WO2020031079A1 - Particule composite organique inorganique, son procédé de fabrication, et son utilisation - Google Patents

Particule composite organique inorganique, son procédé de fabrication, et son utilisation Download PDF

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Publication number
WO2020031079A1
WO2020031079A1 PCT/IB2019/056673 IB2019056673W WO2020031079A1 WO 2020031079 A1 WO2020031079 A1 WO 2020031079A1 IB 2019056673 W IB2019056673 W IB 2019056673W WO 2020031079 A1 WO2020031079 A1 WO 2020031079A1
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Prior art keywords
composite particles
weight
particles
organic
inorganic
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PCT/IB2019/056673
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English (en)
Japanese (ja)
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松浦春彦
前山洋輔
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積水化成品工業株式会社
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Priority claimed from JP2019132979A external-priority patent/JP2020026517A/ja
Priority claimed from JP2019133837A external-priority patent/JP2020026518A/ja
Application filed by 積水化成品工業株式会社 filed Critical 積水化成品工業株式会社
Priority to EP19846718.5A priority Critical patent/EP3835328A4/fr
Priority to US17/264,130 priority patent/US20210317317A1/en
Priority to CN201980050397.6A priority patent/CN112513108A/zh
Priority to KR1020217002816A priority patent/KR20210028216A/ko
Publication of WO2020031079A1 publication Critical patent/WO2020031079A1/fr

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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
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/25—Silicon; Compounds thereof
    • 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
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/29—Titanium; Compounds thereof
    • 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
    • A61Q19/00—Preparations for care of the skin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking
    • B01J13/18—In situ polymerisation with all reactants being present in the same phase
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/18—Suspension polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • 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
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • 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
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere

Definitions

  • the present invention relates to organic-inorganic composite particles, a method for producing the same, and uses thereof.
  • the organic-inorganic composite particles of the present invention have a unique shape, and make use of the characteristics thereof, such as cosmetics, coating compositions, heat-insulating resin compositions, light-diffusing resin compositions, and light-diffusing films. Suitable for applications such as This application filed Japanese Patent Application No. 2018-150712 filed on Aug. 9, 2018, Japanese Patent Application No. 2018-150714 filed on Aug. 9, 2018, and filed on Jul. 18, 2019.
  • Priority is claimed based on Japanese Patent Application No. 2019-132979 and Japanese Patent Application No. 2019-133837 filed on Jul. 19, 2019, the contents of which are incorporated herein by reference.
  • inorganic particles such as resin particles, silica particles, glass particles, titanium oxide, aluminum oxide, and calcium carbonate are used as additives.
  • hollow resin particles have been proposed (see Patent Documents 1 and 2).
  • a method of obtaining microcapsule particles containing single or plural silica particles by applying a microparticle-size hollow particle synthesis method to produce microcapsule particles containing silica precursor and then performing a sol-gel reaction. has been proposed (see Non-Patent Document 1).
  • the microcapsule particles containing the hollow resin particles of Patent Documents 1 and 2 and the single or plural silica particles of Non-Patent Document 1 do not have sufficient light scattering properties due to the internal space, for example. There is a problem that it is insufficient to obtain excellent light diffusion and hiding properties, and excellent reflectivity of visible light and near-infrared light when added to a resin composition such as a paint. Accordingly, the present applicant has reported that the above-mentioned problems can be solved by using organic-inorganic composite particles having a shell composed of a crosslinked polymer and containing silica having a porous structure inside the capsule. (See Patent Document 3).
  • an organic-inorganic composite particle is produced using an organic solvent as a porogen for forming a porous structure composed of silica particles inside a capsule. From the viewpoint of the influence on the manufacturer at the time of manufacture, it is desirable to use as little as possible. Therefore, it has been desired to provide a method for producing organic-inorganic composite particles without using an organic solvent. Then, an object of the present invention is to provide organic-inorganic composite particles which are excellent in the reflectivity of visible light and near-infrared light, have high light diffusivity and opacity, a method for producing the same, and uses thereof.
  • organic-inorganic composite particles having an outer shell composed of a crosslinked polymer and containing silica having a porous structure inside the capsule, further containing particles made of an inorganic substance other than silica inside the capsule. It has been found that the above problem can be solved by doing so.
  • the present inventors have found that by adding an inorganic thickener to a monomer mixture, organic-inorganic composite particles can be produced without using an organic solvent, and have led to the present invention.
  • an outer shell composed of a crosslinked polymer and a cavity defined by the outer shell are provided, and silica particles as first inorganic particles are mutually contained inside the hollow.
  • An organic-inorganic composite particle comprising a connected porous structure and second inorganic particles other than silica particles, and having a volume average particle diameter of 0.5 to 100 ⁇ m is provided.
  • the method for producing the organic-inorganic composite particles wherein the radical polymerizable monofunctional monomer 100 parts by weight and the crosslinkable monomer 20 to 150 parts by weight, as a silica precursor
  • a mixture containing 60 to 400 parts by weight of silicon alkoxide and 0.1 to 10 parts by weight of the second inorganic particles is subjected to suspension polymerization in an aqueous medium in the presence of a radical polymerization initiator to form a crosslinked polymer.
  • a shell defined by the outer shell Forming a shell defined by the outer shell, and gelling silicon alkoxide after or simultaneously with the formation of the outer shell, thereby forming silica particles inside the hollow. And forming a porous structure connected to each other.
  • a mixture containing a radically polymerizable monofunctional monomer and a crosslinkable monomer, a silicon alkoxide as a silica precursor, and an inorganic thickener, a radical polymerization initiator A step of forming an outer shell composed of a crosslinked polymer by suspension polymerization in an aqueous medium in the presence and in the absence of an organic solvent, and forming a silicon alkoxide after forming the outer shell or simultaneously with forming the outer shell.
  • a porous structure in which silica particles are connected to each other inside the outer shell thereby providing a method for producing organic-inorganic composite particles.
  • a cosmetic containing the organic-inorganic composite particles.
  • a coating composition containing the organic-inorganic composite particles.
  • a heat-insulating resin composition containing the organic-inorganic composite particles.
  • a light-diffusing resin composition containing the organic-inorganic composite particles.
  • a light diffusion film in which the organic-inorganic composite particles are blended.
  • organic-inorganic composite particles excellent in reflectivity of visible light and near-infrared light, exhibiting high light diffusion and hiding properties, and cosmetics and coating compositions containing the organic-inorganic composite particles , A heat-insulating resin composition, a light-diffusing resin composition, and a light-diffusing film.
  • the second inorganic particles have a refractive index of 1.8 or more.
  • the second inorganic particles have a particle size of 0.001 to 3 ⁇ m measured by a dynamic light scattering method.
  • the first inorganic particles and the second inorganic particles have 5 to 50% by weight with respect to the total weight of the organic-inorganic composite particles, and provide a hollow structure to the cavity.
  • the second inorganic particles are particles selected from titanium oxide, zirconium oxide, cerium oxide, zinc oxide, niobium oxide, and zirconium silicate.
  • organic-inorganic composite particles exhibiting remarkable effects of more excellent light diffusion and hiding properties and near-infrared light reflectivity can be more easily produced.
  • Gelation is performed using an acid or a base in a cavity defined by an outer shell as a catalyst, and the acid or the base is generated by an external stimulus caused by energy radiation or heat of the latent pH adjuster, and the latent pH is adjusted.
  • An agent is present in the cavity by dissolving the latent pH adjuster in the mixture during suspension polymerization.
  • organic-inorganic composite particles that are more excellent in the reflectivity of visible light and near-infrared light and have higher light diffusivity can be more easily produced without using an organic solvent.
  • the mixture has a viscosity of 0.90 mPa ⁇ s or more at 25 ° C.
  • the inorganic thickener is silicic anhydride or clay mineral.
  • the porous structure in which the silica particles are connected to each other shows that the carbon component is contained in the EDX measurement.
  • the inorganic thickener is hydrophobic silica particles of silicic anhydride, and the hydrophobic silica particles have a specific surface area of 15 to 330 m 2 / g by a BET method.
  • the organic-inorganic composite particles have a volume average particle diameter of 0.5 to 100 ⁇ m.
  • the porous structure has 5 to 50% by weight based on the total weight of the organic-inorganic composite particles.
  • the hydrophobic silica particles are contained in an amount of 0.5 to 100 parts by weight based on 100 parts by weight of the mixture.
  • the mixture contains 100 parts by weight of the monofunctional monomer, 20 to 150 parts by weight of the crosslinkable monomer, and 60 to 400 parts by weight of the silica precursor.
  • FIG. 3 is a surface photograph, a cross-sectional photograph, and a SEM-EDS mapping diagram of the organic-inorganic composite particles of Example 1.
  • 5 is a surface photograph and a cross-sectional photograph of the organic-inorganic composite particles of Example 2.
  • 9 is a surface photograph and a sectional photograph of the organic-inorganic composite particles of Example 3.
  • 9 is a surface photograph and a cross-sectional photograph of the organic-inorganic composite particles of Example 4.
  • 4 is a surface photograph and a cross-sectional photograph of the organic-inorganic composite particles of Comparative Example 1.
  • 9 is a surface photograph and a cross-sectional photograph of the organic-inorganic composite particles of Comparative Example 2.
  • FIG. 4 is a graph showing the light reflectance for each wavelength of a coating film containing various particles in the evaluation of the reflection characteristics of ultraviolet, visible, and near infrared light. It is a figure which shows an example of the analysis area
  • 9 is a surface photograph and a cross-sectional photograph of the organic-inorganic composite particles of Example 5.
  • 9 is a surface photograph and a cross-sectional photograph of the organic-inorganic composite particles of Example 6.
  • 9 is a surface photograph and a cross-sectional photograph of the organic-inorganic composite particles of Example 7.
  • 9 is a surface photograph and a sectional photograph of the organic-inorganic composite particles of Example 8.
