxane elastomer or the composition containing the same from the absorbance of a reaction solution obtained by reacting the organopolysiloxane elastomer containing a carbonyl compound or the composition containing the same and 2,4-dinitrophenylhydrazine in a reaction medium containing at least one type of monovalent lower alcohol having from 1 to 4 carbon atoms.
• the carbonyl value measured with the method described above for the organopolysiloxane elastomer of the present invention, which is a sugar alcohol-modified silicone, or the composition containing the same is preferably not more than 4.0 Abs/g, more preferably not more than 3.0 Abs/g, and even more preferably not more than 2.0 Abs/g.
• carbonyl value of an organopolysiloxane elastomer or a composition comprising the same is determined based on the absorbance of the reaction solution obtained by reacting 2,4-DNPH and a carbonyl compound in the organopolysiloxane elastomer or the composition comprising the same, and from this carbonyl value, it is possible to measure the total amount of carbonyl (calculated on a propanal basis) in the organopolysiloxane elastomer or in the composition by using a pre-plotted calibration curve.
• the “carbonyl value” is the carbonyl content index value, and is a value obtained by converting the absorbance (absorbance at 430 nm or 460 nm) of the reaction solution, obtained by reacting 2,4-DNPH with the sample, to per 1 g of sample.
• Measurement of the carbonyl value uses the property of hydrazone, produced by reacting a carbonyl and 2,4-DNPH in the presence of an acid, that the hydrazone becomes quinoid ions in a base and gives color.
• the carbonyl value is determined based on the absorbance, which indicates the degree of coloring at 430 nm (a maximum wavelength attributable to saturated carbonyl exists in the vicinity thereof) and at 460 nm (a maximum wavelength attributable to unsaturated carbonyl exists in the vicinity thereof).
• total amount of carbonyl is the total amount of carbonyl compound for an organopolysiloxane elastomer or a composition comprising the same.
• concentration of carbonyl compounds (total amount of carbonyl) of various samples can be measured by obtaining a calibration curve by measuring carbonyl values of standard samples having known concentrations of the carbonyl compound (concentration of propionaldehyde).
• At least a monovalent lower alcohol having from 1 to 4 carbon atoms is used as the reaction solvent in the reaction between a carbonyl compound and 2,4-DNPH, but it is preferable to use water at the same time.
• the mixing ratio (mass ratio) of the monovalent lower alcohol having from 1 to 4 carbon atoms to water is preferably from 99.9:0.1 to 50:50, and more preferably from 99:1 to 75:25.
• reaction solvent indicates a solvent that is present in the reaction system containing 2,4-DNPH and a carbonyl compound in a sample.
• a reaction solvent is formed by using, in addition to (a) a solvent used to prepare a sample solution, (b) a solvent used to prepare the added acid solution, (c) a solvent used to prepare a solution of 2,4-DNPH, and the like.
• Each of (a) an alcohol that forms a sample solution, (b) an alcohol that forms an acid solution, and (c) an alcohol that forms a 2,4-DNPH solution need not be a monovalent lower alcohol having from 1 to 4 carbon atoms, provided that the alcohol in the reaction solvent resulting from mixture thereof contains a monovalent lower alcohol having from 1 to 4 carbon atoms.
• diluent solvent an alcohol as the solvent
• a monovalent lower alcohol having from 1 to 4 carbon atoms.
• all of the diluent solvent need not be an alcohol.
• Water and/or an organic solvent organic solvent not having a carbonyl group in its structure, and having low toxicity can be used as a part of the diluent solvent.
• the monovalent lower alcohol having from 1 to 4 carbon atoms is preferably a saturated alcohol. Examples thereof include methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, and sec-butanol. Of these, n-butanol is preferable.
• the monovalent lower alcohol having from 1 to 4 carbon atoms one type can be used independently, or two or more types can be mixed and used.
• These alcohols lack toxicity (toxicity such as the toxicity that benzene has), and the alcohols are capable of dissolving various substances having different polarities and molecular weights. Consequently, by using these alcohols as the reaction solvent and diluent solvent, it is possible to safely and easily perform each operation for determining the carbonyl value.
• a monovalent lower alcohol having from 1 to 4 carbon atoms it is preferable to use a monovalent lower alcohol having a total aldehyde/ketone content of not more than 3 ppm, preferably not more than 2 ppm, and more preferably not more than 1 ppm (hereinafter, also referred to as “ultrapure alcohol”).
• the total aldehyde/ketone content exceeds 3 ppm, the baseline increases when measuring the absorbance for the resulting reaction solution, and it may not be possible to obtain proper (highly precise) index values due to the absorbance measured for a reaction solution containing a sample with a low carbonyl content being smaller than the absorbance measured for a solution for a blank test (solution not containing the sample).
• a method of preparing (refining) an ultrapure alcohol a method that distills an alcohol under normal pressure or under reduced pressure after adding proper quantities of 2,4-DNPH and an acid lacking oxidative action (e.g., hydrochloric acid or trichloroacetic acid) to the alcohol to be refined and heating and stirring this system over several hours, can be used. Furthermore, it is preferable to perform these refining treatments within 24 hours before measuring the absorbance of the reaction solution.
• an acid lacking oxidative action e.g., hydrochloric acid or trichloroacetic acid
• ultrapure alcohol it is preferable to use a commercially available highly pure reagent that has been refined so that a total amount of aldehydes and ketones is 3 ppm or less.
• commercially available highly pure reagents that can be used as an ultrapure alcohol include ethanol (99.8%) Infinity Pure; ethanol (99.8%) for precise analysis; ethanol (99.5%) for high-performance liquid chromatography; ethanol (99.5%) for spectrometry; 2-propanol (99.9%) Infinity Pure, 2-propanol (99.9%) for precise analysis; 2-propanol (99.5%) for high-performance liquid chromatography; 2-propanol (99.5%) for spectrometry; 1-propanol (99.8%) Infinity Pure, 1-propanol (99.5%) for high-performance liquid chromatography; methanol (99.8%) Infinity Pure, methanol (99.8%) for precise analysis; methanol (99.5%) for high-performance liquid chromatography; methanol (99.5%) for high-
• the total amount of aldehydes and ketones increases over time, and sometimes exceeds 3 ppm.
• the total amount of aldehydes and ketones exceeds 3 ppm in a relatively short time period after opening (e.g. within 24 hours). Therefore, from the perspective of satisfying the essential requirement for ultrapure alcohols (that is, the total aldehyde/ketone content is not more than 3 ppm), the following commercially available highly pure reagents are preferable:
• the solvent used as the reaction solvent need not be composed solely of a monovalent lower alcohol having from 1 to 4 carbon atoms, or a mixed solvent of water and a monovalent lower alcohol having from 1 to 4 carbon atoms.
• a low toxicity organic solvent also may be used as a part of the reaction solvent as long as it does not have a carbonyl group in the structure thereof.
• the total amount of aldehydes and ketones contained in the reaction solvent is preferably not more than 3 ppm.
• a basic reaction solution (the reaction solution for absorbance measurement) can be prepared by adding an acid and 2,4-DNPH to a sample solution prepared by uniformly dispersing a sample in a solvent, reacting the carbonyl compound in the sample and 2,4-DNPH by heat treating this system, adding an alkali in the system after cooling, and then adjusting the volume of to a prescribed volume with a diluent solvent.
• a volumetric flask with a volume of 10 to 100 mL as the container for preparing a basic reaction solution.
• the solvent used to prepare the sample solution also constitutes the reaction solvent as is, so such a solvent is preferably a mixed solvent of an ultrapure alcohol and water.
• the mass of the sample solution (sample and solvent) used to measure absorbance is normally about 2 to 6 g, and preferably about 5 g.
• the mass of the sample contained in a sample solution differs according to the carbonyl content of the sample (i.e., the carbonyl value) and the prepared quantity of reaction solution for absorbance measurement (i.e., the volume of the used volumetric flask).
• the mass of the sample contained in a sample solution is preferably from 5 to 250 mg, and more preferably from 10 to 150 mg.
• acids added to the sample solution include mineral acids such as dilute sulfuric acid, hydrochloric acid, dilute nitric acid, phosphoric acid, and the like; organic acids such as trichloroacetic acid, trifluoroacetic acid, formic acid, acetic acid, sulfonic acid, phenolic acid, and the like; and Lewis acids such as AlCl 3 , FeCl 3 , TiCl 4 , and the like; and the like. These acids can be used alone or in combinations of two or more.
• trichloroacetic acid particularly, the dilute sulfuric acid with a concentration of 20% or less
• hydrochloric acid particularly, the hydrochloric acid with a concentration of 37% or less
• the acid used in the measurement method described above is preferably an acid with the highest purity (reagent-grade or higher purity).
• these acids may be added as is to a sample solution. However, from the perspective of performing accurate measurement or the like, it is preferable to add the acids in a solution state obtained by dissolving in an appropriate solvent.
• the solvent used to prepare an acid solution also constitutes the reaction solvent as is, thus, as such the solvent, it is preferable to use a monovalent lower alcohol having from 1 to 4 carbon atoms or a mixed solvent of monovalent lower alcohol having from 1 to 4 carbon atoms and water.
• the added amount of acid is preferably from 0.03 to 5.0 g.
• the 2,4-DNPH added to the sample solutions is preferably a 2,4-DNPH having a purity of at least a reagent-grade and containing an equal amount of water. Also, the purity can be further raised by recrystallization or a similar refining operation. 2,4-DNPH can be added as is to a sample solution. However, from the standpoint of performing an accurate measurement, it is preferable to add the 2,4-DNPH in a solution state obtained by dissolving in an appropriate solvent. Furthermore, the solvent used to prepare the 2,4-DNPH solution also constitutes the reaction solvent as is.
• the solvent it is preferable to use a monovalent lower alcohol having from 1 to 4 carbon atoms, or a mixed solvent of water and a monovalent lower alcohol having from 1 to 4 carbon atoms.
• a reaction solution reaction solution that contains from 5 to 250 mg of sample
• a condition for the heat treatment of a mixed solution containing a sample, acid, and 2,4-DNPH is 20 to 180 minutes at 30 to 120° C. (however, the temperature is lower than the boiling point of the reaction solvent). At a treatment temperature below 30° C., it takes a long time to react the 2,4-DNPH and the carbonyl compound in a sample, which is inefficient. On the other hand, when heating at a temperature above 120° C., there is a risk that the generated hydrazone will decompose. When the treatment time is less than 20 minutes, it becomes difficult to complete the reaction with 2,4-DNPH. On the other hand, if the treatment time exceeds 180 minutes, there is a risk that the generated hydrazone will decompose.
• an inorganic strong base such as potassium hydroxide, sodium hydroxide, and the like
• these alkalis can be added as is to a sample solution.
• solvents one or two or more solvents can be selected from among solvents that can dissolve an alkali, do not have a carbonyl group in the structure thereof, are compatible with the solvent used as the reaction solvent, and that have low toxicity.
• reaction solution reaction solution that contains from 5 to 250 mg of sample
• the added amount of alkali is preferably from 0.05 to 5.0 g.
• the reaction solution to which alkali was added is adjusted to a specific volume (for example, 50 mL) with a diluent solvent having an alcohol as a main constituent.
• the alcohol forming the diluent solvent is preferably an ultrapure alcohol.
• An example of a method of preparing a reaction solution for absorbance measurement is as follows. In a 50 mL volumetric flask, 5 g of a sample solution is placed, prepared by uniformly dispersing from 5 to 250 mg of a sample in a mixed solvent of water and a monovalent lower alcohol having from 1 to 4 carbon atoms. Next, a solution prepared by dissolving from 0.03 to 5.0 g of acid in a monovalent lower alcohol having from 1 to 4 carbon atoms and a solution prepared by dissolving from 0.5 to 500 mg of 2,4-DNPH in a monovalent lower alcohol having from 1 to 4 carbon atoms are added to the flask.
• This solution is then mixed well and homogenized, and heat treatment is performed for 20 to 180 minutes at 30 to 120° C., thereby reacting the 2,4-DNPH and the carbonyl compound in the sample, while the volumetric flask is capped.
• a solution prepared by dissolving from 0.05 to 5.0 g of an alkali in an alcohol is added.
• a diluent solvent composed of an alcohol is then added, mixed well, and homogenized to adjust the volume of the mixture to 50 mL.
• the absorbance at 430 nm or 460 nm is measured for the basic reaction solution obtained as described above.
• the absorbance at 430 nm is measured for the reaction solution
• the absorbance at 460 nm is measured for the reaction solution.
• the absorbance cell that contains the reaction solution is made of quartz.
