WO2011111179A1 - 有機シリコーン微粒子、有機シリコーン微粒子の製造方法、有機シリコーン微粒子を含有する化粧料、樹脂組成物及び塗料組成物 - Google Patents
有機シリコーン微粒子、有機シリコーン微粒子の製造方法、有機シリコーン微粒子を含有する化粧料、樹脂組成物及び塗料組成物 Download PDFInfo
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
- A61Q1/02—Preparations containing skin colorants, e.g. pigments
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/0241—Containing particulates characterized by their shape and/or structure
- A61K8/0279—Porous; Hollow
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/66—Additives characterised by particle size
- C09D7/68—Particle size between 100-1000 nm
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/66—Additives characterised by particle size
- C09D7/69—Particle size larger than 1000 nm
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/41—Particular ingredients further characterized by their size
- A61K2800/412—Microsized, i.e. having sizes between 0.1 and 100 microns
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/60—Particulates further characterized by their structure or composition
- A61K2800/65—Characterized by the composition of the particulate/core
- A61K2800/654—The particulate/core comprising macromolecular material
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- 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 an organic silicone fine particle, a method for producing the organic silicone fine particle, a cosmetic containing the organic silicone fine particle, a resin composition, and a coating composition.
- fine particles of various materials have been put to practical use in various fields. Many of the shapes are indefinite, and each of them has played a corresponding role as an industrial material.
- the present invention is an organic silicone fine particle that meets the sophistication of the demand for such fine particles, and the organic silicone exhibits a shape in which a concave portion having a generally circular opening is formed on the surface corresponding to each surface of the tetrahedron as a whole. It relates to fine particles.
- the organic fine particles having a changed shape are hollow organic fine particles having large irregularities (for example, see Patent Document 6), organic fine particles having a plurality of small depressions on the surface (for example, see Patent Document 7), rugby ball-like organic
- modified organic fine particles such as fine particles (for example, see Patent Document 8) and hemispherical organic fine particles (for example, see Patent Document 9).
- these conventional deformed organic fine particles have a problem that it is difficult to sufficiently meet the high demands in actual use scenes in recent years.
- the problem to be solved by the present invention is a high demand in actual use scenes in recent years, for example, in resin compositions, further improvement in optical properties such as total light transmittance and haze, and further in heat-resistant coloring properties. Improvement, further improvement of usability (elongation and spread during use) in cosmetics, further improvement of feeling of use (stickiness, unevenness, sustainability), further improvement of matteness and tactile sensation in coating compositions
- the present invention is to provide an organic silicone fine particle capable of sufficiently satisfying the improvement, a method for producing the organic silicone fine particle, a cosmetic, a resin composition and a coating composition containing the organic silicone fine particle.
- the present invention is an organosilicone fine particle having a shape in which a concave portion (11) having a substantially circular opening is formed on a surface corresponding to each surface of a tetrahedron as a whole, and the maximum diameter (L ) In the range of 0.5 to 20 ⁇ m.
- the present invention also relates to a method for producing such organic silicone fine particles, a cosmetic, a resin composition and a coating composition containing such organic silicone fine particles.
- the average value of the maximum diameter (L) of the external shape of each fine particle is an average value for any 20 particles extracted from the scanning electron micrograph image of the organic silicone fine particles.
- the organosilicone fine particles of the present invention are organosilicone fine particles having a shape in which a concave portion (11) having a substantially circular opening is formed on the surface corresponding to each surface of the tetrahedron as a whole, and the maximum of the individual external shape of the fine particles.
- Organic silicone fine particles having an average diameter (L) in the range of 0.5 to 20 ⁇ m.
- the average value of the maximum diameter (L) of the external shape of each fine particle is an average value for any 20 particles extracted from the scanning electron micrograph image of the organic silicone fine particles.
- the organosilicon fine particles of the present invention have a tetrahedral shape as a whole except for the concave portions (11) formed on each surface, and the bottom surface of the tetrahedron is generally circular, and the remaining three The side faces are generally triangular with rounded ridges and tops.
- a concave portion (11) having a substantially circular opening is formed in each of four surfaces corresponding to the respective surfaces of the tetrahedron, and the concave portion (11) is a substantially hemispherical surface.
- the size of the recess (11) formed on the surface corresponding to each surface of the tetrahedron is not particularly limited, but the maximum diameter (m) of the individual recesses (11) / individual particles
- the average value of the ratio (m / L) of the maximum diameter (L) of the outer shape is preferably in the range of 0.3 to 0.8.
- the average value is an average value for any 20 extracted from the scanning electron micrograph image of the organic silicone fine particles.
- the organosilicon fine particles of the present invention have various characteristics, and one of the useful characteristics is high oil absorption.