  • 9 is a surface photograph and a sectional photograph of the organic-inorganic composite particles of Example 10.
  • 9 is a surface photograph and a sectional photograph of the organic-inorganic composite particles of Example 11.
  • 9 is a surface photograph and a sectional photograph of the organic-inorganic composite particles of Example 12.
  • 14 is a cross-sectional photograph of the organic-inorganic composite particles of Example 14.
  • 14 is a cross-sectional photograph of the organic-inorganic composite particles of Example 15.
  • 9 is a surface photograph and a cross-sectional photograph of the organic-inorganic composite particles of Comparative Example 3.
  • 4 is a graph showing the light reflectance for each wavelength of a coating film containing various particles in the evaluation of the reflection characteristics of ultraviolet, visible, and near infrared light.
  • the organic-inorganic composite particles of the present invention (hereinafter also referred to as “composite particles”) have an outer shell made of a crosslinked polymer. Further, the composite particles may include a cavity defined by an outer shell. Further, the composite particles include a porous structure in which silica particles (hereinafter, also referred to as “first inorganic particles”) are connected to each other in an outer shell or a cavity. Further, the composite particles may include particles made of an inorganic substance other than silica (hereinafter, also referred to as “second inorganic particles”) inside the outer shell or the cavity. Further, the composite particles have a volume average particle size of 0.5 to 100 ⁇ m. The composite particles are sometimes referred to as composite fine particles.
  • the type of the crosslinked polymer is not particularly limited as long as it can constitute the outer shell.
  • the crosslinking polymers include polymers derived from radical polymerizable monomers, specifically, a monofunctional monomer having one vinyl group, the crosslinkable monomer having two or more vinyl groups And copolymers thereof.
  • Examples of the monofunctional monomer having one vinyl group include alkyl (meth) acrylates having 1 to 16 carbon atoms such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and cetyl (meth) acrylate.
  • crosslinkable monomer having two or more vinyl groups examples include polyfunctional acrylic esters such as ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and glycerin tri (meth) acrylate; Polyfunctional acrylamide derivatives such as -methylenebis (meth) acrylamide and N, N'-ethylenebis (meth) acrylamide; polyfunctional allyl derivatives such as diallylamine and tetraallyloxyethane; and aromatic divinyl compounds such as divinylbenzene. No. These crosslinkable monomers can be used alone or in combination.
  • the crosslinkable monomer is preferably contained in the outer shell at a ratio of 20 parts by weight or more based on 100 parts by weight of the monofunctional monomer.
  • the content of the crosslinking monomer is less than 20 parts by weight, an outer shell having sufficient strength may not be formed.
  • the content is more preferably from 20 to 150 parts by weight, and even more preferably from 80 to 120 parts by weight.
  • Porous structure has a configuration in which silica particles are connected to each other.
  • the porous structure means a structure in which some of the plurality of silica particles are connected to each other, and a macroporous space is formed between the silica particles in an unconnected portion. It is preferable that the porous structure has a volume in the range of the ratio to the total volume of the cavities described in the columns of various physical properties below.
  • the individual silica particles are mainly composed of SiO 2. Silica particles can be obtained, for example, by gelling a silica precursor.
  • silica precursor examples include a silicon alkoxide having one or more silicon atoms and an alkoxy group (for example, having 1 to 4 carbon atoms) in the same molecule.
  • Specific examples include tetraethoxysilane (TEOS), tetramethoxysilane, tetrapropoxysilane, and the like.
  • methyl silicate oligomer (MKC silicate, trade name, manufactured by Mitsubishi Chemical Corporation) which is a partially hydrolyzed oligomer of tetramethoxysilane, and ethyl silicate oligomer (product name, silicate 45, manufactured by Tama Chemical Co., Ltd.) which is a partially hydrolyzed oligomer of tetraethoxysilane (Pentamer), silicate 48 (10-mer)), and oligomers such as siloxane oligomers.
  • MKC silicate trade name, manufactured by Mitsubishi Chemical Corporation
  • ethyl silicate oligomer product name, silicate 45, manufactured by Tama Chemical Co., Ltd.
  • silicate 48 10-mer
  • oligomers such as siloxane oligomers.
  • tetraethoxysilane is preferable as the monofunctional silica precursor
  • ethylsilicate oligomer is preferable as the silica precursor which is an oligomer.
  • the porous structure is preferably present on the inner wall of the outer shell in order to provide the composite particles with excellent light diffusion and hiding properties.
  • the silica precursor is preferably contained in the mixture at a ratio of 60 to 400 parts by weight based on 100 parts by weight of the monofunctional monomer. When the content of the silica precursor is less than 60 parts by weight, particles having sufficient optical performance may not be obtained. When the content is more than 400 parts by weight, the components of the outer shell are relatively reduced, so that particles having sufficient strength may not be obtained.
  • the content is more preferably 70 to 270 parts by weight, further preferably 80 to 250 parts by weight.
  • the content ratio of the monofunctional monomer-derived component and the silica precursor-derived component in the composite particles substantially matches the above-mentioned ratio of the monofunctional monomer and the silica precursor.
  • the porous structure may contain a crosslinked polymer component, and the crosslinked polymer component may be a crosslinked polymer component forming an outer shell.
  • the porous structure may include a carbon component indicated by EDX measurement using SEM-EDX.
  • the second inorganic particle is not particularly limited as long as it is a particle made of an inorganic substance having a composition other than silica.
  • the second inorganic particles include particles such as titanium oxide, zirconium oxide, cerium oxide, zinc oxide, niobium oxide, and zirconium silicate. Titanium oxide may be surface-treated with alumina, silica, or the like. These second inorganic particles can be used alone or in combination.
  • the second inorganic particles preferably have a refractive index of 1.8 or more. When the refractive index is less than 1.8, a sufficient effect of improving light diffusibility may not be obtained.
  • the refractive index is more preferably from 2.0 to 4.0.
  • Examples of the inorganic particles having a refractive index of 1.8 or more include particles of titanium oxide, zirconium oxide, cerium oxide, zinc oxide, niobium oxide, zirconium silicate, and the like.
  • the inorganic particles are preferably titanium oxide, zirconium oxide, and cerium oxide.
  • the method for measuring the refractive index is not particularly limited. For example, as for the measuring method, the measurement is performed with reference to pages 635 to 640 of “Introduction to Ceramics Material Science (Applied Edition), Issued by Uchida Lao Tsuruho Shinsha, Issued on May 25, 1981”. And known methods (for example, the minimum declination method, the critical angle method, the V-block method, etc.).
  • the refractive index means a relative refractive index to air. A reference wavelength of 550 nm can be used for the measurement.
  • the second inorganic particles preferably have a particle size of 0.001 to 3 ⁇ m measured by a dynamic light scattering method. If the particle size is larger than 3 ⁇ m, the particles may settle during polymerization, and the desired particles may not be obtained. If the particle size is less than 0.001 ⁇ m, particles can be produced but sufficient light reflection performance may not be obtained. The particle size is more preferably 0.001 to 1 ⁇ m.
  • the surface of the second inorganic particles may be treated with a surface treating agent to improve dispersibility in the composite particles. Examples of the surface treatment include water repellent treatment such as silicon treatment, silane coupling treatment, and polymer treatment.
  • the first inorganic particles and the second inorganic particles preferably have 5 to 50% by weight based on the total weight of the composite particles. .
  • the weight of the first inorganic particles and the second inorganic particles is less than 5% by weight, the formation of the porous body by the silica may be insufficient.
  • the weight is more than 50% by weight, the ratio of the outer shell is relatively reduced, and the strength may not be sufficient.
  • the weight of these inorganic particles is more preferably from 10 to 45% by weight.
  • the second inorganic particles are preferably contained in the composite particles in the range of 0.01 to 5 parts by weight, where the total amount of the first inorganic particles and the second inorganic particles is 100 parts by weight.
  • the content When the content is less than 0.01 part by weight, a sufficient effect of improving light diffusibility may not be obtained. If the content is more than 5 parts by weight, the polymerization reaction of the particles may not proceed well. The content is more preferably in the range of 0.05 to 2.5 parts by weight.
  • the weight of the first inorganic particles and / or the second inorganic particles contained in the composite particles can be measured by X-ray fluorescence measurement.
  • the composite particles preferably have a volume average particle size of 0.5 to 100 ⁇ m. When the volume average particle diameter is less than 0.5 ⁇ m, it may be difficult to obtain fine capsule particles. When the volume average particle diameter is larger than 100 ⁇ m, the production may be difficult due to the collapse of the capsule particles.
  • the volume average particle size is preferably from 3 to 80 ⁇ m, more preferably from 5 to 50 ⁇ m, depending on the use.
  • the composite particles preferably have an apparent specific gravity of 0.3 to 1.0 g / cm 3 .
  • the apparent specific gravity is less than 0.3 g / cm 3 , the resin layer of the outer shell is thin and the strength may be reduced. If the apparent specific gravity is greater than 1.0 g / cm 3, there is the effect due to the porous structure consisting of the interior of the silica may not be sufficiently exhibited.
  • the apparent specific gravity is preferably from 0.3 to 0.9 g / cm 3 .
  • the outer shape of the composite particles is not particularly limited, but is preferably as close to spherical as possible.
  • the thickness of the outer shell is preferably 5 to 40% of the volume average particle diameter. When the thickness of the outer shell is less than 5% of the volume average particle diameter, the outer shell may not have sufficient strength. When the thickness of the outer shell is larger than 40% of the volume average particle diameter, the effect of the inner silica structure may be insufficient.
  • the thickness of the outer shell is more preferably 10 to 30% of the volume average particle diameter.
  • the outer shell may be porous. By being porous, improvement in the strength of the particles themselves can be expected as compared with general silica porous resin particles, and particles that are difficult to collapse can be provided.
  • the porosity can be improved.