• the length (thickness) of the liquid layer specified by the absorption cell is preferably 1 cm.
• the absorbance it is preferable to measure the absorbance within 10 to 20 minutes after the addition of an alkali to the reaction solution resulting from the reaction of the 2,4-DNPH and the carbonyl compound in a sample. Absorbance measured before 10 minutes after the addition of an alkali sometimes lacks stability. Also, more than 20 minutes after the addition of an alkali, the absorbance tends to drop as a result of the discoloration of the reaction solution. Based on experience with various samples, if the absorbance is measured 15 minutes after the addition of an alkali, the value with best reproducibility is obtained.
• the carbonyl value of a sample is determined based on the absorbance measured as described above. It is possible to measure the total amount of carbonyl in the sample, by using a premeasured calibration curve based on this carbonyl value.
• the calibration curve is obtained by measuring, according to the method (carbonyl value measurement method) described above, the carbonyl values of a plurality of standard samples whose total amount of carbonyl (propionaldehyde concentration) is known.
• the same method as aforementioned, which was adopted to obtain this calibration curve is used to measure the carbonyl value of a sample (an organopolysiloxane elastomer or a composition comprising the same) for which the total amount of carbonyl is unknown.
• the solvent described below for use in the following processes (1) and (9) contains an ultrapure alcohol and water
• the solvent described below for use in the following process (7) contains an ultrapure alcohol.
• Process of preparing a sample solution by uniformly dispersing a sample in a solvent (2) Process of adding 3 mL of an alcohol solution of 4.3% (wt/vol) trichloroacetic acid to 5.000 g of the sample solution and homogenizing by mixing well (3) Process of adding 5 mL of an alcohol solution of 2,4-DNPH ([0.025% (wt/vol)] to the mixed solution obtained in the aforementioned process (2) and homogenizing by mixing well (4) Process that reacts the carbonyl compound in a sample and 2,4-DNPH by heating the mixed solution obtained in the aforementioned process (3) for 30 minutes at 60° C.
• Process (1) is a process of preparing a sample solution by uniformly dispersing a sample in a solvent containing a monovalent lower alcohol (and preferably, water) having from 1 to 4 carbon atoms.
• the proportion of the sample in a sample solution is modified in accordance with the carbonyl value estimated for the sample. For example, the following settings are preferable: if the carbonyl value is estimated to be less than 6 in the sample, from 2 to 3 wt. % (mass %) (from 100 to 150 mg per 5.000 g of sample solution); if the carbonyl value is estimated to be in a range from 6 to 15 in the sample, from 0.8 to 2 wt.
• a sample solution it is preferable to dilute the sample stepwise.
• 25.00 g of an 8 wt. % (mass %) dispersion is first prepared by uniformly dispersing 2.00 g of a sample in 21.00 g of a monovalent lower alcohol having from 1 to 4 carbon atoms and 2.00 g of water.
• 1.250 g of the 8 wt. % (mass %) dispersion and 3.750 g of a monovalent lower alcohol having from 1 to 4 carbon atoms are accurately added to a 50 mL volumetric flask and mixed well to dilute the solution four-fold.
• Process (2) is a process of adding 3 mL of an alcohol solution of 4.3% (wt/vol) of trichloroacetic acid to 5.000 g (sample: 0.100 g) of the 2 wt. % (mass %) sample obtained in the aforementioned process (1) using a volumetric pipette or the like and homogenizing the solution by mixing well.
• the solvent (a monovalent lower alcohol having from 1 to 4 carbon atoms) of this alcohol solution is preferably an ultrapure alcohol.
• alcohol solution of trichloroacetic acid it is preferable to prepare the alcohol solution of trichloroacetic acid by opening a bottle containing 100 mL of ultrapure alcohol, directly adding 4.3 g of trichloroacetic acid to this bottle, covering the bottle, and then shaking the bottle to uniformly mix the contents in the bottle. Also, alcohol solution of trichloroacetic acid is preferably prepared within 24 hours before measuring the absorbance of the reaction solution.
• Process (3) is a process of adding 5 mL of an alcohol solution [0.025% (wt/vol)] of 2,4-DNPH to the mixed solution obtained in the aforementioned process (2) using a volumetric pipette or the like and homogenizing the solution by mixing well.
• the solvent (a monovalent lower alcohol having from 1 to 4 carbon atoms) of this alcohol solution of 2,4-DNPH is preferably an ultrapure alcohol.
• the alcohol solution of 2,4-DNPH is preferably prepared by opening a bottle containing 100 mL of ultrapure alcohol, directly adding 50 mg of 2,4-DNPH (reagent-grade product containing an equal amount of water) to this bottle, covering the bottle, and then putting the bottle into an ultrasonic bath for about 5 minutes to completely dissolve the 2,4-DNPH in the bottle.
• the alcohol solution of 2,4-DNPH is preferably prepared within 24 hours before measuring the absorbance of the reaction solution. It is preferable to add more water to hydrolyze the precursors of the carbonyl compound of acetal and the like present in the sample, to detect the precursors as carbonyl compounds.
• process (4) the mixed solution obtained in the aforementioned process (3) is heated for 30 minutes at 60° C. to react the 2,4-DNPH and the carbonyls in the sample, thereby yielding a reaction solution containing hydrazone.
• reaction solution obtained in the process (4) is cooled by letting the reaction solution stand for 30 to 70 minutes at room temperature.
• the alcohol solution of potassium hydroxide is preferably prepared by opening a bottle containing 100 mL of ultrapure alcohol, directly adding 4.0 g of potassium hydroxide (pellet shaped reagent-grade product) to this bottle, and covering the bottle, and after shaking until the pellets disappear, this bottle is placed in an ultrasonic bath for about 5 to 10 minutes, to completely dissolve the potassium hydroxide in the bottle. Also, it is preferable to prepare the alcohol solution of potassium hydroxide within 24 hours before measuring the absorbance of the reaction solution.
• Process (7) is a process of preparing a reaction solution (basic reaction solution) with a total volume of 50 mL by adding a diluent solvent consisting of a monovalent lower alcohol having from 1 to 4 carbon atoms (preferably, an ultrapure alcohol) to the reaction solution and homogenizing the solution by mixing well, 5 to 10 minutes after the aforementioned process (6).
• a diluent solvent consisting of a monovalent lower alcohol having from 1 to 4 carbon atoms (preferably, an ultrapure alcohol)
• the absorbance (A 1 ) is measured at 430 nm (when the carbonyl in the sample is estimated to be mainly a saturated carbonyl) or at 460 nm (when the carbonyl in the sample is estimated to be mainly an unsaturated carbonyl).
• the absorbance must be measured 10 to 20 minutes after addition of the alcohol solution of potassium hydroxide of the aforementioned process (6), and it is most preferable to measure the absorbance 15 minutes after the addition of the alcohol solution of potassium hydroxide.
• Process (9) is a process of measuring the absorption (A 2 ) at 430 nm and 460 nm for a solution obtained by performing the same operations as in the aforementioned processes (2) to (7) (addition of an alcohol solution of trichloroacetic acid; addition of an alcohol solution of 2,4-DNPH; heating and cooling of the obtained mixed solution; addition of an alcohol solution of potassium hydroxide; and addition of a diluent solvent consisting of a monovalent lower alcohol having from 1 to 4 carbon atoms) using 5.000 g of a monovalent lower alcohol having from 1 to 4 carbon atoms (preferably, a mixed solution with monovalent lower alcohol water having from 1 to 4 carbon atoms) instead of the sample solution described above as a blank test.
• the organopolysiloxane elastomer of the present invention or the composition containing the same has, in essence, a small tendency to deteriorate due to oxidation caused by the oxygen in the air.
• a phenol, a hydroquinone, a benzoquinone, an aromatic amine, a vitamin, or similar antioxidant in order to prevent oxidation deterioration; or take steps to increase oxidation stability.
• adding such an antioxidant for example, BHT(2,6-di-t-butyl-p-cresol), vitamin C, vitamin E, or the like, will result in a further increase in stability.
• an added amount of the antioxidant that is used is in a range (by weight (mass)) from 10 to 1,000 ppm, and preferably from 50 to 500 ppm, of the organopolysiloxane elastomer.
• the organopolysiloxane elastomer of the present invention or the composition comprising the same can be advantageously used as a raw material for an external use preparation and a raw material for a cosmetic composition for use on a human body.
• a paste-like composition containing the particulate organopolysiloxane elastomer of the present invention and an oil agent can be used directly as a raw material for an external use preparation and a raw material for a cosmetic composition.
• a proportion of the organopolysiloxane elastomer or the composition comprising the same in the raw material for an external use preparation and the raw material for a cosmetic composition is preferably from 50 to 100 wt. % (mass %), more preferably from 80 to 100 wt. % (mass %), and even more preferably from 90 to 100 wt. % (mass %) based on the total weight (mass) of the raw material.
• a proportion of the raw material compounded in the external use preparation or the cosmetic composition is not particularly limited but, for example, can be from 0.1 to 90 wt. % (mass %), and is preferably from 1 to 80 wt.
• Examples of the raw material for an external use preparation and the raw material for a cosmetic composition of the present invention include a thickening agent, a gelling agent, a tactile sensation improver, a surfactant, an emulsifier, and a powder dispersion stabilizer.
• the organopolysiloxane elastomer of the present invention or the composition comprising the same, or the raw material for use in an external use preparation and a cosmetic composition comprising the organopolysiloxane elastomer or the composition comprising the same, can be advantageously compounded in an external use preparation or a cosmetic composition and can constitute the external use preparation or the cosmetic composition of the present invention.
• the external use preparation or the cosmetic composition of the present invention is preferably stored in a container formed from a thermoplastic material or a container formed from a non-thermoplastic material.
• at least one compartment can be defined in the container so as to constitute a cosmetic product unit or external use preparation unit consisting of the container and the cosmetic composition or the external use preparation according to the present invention.
• the external use preparation or the cosmetic composition of the present invention can be primarily applied to and used on keratinous substances such as skin or hair as a non-therapeutic beauty technique for the purpose of doing applying cosmetics (makeup) or performing care (that is, dry skin
• the external use preparation is a product to be applied to human skin, nails, hair, and the like and, for example, medicament active components can be compounded therein and used in the treatment of various disorders.
• the cosmetic composition is also a product to be applied to human skin, nails, hair, and the like, and is used for beauty purposes.
• the external use preparation or the cosmetic composition is preferably a skin external use preparation or a skin cosmetic composition, skin care cosmetic composition, sun care cosmetic composition, antiperspirant, foundation, color cosmetic, or a hair external use preparation or a hair cosmetic composition product.
• the skin external use preparation or the skin cosmetic composition product of the present invention comprises the organopolysiloxane elastomer of the present invention or the composition comprising the same and, although the form thereof is not particularly limited, the product may be in the form of a solution, cream-like, solid, semi-solid, paste-like, gel-like, powder-like, multi-layer, mousse-like, or spray-like form.
• the skin external use preparation or the skin cosmetic composition product according to the present invention include skin lotions, emulsions, creams, sunscreen emulsions, sunscreen creams, hand creams, cleansing compositions, massage lotions, cleansing agents, anti-perspirants, deodorants, and similar basic cosmetic products; foundations, make-up bases, blushers, rouges, eye shadows, eye liners, mascaras, nail enamels, and similar make-up cosmetic products; and the like.
• the hair external use preparation or the hair cosmetic composition product according to the present invention comprises the organopolysiloxane elastomer of the present invention or the composition comprising the same and can be used in various forms.
• the hair external use preparation or the hair cosmetic composition product according to the present invention may be dissolved or dispersed in an alcohol, a hydrocarbon, a volatile cyclic silicone, or the like and used, or the product may also be used in the form of an emulsion by dispersing the organopolysiloxane elastomer of the present invention and a desired emulsifier in water.
• the hair external use preparation or the hair cosmetic composition product according to the present invention can be used as a spray by using propane, butane, trichloromonofluormethane, dichlorodifluoromethane, dichlorotetrafluoroethane, carbonic acid gas, nitrogen gas, or a similar propellant.
• Examples of other forms include milk-like, cream-like, solid, semi-solid, paste-like, gel-like, powder-like, multi-layer, mousse-like, and similar forms.
• There various forms can be used as shampooing agents, rinsing agents, conditioning agents, setting lotions, hair sprays, permanent wave agents, mousses, hair colorants, and the like.