- the amount of oil absorption is not particularly limited, but is preferably 50 to 150 ml / 100 g.
- the organic silicone fine particles of the present invention are composed of a polysiloxane crosslinked structure in which siloxane units form a three-dimensional network structure.
- the type and ratio of the siloxane unit constituting the polysiloxane crosslinked structure is not particularly limited, but is composed of the siloxane unit represented by the following chemical formula 1, the siloxane unit represented by the chemical formula 2 and the siloxane unit represented by the chemical formula 3 Is preferred.
- R 1 , R 2 , R 3 alkyl group having 1 to 4 carbon atoms or phenyl group
- R 1 in Chemical formula 2 , R 2 and R 3 in Chemical formula 3 are alkyl groups having 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, or phenyl group. Is preferred.
- Examples of the siloxane unit represented by Chemical Formula 2 and the siloxane unit represented by Chemical Formula 3 include a methylsiloxane unit, an ethylsiloxane unit, a propylsiloxane unit, a butylsiloxane unit, and a phenylsiloxane unit.
- a preferred siloxane unit is methylsiloxane. Units are listed.
- the siloxane crosslinked structure when the polysiloxane crosslinked structure is composed of the siloxane units as described above, 30 to 50 mol% of the siloxane units represented by Chemical Formula 1 and 45 to 65 of the siloxane units represented by Chemical Formula 2 are used. It is preferable that the siloxane units represented by mol% and chemical formula 3 have a composition ratio of 3 to 9 mol% (total of 100 mol%).
- the organosilicone fine particles of the present invention can be produced by the following method. That is, 30 to 50 mol% of the silanol group-forming silicon compound represented by the following chemical formula 4, 45 to 65 mol% of the silanol group-forming silicon compound represented by chemical formula 5 and the silanol group-forming silicon represented by chemical formula 6 First, a silanol group-forming silicon compound represented by the chemical formula 4 and a silanol group-forming silicon compound represented by the chemical formula 6 are used as basic catalysts by using the compounds in a ratio of 3 to 9 mol% (total 100 mol%).
- a silanol compound is produced by contact with water in the presence of the product to generate a silanol compound, and then the silanol compound and the silanol group-forming silicon compound represented by Chemical Formula 5 are present in the presence of a basic catalyst and an anionic surfactant. It can be obtained by carrying out a condensation reaction under high aqueous conditions.
- R 4 , R 5 , R 6 an alkyl group having 1 to 4 carbon atoms or a phenyl group
- X, Y, Z an alkoxyethoxy group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, carbon N, N-dialkylamino group having 2 to 4 acyloxy group, alkyl group having 1 to 4 carbon atoms, hydroxy group, halogen atom or hydrogen atom
- R 4 in Chemical formula 5, and R 5 and R 6 in Chemical formula 6 are alkyl groups or phenyl groups having 1 to 4 carbon atoms, and among them, a methyl group is preferable.
- the silanol group-forming silicon compound represented by Chemical Formula 4 is a compound that will form the siloxane unit represented by Chemical Formula 1 as a result.
- X in Chemical Formula 4 represents 1) an alkoxyethoxy group having 1 to 4 carbon atoms such as methoxy group or ethoxy group, and 2) an alkoxyethoxy group having 1 to 4 carbon atoms such as methoxyethoxy group or butoxyethoxy group.
- an acyloxy group having 2 to 4 carbon atoms such as an acetoxy group or a propioxy group
- an N, N-dialkylamino group having an alkyl group having 1 to 4 carbon atoms such as a dimethylamino group or a diethylamino group, 5) a hydroxy group, 6) a halogen atom such as a chlorine atom or a bromine atom, or 7) a hydrogen atom.
- the silanol group-forming silicon compound represented by Chemical formula 4 includes tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, trimethoxyethoxysilane, tributoxyethoxysilane, tetraacetoxysilane, tetrapropoxysilane, Examples include tetraacetoxysilane, tetra (dimethylamino) silane, tetra (diethylamino) silane, silanetetraol, chlorosilanetriol, dichlorodisianol, tetrachlorosilane, chlorotrihydrogensilane, and the like. Tetraethoxysilane and tetrabutoxysilane are preferred.
- the silanol group-forming silicon compound represented by Chemical formula 5 is a compound that results in the formation of the siloxane unit represented by Chemical formula 2.
- Y in Chemical formula 5 is the same as X in Chemical formula 4, and R 4 in Chemical formula 5 is the same as R 1 in Chemical formula 2.
- silanol group-forming silicon compounds represented by Chemical formula 5 include methyltrimethoxysilane, ethyltriethoxysilane, propyltributoxysilane, butyltributoxysilane, phenyltris (2-methoxyethoxy) silane, methyltris ( 2-butoxyethoxy) silane, methyltriacetoxysilane, methyltripropoxysilane, methyltriacetoxysilane, methylsilanetriol, methylchlorodisianol, methyltrichlorosilane, methyltrihydrogensilane, and the like.