  • general porous resin particles are made porous by using a large amount of a porogen (solvent), so that it is necessary to use a large amount of a porogen to obtain fine particles having a large oil absorption.
  • the porosity can exceed 90% in the porous structure made of silica inside the microcapsules without using a large amount of the porogen.
  • the degree of porosity can be defined by the amount of oil absorption.
  • the oil absorption is preferably from 150 to 500 ml / 100 g. It is also possible to define the degree of porosity by other indices such as pore diameter and pore volume.
  • the porous structure preferably has 5 to 50% by weight based on the total weight of the composite particles.
  • the weight of the porous structure is less than 5%, formation of the porous body by silica may be insufficient.
  • the weight of the porous structure is more than 50%, the ratio of the outer shell is relatively reduced, and the strength may not be sufficient.
  • the weight of the porous structure is preferably from 10 to 45% by weight.
  • the method for producing organic-inorganic composite particles according to the first embodiment of the present invention includes a method for preparing a single particle in a mixture containing a silica precursor emulsified and dispersed in an aqueous medium, second inorganic particles, and a radical polymerizable monomer.
  • (1) Polymerization Step In the polymerization step, first, a mixture containing a silica precursor, second inorganic particles, and a monomer is dispersed in an aqueous medium by emulsification. The amount of the monomer used and the content of the component derived from the monomer constituting the outer shell substantially match.
  • the second inorganic particles the particles themselves may be dispersed in an aqueous medium, or a solution in which the particles are previously dispersed in a solvent may be dispersed in an aqueous medium.
  • a thickener may be added to this solution. Examples of the thickener include organic thickeners such as acrylic thickeners, urethane thickeners, polyether thickeners, polyvinyl alcohols, and cellulose derivatives.
  • Examples of the inorganic thickener include a clay mineral.
  • Examples of the clay mineral include natural clays such as bentonite, montmorillonite, saponite, beidellite, hectorite, stevensite, sauconite, nontronite, etc., vermiculite, halloysite, swelling mica, zeolite, attapulgite and other natural clays, or synthetic clays. Can be These may contain only one kind or two or more kinds.
  • the emulsification and dispersion are not particularly limited, and are performed while appropriately adjusting various conditions such as a stirring speed and a stirring time so as to obtain composite particles having a desired particle size.
  • the polymerization of the monomer is preferably performed in the presence of a radical polymerization initiator.
  • the radical polymerization initiator is not particularly limited, and examples thereof include persulfates such as ammonium persulfate, potassium persulfate, and sodium persulfate, cumene hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, and benzoyl peroxide.
  • the polymerization initiator is preferably contained in the mixture in an amount of 0.05 to 5 parts by weight based on 100 parts by weight of the monomer.
  • the aqueous medium include water, a mixture of water and a water-soluble organic solvent (for example, a lower alcohol such as methanol and ethanol), and the like. Further, the polymerization may be performed in the presence of a non-reactive organic solvent.
  • non-reactive organic solvent for example, pentane, hexane, cyclohexane, heptane, decane, hexadecane, toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, 1,4-dioxane, methyl chloride, methylene chloride, Chloroform, carbon tetrachloride and the like can be mentioned.
  • These non-reactive organic solvents can be used alone or in combination.
  • the addition amount of the non-reactive solvent is not particularly limited, but is 0 to 300 parts by weight based on 100 parts by weight of the monomer.
  • the outer shell may be insufficiently formed.
  • the non-reactive organic solvent in order to obtain composite particles having a non-porous outer shell, may be used in an amount of 10 to 50 parts by weight based on 100 parts by weight of the monomer. Although it depends on the kind of the solvent to be used, if it exceeds 50 parts by weight, it becomes easy to obtain composite particles having a porous outer shell.
  • an alkoxide compound of titanium, zirconium or aluminum having a higher hydrolyzability than silicon alkoxide a porous structure can be easily formed in the capsule.
  • these alkoxide compounds it is not necessary to use a non-reactive organic solvent. That is, since these compounds are more hydrolyzable than silica precursors such as silicon alkoxides, they gel in microcapsules, suppress the movement of silica precursors in microcapsules, and promote porosity. The present inventors believe that the above-mentioned effect is obtained.
  • titanium alkoxide compound examples include isopropyl triisostearoyl titanate, isopropyl tristearoyl titanate, isopropyl trioctanoyl titanate, isopropyl dimethacryl isostearyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl isostearoyl diacryl titanate, and isopropyl tri ( Dioctyl phosphate) titanate, isopropyl tricumyl phenyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri (n-aminoethyl-aminoethyl) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphate) Fight) Titanate,
  • zirconium alkoxide compounds examples include zirconium butyrate, zirconium acetylacetonate, acetylacetone zirconium butyrate, zirconium lactate, zirconium stearate butyrate, tetra (triethanolamine) zirconate, and tetraisopropyl zirconate.
  • Examples of aluminum alkoxide compounds include acetoalkoxyaluminum diisopropylate, ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethylacetoacetate), alkyl acetoacetate aluminum diisopropylate (alkyl has 1 to 20 carbon atoms), Aluminum monoacetylacetonate bis (ethylacetoacetate), aluminum tris (acetylacetonate) and the like can be mentioned. These alkoxide compounds can be used alone or in combination of two or more. The amount of the alkoxide compound is not particularly limited, but is not more than 10 parts by weight based on 100 parts by weight of the monomer.
  • the emulsified and dispersed mixture is subjected to polymerization of the monomers therein to form microcapsules containing a silica precursor therein.
  • the polymerization is not particularly limited, and is performed while appropriately adjusting various conditions such as a polymerization temperature and a polymerization time according to the types of the monomer and the polymerization initiator contained in the mixture.
  • the polymerization temperature can be 30 to 80 ° C.
  • the polymerization time can be 1 to 20 hours.
  • the silica precursor in the microcapsules present in the emulsion is converted into silica particles by a gelation reaction, whereby composite particles are obtained.
  • the gelation reaction is preferably performed while maintaining the emulsion at an alkaline level (eg, pH 7 or higher, specifically pH 10 to 14).
  • the alkalinity can be maintained by adding a base such as an aqueous ammonia solution, sodium hydroxide, or potassium hydroxide to the emulsion.
  • the amount of the base to be added is preferably 1 to 10 equivalents to the silica precursor.
  • the gelation step is not particularly limited, and can be performed under conditions (temperature, time, stirring speed, and the like for gelation) necessary for the silica precursor to gel to become silica particles.
  • the gelling temperature can be 30 to 80 ° C.
  • the gelling time can be 1 to 24 hours.
  • the gelation step may be performed in the presence of a latent pH adjuster.
  • the coexistence of the latent pH adjuster makes it possible to reduce the amount of base added to the emulsion. For example, when ammonia is used as a base, and when a latent pH adjuster is present, gelation can be performed efficiently even if the amount of ammonia is reduced to 3 equivalents or less (for example, ammonia not used, 0.01 to 3 equivalents).
  • the amount of the latent pH adjuster varies depending on the type of the agent, production conditions, and the like, but is preferably, for example, 0.01 to 10 parts by weight based on 100 parts by weight of the silica precursor. The use amount is more preferably 0.1 to 5 parts by weight.
  • the latent pH adjuster includes a substance that generates an acid or a base by an external stimulus such as irradiation with energy radiation or heating. Energy radiation includes infrared rays, visible light, ultraviolet rays, and the like.
  • latent pH adjusters thermal acid generators
  • latent pH adjusters thermal acid generators
  • examples of latent pH adjusters include aryldiazonium salts, sulfonium salts, iodonium salts, ammonium salts, phosphonium salts, oxonium salts, iron-allene complexes, and aromatics
  • Aromatic silanol / ammonium complex diallyliodonium salt-dibenzyloxy copper, imidazole derivative, benzylsulfonium salt, hemiacetal ester, sulfonic acid ester and the like.
  • latent pH adjuster thermal base generator
  • latent pH adjuster thermal base generator
  • examples of the latent pH adjuster thermal base generator
  • latent pH adjusters photobase generators
  • Examples of latent pH adjusters (photobase generators) that generate bases upon irradiation with energy radiation include (Z)- ⁇ [bis (dimethylamino) methylidene] amino ⁇ -N-cyclohexyl (cyclohexylamino) methane Iminium tetrakis (3-fluorophenyl) borate, 1,2-dicyclohexyl-4,4,5,5-tetramethylbiguadinium n-butylloriliphenyl borate, 1,2-diisopropyl-3- [bis (dimethylamino ) Methylene] guadinium 2- (3-benzoylphenyl) propionate, 9-anthrylmethyl N, N-diethylcarbamate, (E) -1-piperidino-3- (2-hydroxyphenyl) -2-propen-1-one , 1- (anthraquinon-2-yl) ethylimid
  • the timing of adding the latent pH adjuster is not particularly limited as long as the latent pH adjuster is present at least in the cavity defined by the outer shell during gelation.
  • the latent pH adjuster can be made to exist in the cavity by dissolving the latent pH adjuster in a mixture containing the silica precursor and the monomer during suspension polymerization.
  • the gelation temperature can be 35 to 180 ° C.
  • the gelation time can be 0.1 to 48 hours.
  • the composite particles after the gelation step can be taken out of the emulsion by subjecting them to centrifugation, washing with water and drying as necessary.
  • the method for producing the organic-inorganic composite particles according to the second embodiment of the present invention comprises a radical-polymerizable monofunctional monomer and a crosslinkable monomer, a silicon alkoxide as a silica precursor, and an inorganic thickener.
  • the mixture contains a radically polymerizable monofunctional monomer and a crosslinkable monomer, a silicon alkoxide as a silica precursor, and an inorganic thickener.
  • the radical polymerizable monofunctional monomer is, for example, a monomer having one vinyl group
  • the radical polymerizable crosslinkable monomer is, for example, a monomer having two or more vinyl groups.