• the following other components generally used in external use preparations or cosmetic compositions may be added to the external use preparation or the cosmetic composition of the present invention, provided that such components do not inhibit the effectiveness of the present invention: water, powders or coloring agents, alcohols, water-soluble polymers, film-forming agents, oil agents, oil-soluble gelling agents, organomodified clay minerals, surfactants, resins, mediums allowable in cosmetic products, adipose phases, film-forming polymers, fibers, light protection systems capable of blocking UV rays, UV absorbers, moisturizing agents, preservatives, antimicrobial agents, perfumes, salts, antioxidants, pH adjusting agents, chelating agents, refreshing agents, anti-inflammatory agents, skin beautifying components (skin-lightening agents, cell activating agents, agents for ameliorating skin roughness, circulation promoters, skin astringents, antiseborrheic agents, and the like), vitamins, amino acids, nucleic acids, hormones, clathrates, and the like; bioactive substances, medicament
• the water must be free of components that are harmful to the human body and to be clean, and examples thereof include tap water, purified water, mineral water, and deep sea water.
• water soluble additives can be compounded as needed, provided that such components do not inhibit the effectiveness of the present invention.
• components that can be compound to constitute the aqueous phase include water soluble active materials such as vitamin Bs (described below), vitamin C and derivatives thereof, pantothenic acid and derivatives thereof, vitamins such as biotins; antiperspiration active components, water soluble UV absorbers, and various water soluble pigments, but the components are not limited thereto.
• a known pH adjusting agent, preservative, antimicrobial agent, or antioxidant can be compounded as needed for the purpose of improving the storage stability of the external use preparation or the cosmetic composition.
• the powder and/or coloring agent can be any powder provided that it is normally used in external use preparations and cosmetic compositions, and is not limited to form (sphere, bar, needle, plate, amorphous, spindle, or the like), particle diameter (aerosol, micro-particle, pigment-grade particle, or the like), or particle structure (porous, nonporous, or the like) thereof.
• a pigment preferably, one or two or more selected from an inorganic pigment powder, an organic pigment powder, and a resin powder having an average particle diameter in a range from 1 nm to 20 ⁇ m is compounded.
• a coated pigment is more preferable.
• recessed fine particles formed from a silicone material and particularly recessed fine particles with a structure that is partially spherical and hollow having an average particle size of less than 5 ⁇ m (having an arch shape or a horse hoof-shaped cross section), can also be advantageously used for the purpose of thickening the oil phase, improving tactile sensation, or the like.
• powder or coloring agent examples include flakes, inorganic powders, organic powders, surfactant metal salt powders (metallic soaps), colored pigments, pearl pigments, organo-modified clay minerals, and metal powder pigments. Further, compounded products of these pigments can also be used.
• inorganic powders include titanium oxide, zirconium oxide, zinc oxide, cerium oxide, magnesium oxide, barium sulfate, calcium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, talc, mica, kaolin, sericite, white mica, synthetic mica, phlogopite, lepidolite, black mica, lithia mica, silicic acid, silicic acid anhydride, aluminum silicate, sodium silicate, magnesium sodium silicate, magnesium silicate, aluminum magnesium silicate, calcium silicate, barium silicate, strontium silicate, metal salts of tungstic acid, hydroxyapatite, vermiculite, higilite, bentonite, montmorillonite, hectorite, zeolite, ceramic powder, dicalcium phosphate, alumina, aluminum hydroxide, boron nitride, and the like.
• organic powders examples include polyamide powder, polyester powder, polyethylene powder, polypropylene powder, polystyrene powder, polyurethane powder, benzoguanamine powder, polymethylbenzoguanamine powder, polytetrafluoroethylene powder, poly (methyl methacrylate) powder, cellulose, silk powder, nylon powder, nylon 12, nylon 6, silicone powder, silicone rubber spherical powder, silicone rubber spherical powder that is surface-coated with polymethylsilsesquioxane, polymethylsilsesquioxane spherical powder, copolymers of styrene and acrylic acid, copolymers of divinylbenzene and styrene, vinyl resin, urea resin, phenol resin, fluorine resin, silicone resin, acrylic resin, melamine resin, epoxy resin, polycarbonate resin, macrocrystalline fiber powder, starch powder, lauroyl lysine, and the like.
• surfactant metal salt powders include zinc stearate, aluminum stearate, calcium stearate, magnesium stearate, zinc myristate, magnesium myristate, zinc palmitate, zinc laurate, zinc cetylphosphate, calcium cetylphosphate, sodium zinc cetylphosphate, and the like.
• colored pigments include inorganic red pigments such as red iron oxide, iron oxide, iron hydroxide, iron titanate, and the like; inorganic brown pigments such as gamma-iron oxide and the like; inorganic yellow pigments such as yellow iron oxide, ocher, and the like; inorganic black pigments such as black iron oxide, carbon black and the like; inorganic purple pigments such as manganese violet, cobalt violet, and the like; inorganic green pigments such as chromium hydroxide, chromium oxide, cobalt oxide, cobalt titanate, and the like; inorganic blue pigments such as Prussian blue, ultramarine blue, and the like; laked pigments of tar pigments such as Red No. 3, Red No.
• Red No. 106 Red No. 201, Red No. 202, Red No. 204, Red No. 205, Red No. 220, Red No. 226, Red No. 227, Red No. 228, Red No. 230, Red No. 401, Red No. 505, Yellow No. 4, Yellow No. 5, Yellow No. 202, Yellow No. 203, Yellow No. 204, Yellow No. 401, Blue No. 1, Blue No. 2, Blue No. 201, Blue No. 404, Green No. 3, Green No. 201, Green No. 204, Green No. 205, Orange No. 201, Orange No. 203, Orange No. 204, Orange No. 206, Orange No.
• laked pigments of natural pigments such as carminic acid, laccaic acid, carthamin, brazilin, crocin, and the like.
• pearl pigments include a pearl essence agent, titanium oxide-coated mica, titanium mica, iron oxide-coated titanium mica, titanium oxide-coated mica, bismuth oxychloride, titanium oxide-coated bismuth oxychloride, titanium oxide-coated talc, fish scale foil, titanium oxide-coated colored mica, and the like.
• the metal powder pigment include powders of metals such as aluminum, gold, silver, copper, platinum, stainless steel, and the like.
• a powder that absorbs and scatters ultraviolet light such as microparticulate titanium oxide, microparticulate iron-containing titanium oxide, microparticulate zinc oxide, microparticulate cerium oxide, compound products thereof, and the like may be used as the inorganic powder.
• an inorganic ultraviolet light blocking component may be compounded as an ultraviolet light scattering agent such as the inorganic powder pigments and metal powder pigments described above, and examples thereof include metal oxides such as titanium oxide, zinc oxide, cerium oxide, titanium suboxide, and iron-doped titanium oxides; metal hydroxides such as iron hydroxides; metal flakes such as platy iron oxide and aluminum flakes; and ceramics such as silicon carbide.
• at least one type of a material selected from fine particulate metal oxides and fine particulate metal hydroxides with an average particle size in a range from 1 to 100 nm is particularly preferable.
• organo-modified clay mineral examples include dimethylbenzyl dodecylammonium montmorillonite clay, dimethyldioctadecylammonium montmorillonite clay, dimethylalkylammonium hectorite, benzyldimethylstearylammonium hectorite, distearyldimethylammonium chloride-treated aluminum magnesium silicate, and the like.
• examples of commercially available products include Benton 27 (benzyldimethylstearylammonium chloride-treated hectorite, manufactured by Nationalred Co.), Benton 38 (distearyldimethylammonium chloride-treated hectorite, manufactured by Nationalred Co.), and the like.
• the silicone rubber spherical powder (also known as a silicone elastomer spherical powder) preferably has a primary particle size in a range from 0.1 to 50 ⁇ m.
• examples of commercially available products of the silicone rubber spherical powder include Trefil E-506S, Trefil E-508, 9701 Cosmetic Powder, 9702 Powder, EP-9215 Cosmetic Powder, EP-9261 TI Cosmetic Powder, EP-9293 AL Cosmetic Powder, EP-9289 LL Cosmetic Powder (all manufactured by Dow Corning Toray Co., Ltd.).
• the silicone rubber spherical powder can also be used in the external use preparation or cosmetic composition of the present invention in the form of an aqueous dispersion liquid. Examples of such commercially available aqueous dispersion liquids include BY29-129, and PF-2001 PIF Emulsion manufactured by Dow Corning Toray Co., Ltd.
• the powder or coloring agent is preferably subjected to a water-repellent treatment.
• a product can be used in which these powders and/or coloring agents are compounded together; or subjected to surface treatment using a general oil agent, a silicone compound other than the organopolysiloxane elastomer according to the present invention, a fluorine compound, a surfactant, or the like.
• a general oil agent e.g., a silicone compound other than the organopolysiloxane elastomer according to the present invention
• fluorine compound e.g., a fluorine compound, a surfactant, or the like.
• One type thereof or two or more types thereof can be used, as necessary.
• these water-repellent treatments include various treatments in which the powder and/or coloring agent is surface treated with a water repellency agent.
• organosiloxane treatments such as a methylhydrogenpolysiloxane treatment, a silicone resin treatment, a silicone gum treatment, an acryl silicone treatment, a fluorinated silicone treatment, a glycerin-modified silicone treatment, and the like; metallic soap treatments such as a zinc stearate treatment and the like; silane treatments such as a silane coupling agent treatment, an alkylsilane treatment, and the like; fluorine compound treatments such as a perfluoroalkylsilane treatment, a perfluoroalkyl phosphate treatment, a perfluoro polyether treatment, and the like; amino acid treatments such as an N-lauroyl-L-lysine treatment and the like; oil agent treatments such as a squalane treatment and the like; and acryl treatments such as an alkyl acrylate treatment and the like
• these powders or coloring agents include at least one type of powder or coloring agent selected from the group consisting of a silicone resin powder, a silicone rubber powder, an organic resin powder (excluding silicone resin powders), an organo-modified clay mineral, titanium oxide, zinc oxide, a titanated mica, a metal soap, an inorganic body pigment, an inorganic coloration pigment and a coated pigment.
• alcohols include at least one type selected from a lower alcohol, a sugar alcohol, and a higher alcohol.
• specific examples include lower alcohols such as ethanol and isopropanol; sugar alcohols such as sorbitol and maltose; and higher alcohols such as lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, behenyl alcohol, hexadecyl alcohol, oleyl alcohol, isostearyl alcohol, hexyldodecanol, octyldodecanol, cetostearyl alcohol, 2-decyltetradecinol, cholesterol, sitosterol, phytosterol, lanosterol, POE cholesterol ether, monostearyl glycerol ether (batyl alcohol), and monooleyl glycerol ether (selachyl alcohol).
• lower alcohols such as ethanol and isopropanol
• sugar alcohols such as sorbitol and maltos
• the water-soluble polymer can be compounded for the purpose of enhancing sensation during use of the external use preparation or the cosmetic composition or as a water soluble moisturizing agent or film-forming polymer. Any of amphoteric, cationic, anionic, and nonionic polymers, and water-swellable clay minerals can be used, provided that the water-soluble polymer is one that is commonly used in external use preparations or cosmetic products, and it is possible to use one or two or more types of these water-soluble polymers.
• water-soluble polymers have an effect of thickening the hydrous component, so the polymers are particularly useful for stabilizing the system when obtaining a gel-like hydrous external use preparation or cosmetic composition, a water-in-oil emulsion external use preparation or cosmetic composition, and an oil-in-water emulsion external use preparation or cosmetic composition.
• amphoteric water-soluble polymers include amphoteric starches, dimethyldiallylammonium chloride derivatives (for example, acrylamide-acrylic acid-dimethyldiallylammonium chloride copolymers and acrylic acid-dimethyldiallylammonium chloride copolymers), and methacrylic acid derivatives (for example, polymethacryloylethyldimethylbetaines, N-methacryloyloxyethyl-N,N-dimethylammonium- ⁇ -methylcarboxybetaine-alkyl methacrylate copolymers, and the like).