- Silanol resulting in the formation of methylsiloxane units, ethylsiloxane units, propylsiloxane units, butylsiloxane units or phenylsiloxane units as described above for R 1 in 2 A group-forming silicon compound is preferable, and a silanol group-forming silicon compound that forms a methylsiloxane unit is more preferable.
- the silanol group-forming silicon compound represented by Chemical formula 6 is a compound that results in the formation of the siloxane unit represented by Chemical formula 3.
- Z in Chemical Formula 6 is the same as X in Chemical Formula 4, and R 5 and R 6 in Chemical Formula 6 are the same as R 2 and R 3 in Chemical Formula 3 .
- silanol group-forming silicon compounds represented by Chemical Formula 6 include dimethyldimethoxysilane, diethyldiethoxysilane, dipropyldibutoxysilane, dibutyldimethoxysilane, methylphenylmethoxyethoxysilane, dimethylbutoxyethoxysilane, dimethyldi Examples include acetoxysilane, dimethyldipropioxysilane, dimethyldi (dimethylamino) silane, dimethyldi (diethylamino) silane, dimethylsilanediol, dimethylchlorosilanol, dimethyldichlorosilane, and dimethyldihydrogensilane.
- the silanol group-forming silicon compound represented by the chemical formula 4 described above, the silanol group-forming compound represented by the chemical formula 5 and the silanol group-forming compound represented by the chemical formula 6 are 30 to 50 mol% of the silanol group-forming silicon compound shown, 45 to 65 mol% of the silanol group-forming compound shown in Chemical formula 5 and 3 to 9 mol% of the silanol group-forming compound shown in Chemical formula 6 (total)
- a silanol group-forming silicon compound represented by Chemical Formula 4 and a silanol group-forming silicon compound represented by Chemical Formula 6 are hydrolyzed by contacting them with water in the presence of a basic catalyst. To produce a silanol compound.
- a conventionally known catalyst can be used as the basic catalyst for hydrolysis.
- This includes, for example, inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, ammonia, trimethylamine, triethylamine, tetraethylammonium hydroxide, dodecyldimethylhydroxyethylammonium hydroxide, sodium methoxide, etc.
- Organic bases are mentioned.
- the amount of catalyst during hydrolysis is preferably 0.001 to 0.500% by mass with respect to the total amount of silanol group-forming silicon compound used as a raw material.
- the silanol compound produced as described above and the silanol group-forming silicon compound represented by Chemical Formula 5 are subjected to a condensation reaction under an aqueous condition in which a basic catalyst and an anionic surfactant are present.
- a basic catalyst for the condensation reaction a conventionally known catalyst can be used in the same manner as the basic catalyst for hydrolysis.
- the basic catalyst for the condensation reaction is preferably used in an amount of 0.001 to 0.500 mass% with respect to the total amount of silanol group-forming silicon compound used as a raw material.
- anionic surfactant As the anionic surfactant to be added to the reaction system together with the basic catalyst, a known anionic surfactant can be used.
- anionic surfactant include organic sulfates having 8 to 18 carbon atoms such as octyl sulfate, cetyl sulfate, and lauryl sulfate, octyl sulfonate, cetyl sulfonate, lauryl sulfonate, and stearyl sulfonate.
- Organic sulfonates having 8 to 30 carbon atoms such as salts, oleyl sulfonate, p-toluene sulfonate, dodecylbenzene sulfonate, oleyl benzene sulfonate, naphthyl sulfonate, diisopropyl naphthyl sulfonate, etc.
- the anionic surfactant is preferably used in an amount of 0.001 to 0.550% by mass based on the total amount of silanol group-forming silicon compound used as a raw material.
- the charging ratio of the total amount of water / silanol group-forming silicon compound is usually 10/90 to 70/30 (mass ratio).
- the amount of the catalyst used varies depending on the type and the type of silanol group-forming silicon compound, but is usually 1% by mass or less with respect to the total amount of silanol group-forming silicon compound, preferably 0.001 to It shall be 0.550 mass%.
- the reaction temperature is usually 0 to 40 ° C., but is preferably 30 ° C. or less in order to avoid an immediate condensation reaction of the silanol compound produced by the hydrolysis reaction.
- organic silicone fine particles are produced through hydrolysis and condensation reaction of the silanol group-forming silicon compound as described above.
- the catalyst as described above in the hydrolysis can be used as the catalyst for the condensation reaction
- the reaction solution containing the silanol compound produced by the hydrolysis can be used for the condensation reaction as it is.