  • Examples of the radically polymerizable monofunctional monomer include alkyl (meth) acrylates having 1 to 16 carbon atoms such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and cetyl (meth) acrylate.
  • radical polymerizable crosslinkable monomer examples include polyfunctional acrylic esters such as ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and glycerin tri (meth) acrylate, and N, N′-methylenebis ( Examples thereof include polyfunctional acrylamide derivatives such as (meth) acrylamide and N, N'-ethylenebis (meth) acrylamide; polyfunctional allyl derivatives such as diallylamine and tetraallyloxyethane; and aromatic divinyl compounds such as divinylbenzene. These crosslinkable monomers can be used alone or in combination.
  • the crosslinkable monomer is preferably contained in the mixture at a ratio of 20 to 150 parts by weight based on 100 parts by weight of the monofunctional monomer.
  • the content of the crosslinking monomer is less than 20 parts by weight, an outer shell having sufficient strength may not be formed.
  • an outer shell may not be formed.
  • the content is more preferably 80 to 120 parts by weight.
  • Examples of the silicon alkoxide as the silica precursor include a silicon alkoxide having one or more silicon atoms and an alkoxy group (for example, having 1 to 4 carbon atoms) in the same molecule. Specific examples include tetraethoxysilane (TEOS), tetramethoxysilane, tetrapropoxysilane, and the like.
  • TEOS tetraethoxysilane
  • tetramethoxysilane tetrapropoxysilane
  • methyl silicate oligomer (MKC silicate, trade name, manufactured by Mitsubishi Chemical Corporation) which is a partially hydrolyzed oligomer of tetramethoxysilane, and ethyl silicate oligomer (product name, silicate 45, manufactured by Tama Chemical Co., Ltd.) which is a partially hydrolyzed oligomer of tetraethoxysilane (Pentamer), silicate 48 (10-mer)), and oligomers such as siloxane oligomers.
  • MKC silicate trade name, manufactured by Mitsubishi Chemical Corporation
  • ethyl silicate oligomer product name, silicate 45, manufactured by Tama Chemical Co., Ltd.
  • silicate 48 10-mer
  • oligomers such as siloxane oligomers.
  • tetraethoxysilane is preferable as a monofunctional silica precursor
  • ethylsilicate oligomer is preferable as a silica precursor which is an oligomer.
  • the silica precursor is preferably contained in the mixture at a ratio of 60 to 400 parts by weight based on 100 parts by weight of the monofunctional monomer.
  • the content of the silica precursor is less than 60 parts by weight, particles having sufficient optical performance may not be obtained.
  • the content is more than 400 parts by weight, the components of the outer shell are relatively reduced, so that particles having sufficient strength may not be obtained.
  • the content is more preferably 70 to 270 parts by weight, further preferably 80 to 250 parts by weight.
  • the inorganic thickener is not particularly limited as long as composite particles can be produced in the absence of an organic solvent.
  • an inorganic thickener capable of adjusting the viscosity of the mixture to 0.90 mPa ⁇ s or more at 25 ° C. can be suitably used.
  • the viscosity is less than 0.90 mPa ⁇ s, the effect of suppressing this becomes insufficient, and it may not be possible to obtain particles having a porous inside microcapsule.
  • the viscosity is more preferably in the range of 0.9 to 1000 mPa ⁇ s.
  • the inorganic thickener include silicic anhydride and clay minerals.
  • the clay mineral include natural clays such as bentonite, montmorillonite, saponite, beidellite, hectorite, stevensite, sauconite, nontronite, etc., vermiculite, halloysite, swelling mica, zeolite, attapulgite and other natural clays, or synthetic clays. Can be Since these have the effect of increasing the viscosity of the silicon alkoxide in the microcapsules, they can suppress the movement of the silica precursor and promote the porosity in the microcapsules.
  • silicic anhydride is preferred because of easy dispersion in silicon alkoxide, and hydrophobic silica particles are more preferred.
  • the hydrophobicity means that the surface treatment has been performed with a hydrophobicizing agent such as an organic silane or silicone oil.
  • hydrophobizing agent for example, hexamethyldisilazane, vinyltriethoxysilane, vinyltrimethoxysilane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, Benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, ⁇ -chloroethyltrichlorosilane, ⁇ -chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilyl acrylate, vinylmethylacetoxysilane, dimethylethoxysilane, Dimethyldimethoxysilane, diphenyldiethoxy
  • the surface treatment with the hydrophobizing agent is not particularly limited, and any known method can be used.
  • any known method can be used.
  • the hydrophobic silica particles preferably have a specific surface area of 15 m 2 / g or more by a BET method.
  • the specific surface area is more preferably from 15 to 330 m 2 / g, even more preferably from 90 to 290 m 2 / g.
  • the specific surface area by the BET method is measured, for example, according to DIN 66131.
  • hydrophobic silica particles examples include hydrophobic fumed silica AEROSIL (trade name) series commercially available from EVONIK (eg, R972, R974, R104, R106, R202, R208, R805, R812, R812S, R816, R7200, R8200, R9200, R711, RY50, NY50, NY50L, RX50, NAX50, RX200, RX300, R504, NX90S, NX90G, RY300, REA90, REA200, RY51, NA50Y, RA200HS, NA50H, NA130K, NA200Y, NX130R RY200L, R709, R976S, etc.), hydrophobic grades of highly dispersed silica WACKER HDK (trade name) commercially available from Asahi Kasei Corporation (for example, H15, H18, H20, H30, etc.).
  • hydrophobic silica particles can be used alone or in combination of two or more.
  • the hydrophobic silica particles are preferably contained in the mixture at a ratio of 0.5 to 100 parts by weight with respect to 100 parts by weight of the mixture.
  • the content of the hydrophobic silica particles is less than 0.5 part by weight, the effect of increasing the viscosity of the silicon alkoxide in the microcapsules becomes insufficient, and a silica porous structure may not be formed in the capsules.
  • the content is more than 100 parts by weight, formation of microcapsules may be insufficient.
  • the content is more preferably 0.5 to 25 parts by weight, even more preferably 2.5 to 15 parts by weight.
  • the hydrophobic silica particles are mixed with silica particles derived from silicon alkoxide.
  • a mixture containing a silica precursor, a monomer, and an inorganic thickener is dispersed in an aqueous medium by emulsification.
  • the amount of the monomer used and the content of the component derived from the monomer constituting the outer shell substantially match.
  • the emulsification and dispersion are not particularly limited, and are performed while appropriately adjusting various conditions such as a stirring speed and a stirring time so as to obtain composite particles having a desired particle size.
  • the polymerization of the monomer is carried out in the presence of a radical polymerization initiator and in the absence of an organic solvent.
  • the organic solvent here is, for example, pentane, hexane, cyclohexane, heptane, decane, hexadecane, toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl chloride, methylene chloride, chloroform, carbon tetrachloride, etc.
  • It is a hydrophobic organic solvent hydrophobic here means that the solubility in water at 25 ° C.
  • this organic solvent does not include a water-soluble organic solvent of a lower alcohol (for example, methanol, ethanol, or the like) (the water solubility here indicates that the solubility in water at 25 ° C. is 10 g / 100 g (water) or more). That is).
  • a water-soluble organic solvent of a lower alcohol for example, methanol, ethanol, or the like
  • the radical polymerization initiator and the aqueous medium can be used in the same types and amounts as in the production method of the first embodiment.
  • silica porous structure can be easily formed in the capsule.
  • These compounds are more hydrolyzable than silica precursors such as silicon alkoxides, so they gel in microcapsules, suppress the movement of silica precursors in capsules, and have the effect of promoting porosity. The present inventors believe that there is.
  • An alkoxide compound such as an alkoxide compound of titanium, an alkoxide compound of zirconium, and an alkoxide compound of aluminum can be used in the same kind and amount as in the production method of the first embodiment.
  • the emulsified and dispersed mixture is subjected to polymerization of the monomers therein to form microcapsules containing a silica precursor therein.
  • the polymerization is not particularly limited, and is performed while appropriately adjusting various conditions such as a polymerization temperature and a polymerization time according to the types of the monomer and the polymerization initiator contained in the mixture.
  • the polymerization temperature can be 30 to 80 ° C.
  • the polymerization time can be 1 to 20 hours.
  • porous structure Forming Step is performed substantially in the same manner as the “(2) gelling step” in the manufacturing method of the first embodiment, and therefore the description is omitted here. .
  • the composite particles after the porous structure forming step can be taken out of the emulsion by, if necessary, undergoing centrifugation, washing and drying.
  • the composite particles can be used for applications such as cosmetics, coating compositions, heat-insulating resin compositions, light-diffusing resin compositions, and light-diffusing films.
  • Cosmetic The cosmetic preferably contains the composite particles in a range of 1 to 40% by weight.
  • Cosmetics include soaps, body shampoos, facial cleansers, facial cleansers, scrubs, etc.
  • components generally used in cosmetics can be blended according to the purpose within a range that does not impair the effects of the present invention.
  • components for example, water, lower alcohols, fats and waxes, hydrocarbons, higher fatty acids, higher alcohols, sterols, fatty acid esters, metal soaps, humectants, surfactants, polymer compounds, coloring material raw materials, Perfumes, preservatives / bactericides, antioxidants, ultraviolet absorbers, and special compounding ingredients.
  • Oils and waxes include avocado oil, almond oil, olive oil, cocoa butter, beef tallow, sesame oil, wheat germ oil, safflower oil, shea butter, turtle oil, camellia oil, persic oil, castor oil, grape oil, macadamia nut oil, mink
  • examples include oil, egg yolk oil, mokuro, coconut oil, rosehip oil, hardened oil, silicone oil, orange roughy oil, carnauba wax, candelilla wax, whale wax, jojoba oil, montan wax, beeswax, lanolin and the like.
  • Examples of the hydrocarbon include liquid paraffin, vaseline, paraffin, ceresin, microcrystalline wax, squalane, and the like.