• dimethyldiallylammonium chloride derivatives for example, acrylamide-acrylic acid-dimethyldiallylammonium chloride copolymers and acrylic acid-dimethyldiallylammonium chloride copolymers
• methacrylic acid derivatives for example, polymethacryloylethyldimethylbetaines, N-methacryloyloxyeth
• cationic water-soluble polymers examples include quaternary nitrogen-modified polysaccharides (for example, cation-modified cellulose, cation-modified hydroxyethylcellulose, cation-modified guar gum, cation-modified locust bean gum, cation-modified starch, and the like); dimethyldiallylammonium chloride derivatives (for example, copolymers of dimethyldiallylammonium chloride and acrylamide, poly(dimethylmethylene piperidinium chloride), and the like); vinylpyrrolidone derivatives (for example, copolymers of vinylpyrrolidone and dimethylaminoethyl methacrylic acid, copolymers of vinylpyrrolidone and methacrylamide propyltrimethylammonium chloride, copolymers of vinylpyrrolidone and methylvinylimidazolium chloride, and the like); and methacrylic acid derivatives (for example, methacryloyleth
• anionic water-soluble polymers include poly(acrylic acid) and alkali metal salts thereof, poly(methacrylic acid) and alkali metal salts thereof, hyaluronic acid and alkali metal salts thereof, acetylated hyaluronic acid and alkali metal salts thereof, water-soluble polymers of aliphatic carboxylic acids or metal salts thereof, such as hydrolysates of methyl vinyl ether-maleic anhydride copolymers, carboxymethyl cellulose and alkali metal salts thereof, methyl vinyl ether-maleic acid half ester copolymers, alkanolamine solutions of acrylic resins, carboxyvinyl polymers, 2-acrylamide-2-methylpropane sulfonate polymers, or the like.
• nonionic water-soluble polymers examples include poly(vinyl pyrrolidone), highly polymerized polyethylene glycols, PEG/PPG-36/41 dimethyl ethers, PEG/PPG-14/7 dimethyl ethers, vinyl pyrrolidone-vinyl acetate copolymers, vinyl pyrrolidone-dimethylaminoethyl methacrylate copolymers, vinyl caprolactam-vinyl pyrrolidone-dimethylaminoethyl methacrylate copolymers, cellulose and derivatives thereof (for example, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, and carboxymethyl cellulose), keratin and collagen and derivatives thereof, calcium alginate, pullulan, agar, gelatin, tamarind seed polysaccharides, xanthan gum, carrageenan, high-methoxylpectin, low-methoxylpe
• the water-swellable clay mineral is an inorganic water-soluble polymer and is a type of colloid-containing aluminum silicate having a three-layer structure. Typical examples thereof are expressed by the following formula (A).
• 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
• inorganic water-soluble polymers include bentonite, montmorillonite, beidellite, nontronite, saponite, hectorite, magnesium aluminum silicate, and silicic anhydride, and these may be natural or synthetic products.
• An oil agent described above can be used, and one type or two or more types thereof can be used as necessary.
• oil-soluble gelling agent examples include metal soaps such as aluminum stearate, magnesium stearate, and zinc myristate; amino acid derivatives such as N-lauroyl-L-glutamic acid, and ⁇ , ⁇ -di-n-butylamine; dextrin fatty acid esters such as dextrin palmitate esters, dextrin stearate esters, and dextrin 2-ethylhexanoate palmitate esters; sucrose fatty acid esters such as sucrose palmitate esters and sucrose stearate esters; fructooligosaccharide fatty acid esters such as inulin stearate esters and fructooligosaccharide 2-ethylhexanoate esters; semi-crystalline homopolymers or copolymers obtained by the polymerization of a monomer comprising a long chain alkyl acrylate and/or a long chain alkyl methacrylate having from 14 to 24 carbon atoms or the like;
• Surfactants other than the components described above can be compounded in the external use preparation or the cosmetic composition of the present invention.
• one type or two or more types of surfactants selected from the group consisting of a silicone-based surfactant other than the organopolysiloxane elastomer according to the present invention, an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, and a semipolar surfactant can be used in combination as the surfactant.
• the silicone-based surfactant is a silicone-based surfactant other than the organopolysiloxane elastomer according to the present invention.
• This silicone-based surfactant is often used as a component for the emulsification or washing of an oil agent, and the dispersion or surface treatment of a powder, and representative examples include polyglyceryl-modified silicones, glyceryl-modified silicones, sugar-modified silicones, fluoropolyether-modified silicones, polyether-modified silicones, carboxylic acid-modified silicones, sugar-modified silicones, block copolymers of straight-chain silicones and polyethers (polysilicone-13 and the like), and long-chain alkyl-polyether comodified silicones.
• the organopolysiloxane elastomer according to the present invention consists of elastomer particles having a hydrophilic portion and a hydrophobic portion, the elastomer functions as a stabilizer for a powder dispersed in an oil.
• the organopolysiloxane also functions as an aid to enhance the compounding stability of the nonionic surfactant and may improve overall stability of the formulation.
• the organopolysiloxane elastomer according to the present invention can be advantageously used in combination with a glycerin derivative-modified silicone, a sugar-modified silicone, a sugar alcohol-modified silicone, a carboxylic acid-modified silicone, and a polyglycerin-modified silicone elastomer (otherwise known as a polyglycerated silicone elastomer), and a silicone-based nonionic surfactant in which alkyl branching, straight-chain silicone branching, siloxane dendrimer branching or the like is performed along with the hydrophilic group as necessary can be advantageously used.
• a polyoxyalkylene-modified silicone a polyether-modified silicone, a fluorine polyether-modified silicone, or the like
• a polyether-modified silicone elastomer otherwise known as a polyoxyalkylated silicone elastomer
• an organopolyoxyalkylene group-containing surfactant a polyoxyalkylene-modified silicone (a polyether-modified silicone, a fluorine polyether-modified silicone, or the like), a polyether-modified silicone elastomer (otherwise known as a polyoxyalkylated silicone elastomer), or an organopolyoxyalkylene group-containing surfactant.
• anionic surfactants include those in which carboxylic acid-modified silicone is neutralized using an alkaline substance; saturated or unsaturated fatty acid salts (for example, sodium laurate, sodium stearate, sodium oleate, sodium linolenate, and the like); alkylsulfuric acid salts; alkylbenzene sulfonic acids (for example, hexylbenzenesulfonic acid, octylbenzenesulfonic acid, dodecylbenzenesulfonic acid, and the like) and salts thereof; polyoxyalkylene alkyl ether sulfuric acid salts; polyoxyalkylene alkenyl ether sulfuric acid salts; polyoxyethylene alkylsulfuric ester salts; sulfosuccinic acid alkyl ester salts; polyoxyalkylene sulfosuccinic acid alkyl ester salts; polyoxyalkylene alkylphenyl ether
• cationic surfactants include alkyltrimethylammonium chloride, stearyltrimethylammonium chloride, lauryltrimethylammonium chloride, cetyltrimethylammonium chloride, beef tallow alkyltrimethylammonium chloride, behenyltrimethylammonium chloride, stearyltrimethylammonium bromide, behenyltrimethylammonium bromide, distearyldimethylammonium chloride, dicocoyldimethylammonium chloride, dioctyldimethylammonium chloride, di(POE)oleylmethylammonium (2 EO) chloride, benzalkonium chloride, alkyl benzalkonium chloride, alkyl dimethylbenzalkonium chloride, benzethonium chloride, stearyl dimethylbenzylammonium chloride, lanolin derivative quaternary ammonium salt, diethylaminoethylamide stearate, dimethylacetate
• nonionic surfactants include polyglyceryl diisostearate and polyhydroxy diglyceryl stearate, isostearyl glyceryl ethers, polyoxyalkylene ethers, polyoxyalkylene alkyl ethers, polyoxyalkylene fatty acid esters, polyoxyalkylene fatty acid diesters, polyoxyalkylene resin acid esters, polyoxyalkylene (cured) castor oils, polyoxyalkylene alkyl phenols, polyoxyalkylene alkyl phenyl ethers, polyoxyalkylene phenyl ethers, polyoxyalkylene alkyl esters, polyoxyalkylene alkyl esters, sorbitan fatty acid esters, polyoxyalkylene sorbitan alkyl esters, polyoxyalkylene sorbitan fatty acid esters, polyoxyalkylene sorbitol fatty acid esters, polyoxyalkylene glycerol fatty acid esters, polyglycerol alkyl
• amphoteric surfactants include imidazoline-type, amidobetaine-type, alkylbetaine-type, alkylamidobetaine-type, alkylsulfobetaine-type, amidosulfobetaine-type, hydroxysulfobetaine-type, carbobetaine-type, phosphobetaine-type, aminocarboxylic acid-type, and amidoamino acid-type amphoteric surfactants.
• examples include imidazoline-type amphoteric surfactants such as 2-undecyl-N,N,N-(hydroxyethylcarboxymethyl)-2-imidazoline sodium, 2-cocoyl-2-imidazolinium hydroxide-1-carboxyethyloxy disodium salt, and the like; alkylbetaine-type amphoteric surfactants such as lauryl dimethylaminoacetic betaine, myristyl betaine, and the like; amidobetaine-type amphoteric surfactants such as coconut oil fatty acid amidopropyl dimethylamino acetic acid betaine, palm kernel oil fatty acid amidopropyl dimethylamino acetic acid betaine, beef tallow fatty acid amidopropyl dimethylamino acetic acid betaine, hardened beef tallow fatty acid amidopropyl dimethylamino acetic acid betaine, lauric acid amidopropyl dimethylamino acetic acid
• semipolar surfactants include alkylamine oxide-type surfactants, alkylamine oxides, alkylamide amine oxides, alkylhydroxyamine oxides, and the like. Alkyldimethylamine oxides having from 10 to 18 carbon atoms, alkoxyethyl dihydroxyethylamine oxides having from 8 to 18 carbon atoms, and the like are preferably used.
• Specific examples thereof include dodecyldimethylamine oxide, dimethyloctylamine oxide, diethyldecylamine oxide, bis-(2-hydroxyethyl)dodecylamine oxide, dipropyltetradecylamine oxide, methylethylhexadecylamine oxide, dodecylamidopropyldimethylamine oxide, cetyldimethylamine oxide, stearyldimethylamine oxide, tallow dimethylamine oxide, dimethyl-2-hydroxyoctadecylamine oxide, lauryldimethylamine oxide, myristyldimethylamine oxide, stearyldimethylamine oxide, isostearyldimethylamine oxide, coconut fatty acid alkyldimethylamine oxide, caprylic amide propyldimethylamine oxide, capric amide propyldimethylamine oxide, lauric amide propyldimethylamine oxide, myristic amide propyldimethylamine oxide, palmi
• the ultraviolet light blocking agent can be an inorganic ultraviolet light blocking agent or an organic ultraviolet light blocking agent.
• the composition it is preferable for the composition to contain at least one type of organic ultraviolet light blocking agent.
• using both inorganic and organic ultraviolet light blocking agents in combination is preferable, and using a UV-A blocking agent in combination with a UV-B blocking agent is more preferable.
• the inorganic ultraviolet light blocking agent may be compounded as an ultraviolet light scattering agent such as the inorganic pigment powders and metal powder pigments mentioned above.
• examples thereof include metal oxides such as titanium oxide, zinc oxide, cerium oxide, titanium suboxide, iron-doped titanium oxides, and the like; metal hydroxides such as iron hydroxides and the like; metal flakes such as platy iron oxide, aluminum flake, and the like; and ceramics such as silicon carbide, and the like.
• metal oxides such as titanium oxide, zinc oxide, cerium oxide, titanium suboxide, iron-doped titanium oxides, and the like
• metal hydroxides such as iron hydroxides and the like
• metal flakes such as platy iron oxide, aluminum flake, and the like
• ceramics such as silicon carbide, and the like.
• These powders are preferably subjected to conventionally known surface treatment such as, for example, fluorine compound treatment (of which perfluoroalkyl phosphate treatment, perfluoroalkylsilane treatment, perfluoropolyether treatment, fluorosilicone treatment, and fluorinated silicone resin treatment are preferable), silicone treatment (of which methylhydrogen polysiloxane treatment, dimethylpolysiloxane treatment, vapor-phase tetramethyltetrahydrogen cyclotetrasiloxane treatment, and glycerin-modified silicone treatment are preferable), silicone resin treatment (of which trimethylsiloxysilicic acid treatment is preferable), pendant treatment (which is a method of adding alkyl chains after vapor-phase silicone treatment), silane coupling agent treatment, titanium coupling agent treatment, silane treatment (of which alkylsilane or alkylsilazane treatment is preferable), oil agent treatment, N-acylated lysine treatment, polyacrylic acid treatment, metal soap
• the surface of the fine particulate titanium oxide can be coated with a metal oxide such as silicon oxide and alumina, and, thereafter, surface treating using an alkylsilane can be carried out.
• a total amount of the surface treatment agent is preferably in a range from 0.1 to 50 wt. % (mass %) of the powder.