- a catalyst may be added to the reaction solution for the condensation reaction, or the catalyst remaining in the reaction solution and the unreacted silanol group-forming silicon compound may be deactivated or removed before the condensation reaction.
- the solid content of the organic silicone fine particles in the aqueous suspension is usually 2 to 20% by mass, but the amount of water is preferably adjusted to 5 to 15% by mass.
- the organosilicone fine particles of the present invention are separated from the aqueous suspension of the reaction system after the hydrolysis and condensation reaction as described above, extracted through a wire mesh, for example, and dehydrated by a centrifugal separation method or a pressure filtration method. Further, it can be used as a water-containing product having a solid content adjusted to 30 to 70% by mass, but a dried product can also be used.
- the aqueous suspension is drawn through a wire mesh, dehydrated by centrifugation or pressure filtration, etc., and the dehydrated product is heated and dried at 100 to 250 ° C. Can be obtained by a method of drying at 30 to 150 ° C. under heat, a method of directly drying an aqueous suspension at 100 to 250 ° C. with a spray dryer, etc. It is preferable to use after crushing.
- the organosilicon fine particles thus obtained are organic silicone fine particles having a shape in which a concave portion (11) having a substantially circular opening is formed on the surface corresponding to each surface of the tetrahedron as a whole, and the maximum of the individual external shape of the fine particles.
- Organic silicone fine particles having an average diameter (L) in the range of 0.5 to 20 ⁇ m.
- the cosmetic of the present invention contains 0.1 to 10% by mass of the organic silicone fine particles of the present invention.
- the cosmetic of the present invention utilizes the excellent optical properties, high oil absorption, etc. of the organosilicone fine particles of the present invention, and is used as a component of a liquid, creamy or pressed basic cosmetic or makeup cosmetic. In this case, the soft focus effect with less unevenness and less glare, concealment of skin stains and the like, and excellent adhesion and adhesion to the skin are useful for removing makeup due to sebum.
- the cosmetics of the present invention in addition to the organic silicone fine particles of the present invention, extender pigments, white pigments, pearl pigments, colored pigments (dyes), binding oils, water, surfactants, thickeners, preservatives Antioxidants, fragrances, and the like can be used as appropriate.
- the cosmetic of the present invention can be prepared by a known method in which these other raw materials are uniformly dispersed together with the organic silicone fine particles of the present invention.
- the resin composition of the present invention contains 0.1 to 10% by mass of the organic silicone fine particles of the present invention.
- the resin composition of the present invention is useful in applications where there is a strong demand for improving the properties of resin compositions mainly composed of polymer materials. For example, in lighting fixtures and display parts, due to the efficient use of light and advanced functions, both light transmission and haze are high, while on the other hand, the appearance of resin compositions with excellent heat-resistant coloring properties is strong. Although demanded, the resin composition of the present invention is useful in these fields.
- the coating composition of the present invention contains 0.1 to 10% by mass of the organic silicone fine particles of the present invention.
- the coating composition of the present invention is useful for imparting releasability, slipperiness, antiblocking properties, abrasion resistance, matteness and the like to a coating film formed after application of the coating material.
- the coating film of the present invention has been required to have high optical properties and improved tactile sensation with respect to the coating film, and lacks the excellent matteness and comfortable hand feeling required for conventional fine particles.
- the composition is useful as satisfying these.
- the present invention described above has a high degree of demand in actual use scenes in recent years, for example, further improvement of optical properties such as total light transmittance and haze in resin compositions, and usability and use in cosmetics. There is an effect that it is possible to provide a novel organosilicone fine particle which can further improve the feeling and further improve the matteness and the touch feeling in the coating composition.
- FIG. 2 is an enlarged plan view schematically showing the organic silicone fine particles of the present invention.
- FIG. 2 is an enlarged perspective view schematically showing the same organosilicon fine particles as in FIG. 1.
- the scanning electron micrograph of 3500 times which illustrates the organosilicon fine particle of this invention.
- Test category 1 (synthesis of organosilicone fine particles)
- Example 1 ⁇ Synthesis of organosilicone fine particles (P-1) ⁇
- 2000 g of ion-exchanged water was taken, and 0.19 g of 30% aqueous sodium hydroxide solution was added and dissolved therein. Further, 308.57 g (1.49 mol) of tetraethoxysilane and 22.2 g (0.19 mol) of dimethyldimethoxysilane were added, and hydrolysis was carried out with stirring at 15 ° C. for 60 minutes.
- an aqueous solution prepared by dissolving 7.54 g of 10% sodium dodecylbenzenesulfonate aqueous solution and 2.90 g of 30% hydrochloric acid aqueous solution in 350 g of ion-exchanged water was cooled to 10 ° C.