  • Higher fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, undecylenic acid, oxystearic acid, linoleic acid, lanolin fatty acid, and synthetic fatty acids.
  • Sterols include cholesterol, dihydrocholesterol, phytocholesterol and the like.
  • Fatty acid esters include ethyl linoleate, isopropyl myristate, isopropyl lanolin fatty acid, hexyl laurate, myristyl myristate, cetyl myristate, octyl dodecyl myristate, decyl oleate, octyl dodecyl oleate, hexadecyl dimethyl octanoate, isooctanoic acid Cetyl, decyl palmitate, glyceryl trimmyristate, glycerin tri (caprylate / caprate), propylene glycol dioleate, glycerin triisostearate, glycerin triisooctanoate, cetyl lactate, myristyl lactate, diisostearyl malate or cholesteryl isostearate And cyclic alcohol fatty acid esters such as choleste
  • Examples of the metal soap include zinc laurate, zinc myristate, magnesium myristate, zinc palmitate, zinc stearate, aluminum stearate, calcium stearate, magnesium stearate, and zinc undecylenate.
  • Examples of the humectant include glycerin, propylene glycol, 1,3-butylene glycol, polyethylene glycol, sodium dl-pyrrolidonecarboxylate, sodium lactate, sorbitol, sodium hyaluronate, polyglycerin, xylitol, maltitol and the like.
  • surfactant examples include anionic surfactants such as higher fatty acid soaps, higher alcohol sulfates, N-acyl glutamates and phosphates, cationic surfactants such as amine salts and quaternary ammonium salts, and betaine.
  • Surfactants such as amino acid type, amino acid type, imidazoline type and lecithin, and nonionic surfactants such as fatty acid monoglyceride, propylene glycol fatty acid ester, sorbitan fatty acid ester, sucrose fatty acid ester, polyglycerin fatty acid ester, and ethylene oxide condensate.
  • Color material raw materials include iron oxide, ultramarine, konjo, chromium oxide, chromium hydroxide, carbon black, manganese violet, titanium oxide, zinc oxide, talc, kaolin, mica, calcium carbonate, magnesium carbonate, mica, aluminum silicate, Inorganic pigments such as barium silicate, calcium silicate, magnesium silicate, silica, zeolite, barium sulfate, calcined calcium sulfate (baked gypsum), calcium phosphate, hydroxyapatite, ceramic powder, etc., azo type, nitro type, nitroso type, xanthene type And quinoline, anthraquinoline, indigo, triphenylmethane, phthalocyanine and pyrene tar dyes.
  • Inorganic pigments such as barium silicate, calcium silicate, magnesium silicate, silica, zeolite, barium sulfate, calcined calcium sulfate (baked g
  • the powder material such as the polymer compound or the coloring material may be subjected to a surface treatment in advance.
  • a conventionally known surface treatment technique can be used.
  • oil treatment with hydrocarbon oil, ester oil, lanolin, etc. silicone treatment with dimethylpolysiloxane, methylhydrogenpolysiloxane, methylphenylpolysiloxane, etc., perfluoroalkyl group-containing ester, perfluoroalkylsilane, perfluoropolyether ,
  • a fluorine compound treatment with a polymer having a perfluoroalkyl group a silane coupling agent treatment with 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, etc., isopropyl triisostearoyl titanate, isopropyl tris ( Titanium coupling agent treatment with dioctyl pyrophosphate) titanate, etc.
  • Examples of the flavor include natural flavors such as lavender oil, peppermint oil, and lime oil, and synthetic flavors such as ethylphenyl acetate, geraniol, and p-tert-butylcyclohexyl acetate.
  • Examples of the preservative / bactericide include methyl paraben, ethyl paraben, propyl paraben, benzalkonium, benzethonium and the like.
  • Examples of the antioxidant include dibutylhydroxytoluene, butylhydroxyanisole, propyl gallate, and tocopherol.
  • the ultraviolet absorber examples include inorganic absorbers such as titanium oxide, zinc oxide, cerium oxide, iron oxide, and zirconium oxide, benzoic acid, p-aminobenzoic acid, anthranilic acid, salicylic acid, and cinnamic acid.
  • organic absorbents such as benzophenone and dibenzoylmethane are exemplified.
  • Special compounding ingredients include hormones such as estradiol, estrone, ethinyl estradiol, cortisone, hydrocortisone, prednisone, vitamins such as vitamin A, vitamin B, vitamin C, vitamin E, citric acid, tartaric acid, lactic acid, aluminum chloride, sulfuric acid Skin astringents such as aluminum / potassium, allantoinchlorohydroxyaluminum, zinc paraphenolsulfonate, zinc sulfate, etc. Hair growth promoters such as E, estrogen, and photosensitizer; and whitening agents such as magnesium phosphate-L-ascorbate and kojic acid.
  • hormones such as estradiol, estrone, ethinyl estradiol, cortisone, hydrocortisone, prednisone
  • vitamins such as vitamin A, vitamin B, vitamin C, vitamin E, citric acid, tartaric acid, lactic acid, aluminum chloride, sulfuric acid
  • Skin astringents
  • compositions contain a binder resin, a UV-curable resin, a solvent, and the like, if necessary.
  • a binder resin a resin soluble in an organic solvent or water or an emulsion-type aqueous resin dispersible in water can be used.
  • the addition amount of the binder resin or the UV curable resin and the composite particles also varies depending on the thickness of the formed coating film, the average particle size of the composite particles, and the coating method.
  • the added amount of the composite particles is preferably 5 to 50% by weight based on the total amount of the binder resin (solid content when an emulsion type aqueous resin is used) and the composite particles.
  • a more preferred content is 10 to 50% by weight, and a still more preferred content is 20 to 40% by weight.
  • the binder resin include an acrylic resin, an alkyd resin, a polyester resin, a polyurethane resin, a chlorinated polyolefin resin, an amorphous polyolefin resin, an acrylic silicone resin, an acrylic urethane resin, and a fluorine-based resin.
  • Polyfunctional (meth) acrylate resins such as alcohol polyfunctional (meth) acrylates; and polyfunctional urethane acrylate resins synthesized from diisocyanates, polyhydric alcohols, and hydroxy-containing (meth) acrylates, and the like. No.
  • a polyfunctional (meth) acrylate resin is preferable, and a polyhydric alcohol polyfunctional (meth) acrylate resin having three or more (meth) acryloyl groups in one molecule is more preferable.
  • polyhydric alcohol polyfunctional (meth) acrylate resin having three or more (meth) acryloyl groups in one molecule, specifically, trimethylolpropane tri (meth) acrylate, trimethylolethanetri (meth) acrylate 1,2,4-cyclohexanetetra (meth) acrylate, pentaglycerol triacrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol Examples include tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol triacrylate, and tripentaerythritol hexaacrylate. It is, or may be even alone, or two or more are used alone.
  • a photopolymerization initiator When using a UV curable resin, a photopolymerization initiator is usually used in combination.
  • the photopolymerization initiator is not particularly limited. Examples of the photopolymerization initiator include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, ⁇ -hydroxyalkylphenones, ⁇ -aminoalkylphenones, anthraquinones, thioxanthones, azo compounds, and peroxides. (See Japanese Patent Application Laid-Open No.
  • binder resins or UV-curable resins can be appropriately selected depending on the adhesion of the paint to the substrate to be coated, the environment in which the paint is used, and the like.
  • the solvent is not particularly limited, but it is preferable to use a solvent that can dissolve or disperse the binder resin or the UV-curable resin.
  • a solvent that can dissolve or disperse the binder resin or the UV-curable resin.
  • hydrocarbon solvents such as toluene and xylene
  • ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone
  • ester solvents such as ethyl acetate and butyl acetate
  • dioxane ethylene glycol diethyl ether, and ethylene glycol
  • ether solvents such as monobutyl ether. If it is a water-based paint, water, alcohols and the like can be used.
  • These solvents may be used alone or as a mixture of two or more.
  • the content of the solvent in the coating material is usually about 20 to 60% by weight based on the total amount of the composition.
  • the composition contains, if necessary, a known coating surface adjuster, a fluidity adjuster, an ultraviolet absorber, a light stabilizer, a curing catalyst, an extender pigment, a color pigment, a metal pigment, a mica powder pigment, a dye, and the like. It may be.
  • the method for forming a coating film using the composition is not particularly limited, and any known method can be used. For example, methods such as spray coating, roll coating, brush coating, and coating a substrate such as a film as a thin layer by coating reverse roll coating, gravure coating, die coating, comma coating, spray coating, etc. Is mentioned.
  • the composition may be diluted if necessary to adjust the viscosity.
  • diluent examples include hydrocarbon solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate and butyl acetate; ether solvents such as dioxane and ethylene glycol diethyl ether; An alcohol-based solvent and the like.
  • hydrocarbon solvents such as toluene and xylene
  • ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone
  • ester solvents such as ethyl acetate and butyl acetate
  • ether solvents such as dioxane and ethylene glycol diethyl ether
  • An alcohol-based solvent and the like examples of the diluents may be used alone or in combination of two or more.
  • a coating film can be formed by applying a coating film on an arbitrary coating surface such
  • the coating film using the coating composition is used after being coated on various substrates, and is not particularly limited to metal, wood, glass, plastics and the like. Further, a transparent base material such as polyethylene terephthalate (PET), polycarbonate (PC), and acryl can be coated and used.
  • PET polyethylene terephthalate
  • PC polycarbonate
  • acryl can be coated and used.
  • the light-diffusing film is a base material such as glass, polycarbonate (PC), acrylic resin, polyethylene terephthalate (PET), triacetyl cellulose (TAC), and other plastic sheets, plastic films, plastic lenses, and plastic panels. And a light diffusion layer of the light diffusing composition formed on the surface of a base material such as a cathode ray tube, a fluorescent display tube, a liquid crystal display panel and the like.