• the organic ultraviolet light blocking agent is a lipophilic ultraviolet light blocking agent, and examples thereof include benzoic acid-based UV absorbers such as paraminobenzoic acid (hereinafter abbreviated as “PABA”), PABA monoglycerol ester, N,N-dipropoxy-PABA ethyl ester, N,N-diethoxy-PABA ethyl ester, N,N-dimethyl-PABA ethyl ester, N,N-dimethyl-PABA butyl ester, and 2-[4-(diethylamino)-2-hydroxybenzoyl]hexylester benzoate (trade name: Uvinul A plus); anthranilic acid-based UV absorbers such as homomethyl-N-acetylanthranilate; salicylic acid-based UV absorbers such as amyl salicylate, menthyl salicylate, homomethyl salicylate, octyl salicylate, phenyl salicylate, benzyl
• the organic-based UV absorber has high polarity and does not readily dissolve. Therefore, conventionally, it has been difficult to stably compound a desired (high) amount of the organic-based UV absorber in water-in-oil (W/O) emulsion cosmetic compositions.
• W/O water-in-oil
• the organopolysiloxane elastomer of the present invention is used as an emulsifier and a medium polarity oil such as an ester oil or the like is combined therewith as a binding agent, a stable UV absorber-containing W/O emulsion cosmetic composition can be obtained even when the oil phase contains a low polarity oil such as a silicone oil, a hydrocarbon oil, or the like.
• the compounded amount of the organic-based UV absorber is preferably in a range from 0.1 to 10 mass % and the compounded amount of the binding agent is preferably in a range from 0.005 to 5 mass %.
• the polymer powder may be or may not be hollow, and preferably has an average primary particle size in a range from 0.1 to 50 ⁇ m. Particle size distribution may be broad or sharp.
• Types of polymer include acrylic resins, methacrylic resins, styrene resins, polyurethane resins, polyethylene, polypropylene, polyethylene terephthalate, silicone resins, nylons, acrylamide resins, and silylated polypeptide resins.
• a polymer powder comprising from 0.1 to 30 wt.
• an organic ultraviolet light blocking agent is preferable, and a polymer powder comprising 4-tert-butyl-4′-methoxydibenzoylmethane, which is a UV-A absorber, is particularly preferable.
• the ultraviolet light blocking agent that can be preferably used is at least one selected from the group consisting of fine particulate titanium oxide, fine particle zinc oxide, paramethoxy cinnamic acid 2-ethylhexyl, 4-tert-butyl-4′-methoxydibenzoylmethane, a benzotriazole-based UV absorber, and a triazine-based UV absorber.
• These ultraviolet light blocking agents are generally used, are easy to acquire, and have high ultraviolet light blocking effects and, thus can be beneficially used.
• Examples of salts include inorganic salts, organic salts, amine salts, and amino acid salts.
• inorganic salts include sodium salts, potassium salts, magnesium salts, calcium salts, aluminum salts, zirconium salts, and zinc salts of inorganic acids such as hydrochloric acid, sulfuric acid, carbonic acid, and nitric acid.
• organic acid salts include salts of organic acids such as acetic acid, dehydroacetic acid, citric acid, malic acid, succinic acid, ascorbic acid, and stearic acid.
• amine salts and amino acid salts include salts of amines such as triethanolamine and salts of amino acids such as glutamic acid.
• salts of hyaluronic acid, chondroitin sulfuric acid, and the like, aluminum zirconium glycine complexes and the like, and acid-alkali neutralization salts and the like used in cosmetic product formulations can be used.
• moisturizing agents include polyhydric alcohols such as glycerin, sorbitol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, glucose, xylitol, maltitol, and polyethyleneglycol; hyaluronic acid, chondroitin sulfuric acid, pyrrolidone carboxylic acid salts, polyoxyethylene methylglucoside, polyoxypropylene methylglucoside, PEG/PPG dimethylether, polyols, glycols, glycol esters, and the like.
• polyhydric alcohols such as glycerin, sorbitol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, glucose, xylitol, maltitol, and polyethyleneglycol
• hyaluronic acid chondroitin sulfuric acid, pyrrolidone carboxylic acid salts
• polyoxyethylene methylglucoside polyoxypropylene methyl
• preservatives include alkyl paraoxybenzoates, benzoic acid, sodium benzoate, sorbic acid, potassium sorbate, phenoxyethanol, and the like.
• antimicrobial agents include benzoic acid, salicylic acid, carbolic acid, sorbic acid, alkyl paraoxybenzoates, parachloromethacresol, hexachlorophene, benzalkonium chloride, chlorhexidine chloride, trichlorocarbanilide, triclosan, photosensitizers, phenoxy ethanol and the like.
• the cosmetic composition is a rouge, it is preferable that these are not included.
• antioxidants examples include tocopherol, butylhydroxyanisole, dibutylhydroxytoluene, phytic acid, and the like.
• pH adjusting agents 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.
• chelating agent examples include alanine, sodium salt of edetic acid, sodium polyphosphate, sodium metaphosphate, phosphoric acid, and the like.
• Examples of the refreshing agents include L-menthol and camphor, and examples of the anti-inflammatory agents include allantoin, glycyrrhetic acid, glycyrrhizinic acid, tranexamic acid, and azulene.
• examples of skin beautifying components include skin-lightening agents such as placenta extracts, arbutin, glutathione, saxifrageous extracts, and the like; cell activating agents such as royal jelly and the like; agents for ameliorating skin roughness; circulation promoters such as nonylic acid vanillylamide, benzyl nicotinate, beta-butoxyethyl nicotinate, capsaicin, zingerone, cantharide tincture, ichthammol, caffeine, tannic acid, ⁇ -borneol, tocopherol nicotinate, inositol hexanicotinate, cyclandelate, cinnarizine, tolazoline, acetylcholine, verapamil, cepharanthine, ⁇ -oryzanol, and the like; astringents such as zinc oxide, tannic acid, and the like; antiseborrheic agents such as sulfur, thiant
• vitamins examples include vitamin As such as vitamin A oil, retinol, retinol acetate, retinol palmitate, and the like; vitamin Bs such as vitamin B2s such as riboflavin, riboflavin butyrate, flavin adenine dinucleotide, and the like; vitamin B6s such as pyridoxine hydrochloride, pyridoxine dioctanoate, pyridoxine tripalmitate, and the like; vitamin B12 and derivatives thereof; vitamin B15 and derivatives thereof, and the like; vitamin Cs such as L-ascorbic acid, L-ascorbyl dipalmitic acid esters, sodium L-ascorbyl 2-sulfate, dipotassium L-ascorbyl phosphoric acid diester, and the like; vitamin Ds such as ergocalciferol, cholecalciferol, and the like; vitamin Es such as ⁇ -tocopherol, 13-tocopherol, y
• amino acids examples include amino acids such as glycine, valine, leucine, isoleucine, serine, threonine, phenylalanine, arginine, lysine, aspartic acid, glutamic acid, cysteine, cysteine, methionine, tryptophan, and the like, and/or salts thereof.
• nucleic acids examples include deoxyribonucleic acid, and examples of hormones include estradiol and ethenyl estradiol.
• the bioactive component is a substance that imparts some sort of bioactivity to the skin or the hair when applied to the skin or the hair, and examples thereof are lipophilic substances.
• examples thereof include anti-inflammatory agents, anti-aging agents, tightening agents, hair regrowth agents, hair growth promoters, moisturizing agents, circulation promoters, drying agents, warming agents, vitamins, wound healing accelerators, irritation mitigation agents, analgesics, cell activating agents, enzyme components, and the like.
• natural vegetable extract components, seaweed extract components and herbal medicine components can be preferably blended.
• the medicament active component is a substance having a disease-treating effect, and examples thereof include proteins, peptides, and low molecular weight compounds.
• the perfume is not particularly limited as long as it is a lipophilic perfume, and examples thereof include perfumes that are extracted from a variety of plant flowers, seeds, leaves, roots, and the like, perfumes extracted from seaweed, perfumes extracted from a variety of animal parts and secretions (for example, musk or sperm oil), and artificially synthesized perfumes (for example, menthol, musk, acetic acid esters, and vanilla).
• the perfume is compounded for the purpose of imparting a fragrance or scent to the external use preparation or the cosmetic composition.
• the pigment include oil-soluble dyes, water-soluble dyes, extender pigments, inorganic pigments, organic pigments, and lipophilic optical brighteners.
• the external use preparation or the cosmetic composition according to the present invention may further contain a solid silicone resin or crosslinking organopolysiloxane (excluding the organopolysiloxane elastomer of the present invention), an acryl silicone dendrimer copolymer, a silicone raw rubber (silicone gum), a polyamide-modified silicone, an alkyl-modified silicone wax, or an alkyl-modified silicone resin wax.
• the main chain of the organopolysiloxane elastomer of the present invention comprises a polysiloxane chain, and the organopolysiloxane elastomer has a hydrophilic sugar alcohol modified group as a modifying group. This is advantageous in that it is possible to design a cosmetic composition that has excellent compounding stability with these silicone-based compounds and that takes advantage of the tactile sensation that is characteristic to these silicone-based cosmetic raw materials.
• the external use preparation or cosmetic composition of the present invention may further contain a solid silicone resin or crosslinking organopolysiloxane.
• the solid silicone resin or crosslinking organopolysiloxane preferably is hydrophobic, having absolutely no solubility in water at room temperature, or a solubility of less than 1 wt. % (mass %) per 100 g of water.
• the solid silicone resin is an organopolysiloxane having a highly branched structure, a net-like structure, or a cage structure, and is solid at room temperature. Any type of product may be used, provided that it is a silicone resin that is commonly used in cosmetic compositions and does not oppose the object of the present invention.
• the solid silicone resin may be a spherical powder, a flaky powder, a needle like powder, a plate-like flaky powder (including plate-like powders having appearances and particle aspect ratios commonly identified with plate-like forms), or a similar particulate.
• a silicone resin powder having monoorganosiloxy units (T units) and/or siloxy units (Q units), described below, can be preferably used.
• Compounding the organopolysiloxane elastomer of the present invention along with the solid silicone resin is useful because the compatibility with the oil agent and uniform dispersibility are improved, improvement effects in sensation during use can be obtained, namely uniform adhesion to the applied area due to the compounding of the solid silicone resin, and improvement effects in cosmetic retainability such as moisture resistance and sebum resistance can be obtained.
• solid silicone resins are often used as film-forming polymers that can be compounded in an oil-based system.
• the solid silicone resin examples include MQ resins, MDQ resins, MTQ resins, MDTQ resins, TD resins, TQ resins, and TDQ resins formed from arbitrary combinations of triorganosiloxy units (M units) (where the organo groups are only methyl groups, or are methyl groups and vinyl groups or phenyl groups), diorganosiloxy units (D units) (where the organo groups are only methyl groups, or are methyl groups and vinyl groups or phenyl groups), monoorganosiloxy units (T units) (where the organo groups are methyl groups, vinyl groups, or phenyl groups), and siloxy units (Q units).
• M units triorganosiloxy units
• D units diorganosiloxy units
• T units monoorganosiloxy units
• Q units siloxy units
• silicone resins are preferably oil soluble and can be dissolved in volatile silicone.
• a phenyl silicone resin having a high refractive index and a high content of phenyl groups can be easily used as a flaky silicone resin powder and, when compounded in a cosmetic composition, in particular, can impart a radiant feeling of sheerness to the skin or hair.
• Types of crosslinking organopolysiloxanes include non-emulsifiable crosslinking organopolysiloxanes and emulsifiable crosslinking organopolysiloxanes, but the organopolysiloxane chain preferably has a structure which is three-dimensionally crosslinked by a reaction between a crosslinking component consisting of a polyether unit, an alkylene unit having from 4 to 20 carbon atoms, or an organopolysiloxane unit and other optional modifying agents or the like.
• the crosslinking organopolysiloxane (excluding the organopolysiloxane elastomer of the present invention) can be obtained by performing an addition reaction on an organohydrogenpolysiloxane having a silicon-bonded hydrogen atom, a polyether compound or glycerin derivative having reactive unsaturated groups at both terminals of the molecular chain, an unsaturated hydrocarbon having more than one double bond in the molecule, and an organopolysiloxane having more than one double bond in the molecule.
• the crosslinking organopolysiloxane may have or may be free of unreacted silicon-bonded hydrogen atoms, phenyl groups, and similar aromatic hydrocarbon groups; octyl groups and similar long chain alkyl groups having from 6 to 30 carbon atoms; polyether groups, carboxyl groups, and similar modifying functional groups.
• any crosslinking organopolysiloxane can be used without limitations to physical modes or preparation methods such as dilution, properties, and the like.