- the hydrolyzate solution adjusted to the temperature was gradually added dropwise.
- 277.4 g (2.04 mol) of methyltrimethoxysilane was added, and the mixture was allowed to stand for 1 hour so that the temperature did not exceed 30 ° C.
- the mixture was subjected to a condensation reaction at the same temperature for 4 hours, and then subjected to a condensation reaction for 10 hours to obtain a white suspension.
- the obtained white suspension was allowed to stand overnight, and then the white solid phase obtained by removing the liquid phase by decantation was washed with water by a conventional method and dried to obtain organic silicone fine particles (P-1). .
- the organosilicon fine particles (P-1) were observed and measured with a scanning electron microscope, measured for oil absorption, elemental analysis, ICP emission spectral analysis, FT-IR spectral analysis, and NMR spectral analysis as follows. It was.
- the organosilicone fine particles (P-1) are organosilicone fine particles having a shape in which a concave portion (11) having a substantially circular opening is formed on a surface corresponding to each surface of the tetrahedron as a whole.
- the average value of the maximum diameter (L) of 4.9 ⁇ m, and the average value of the ratio (m / L) of the maximum diameter (m) of the concave portion (11) of each fine particle / the maximum diameter (L) of the external shape of each fine particle is It was 0.65.
- the obtained organosilicone fine particles (P-1) were composed of 40 mol% of the siloxane unit represented by Chemical Formula 1, 55 mol% of the siloxane unit represented by Chemical Formula 2, and 5 mol% of the siloxane unit represented by Chemical Formula 3. It was an organosilicone fine particle composed of a polysiloxane crosslinked structure having a ratio of (total 100 mol%).
- organosilicone fine particles P-1 ⁇ Analysis of siloxane units constituting organosilicone fine particles (P-1): Weigh accurately 5 g of organosilicone fine particles (P-1) and add to 250 ml of 0.05N sodium hydroxide aqueous solution to hydrolyze in organosilicone fine particles. All the sex groups were extracted into an aqueous sodium hydroxide solution. The organic silicone fine particles are separated from the extracted solution by ultracentrifugation, and the separated organic silicone fine particles are washed with water and dried at 200 ° C. for 5 hours for elemental analysis, ICP emission spectral analysis, and FT-IR spectral analysis. The total carbon content and silicon content were measured, and silicon-carbon bonds and silicon-oxygen-silicon bonds were confirmed.
- Examples 2 to 7 ⁇ Synthesis of organosilicone fine particles (P-2) to (P-7) ⁇
- the organic silicone fine particles (P-2) to (P-7) of Examples 2 to 7 were synthesized in the same manner as the organic silicone fine particles (P-1) of Example 1, and the same observation and measurement as in Example 1 were performed. And analysis.
- Test Category 2 (Foundation preparation and evaluation) As shown below, foundations were prepared and evaluated using the organic silicone fine particles of each example shown in Table 5.
- R-2 Spherical silicone fine particles (trade name Tospearl 120 manufactured by Momentive Performance Materials)
- R-3 Spherical vinyl fine particles (trade name Gantz Pearl GSM1261 manufactured by Gantz Kasei)
- R-4 Talc
- the organosilicon fine particles of the present invention exhibit excellent effects in usability and usability when used in cosmetics.
- Test category 3 Preparation and evaluation of polycarbonate resin composition
- a polycarbonate resin composition was prepared and evaluated using the organic silicone fine particles of each example shown in Table 6.
- polycarbonate resin composition 0.7 parts of organosilicon fine particles listed in Table 7 are added to 100 parts of polycarbonate resin (trade name Panlite K1285 manufactured by Teijin Chemicals Ltd.), mixed, and then 40 mm ⁇ twin screw extrusion with vent Using a machine, the mixture was melt-kneaded at a resin temperature of 280 ° C. and extruded to produce pellets as a polycarbonate resin composition. This pellet was subjected to an injection molding machine and molded at a cylinder temperature of 230 ° C. and a mold temperature of 60 ° C. to obtain a test piece having a thickness of 3 mm and a width of 200 mm.
- polycarbonate resin trade name Panlite K1285 manufactured by Teijin Chemicals Ltd.
- Total light transmittance and haze Measured using a product name NDH-2000 manufactured by Nippon Denshoku in accordance with JIS-K7105 (1981).
- Heat resistant colorability The test piece was placed in a hot air circulating oven at a temperature of 80 ° C and held for 180 minutes. The degree of coloration of the test piece before and after the heat treatment was measured by using a color difference meter (trade name CR-300, manufactured by Minolta Co., Ltd.) and indicated by a color index defined in JIS-Z8729 (2004). ⁇ b was calculated according to the following formula 1.