  • the coating may be used alone or on a substrate, such as a protective film, a hard coat film, a flattening film, a high refractive index film, an insulating film, a conductive resin film, a conductive metal particle film, or a conductive metal oxide particle. It is formed in combination with a film and other primer films used as necessary. When used in combination, the light diffusion layer does not necessarily need to be formed on the outermost surface.
  • the volume average particle diameter of the composite particles was measured using Coulter Multisizer TM 3 (a measuring device manufactured by Beckman Coulter, Inc.). The measurement was performed using an aperture calibrated according to the Multisizer TM 3 User's Manual issued by Beckman Coulter.
  • the aperture used for the measurement is selected as follows. When the assumed volume average particle diameter of the particles to be measured is 1 ⁇ m or more and 10 ⁇ m or less, an aperture having a size of 50 ⁇ m is selected, and the assumed volume average particle diameter of the particles to be measured is 10 ⁇ m. If the size is larger than 30 ⁇ m or less, an aperture having a size of 100 ⁇ m is selected.
  • an aperture having a size of 400 ⁇ m was appropriately selected.
  • the aperture was changed to an aperture having an appropriate size, and the measurement was performed again.
  • 0.1 g of the polymer particles was put in 10 ml of a 0.1% by weight aqueous nonionic surfactant solution, and a touch mixer ("TOUCHMIXER MT-31" manufactured by Yamato Scientific Co., Ltd.) and an ultrasonic cleaner (Vervok) were used. Dispersion was performed using "ULTRASONICCLEANER VS-150" manufactured by Leer Co., Ltd. to obtain a dispersion. During the measurement, the inside of the beaker was gently stirred so as not to cause bubbles, and the measurement was terminated when 100,000 particles were measured. The volume average particle diameter of the particles was an arithmetic mean in a volume-based particle size distribution of 100,000 particles.
  • the composite particles were mixed with a photocurable resin D-800 (manufactured by JEOL Ltd.) and irradiated with light to obtain a cured product. Thereafter, the cured product was immersed in liquid nitrogen for 5 minutes, then cut, and affixed to a sample table with a carbon tape with the cross section facing upward. Platinum vapor deposition (15 mV, 240 seconds, 6.0 Pa, distance between target and sample surface: 30 mm) was performed using a Hitachi High-Technologies “Ion Sputter E-1045” sputtering apparatus.
  • the cross section of the particles in the sample was photographed using a secondary electron detector of a “Regulus 8230” scanning electron microscope manufactured by Hitachi High-Technologies Corporation (magnification of the photograph of the particle cross section: 5,000 times).
  • the accelerating voltage during observation was 10 kV.
  • elemental analysis was performed using "X-MaxN150” manufactured by Oxford Instruments Inc. provided for "Regulus 8230" manufactured by Hitachi High-Technologies Corporation.
  • the internal porous portion in the particle cross section was arbitrarily set as an analysis region, and the atomic number concentration (%) of carbon atoms and the atomic number concentration (%) of silicon atoms in the analysis region were measured.
  • the values were re-analyzed using software attached to “X-MaxN150” manufactured by Oxford Instruments Inc. so that the total atomic concentration (%) of atoms becomes 100%.
  • the acceleration voltage at the time of analysis was 10 kV.
  • the resolution in the image scan setting was 1024, the dwell time was 5 ⁇ s, and the input signal was SE.
  • the energy range, the number of channels, and the acquisition mode in the EDS acquisition spectrum setting were set automatically, and the process time was set to 6.
  • FIG. 8 shows an example of an analysis region set as an internal porous portion in a photograph of a particle cross section.
  • the inside of the white frame described as spectrum 19 in FIG. 8 was set as the analysis region.
  • the number of carbon atoms (%) and the number of silicon atoms (%) in the white frame are the number of carbon atoms (%) and the number of silicon atoms (%) in the internal porous structure.
  • the mixed solution whose temperature was adjusted in a 25 ° C. constant temperature bath was added to a 25 mL pycnometer.
  • the density of the mixture was determined by dividing the weight (g) of the added mixture by the volume (mL) of the pycnometer.
  • Viscosity of the mixture The viscosity of the mixed solution whose temperature was adjusted in a 25 ° C. constant temperature bath was measured using a tuning fork vibrating viscometer SV-10 (manufactured by A & D). The viscosity (unit: mPa ⁇ s) of the mixed solution was determined by dividing the indicated viscosity value on the apparatus (unit: mPa ⁇ s ⁇ g / cm 3 ) by the calculated density of the mixed solution.
  • the sample was cut out, a conductive tape was stuck on the sample stage, and the sample was mounted thereon.
  • the particles were subjected to a surface treatment (10 Pa, 5 mA, 10 seconds) using an “Osmium Coater Neoc-Pro” coating device manufactured by Meiwa Forsys. Next, the surface of the particles was photographed using a secondary electron detector of a scanning electron microscope “SU1510” manufactured by Hitachi High-Technologies Corporation.
  • the cross section of the sample was subjected to element mapping by SEM-EDS (Scanning Electron Microscope Energy Dispersive X-ray Spectrometry) to determine whether or not silica and titanium oxide exist inside the cavity.
  • SEM-EDS Sccanning Electron Microscope Energy Dispersive X-ray Spectrometry
  • EDS Electronic Data Dispersive X-ray Spectrometry
  • an acceleration voltage of 15 KV and 10 frames 800 seconds
  • silicon is captured. Elemental maps were obtained with K ⁇ rays and K ⁇ rays of titanium.
  • the particle diameter of the second inorganic particles was an average particle diameter measured using a method called a dynamic light scattering method or a photon correlation method. That is, at 25 ° C., a dispersion of an organic solvent of inorganic particles adjusted to 0.1% by volume was irradiated with laser light, and the intensity of scattered light scattered from the inorganic particles was measured over time in microsecond units. The distribution of scattering intensity resulting from the detected inorganic particles was applied to a normal distribution, and the Z-average particle diameter was calculated by cumulant analysis. This average particle size could be easily measured with a measuring device equipped with commercially available data analysis software, and could be automatically analyzed. In the present example, the measurement was carried out using a particle size measuring apparatus “Zetasizer Nano ZS” manufactured by Malvern (Spectris).
  • titanium oxide (X) titanium oxide content: 60.6%, solid content: 68.7% Obtained.
  • the Z-average particle diameter of the titanium oxide was 780 nm.
  • Example 1 100 g of methyl methacrylate (MMA) as a monofunctional monomer, 100 g of ethylene glycol dimethacrylate (EGDMA) as a crosslinkable monomer, 160 g of tetraethoxysilane (TEOS) as a silica precursor, and ( 1R, 2S, 5R) -5-Methyl-2- (propan-2-yl) cyclohexyl 4-methylbenzenesulfonate (product name WPAG-699, manufactured by Wako Pure Chemical Industries, Ltd.), 1 g of toluene as a non-reactive organic solvent 39.75 g, 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator (manufactured by Wako Pure Chemical Industries, Ltd .; product name V-65), 2.0 g, oxidation as second inorganic particles 0.77 g of a toluene solution (X) of titanium particles was mixed and
  • the obtained mixture was mixed with 1200 g of an aqueous solution of polyvinyl alcohol (PVA) (manufactured by Nippon Synthetic Chemical Company; product name: Gohsenol GL-5) prepared at a concentration of 1.7% by weight.
  • PVA polyvinyl alcohol
  • the obtained mixture was put into a 2 L beaker, and emulsification / dispersion treatment was performed at a rotation speed of 5000 rpm for 6 minutes using a homogenizer (manufactured by Central Science and Trading; product name: Polytron homogenizer PT10-35GT).
  • the obtained emulsion was put into a 2 L stainless steel autoclave, and polymerization was carried out at a temperature of 50 ° C.
  • FIG. 1A shows a photograph of the surface of the obtained composite particles
  • FIG. 1B shows a photograph of a cross section thereof.
  • FIGS. 1C to 1E show metal element mapping diagrams by SEM-EDS.
  • FIG. 1 (c) is a cross-sectional photograph
  • FIG. 1 (d) is a diagram showing the presence of silicon
  • FIG. 1 (e) is a diagram showing the presence of titanium.
  • Example 2 Composite particles were obtained in the same manner as in Example 1, except that 3.85 g of a toluene solution (X) of titanium oxide particles as second inorganic particles and 38.76 g of toluene of a non-reactive organic solvent were used. .
  • FIG. 2A shows a photograph of the surface of the obtained composite particles
  • FIG. 2B shows a photograph of a cross section thereof. It was confirmed that an outer shell composed of a monofunctional monomer and a crosslinkable monomer was formed, and that a porous structure in which silica particles were connected to each other was formed inside. Further, the volume average particle diameter was 10.4 ⁇ m, and the amount of the inorganic component in the composite particles was 7.5% by weight.
  • Example 3 1.54 g of a methanol dispersion of zirconium oxide particles as second inorganic component particles (manufactured by Sakai Chemical Co .; product name SZR-M, zirconia content 30% by weight, particle diameter: 3 nm), as a non-reactive organic solvent Except that 38.9 g of toluene was used, composite particles were obtained in the same manner as in Example 1.
  • FIG. 3A shows a photograph of the surface of the obtained composite particles
  • FIG. 3B shows a photograph of a cross section thereof. It was confirmed that an outer shell composed of a monofunctional monomer and a crosslinkable monomer was formed, and that a porous structure in which silica particles were connected to each other was formed inside.
  • the volume average particle diameter was 11.4 ⁇ m, and the amount of the inorganic component in the composite particles was 16.8% by weight.
  • Example 4 0.46 g of cerium oxide as second inorganic component particles (manufactured by I-Tech Co., Ltd .; product name: ceria nanoparticle powder, particle diameter: 10 nm); Composite particles were obtained in the same manner as in Example 1, except that 0.046 g of product name (Plenact ALM) and 40 g of toluene as a non-reactive organic solvent were used.