• the crosslinking organopolysiloxane can be obtained via an addition reaction of crosslinking components selected from an organohydrogenpolysiloxane formed from a structural unit selected from the group consisting of an SiO 2 unit, an HSiO 15 unit, a R b SiO 1.5 unit, a R b HSiO unit, a R b 2 SiO unit, a R b 3 SiO 0.5 unit, and a R b 2 HSiO 0.5 unit (where R b is a substituted or unsubstituted monovalent hydrocarbon group having from 1 to 30 carbon atoms, with the exception of aliphatic unsaturated groups; and a portion of R b is a monovalent hydrocarbon group having from 8 to 30 carbon atoms), the organohydrogenpolysiloxane having an average of 1.5 or more silicon-bonded hydrogen atoms in the molecule; a polyoxyalkylene compound having unsaturated hydrocarbon groups at both molecular terminals; a poly
• the modifying functional groups described above can be introduced.
• hexyl groups C6 alkyl groups
• Such a crosslinking organopolysiloxane can be used without limitations, regardless of the physical modes or preparation methods such as dilution, properties, and the like, but particularly preferable examples thereof include ⁇ , ⁇ -diene crosslinking silicone elastomers (commercially available products include DC 9040 Silicone Elastomer Blend, DC 9041 Silicone Elastomer Blend, DC 9045 Silicone Elastomer Blend, DC 9046 Silicone Elastomer Blend, EL-9140 DM Silicone Elastomer Blend, 9546 Silicone Elastomer Blend, 9027 Silicone Elastomer Blend, FB-9586 Silicone Elastomer Blend, and EL-8040 ID Silicone Organic Blend manufactured by Dow Corning USA) described in U.S. Pat. No.
• organopolysiloxane polymers include a (dimethicone/vinyldimethicone) crosspolymer, a (dimethicone/phenylvinyldimethicone) crosspolymer, a (PEG-8 to 30/C 6 to C 30 alkyldimethicone) crosspolymer, a (vinylmethicone/C 6 to C 30 alkyldimethicone) crosspolymer, and a (dimethicone/polyglycerin) crosspolymer according to the INCI names (International Nomenclature Cosmetic Ingredient Labeling Names).
• crosslinkable organopolysiloxanes include a silicone polyester elastomer gel disclosed in WO2007/109240 and WO2009/006091 in which compatibility with various organic components is enhanced and stable thickening effects are displayed as a result of introducing a polyoxypropylene group; commercially available Dow Corning EL-8050 ID SILICONE ORGANIC ELASTOMER BLEND, Dow Corning EL-8051 IN SILICONE ORGANIC ELASTOMER BLEND, and Dow Corning EL-7040 HYDRO ELASTOMER BLEND; and PITUITOUS SILICONE FLUIDS disclosed in WO2011/028765 and WO2011/028770.
• the organopolysiloxane elastomer of the present invention When compounded in an external use preparation or a cosmetic composition as an emulsifiable crosslinking organopolysiloxane that is crosslinked by a polyether compound, the organopolysiloxane elastomer of the present invention functions as a dispersion stabilizer, which yields the advantage that a uniform emulsification system (dosage form) can be formed.
• a non-emulsifiable crosslinking organopolysiloxane also called a non-emulsifiable silicone elastomer
• an unsaturated group-containing organopolysiloxane or an unsaturated hydrocarbon group such as a diene, a polyoxypropylene having reactive unsaturated groups at both molecular terminals of the molecular chain, or the like
• a thick, smooth tactile sensation can be imparted to the skin or the hair, and a matte finish and effects of concealing wrinkles, pigmented spots, and the like can be obtained.
• this configuration is advantageous in that the feel of adhesion to the skin of the cosmetic composition is improved and cosmetic retainability is enhanced because the effects of retaining various oil agents and increasing the viscosity are high.
• One type or two or more types of the solid silicone resin or crosslinking organopolysiloxane can be compounded in accordance with the purpose thereof and are preferably compounded in a range from 0.05 to 25 wt. % (mass %) and more preferably in a range from 0.1 to 15 wt. % (mass %) of the entire cosmetic composition or the external use preparation, depending on the purpose and the intention of compounding.
• the external use preparation or the cosmetic composition of the present invention may further contain an acryl silicone dendrimer copolymer.
• the acryl silicone dendrimer copolymer is a vinyl polymer having a carbosiloxane dendrimer structure on the sidechain, and particularly preferable examples thereof include the vinyl polymer described in Japanese Patent No. 4009382 (Japanese Unexamined Patent Application Publication No. 2000-063225). Examples of commercially available products include FA 4001 CM Silicone Acrylate, FA 4002 ID Silicone Acrylate, and the like manufactured by Dow Corning Toray Co., Ltd.
• acryl silicone dendrimer copolymers having a long chain alkyl group on the sidechain or the like having from 8 to 30 carbon atoms and preferably from 14 to 22 carbon atoms.
• superior film formability can be obtained. Therefore, by compounding the acryl silicone dendrimer copolymer in the external use preparation or cosmetic composition according to the present invention, a strong coating film can be formed on the applied part, and cosmetic durability such as sebum resistance, rubbing resistance, and the like can be significantly improved.
• organopolysiloxane elastomer of the present invention in combination with the acryl silicone dendrimer copolymer yields advantages in that the surface protective properties such as sebum resistance can be improved due to strong water repellency provided by the carbosiloxane dendrimer structure, and irregularities such as pores can also be effectively concealed.
• the organopolysiloxane elastomer of the present invention causes the acryl silicone dendrimer copolymer to blend well with the other oil agents and has excellent compatibility with the skin and surface of the hair, so the hardness of the acryl silicone dendrimer copolymer can be reduced, and a film with an excellent adhesive sensation and a lasting feel of moisture can be achieved.
• cosmetic retainability is improved, which has the advantage that degradation of the skin surface or hair can be suppressed for an extended period of time.
• a compounded amount of the acryl silicone dendrimer copolymer can be suitably selected based on the purpose and compounding intent thereof, but is preferably in a range from 1 to 99 wt. % (mass %) and more preferably in a range from 30 to 70 wt. % (mass %) of the entire external use preparation or cosmetic composition.
• an ultra-high viscous yet fluid component having a viscosity at room temperature of 1,000,000 mm 2 /s or higher which is referred to as a silicone raw rubber (silicone gum)
• silicone raw rubber silicone gum
• Silicone rubber is a straight-chained diorganopolysiloxane with an ultra-high degree of polymerization and is also called silicone raw rubber or organopolysiloxane rubber. Silicone rubber is differentiated from the oily silicones described above because the degree of polymerization of silicone rubber is high and, as a result, it has a degree of plasticity that is measurable.
• silicone gums can be compounded directly in the external use preparation or the cosmetic composition of the present invention—in a hair cosmetic composition for the purpose of imparting a tactile sensation—or can be compounded as liquid gum dispersions in which an oil-like silicone is dispersed (oil dispersions of silicone gums).
• Examples of such a silicone raw rubber include substituted or unsubstituted organopolysiloxanes having a dialkylsiloxy unit (D unit) such as a dimethylpolysiloxane, a methylphenylpolysiloxane, an aminopolysiloxane, or a methylfluoroalkylpolysiloxane, or products having micro-crosslinked structures thereof, and typical examples thereof include products expressed by the general formula: R 10 (CH 3 ) 2 SiO[(CH 3 ) 2 SiO] s [(CH 3 )R 12 SiO] t Si(CH 3 ) 2 R 10 (wherein R 12 moieties are each independently a group selected from vinyl groups, phenyl groups, alkyl groups having from 6 to 20 carbon atoms, aminoalkyl groups having from 3 to 15 carbon atoms, perfluoroalkyl groups having from 3 to 15 carbon atoms, and quaternary ammonium salt group-containing alkyl groups having
• a dimethylpolysiloxane raw rubber having a degree of polymerization of 3,000 to 20,000 is preferable.
• an amino-modified methylpolysiloxane raw rubber having a 3-aminopropyl group, an N-(2-aminoethyl)-3-aminopropyl group, or the like on the molecular sidechain or terminal is preferable.
• one or two or more types of silicone gums can be used as necessary.
• Silicone gum has an ultra-high degree of polymerization and, therefore forms a protective film with superior breathability and retention on hair. Therefore, the silicone gum is a component which can particularly provide glossiness and luster to hair and can impart a texture of firmness and body to the entire hair during use and after use.
• a silicone gum with a high degree of polymerization can also be compounded in the external use preparation or the cosmetic composition in a form that is diluted with a silicone oil to reduce the viscosity.
• organopolysiloxane elastomer of the present invention imparts a smooth, sliding feeling to wet hair at the time of rinsing or the like, and the substance is effectively absorbed by the surface of the hair, which yields a sustained moisturizing effect to the hair after drying and a protective effect to the hair surface and makes it possible to suppress flyaway.
• a compounded amount of the silicone gum is, for example, from 0.05 to 30 wt. % (mass %) and preferably from 1 to 15 wt. % (mass %) of the entire external use preparation or cosmetic composition.
• the silicone gum is used as an emulsion composition prepared via a process of pre-emulsifying (including emulsion polymerization)
• the silicone gum can easily be compounded, and can be stably compounded in the hair cosmetic composition of the present invention.
• An effect of imparting a specific feeling to touch or glossiness of the hair may be insufficient if the compounded amount of the silicone gum is less than the lower limit described above.
• This polyamide-modified silicone also functions as an oil-based raw material, specifically as a thickening/gelling agent of a silicone oil.
• the external use preparation or the cosmetic composition of the present invention has good spreading and setting as well as an excellent sense of stability and adhesion when applied to the skin, the hair, or the like. Additionally, there are advantages from a quality standpoint such that a glossy feeling of sheerness and superior luster can be provided, the viscosity or hardness (softness) of the entire cosmetic composition containing the oil-based raw material can be appropriately adjusted, and an oily sensation (oily and sticky feeling to touch) can be totally suppressed. Furthermore, by using the organopolysiloxane elastomer, the dispersion stability of perfumes, powders, and the like will be improved. Therefore, the obtained cosmetic composition will be characterized by being able to maintain a uniform and fine cosmetic sensation for an extended period of time.
• Silicone waxes that can be preferably compounded in the external use preparation or the cosmetic composition of the present invention are higher alkyl-modified silicones and alkyl-modified silicone resins.
• the higher alkyl-modified silicone is a wax at room temperature and is a component that is useful as a portion of the base material of a solid cosmetic composition (for example, an oil-based solid skin cosmetic composition or a solid hair cosmetic composition). Therefore, the higher alkyl-modified silicone can be preferably used in the external use preparation or the cosmetic composition of the present invention.
• Examples of the higher alkyl-modified silicone wax include methyl (long chain alkyl) polysiloxanes having both molecular terminals capped with trimethylsiloxy groups, copolymers of a dimethylpolysiloxane having both molecular terminals capped with trimethylsiloxy groups and a methyl (long chain alkyl) siloxane, dimethylpolysiloxane modified with long chain alkyls at both molecular terminals, and the like.
• Examples of commercially available products include AMS-C30 Cosmetic Wax, 2503 Cosmetic Wax, and the like (manufactured by Dow Corning Corporation, in the USA).
• the organopolysiloxane elastomer of the present invention has good affinity with the higher alkyl-modified silicone wax and has excellent dispersibility properties in wax, so an external use preparation or a cosmetic composition having excellent storage stability over time can be obtained.
• the moldability of the external use preparation or the cosmetic composition, and particularly of a solid cosmetic composition is excellent.
• a system comprising a powder an effect of uniformly and stably dispersing the powder in the base material containing the higher alkyl-modified silicone wax is obtained, and the hardness of the base material after molding can be moderately mitigated, which makes it possible to provide an external use preparation or a cosmetic composition that spreads smoothly and uniformly when applied.
• the higher alkyl-modified silicone wax preferably has a melting point of not lower than 60° C. because such will lead to cosmetic retainability effects and stability at high temperatures.
• the alkyl-modified silicone resin is a type of film-forming polymer that is compoundable in an oil phase and is a component that imparts sebum durability, moisturizing properties, and a fine tactile sensation of the skin to the external use preparation or the cosmetic composition.
• An alkyl-modified silicone resin that is in the form of a wax at room temperature can be suitably used.
• Preferred examples thereof include the silsesquioxane resin wax described in Japanese Unexamined Patent Application Publication (Translation of PCT Application) No. 2007-532754.
• Examples of commercially available products include SW-8005 C30 RESIN WAX (manufactured by Dow Corning Corporation, in the USA), and the like.
• the organopolysiloxane elastomer of the present invention has good affinity with the alkyl-modified silicone resin wax and has excellent dispersion properties in wax, so an external use preparation or a cosmetic composition having superior storage stability over time can be obtained.