- Equation 1 b 1 : b value of the test piece before heat treatment b 2 : b value of the test piece after heat treatment
- organosilicone fine particles of the present invention when used in a resin composition, they exhibit excellent effects in total light transmittance, haze, and heat-resistant colorability.
- Test Category 4 (Preparation and evaluation of paint composition) As described below, a coating composition was prepared and evaluated using the organic silicone fine particles of each example shown in Table 7.
- the prepared coating composition was applied to an aluminum panel, and was cured by heating for 30 minutes in a thermostatic bath set at a temperature of 150 ° C.
- the dispersibility, matteness and feel of the cured coating were evaluated as follows, and the results are summarized in Table 7.
- Evaluation of storage stability The coating composition was allowed to stand at room temperature, and the dispersion state of the organic silicone fine particles and the like in the coating composition after 5 hours was visually observed and evaluated according to the following criteria.
- C Poor (sedimentation of organosilicon fine particles etc. is observed after 2 hours)
- R-6 spherical silicone composite fine particles (trade name KMP-605 manufactured by Shin-Etsu Chemical Co., Ltd.)
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Abstract
Description
R1,R2,R3:炭素数1~4のアルキル基又はフェニル基
R4,R5,R6:炭素数1~4のアルキル基又はフェニル基
X,Y,Z:炭素数1~4のアルコキシ基、炭素数1~4のアルコキシ基を有するアルコキシエトキシ基、炭素数2~4のアシロキシ基、炭素数1~4のアルキル基を有するN,N-ジアルキルアミノ基、ヒドロキシ基、ハロゲン原子又は水素原子
・実施例1{有機シリコーン微粒子(P-1)の合成}
反応容器にイオン交換水2000gを採り、この中に30%水酸化ナトリウム水溶液0.19gを加えて溶解した。更にテトラエトキシシラン308.57g(1.49モル)及びジメチルジメトキシシラン22.2g(0.19モル)を加え、15℃で60分間、攪拌下で加水分解を行った。別の反応容器で10%ドデシルベンゼンスルホン酸ナトリウム水溶液7.54g及び30%塩酸水溶液2.90gをイオン交換水350gに溶解した水溶液を調製して10℃に冷却し、攪拌下、この中に同温度に調整した前記の加水分解物溶液を徐々に滴下した。更にメチルトリメトキシシラン277.4g(2.04モル)を加え、温度が30℃を超えないように、1時間静置した。同温度で4時間縮合反応させ、その後10時間縮合反応させて、白色懸濁液を得た。得られた白色懸濁液を一夜静置した後、デカンテーションにより液相を除去して得た白色固体相を常法により水洗し、乾燥して、有機シリコーン微粒子(P-1)を得た。
実施例1の有機シリコーン微粒子(P-1)と同様にして、実施例2~7の有機シリコーン微粒子(P-2)~(P-7)を合成し、実施例1と同様の観察、測定及び分析を行った。
反応容器にイオン交換水2000gを仕込み、この中に酢酸0.12g及び10%ドデシルベンゼンスルホン酸ナトリウム水溶液7.1gを採り、均一な溶液とした。この水溶液にテトラエトキシシラン270.0g(1.30モル)、メチルトリメトキシシラン277.7g(2.04モル)及びジメチルジメトキシシラン44.4g(0.37モル)を加え、30℃で30分間加水分解反応を行なった。別の反応容器にイオン交換水700g及び30%水酸化ナトリウム水溶液1.86gをとり、均一な水溶液とした。この水溶液を攪拌しながら、これに前記の加水分解反応液を徐々に加え、15℃で5時間、更に80℃で5時間縮合反応を行ない、白色懸濁液を得た。この白色懸濁液を一夜静置した後、デカンテーションにより液相を除去して得た白色固体相を常法により水洗し、乾燥して、有機シリコーン微粒子(R-1)を得た。有機シリコーン微粒子(R-1)について、実施例1と同様の観察、測定及び分析を行なった。以上で合成した各例の有機シリコーン微粒子の内容を表1~3にまとめて示した。