  • FIG. 4A shows a surface photograph of the obtained composite particles
  • FIG. 4B shows a cross-sectional photograph thereof. It was confirmed that an outer shell composed of a monofunctional monomer and a crosslinkable monomer was formed, and that a porous structure in which silica particles were connected to each other was formed inside. Further, the volume average particle diameter was 11.7 ⁇ m, and the amount of the inorganic component in the composite particles was 8.9% by weight.
  • Composite particles were obtained in the same manner as in Example 1, except that the amount of toluene as a non-reactive organic solvent was 40 g and no titanium oxide particles were added.
  • FIG. 5A shows a photograph of the surface of the obtained composite particles
  • FIG. 5B shows a photograph of a cross section thereof. It was confirmed that the shell composed of the monofunctional monomer and the crosslinkable monomer was formed. In addition, a porous structure in which silica particles were connected to each other was confirmed. Further, the volume average particle diameter was 11.9 ⁇ m, and the amount of the inorganic component in the composite particles was 16.0% by weight.
  • Silica-containing particles were prepared with reference to Non-Patent Document 1. Specifically, 100 g of methyl methacrylate (MMA) as a monofunctional monomer, 100 g of ethylene glycol dimethacrylate (EGDMA) as a crosslinkable monomer, 200 g of tetraethoxysilane (TEOS) as a silica precursor, A polymerizable composition was prepared by mixing 2 g of 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) (Wako Pure Chemical Industries, Ltd .; product name V-70) as an agent.
  • MMA methyl methacrylate
  • EGDMA ethylene glycol dimethacrylate
  • TEOS tetraethoxysilane
  • PVA polyvinyl alcohol
  • Gohsenol GL-05 20 g of polyvinyl alcohol (PVA) (manufactured by Nippon Gohsei; Gohsenol GL-05) was added to 1180 g of ion-exchanged water as an aqueous phase.
  • the polymerizable composition was put into the aqueous phase, and emulsification / dispersion treatment was performed at a rotation speed of 5000 rpm for 10 minutes using a homogenizer (manufactured by Central Kagaku Trading Co., Ltd .; product name: Polytron homogenizer PT10-35GT).
  • the obtained emulsion is charged into a 2 L pressure vessel with stirring blades, and the mixture is heated at 30 ° C.
  • FIG. 6A shows a surface photograph of the obtained silica-containing particles
  • 6B shows a cross-sectional photograph thereof. It was confirmed that an outer shell composed of a monofunctional monomer and a crosslinkable monomer was formed, and that one or more silica particles were included therein.
  • the volume average particle diameter was 10.4 ⁇ m, and the amount of the inorganic component in the silica-containing particles was 22.0% by weight.
  • the reflectance of the sample plate to ultraviolet light, visible light, and near-infrared light was evaluated in the following order.
  • An ultraviolet-visible-near-infrared spectrophotometer (Solid Spec 3700) manufactured by Shimadzu Corporation was used as a reflectivity measuring device to measure the reflection characteristics from ultraviolet light to near-infrared light (wavelength 300 to 2500 nm) on the coated surface of the sample plate. It was measured as reflectivity (%).
  • the measurement was carried out using a 60 mm ⁇ integrating sphere and using Spectralon as a standard white plate. The above measurements were performed on the composite particles of Examples 1 to 4 and Comparative Examples 1 and 2.
  • FIG. 7 shows the obtained results.
  • FIG. 7 shows the obtained results.
  • Example 5 80 g of methyl methacrylate (MMA) as a monofunctional monomer, 80 g of ethylene glycol dimethacrylate (EGDMA) as a crosslinkable monomer, 160 g of tetraethoxysilane (TEOS) as a silica precursor, and hydrophobicity as hydrophobic silica particles Fumed silica R972 (EVONIK, BET specific surface area 110 ⁇ 20 m 2 / g) 16 g, 1.6 g of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator (Wako Pure Chemical Industries, Ltd.) (Product name V-65), (1R, 2S, 5R) -5-methyl-2- (propan-2-yl) cyclohexyl 4-methylbenzenesulfonate (manufactured by Wako Pure Chemical Industries, Ltd.) as a thermal acid generator A product consisting of 0.8 g of product name W
  • the viscosity of the mixture was 3.58 mPa ⁇ s.
  • 26 g of magnesium pyrophosphate and 0.128 g of lauryl phosphoric acid were added to 1280 g of ion-exchanged water as a suspension stabilizer to prepare an aqueous phase.
  • the mixture was put into the aqueous phase, and emulsification / dispersion treatment was performed at 7000 rpm for 10 minutes using a homogenizer (manufactured by Central Kagaku Trading Co., Ltd .; product name: Polytron homogenizer PT10-35).
  • the obtained emulsion is put into a 2 L pressure vessel with a stirring blade, and the stirring blade is heated at 50 ° C.
  • FIG. 9A shows a surface photograph of the obtained composite particles
  • FIG. 9B shows a cross-sectional photograph thereof. It was confirmed that an outer shell derived from the monofunctional monomer and the crosslinkable monomer was formed, and that a porous structure in which silica particles were connected to each other was formed inside.
  • the volume average particle diameter was 20.7 ⁇ m, and the weight of the porous structure in the composite particles was 27.0% by weight.
  • Example 6 Composite particles were obtained in the same manner as in Example 5, except that 12 g of hydrophobic silica particles were used. The viscosity of the mixture was 2.39 mPa ⁇ s.
  • FIG. 10A shows a surface photograph of the obtained composite particles
  • FIG. 10B shows a cross-sectional photograph thereof. It was confirmed that an outer shell composed of a monofunctional monomer and a crosslinkable monomer was formed, and that a porous structure in which silica particles were connected to each other was formed inside.
  • the volume average particle size was 9.5 ⁇ m, and the weight of the porous structure in the composite particles was 24.2% by weight.
  • the weight of silica in the composite particles was 25.1%.
  • the atomic number concentration (%) of carbon atoms in the internal porous structure was measured, it was 90.4%, and it was confirmed that the crosslinked polymer component forming the outer shell was included.
  • Example 7 Composite particles were obtained in the same manner as in Example 5, except that 8 g of hydrophobic silica particles were used. The viscosity of the mixture was 1.61 mPa ⁇ s.
  • FIG. 11A shows a surface photograph of the obtained composite particles, and FIG. 11B shows a cross-sectional photograph thereof. It was confirmed that an outer shell composed of a monofunctional monomer and a crosslinkable monomer was formed, and that a porous structure in which silica particles were connected to each other was formed inside. The volume average particle diameter was 11.4 ⁇ m, and the weight of the porous structure in the composite particles was 23.3% by weight.
  • Example 8 Composite particles were obtained in the same manner as in Example 5, except that 1.6 g of hydrophobic silica particles were used. The viscosity of the mixture was 0.93 mPa ⁇ s.
  • FIG. 12A shows a surface photograph of the obtained composite particles
  • FIG. 12B shows a cross-sectional photograph thereof. It was confirmed that an outer shell composed of a monofunctional monomer and a crosslinkable monomer was formed, and that a porous structure in which silica particles were connected to each other was formed inside. The volume average particle diameter was 16.1 ⁇ m, and the weight of the porous structure in the composite particles was 21.6% by weight.
  • Example 9 Composite particles were obtained in the same manner as in Example 5, except that 24 g of hydrophobic silica particles were used.
  • the viscosity of the mixture was 8.07 mPa ⁇ s. It was confirmed that an outer shell composed of a monofunctional monomer and a crosslinkable monomer was formed, and that a porous structure in which silica particles were connected to each other was formed inside.
  • the volume average particle size was 20.3 ⁇ m, and the weight of the porous structure in the composite particles was 29.1% by weight.
  • Example 10 Composite particles were obtained in the same manner as in Example 5, except that 36 g of hydrophobic silica particles were used. The viscosity of the mixture was 46.3 mPa ⁇ s.
  • FIG. 13A shows a surface photograph of the obtained composite particles
  • FIG. 13B shows a cross-sectional photograph thereof. It was confirmed that an outer shell composed of a monofunctional monomer and a crosslinkable monomer was formed, and that a porous structure in which silica particles were connected to each other was formed inside. Further, the volume average particle diameter was 21.6 ⁇ m, and the weight of the porous structure in the composite particles was 31.8% by weight.
  • Example 11 Composite particles were obtained in the same manner as in Example 5, except that 8 g of hydrophobic fumed silica R974 (EVONIK, specific surface area by BET method: 170 ⁇ 20 m 2 / g) was used as the hydrophobic silica particles.
  • the viscosity of the mixture was 1.76 mPa ⁇ s.
  • FIG. 14A shows a surface photograph of the obtained composite particles
  • FIG. 14B shows a cross-sectional photograph thereof. It was confirmed that an outer shell composed of a monofunctional monomer and a crosslinkable monomer was formed, and that a porous structure in which silica particles were connected to each other was formed inside.
  • the volume average particle diameter was 11.0 ⁇ m, and the weight of the porous structure in the composite particles was 23.9% by weight.
  • Example 12 Composite particles were obtained in the same manner as in Example 5, except that 8 g of hydrophobic fumed silica R976S (EVONIK, specific surface area of 240 ⁇ 25 m 2 / g by BET method) was used as the hydrophobic silica particles.
  • the viscosity of the mixture was 1.54 mPa ⁇ s.
  • FIG. 15A shows a photograph of the surface of the obtained composite particles
  • FIG. 15B shows a photograph of a cross section thereof. It was confirmed that an outer shell composed of a monofunctional monomer and a crosslinkable monomer was formed, and that a porous structure in which silica particles were connected to each other was formed inside.
  • the volume average particle diameter was 10.8 ⁇ m, and the weight of the porous structure in the composite particles was 24.0% by weight.