• an aqueous phase can be stably emulsified along with other optional surfactants in the oil phase containing the alkyl-modified silicone resin wax, which makes it possible to impart a luxurious tactile sensation, moisturizing effects, and effects of improving cosmetic retainability exemplified by moisture resistance and sebum resistance to the skin or the hair.
• the external use preparation or the cosmetic composition according to the present invention is an anti-perspirant, or depending on the purpose thereof, the external use preparation or the cosmetic composition can contain an anti-perspiration active component and/or a deodorant agent.
• anti-perspiration active component examples include astringent salts such as aluminum chlorohydrate, aluminum-zirconium tetrachlorohydrex glycine (ZAG), and the like; but aluminum, hafnium, zinc, and zirconium salts (e.g. aluminum halide, aluminum hydroxy halide, zirconium halide, zirconium oxyhalide, zirconium hydroxy halide, zirconyl hydroxide halide, aluminum chloride zirconium, zirconium lactate-aluminum, and basic aluminum halide) can be used.
• astringent salts such as aluminum chlorohydrate, aluminum-zirconium tetrachlorohydrex glycine (ZAG), and the like
• zirconium salts e.g. aluminum halide, aluminum hydroxy halide, zirconium halide, zirconium oxyhalide, zirconium hydroxy halide, zirconyl hydroxide
• Examples thereof include Al 2 (OH) 5 Cl, aluminum bromide, buffer aluminum sulphate, alum, dried alum, various aqueous, alcohol, or glycine complexes thereof (e.g. a complex of an aluminum-zirconium chlorohydrate and glycine comprising aluminum, zirconium, and glycine (a ZAG complex), and the like.
• a single anti-perspiration active component may be used or a combination of two or more may be used.
• these anti-perspiration active components are an aqueous phase component.
• soybean extracts and isoflavones are known for their anti-perspirant effects; and, because they have low water solubility, are preferably used by dissolving them in the oil phase.
• a compounded amount of the anti-perspiration active component is an amount sufficient to reduce perspiration, and suppressing the compounded amount to a small amount can be beneficial in personal care compositions.
• the compounded amount of the anti-perspiration active component in an anti-perspirant composition is preferably from 5 to 25 wt. % (mass %) of the entire cosmetic composition.
• the anti-perspiration active component When using a water soluble anti-perspiration active component, from the standpoint of cost effectiveness, it is preferable to increase the proportion of water in the composition to a maximum limit, while maintaining anti-perspirant effects, but the anti-perspiration active component can also be added to the aqueous phase at amount near the saturation amount.
• a deodorant agent can be compounded together with or instead of the anti-perspiration active component in the external use preparation or the cosmetic composition of the present invention, and particularly an antiperspiration composition.
• the deodorant agent include deodorizers, perfumes, and substances that prevent or remove odors caused by perspiration.
• Such deodorant agents are antimicrobial agents (germicides or fungicides), bacteriostatic agents, odor absorbing substances, deodorizers, perfumes, or the like, and are compounded for the purpose of preventing underarm odor, odor from perspiration, foot odor, and other bodily odors. Note that these deodorant agents are useful in cosmetic compositions or external use preparations other than anti-perspirants and it goes without saying that they can be beneficially compounded in the external use preparation or cosmetic composition of the present invention.
• antimicrobial agents examples include alkyltrimethylammonium bromide, cetylpyridinium chloride, benzethonium chloride, benzalkonium chloride, chlorhexidine hydrochloride, chlorhexidine gluconate, [[(diisobutylphenoxy)ethoxy]ethyl] dimethylbenzylammonium chloride, N-lauroyl sarcosine sodium, N-palmitoyl sarcosine sodium, N-myristoyl glycine, N-lauroyl sarcosine potassium, trimethyl ammonium chloride, aluminum chlorohydroxy sodium lactate, triethyl citrate, tricetyl methyl ammonium chloride, 1,5-pentanediol, 1,6-hexanediol, 2,4,4′-trichloro-2′-hydroxy diphenylether (triclosan), and 3,4,4′-trichlorocarbanilide(triclocarban);
• bacteriostatic agents examples include 1-heptyl glyceryl ether, 1-(2-ethylhexyl)glyceryl ether, 1-octyl glyceryl ether, 1-decyl glyceryl ether, 1-dodecyl glyceryl ether, and similar glyceryl monoalkyl ethers.
• the odor absorbing substance is not particularly limited, provided that it absorbs odor causing substances and reduces odor, is constituted by a portion of the inorganic powders and organic polymers described above, and displays the same characteristics.
• odor absorbing substance examples include zinc oxide, magnesium oxide, zeolite, aluminometasilicate, silicic anhydride, colloidal silica, talc, mica, hydroxyapatite, cellulose, corn starch, silk, nylon powder, crosslinking organopolysiloxane powder, organopolysiloxane elastomer spherical powder, and the like.
• carbonates such as alkali metal carbonates, alkali metal bicarbonate salts, and the like and hydrogen carbonates, ammonium salts, tetraalkylammonium salts, and the like can be used.
• sodium salts and potassium salts are more preferable.
• organic or inorganic porous particles carrying silver, copper, zinc, cerium, or similar metal ions e.g. silver ion-carrying zeolite, silver ion/zinc ion/ammonium ion-carrying zeolite), or aggregates of needle-like crystals including silver cancrinite can be used. Because these function as antimicrobial agents and odor absorbing substances, they can be used beneficially as the deodorant agent.
• hydroxyalkylated cyclodextrin sake cake extract containing rice fermenting liquid
• various extracts derived from animals, vegetables, microorganisms, fungi, and the like such as brown seaweed extract, cinnamon bark, clove, fennel, ginger, mentha, citron, gentiana lutea, apricot, eucalyptus, Sophora flavescens, mulberry, althea, sage, Anthemis nobilis, Scutellaria root, nutgall, gardenia, hamamelis, herbs, and the like can be used as the deodorant agent.
• a part of these components overlaps with a bioactive component described above, but selecting these extracts as the deodorant agent for the purpose of the functional effects thereof is both beneficial and preferable from the standpoint of the composition design of the cosmetic composition.
• the odor absorbing substance Preferably from 0.001 to 60 wt. % (mass %), more preferably from 0.01 to 30 wt. % (mass %), and yet more preferably from 0.01 to 3 wt. % (mass %) of the odor absorbing substance is included in the entire composition.
• the compounded amount of the odor absorbing substance is within this range, there is an advantage that deodorizing performance can be improved while not negatively affecting the strength and feeling to touch of the formulation.
• Suitable perfumes include known topical use substances, topical use substances that are effective in masking malodor accompanied by perspiration, and various topical use substances that provide a composition having a desired aroma. Examples thereof include the whole of perfumes and perfume chemicals such as perfume precursors, deodorizing fragrances, and the like that are suitable for topical application to the skin and, as necessary, may be a blended perfume component.
• the organopolysiloxane elastomer of the present invention or the composition containing the same can be suitably used as a raw material for an external use preparation or a raw material for a cosmetic composition.
• the organopolysiloxane elastomer of the present invention produced via an acidizing process and the composition of the present invention containing the organopolysiloxane elastomer of the present invention and at least one type of acid have a reduced odor and can therefore be suitably compounded in an external use preparation or a cosmetic composition.
• the carbonyl value measurement method described above is capable of accurately and simply assaying a carbonyl compound, so the method can be preferably used for the evaluation of the odor of a product of an external use preparation or a cosmetic composition.
• an Me 3 SiO group (or an Me 3 Si group) is represented by “M”
• an Me 3 SiO group is represented by “D”
• an Me 2 HSiO group (or an Me 2 HSi group) is represented by “M H ”
• an MeHSiO group is represented by “D H ”
• an Me 2 (CH 2 ⁇ CH)SiO group [or an Me 2 (CH 2 ⁇ CH)Si group] is represented by “M Vi ”
• an Me(CH 2 ⁇ CH)SiO group is represented by “D Vi ”.
• Me 2 [CH 2 ⁇ CH—(CH 2 ) 4 ]SiO group [or an Me 2 [CH 2 ⁇ CH—(CH 2 ) 4 ]Si group] is represented by “M Hex ”, an Me[CH 2 ⁇ CH—(CH 2 ) 4 ]SiO group is represented by “D Hex ” an MeSiO 3/2 group is represented by “T”, and an MeSiO 4/2 group is represented by “Q”. Units in which the methyl groups in M and D are modified by one of the substituents are represented by M R and D R .
• the xylitol monoallyl ether and xylitol residue described below are a raw material and functional groups as described in this specification. More specifically, the xylitol monoallyl ether is a raw material containing a xylitol monoallyl ether expressed by the structural formula: CH 2 ⁇ CH—CH 2 —OCH 2 [CH(OH)] 3 CH 2 OH and the structural formula: CH 2 ⁇ CH—CH 2 —OCH[CH(OH)CH 2 OH] 2 at a composition ratio of approximately 9:1, and a xylitol residue represented by the corresponding formula —C 3 H 6 —OCH 2 [CH(OH)] 3 CH 2 OH or —C 3 H 6 —OCH[CH(OH)CH 2 OH] 2 is introduced to the co-modified silicone of the present invention at the same composition ratio.
• hexadecene ( ⁇ -olefin purity: 91.7%) was added to the reaction mixture, and after the mixture was reacted for 6 hours at 80° C., it was confirmed via the same method that the target reaction rate was reached.
• 6.2 g of xylitol monoallyl ether (purity: 91.2%) and 138 g of isopropyl alcohol (IPA) were added to the reaction mixture, and 0.13 ml of the platinum catalyst described above was added. After reacting for 3 hours at 80° C., the mixture was sampled.
• a composition containing a novel organopolysiloxane elastomer modified by a xylitol group was then obtained by heating under reduced pressure to distill out low-boiling-point matter. The composition was then transferred to a Hobart mixture and subjected to kneading and grinding for 3 hours to obtain a homogenized, translucent or white, soft paste-like composition (elastomer concentration: 33%).
• a methylhydrogenpolysiloxane expressed by the average composition formula: MD 43.4 D H 74 M and 23.1 g of hexadecene ( ⁇ -olefin purity: 91.7%) were placed in a reaction vessel, and when 0.10 ml of a hexamethyldisiloxane solution of a platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt concentration: 0.45 wt. %) was added at 30° C. while agitating under a nitrogen stream, heat was generated immediately, and the mixture heated to 60° C. after three minutes.
• the temperature was then maintained at 30 to 60° C., and a small amount of the reaction solution was sampled after one hour.
• the reaction rate had reached the target rate.
• 14.1 g of a xylitol monoallyl ether (purity: 85.3%), 138 g of isopropyl alcohol (IPA), and 0.03 g of natural vitamin E were added to the reaction mixture, and 0.03 ml of the platinum catalyst described above was then added. After a reaction was performed for 6 hours at 65 to 70° C., a small amount of the reaction solution was sampled.
• the aforementioned elastomer was then transferred to a Hobart mixer, and after the elastomer was subjected to kneading and grinding for one hour, the elastomer was subjected to kneading and grinding while slowly adding 409 g of a dimethylpolysiloxane (6 cst) serving as a diluent over the course of 8.5 hours to obtain a translucent or white, soft paste-like composition (elastomer concentration: 33%).
• a dimethylpolysiloxane (6 cst) serving as a diluent
• reaction rate had reached the target rate.
• 6.0 g of 3-methacryloxypropyl(tris(trimethylsiloxy)silylethyldimethylsiloxy)silane was added to the reaction mixture and reacted for 1.5 hours at 55 to 75° C., and it was confirmed by the same method that the reaction rate had reached the target rate.
• the mixture was temporarily cooled to 50° C., and 5.5 g of 5-hexadiene and 0.15 ml of the platinum catalyst described above were added to the mixture.
• a reaction was performed for 2.5 hours at 50 to 60° C., elastomerization occurred, and the reaction mixture turned to a collapsible grease-like or paste-like substance.
• the Vi/H molar ratio when crosslinking was 1.2.
• the hardness increased and the mixture became a dry grease in large drops.
• the elastomer was then subjected to kneading while slowly adding 446 g of a dimethylpolysiloxane (6 cst) serving as a diluent over the course of 7 hours to obtain a translucent or transparent, homogeneous, soft ricecake-like composition (elastomer concentration: 33%).
• a methylhydrogenpolysiloxane represented by the average composition formula: MD 42.9 D H 6.7 M and 6.1 g of 3-methacryloxypropyl(tris(trimethylsiloxy)silylethyldimethylsiloxy)silane were placed in a reaction vessel, and 0.12 ml of an isopropyl alcohol solution of a platinum divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt concentration: 0.45 wt. %) was added while agitating under a nitrogen stream.