使用割合:モル%
濃度:原料として用いたシラノール基形成性ケイ素化合物の合計量に対する質量%
SM-1:テトラエトキシシラン
SM-2:テトラメトキシシラン
SM-3:メチルトリメトキシシラン
SM-4:プロピルトリブトキシシラン
SM-5:フェニルトリメトキシシラン
SM-6:ジメチルジメトシキシラン
SM-7:メチルフェニルメトキシエトキシシラン
CA-1:水酸化ナトリウム
CA-2:アンモニア
CA-3:酢酸
A-1:ドデシルベンゼンスルホン酸ナトリウム
A-2:ラウリルスルホン酸ナトリウム
割合:モル%
S-1:無水ケイ酸単位
S-2:メチルシロキサン単位
S-3:プロピルシロキサン単位
S-4:フェニルシロキサン単位
S-5:ジメチルシロキサン単位
S-6:メチルフェニルシロキサン単位
*1:全体として四面体の各面に相当する面に開口部が概ね円形の凹部(11)が形成された形状
*2:表面に長手方向に沿う1本の割れ目を有する全体としてラグビーボール様の形状
L:微粒子個々の外形の最大径(μm)
m:微粒子個々の凹部(11)の最大径(μm)
次のように、表5記載の各例の有機シリコーン微粒子等を用いてファンデーションを調製し、評価した。
表4記載の番号1~7の顔料を表4記載の配合比率となるようにミキサーを用いて混合した。別に表4記載の番号8~12の成分を表4記載の配合比率となるように採り、40℃に加熱して混合したものを前記のミキサーによる混合物中に加え、再度混合した。得られた混合物を放置し、冷却した後、粉砕し、成型して、ファンデーションを調製した。
調製したファンデーションについて、女性パネラー20名により、その使用性(使用時の伸びや広がり)、使用感(べとつき、凹凸感、持続性)を、下記の評価基準で個々の項目の評価を行った。結果の平均を四捨五入して表5に示した。
4:非常に良い
3:良い
2:やや悪い
1:悪い
R-2:球状シリコーン微粒子(モメンティブ・パフォーマンス・マテリアルズ社製の商品名トスパール120)
R-3:球状ビニル系微粒子(ガンツ化成社製の商品名ガンツパールGSM1261)
R-4:タルク
次のように、表6記載の各例の有機シリコーン微粒子等を用いてポリカーボネート樹脂組成物を調製し、評価した。
ポリカーボネート樹脂(帝人化成社製の商品名パンライトK1285)100部に表7記載の有機シリコーン微粒子等0.7部を加え、混合した後、ベント付40mmφの二軸押出機を用いて、樹脂温度280℃で溶融混練し、押し出しを行い、ポリカーボネート樹脂組成物としてのペレットを作製した。このペレットを射出成形機に供し、シリンダー温度230℃、金型温度60℃で成形し、厚さ3mm、巾200mmの試験片を得た。
ポリカーボネート樹脂組成物としてのペレットを用いて作製した前記の試験片を用い、次のように全光線透過率及びヘイズを測定すると共に、耐熱着色性を求めた。結果を表6にまとめて示した。
b1:加熱処理前の試験片のb値
b2:加熱処理後の試験片のb値
R-5:炭酸カルシウム
全光線透過率:%
耐熱着色性:Δbの値
次のように、表7記載の各例の有機シリコーン微粒子等を用いて塗料組成物を調製し、評価した。
有効成分70%のアクリル樹脂溶液(大日本インキ化学工業社製の商品名アリディックA-416-70S)100部に表7記載の各例の有機シリコーン微粒子等を7部加え、ホモミキサーにより2000rpmで10分間攪拌して混合し、塗料組成物を調製した。
A:非常に良好(5時間経過しても有機シリコーン微粒子等が均一に分散している)
B:良好(2時間後には有機シリコーン微粒子等の沈殿は見られなかったが、5時間後に有機シリコーン微粒子等の沈殿が少し見られる)
C:悪い(2時間後に有機シリコーン微粒子等の沈降が見られる)
A:良好(有機シリコーン微粒子等の凝集が見られず、均一に分散している)
B:悪い(有機シリコーン微粒子等が凝集している)
A:非常に良好(表面は均一で艶がない)
B:良好(表面にやや艶斑がある)
C:悪い(表面は均一で艶がある)
A:良好(滑らかな触感がする)
B:悪い(ざらついた触感がする)
R-6:球状シリコーン複合微粒子(信越化学工業社製の商品名KMP-605)
m 微粒子個々の凹部の最大径
Claims (8)
- 全体として四面体の各面に相当する面に開口部が概ね円形の凹部(11)が形成された形状を呈する有機シリコーン微粒子であって、微粒子個々の外形の最大径(L)の平均値が0.5~20μmの範囲にあることを特徴とする有機シリコーン微粒子。
(但し、平均値は有機シリコーン微粒子の走査型電子顕微鏡写真像から抽出した任意の20個についての平均値) - 微粒子個々の凹部(11)の最大径(m)/微粒子個々の外形の最大径(L)の比の平均値が0.3~0.8の範囲にあるものである請求項1記載の有機シリコーン微粒子。
(但し、平均値は有機シリコーン微粒子の走査型電子顕微鏡写真像から抽出した任意の20個についての平均値) - 吸油量が50~150ml/100gのものである請求項1又は2記載の有機シリコーン微粒子。
- 請求項4記載の有機シリコーン微粒子の製造方法であって、下記の化4で示されるシラノール基形成性ケイ素化合物を30~50モル%、化5で示されるシラノール基形成性ケイ素化合物を45~65モル%及び化6で示されるシラノール基形成性ケイ素化合物を3~9モル%(合計100モル%)となる割合で用いて、先ず化4で示されるシラノール基形成性ケイ素化合物及び化6で示されるシラノール基形成性ケイ素化合物からこれらを塩基性触媒存在下で水と接触させて加水分解することによりシラノール化合物を生成させ、次にこのシラノール化合物と化5で示されるシラノール基形成性ケイ素化合物とを塩基性触媒及びアニオン性界面活性剤を存在させた水性条件下で縮合反応させることを特徴とする有機シリコーン微粒子の製造方法。