  • Example 13 Composite particles were obtained in the same manner as in Example 5, except that 8 g of hydrophobic fumed silica R812 (EVONIK, specific surface area according to BET method: 260 ⁇ 30 m 2 / g) was used as the hydrophobic silica particles.
  • the viscosity of the mixture was 1.27 mPa ⁇ s. It was confirmed that an outer shell composed of a monofunctional monomer and a crosslinkable monomer was formed, and that a porous structure in which silica particles were connected to each other was formed inside.
  • the volume average particle size was 11.5 ⁇ m, and the weight of the porous structure in the composite particles was 24.1% by weight.
  • Example 14 100 g of methyl methacrylate (MMA) as a monofunctional monomer, 100 g of ethylene glycol dimethacrylate (EGDMA) as a crosslinkable monomer, 200 g of tetraethoxysilane (TEOS) as a silica precursor, and 100 g of an inorganic thickener 4 g of smecton-STN (organized smectite manufactured by Kunimine Industries Co., Ltd.), 2 g of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator (product name V-65, manufactured by Wako Pure Chemical Industries, Ltd.), Was prepared.
  • MMA methyl methacrylate
  • EGDMA ethylene glycol dimethacrylate
  • TEOS tetraethoxysilane
  • the viscosity of the mixture was 0.91 mPa ⁇ s.
  • an aqueous phase was prepared by dissolving 60 g of polyvinyl alcohol (GL-05, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) as a suspension stabilizer in 1140 g of ion-exchanged water. The mixture was put into the aqueous phase, and emulsification / dispersion treatment was carried out at 5,000 rpm for 10 minutes using a homomixer (manufactured by Central Kagaku Trading Co., Ltd .; product name: Polytron homogenizer PT10-35).
  • the obtained emulsion is charged into a 2 L pressure vessel with stirring blades, and the mixture is heated at 50 ° C. for 4 hours while stirring the stirring blades at 350 rpm, thereby comprising a monofunctional monomer and a crosslinkable monomer.
  • An outer shell was formed. While maintaining the agitation, the internal temperature is cooled to 30 ° C., 65 g of 25% aqueous ammonia (Wako Pure Chemical Industries, Ltd.) is added, and the mixture is agitated for 16 hours to allow the gelation reaction of TEOS to proceed, thereby containing the composite particles.
  • An emulsion was obtained.
  • the obtained emulsion was subjected to suction filtration to take out composite particles from the emulsion.
  • FIG. 16 shows a cross-sectional photograph of the obtained composite particles. It was confirmed that an outer shell derived from the monofunctional monomer and the crosslinkable monomer was formed, and that a porous structure in which silica particles were connected to each other was formed inside.
  • the volume average particle diameter was 11.5 ⁇ m, and the weight of silica in the composite particles was 22.1% by weight.
  • Example 15 Silica-encapsulated microcapsule resin particles were obtained in the same manner as in Example 14, except that 4 g of Kunibis-110 (organized bentonite) was used as an inorganic thickener. The viscosity of the mixture was 1.01 mPa ⁇ s.
  • FIG. 17 shows a cross-sectional photograph of the obtained composite particles. It was confirmed that an outer shell derived from the monofunctional monomer and the crosslinkable monomer was formed, and that a porous structure in which silica particles were connected to each other was formed inside. The volume average particle diameter was 13.5 ⁇ m, and the weight of silica in the composite particles was 21.9% by weight.
  • FIG. 18A shows a surface photograph of the obtained composite particles
  • FIG. 18B shows a cross-sectional photograph thereof.
  • Table 2 summarizes the raw material species of Examples 5 to 15 and Comparative Example 3, the amount (g) used, and the viscosity of the mixture.
  • the reflectance of the composite particles with respect to ultraviolet light, visible light and near-infrared light was evaluated according to the following procedure. 2.5 g of composite particles were added to 10 g of a commercially available water-based paint (trade name of Asahipen Co .; water-based multi-purpose color clear), and the mixture was stirred well to disperse the particles to prepare a paint for evaluation.
  • the paint for evaluation was applied to the black side of the opacity test paper using an applicator set to a wet thickness of 250 ⁇ m, and then sufficiently dried at room temperature to obtain a sample plate for light reflectivity evaluation.
  • the reflectance of the sample plate to ultraviolet light, visible light, and near-infrared light was evaluated in the following order.
  • An ultraviolet-visible-near-infrared spectrophotometer (Solid Spec 3700) manufactured by Shimadzu Corporation was used as a reflectivity measuring device to measure the reflection characteristics from ultraviolet light to near-infrared light (wavelength 300 to 2500 nm) on the coated surface of the sample plate. It was measured as reflectivity (%).
  • the measurement was carried out using a 60 mm ⁇ integrating sphere and using Spectralon as a standard white plate. The results obtained are shown in FIG. From FIG. 19, it can be seen that the composite particles of the examples have a high reflectivity at almost all wavelengths from ultraviolet light to near-infrared light similar to that of Comparative Example 3 without using an organic solvent such as toluene. Understand.
  • Example of cosmetic formulation Production and blending amount of powder foundation Composite particles obtained in Example 1 10.0 parts by weight Red iron oxide 3.0 parts by weight Yellow iron oxide 2.5 parts by weight Black iron oxide 0.5 parts by weight Titanium oxide 10.0 Parts by weight Mica 20.0 parts by weight Talc 44.0 parts by weight Liquid paraffin 5.0 parts by weight Octyldodecyl myristate 2.5 parts by weight Vaseline 2.5 parts by weight
  • Preservatives proper amount perfume proper amount / production method Yellow iron oxide, black iron oxide, titanium oxide, mica, and talc are mixed with a Henschel mixer, and a mixture obtained by mixing and dissolving liquid paraffin, octyldodecyl myristate, vaseline, and a preservative is added and uniformly mixed. After adding a fragrance to the mixture and mixing, the mixture is pulverized and passed through a sieve. This is compression-molded on a metal plate to obtain a powder foundation.
  • (Formulation Example 2) Production and Compounding Amount of Cosmetic Emulsion 10.0 parts by weight of composite particles obtained in Example 1 2.5 parts by weight of stearic acid 1.5 parts by weight of cetyl alcohol 5.0 parts by weight of petrolatum 10.0 parts by weight of liquid paraffin 10.0 parts by weight of polyethylene ( 10 mol) Monooleate 2.0 parts by weight Polyethylene glycol 1500 3.0 parts by weight Triethanolamine 1.0 part by weight Purified water 64.5 parts by weight Fragrance 0.5 part by weight Preservatives Appropriate amount / production method First, stearin The acid, cetyl alcohol, petrolatum, liquid paraffin, and polyethylene monooleate are heated and dissolved, and the composite particles are added and mixed therein, and the mixture is kept at 70 ° C.
  • oil phase Further, polyethylene glycol and triethanolamine are added to purified water, dissolved by heating, and kept at 70 ° C. (aqueous phase).
  • aqueous phase The oil phase is added to the water phase, preliminarily emulsified, and thereafter uniformly emulsified with a homogenizer. After emulsification, the emulsion is cooled to 30 ° C. with stirring to obtain a cosmetic emulsion.
  • Example 3 Manufacture and blending amount of powder foundation Composite particles obtained in Example 5 10.0 parts by weight Red iron oxide 3.0 parts by weight Yellow iron oxide 2.5 parts by weight Black iron oxide 0.5 parts by weight Titanium oxide 10.0 Parts by weight Mica 20.0 parts by weight Talc 44.0 parts by weight Liquid paraffin 5.0 parts by weight Octyldodecyl myristate 2.5 parts by weight Vaseline 2.5 parts by weight
  • Preservatives proper amount perfume proper amount / production method Yellow iron oxide, black iron oxide, titanium oxide, mica, and talc are mixed with a Henschel mixer, and a mixture obtained by mixing and dissolving liquid paraffin, octyldodecyl myristate, vaseline, and a preservative is added and uniformly mixed. After adding a fragrance to the mixture and mixing, the mixture is pulverized and passed through a sieve. This is compression-molded on a metal plate to obtain a powder foundation.
  • polyethylene glycol and triethanolamine are added to purified water, dissolved by heating, and kept at 70 ° C. (aqueous phase).
  • the oil phase is added to the water phase, preliminarily emulsified, and thereafter uniformly emulsified by a homomixer. After emulsification, the emulsion is cooled to 30 ° C. with stirring to obtain a cosmetic emulsion.

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Abstract

La présente invention concerne: des particules composites organiques inorganiques qui présentent une excellente réflectivité de la lumière visible et de la lumière proche infrarouge et qui ont une capacité de diffusion et une capacité de dissimulation de lumière élevées; et un procédé de production des particules composites inorganiques organiques; et l'utilisation des particules composites inorganiques organiques. Plus spécifiquement, la présente invention concerne des particules composites organiques inorganiques caractérisées en ce qu'elles ont un diamètre de particule moyen en volume entre 0,5 et 100 µm et comprenant chacune: une structure poreuse qui est dotée d'une enveloppe externe composée d'un polymère réticulé et d'une cavité définie par l'enveloppe externe, et dans laquelle des particules de silice en tant que premières particules inorganiques sont mutuellement liées à l'intérieur de la cavité; et des secondes particules inorganiques autres que les particules de silice. La présente invention concerne également: un procédé de production de telles particules composites organiques inorganiques; et l'utilisation de telles particules composites organiques inorganiques.
PCT/IB2019/056673 2018-08-09 2019-08-06 Particule composite organique inorganique, son procédé de fabrication, et son utilisation WO2020031079A1 (fr)

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WO2022212376A1 (fr) * 2021-03-29 2022-10-06 The Regents Of The University Of California Revêtement blanc froid pulvérisable à base de microsphères de céramique
WO2024073831A1 (fr) * 2022-10-05 2024-04-11 Instituto Hercílio Randon Prémélange et procédéde préparation d'une composition cosmétique, composition cosmétique, procédé de photoprotection d'une surface et utilisation du prémélange

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