• the elastomer was then subjected to kneading while slowly adding 450 g of a dimethylpolysiloxane (6 cst) serving as a diluent over the course of 3 hours to obtain a translucent or white, soft paste-like composition (elastomer concentration: 33%).
• a methylhydrogenpolysiloxane represented by the average composition formula: MD 43.4 D H 7.4 M and 5.0 g of 3-methacryloxypropyl(tris(trimethylsiloxy)silylethyldimethylsiloxy)silane were placed in a reaction vessel, and 0.10 ml of a hexamethyldisiloxane solution of a platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt concentration: 0.45 wt. %) was added while agitating under a nitrogen stream.
• the mixture was then maintained at 60 to 80° C., and when a reaction was performed for 8.5 hours (0.10 ml of the aforementioned catalyst was added at an intermediate stage), it was found that the reaction rate had reached the target rate and that an intermediate expressed by the average composition formula: MD 43.4 D R * 31 0.1 D R * 11 4.0 D H 2.98 D OR 0.32 M had been produced.
• 2.3 g of xylitol monoallyl ether (purity: 91.2%), 138 g of isopropyl alcohol (IPA), and 0.03 g of natural vitamin E were added to the reaction mixture, and after a reaction was performed for 2 hours at 70° C., the mixture was sampled.
• D OR is a structural unit produced by the dehydrogenation of D H and an alcoholic hydroxyl group, the unit being an Me(OR)SiO group containing a Si—O—C bond or a Si—O—H bond.
• the elastomer was then subjected to kneading while slowly adding 438 g of a dimethylpolysiloxane (6 cst) serving as a diluent over the course of 8 hours to obtain a white, homogeneous, soft paste-like composition (elastomer concentration: 33%).
• the elastomer was then subjected to kneading while slowly adding 450 g of a dimethylpolysiloxane (6 cst) serving as a diluent over the course of 3 hours to obtain a translucent or white, soft paste-like composition (elastomer concentration: 33%).
• a methylhydrogenpolysiloxane represented by the average composition formula: MD 40 D H 15 M and 12.1 g of 1-dodecene (equivalent to 1 ⁇ 4 the total amount of 1-dodecene added) were placed in a reaction vessel and heated to 50.0° C. while agitating under a nitrogen air flow, and 0.10 g of an ethanol solution of chloroplatinic acid (Pt concentration: 3 wt. %) was then added. The temperature increased to 80° C. due to the reaction heat, and after it was confirmed that the temperature dropped naturally thereafter, a second batch of 12.1 g of 1-dodecene was added and reacted.
• R* 12 —C 12 H 25
• R* 41 —C 2 H 4 SiMe 2 (OSiMe 2 ) 6 OSiMe 3
• the elastomer was then subjected to kneading while slowly adding 450 g of a dimethylpolysiloxane (6 cst) serving as a diluent over the course of 3 hours to obtain a translucent or white, soft paste-like composition (elastomer concentration: 33%).
• the elastomer was then subjected to kneading while slowly adding 450 g of a dimethylpolysiloxane (6 cst) serving as a diluent over the course of 3 hours to obtain a translucent or white, soft paste-like composition (elastomer concentration: 33%).
• ⁇ The composition has excellent elastomeric, soft elasticity and spreads smoothly.
• the composition is characterized by a smoothness with a velvet-like thickness.
• ⁇ The composition has elastomeric, soft elasticity, spreads smoothly, and has a unique thick feel.
• ⁇ The spreadability is good and the sensation during use is smooth and natural when first applied, but there is a conspicuous stickiness and gooeyness while applied to the skin.
• the thick feel unique to elastomers is also minimal.
• x There is no problem with spreadability, but there is a strong, oily stickiness and gooeyness from when the composition is first applied until the end of the test. The thick feel unique to elastomers is also minimal.
• ⁇ Skin compatibility is good, and a favorable moisturizing feel is also achieved. In addition, the oiliness is suppressed, so an extremely natural sensation on the skin with no discomfort in terms of appearance can be obtained.
• ⁇ Skin compatibility is good, and a favorable moisturizing feel is also achieved. In addition, the oiliness is suppressed, and there is practically no discomfort.
• ⁇ The moisturizing feel is reduced, and there is a slightly stronger oily tactile sensation.
• x Oily gooeyness is strong, and there is a feeling of warmth, which is disagreeable.
• the paste-like compositions and mixtures with oil agents obtained in Practical Examples 1 to 6 and Comparative Examples 1 and 2 were prepared as prescribed by the formulations shown in Table 3 (elastomer concentration: 10%) and Table 4 (elastomer concentration: 5%).
• the viscosities of the resulting compositions were measured, and the thickening/gelling effect of the oil agent of the organopolysiloxane elastomer having a sugar alcohol-modified group of the present invention was confirmed.
• the results are shown in Tables 3 and 4. In the table, “parts” indicates “parts by weight (mass)”.
• the paste-like composition was placed in a Hobart mixer, and an oil agent was dripped into the composition while mixing over the course of 5 minutes to form a uniform composition. 2. The viscosity of the mixture was measured under conditions at 25° C.
• the organopolysiloxane elastomer having a sugar alcohol-modified group of the present invention has excellent affinity with various oil agents and that the elastomer can efficiently and stably thicken or gelify various oil agents.
• the conventional hydrophilic organopolysiloxane elastomers used in the comparative examples required that a large amount of the elastomer be compounded in order to demonstrate clear effects as an oil thickening agent, and there was a problem from the perspective of the efficiency of thickening or gelification.
• water-in-oil emulsion compositions having the formulations shown in Tables 5 to 9 were prepared in accordance with the following procedure. These compositions were evaluated in terms of the functionality (tactile sensation and sensation during use), aesthetic appearance and form stability, emulsified particle size stability, and odor over time according to the evaluation criteria below. The results are shown in Tables 5 to 9. In the table, “parts” indicates “parts by weight (mass)”.
• the paste-like composition was placed in the pot of a Hobart mixer. 2. An oil agent was dropped into the mixture while agitating over the course of 5 minutes to obtain a uniform mixture (oil phase A). 3. Table salt and ion exchanged water were placed in a separate container. The salt was dissolved by mixing using a spatula. Furthermore, 1,3-butylene glycol was mixed and dissolved therein (aqueous phase B). 4. An aqueous phase B was dropped into the oil phase A over the course of 10 minutes while agitating the oil phase A with the Hobart mixer. 5. Agitation was halted after agitating for two more minutes. The oily component and water droplets adhering to the inner wall of the container were then scraped off using a spatula and mixed with the produced emulsion. 6. The mixture was further agitated for 3 minutes with the Hobart mixer.
• ⁇ The composition has an extremely watery tactile sensation, and the unique thick and smooth tactile sensation is ongoing.
• ⁇ A watery tactile sensation is achieved, and the unique thick and smooth tactile sensation is ongoing.
• ⁇ A watery tactile sensation is achieved, but smoothness and thickness are not perceived strongly.
• x A slightly thick smoothness is perceived, but the composition otherwise has the feel of a common cream when applied, and practically no watery tactile sensation is perceived. (Cases where the Emulsifying Itself was not Possible are Also Indicated as “x”)
• ⁇ Skin compatibility is good, and a favorable moisturizing feel is also achieved. In addition, the oiliness is suppressed, so an extremely natural sensation during use with no discomfort in terms of appearance can be obtained.
• ⁇ Skin compatibility is good, and a natural sensation on the skin is achieved due to a favorable moisturizing feel, but there is a slight degree of oily shininess.
• ⁇ Although the composition has a moisturizing feeling, the oiliness and shininess are troubling, and there is some discomfort with regard to the sensation on the skin.
• x The composition has no moisturizing feeling and has strong oily gooeyness and shininess. (Cases where the emulsifying itself was not possible are also indicated as “x”)
• ⁇ The entire mixture is uniform and has a cream or gel-like form with a matte texture. ⁇ : Most of the mixture is uniform and has a cream or gel-like form with a matte texture. Slight deposits may be present. ⁇ : The surface roughness of the emulsion can be easily seen, and there is a somewhat large amount of unevenness and deposits. x: Emulsification itself is not complete, and phase separation is observed or the surface is clearly uneven.
• ⁇ Change in emulsified particle size was small, and signs of coalescence were absent.
• ⁇ The emulsified particle size potentially increased slightly but definite coalescence was not observed. Alternatively, the emulsified particle size increased, but the overall particle size was small and the emulsion system was maintained.
• ⁇ It is thought that partial coalescence of the particles occurred. Definite increase in the emulsified particle size.
• x Many particles were coalesced and emulsion was in the state of breaking down. (Cases where the emulsifying itself was not possible are also indicated as “x”)
• the emulsion compositions (the capped 35 mL glass bottles containing 28 g of each water-in-oil emulsion composition, as described above) to sit at rest at 50° C. for two weeks, the compositions were removed and returned to room temperature. The bottles were opened on the next day, and the odor produced was evaluated in accordance with the following criteria. Note that relative comparisons were carried out within groups that used a common oil agent.
• ⁇ Level with practically no noticeable odor. ⁇ : Slight odor (sweet solution-like specific odor) is perceived. ⁇ : Moderate odor (sweet solution-like specific odor) is perceived. x: Strong odor (sweet solution-like specific odor) is perceived.
• the ground partiesl of the sugar alcohol-modified organopolysiloxane elastomer of the present invention can be used with much more versatility than the conventional hydrophilic silicone elastomers used in the comparative examples, and it was confirmed that the elastomer dramatically increases the overall value of the external use preparation or cosmetic composition.
• the emulsion obtained here has the excellent feature that there is very little odor generation due to the passage of time or temperature, which verifies that the emulsion is extremely useful as a raw material for an external use preparation or a cosmetic composition.
• the polyol (non-water)-in oil emulsion composition with the formulation shown in Table 10 was prepared using the paste-like composition obtained in Practical Example 1.
• “parts” indicates “parts by weight (mass)”.
• the cream or gel-like emulsion composition obtained here was stable without any noticeable changes in appearance or form even after being stored for 2 weeks at 50° C.
• the water-in-oil emulsion transparent gel-like antiperspirant composition obtained here was stable with no noticeable changes in appearance or form even after being stored for 2 weeks at 50° C.
• oil-based foundations containing the paste-like compositions obtained in Practical Example 1 and Comparative Examples 1 and 2 were prepared as prescribed by the formulations in Table 12.
• an artificial leather surface was coated with each obtained foundation using a Meyer bar, and the cosmetic retention was evaluated in accordance with the following evaluation criteria for films obtained after the foundations dried.
• the storage stability of the obtained foundations was also evaluated. The results are shown in Table 12. In the table, “parts” indicates “parts by weight (mass)”.
• ⁇ No transfer whatsoever. ⁇ : Very little transfer. ⁇ : Some transfer. x: Severe transfer.
• ⁇ No changes in appearance are observed. ⁇ : Practically no abnormalities in appearance are observed. ⁇ : Slight powder precipitation or slight separation of the oil phase is observed on the surface. x: Powder precipitation or phase separation are clearly observed.
• the moisture resistance and sebum resistance of a cosmetic composition containing the powder improve in comparison to cases in which the conventional hydrophilic group-containing organopolysiloxane elastomers used in the comparative examples are used, and there is little secondary adhesion.
• the oil-based foundations using the organopolysiloxane elastomer of the present invention demonstrated good storage stability.
• organopolysiloxane elastomer of the present invention can be used in formulations 1 to 47 of the specific cosmetic compositions shown in the table below.
• Formulation example 1 W/O cream foundation Formulation example 2: W/O Liquid foundation Formulation example 3: W/O compact foundation Formulation example 4: O/W/O liquid foundation Formulation example 5: W/O makeup foundation Formulation example 6: Rouge Formulation example 7: Powder foundation Formulation example 8: W/O compact foundation Formulation example 10: Eye shadow Formulation example 10: W/O UV cutting cream Formulation example 11: W/O UV cutting emulsion Formulation example 12: O/W UV cutting cream Formulation example 13: W/O/W cream Formulation example 14: O/W/O emulsion Formulation example 15: Skin care emulsion Formulation example 16: Skin care cream Formulation example 17: Foundation Formulation example 18: O/W sunscreen Formulation example 19: Powder eye shadow Formulation example 20: Rouge Formulation example 21: Mascara Formulation example 22: O/W cream Formulation example 23: O/W cream Formulation example 24: Stick-type antiperspirant Formulation example 25: Anhydrous roll-on antiperspirant Formulation example 26: Non

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