R4,R5,R6:炭素数1~4のアルキル基又はフェニル基
X,Y,Z:炭素数1~4のアルコキシ基、炭素数1~4のアルコキシ基を有するアルコキシエトキシ基、炭素数2~4のアシロキシ基、炭素数1~4のアルキル基を有するN,N-ジアルキルアミノ基、ヒドロキシ基、ハロゲン原子又は水素原子) - 請求項1~4のいずれか一つの項記載の有機シリコーン微粒子を0.1~10質量%含有することを特徴とする化粧料。
- 請求項1~4のいずれか一つの項記載の有機シリコーン微粒子を0.1~10質量%含有することを特徴とする樹脂組成物。
- 請求項1~4のいずれか一つの項記載の有機シリコーン微粒子を0.1~15質量%含有することを特徴とする塗料組成物。
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- 2010-03-10 EP EP10847409.9A patent/EP2471841B1/en not_active Not-in-force
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- 2010-03-10 WO PCT/JP2010/053965 patent/WO2011111179A1/ja active Application Filing
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US9864715B2 (en) | 2011-09-29 | 2018-01-09 | Airbus Defence and Space GmbH | Bus system using plurality of non-overlapping frequency bands for communication |
EP2796509A1 (en) | 2013-04-26 | 2014-10-29 | Shin-Etsu Chemical Co., Ltd. | Silicone composite particle and a method for preparing the same |
KR20140128248A (ko) | 2013-04-26 | 2014-11-05 | 신에쓰 가가꾸 고교 가부시끼가이샤 | 실리콘 복합 입자 및 그의 제조 방법 |
US9198839B2 (en) | 2013-04-26 | 2015-12-01 | Shin-Etsu Chemical Co., Ltd. | Silicone composite particle and a method for preparing the same |
US9439840B2 (en) | 2013-04-26 | 2016-09-13 | Shin-Etsu Chemical Co., Ltd. | Silicone composite particle and a method for preparing the same |
JP2016525112A (ja) * | 2013-07-18 | 2016-08-22 | ロレアルL′Oreal | 曲がりの破損部分を有する粒子を含有する油/油エマルジョン、それらを含む組成物および油/油エマルジョンを安定化するための該粒子の使用 |
WO2020050168A1 (ja) | 2018-09-06 | 2020-03-12 | 信越化学工業株式会社 | 多孔質シリコーンゴム球状粒子、多孔質シリコーン複合粒子、及びそれら粒子の製造方法 |
KR20210055730A (ko) | 2018-09-06 | 2021-05-17 | 신에쓰 가가꾸 고교 가부시끼가이샤 | 다공질 실리콘 고무 구상 입자, 다공질 실리콘 복합 입자, 및 그들 입자의 제조 방법 |
US12065568B2 (en) | 2018-09-06 | 2024-08-20 | Shin-Etsu Chemical Co., Ltd. | Porous spherical silicone rubber particles, porous silicone composite particles, and method for producing these particles |
CN113061267A (zh) * | 2021-04-08 | 2021-07-02 | 华南理工大学 | 可控性单分散各向异性凹槽四面体状胶体粒子的制备方法 |
Also Published As
Publication number | Publication date |
---|---|
CN102348742B (zh) | 2014-04-23 |
EP2471841A4 (en) | 2013-03-13 |
EP2471841A1 (en) | 2012-07-04 |
KR20130000314A (ko) | 2013-01-02 |
CN102348742A (zh) | 2012-02-08 |
US8524363B2 (en) | 2013-09-03 |
TW201130890A (en) | 2011-09-16 |
EP2471841B1 (en) | 2014-07-30 |
TWI486382B (zh) | 2015-06-01 |
JP5366341B2 (ja) | 2013-12-11 |
KR101604411B1 (ko) | 2016-03-17 |
JPWO2011111179A1 (ja) | 2013-06-27 |
US20110224308A1 (en) | 2011-09-15 |
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