WO2007037202A1 - Particule de polymère combiné à de la silice, procédé servant à produire celle-ci et utilisation de celle-ci - Google Patents

Particule de polymère combiné à de la silice, procédé servant à produire celle-ci et utilisation de celle-ci Download PDF

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Publication number
WO2007037202A1
WO2007037202A1 PCT/JP2006/318971 JP2006318971W WO2007037202A1 WO 2007037202 A1 WO2007037202 A1 WO 2007037202A1 JP 2006318971 W JP2006318971 W JP 2006318971W WO 2007037202 A1 WO2007037202 A1 WO 2007037202A1
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Prior art keywords
silica
particles
composite polymer
polymer particles
light
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PCT/JP2006/318971
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English (en)
Japanese (ja)
Inventor
Ryosuke Harada
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Sekisui Plastics Co., Ltd.
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Priority claimed from JP2006077455A external-priority patent/JP4716905B2/ja
Application filed by Sekisui Plastics Co., Ltd. filed Critical Sekisui Plastics Co., Ltd.
Priority to JP2007537605A priority Critical patent/JP5087403B2/ja
Publication of WO2007037202A1 publication Critical patent/WO2007037202A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/126—Preparation of silica of undetermined type
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof

Definitions

  • the present invention relates to silica composite polymer particles, a production method thereof, and use thereof. More specifically, the present invention relates to silica composite polymer particles in which a silica component is unevenly distributed on the surface and inside of the polymer component, a method for producing the same, and a use thereof.
  • thermoplastic resins such as polycarbonate resin, polystyrene resin, and acryl resin are used as various resins.
  • the light diffusing particles inorganic particles such as glass, calcium carbonate, and silica, or some other particles such as acrylic resin and styrene resin are used.
  • the light transmittance is lowered and it is difficult to say that the light diffusibility is improved.
  • Patent Document 1 JP-A-10-265580
  • Patent Document 2 JP-A-2005-126683
  • a light diffusing plate in which body particles are blended with a transparent base resin.
  • the light diffusing plates of these publications can improve the light diffusibility as compared with the light diffusing plates containing particles that are made of only inorganic materials or particles made of only polymers.
  • light diffusing particles having various structures are used in fields where diffuse light reflectivity is desired, such as paints and cosmetics.
  • nylon fine particles polymethyl methacrylate fine particles and the like are widely used in cosmetics because of their excellent extensibility.
  • nylon fine particles adsorb components such as preservatives added to cosmetics, the antiseptic effect may change over time, which is not preferable.
  • conventional polymethyl methacrylate fine particles have poor oil resistance and solvent resistance, and therefore have problems such as aggregation between particles in the presence of a moisturizing agent or an oil component such as alcohol.
  • the composite particle in which the surface of the latter polymer particle is covered with an inorganic substance has an advantage that the refractive index at the interface between the polymer particle and the inorganic substance can be made larger than the refractive index at the interface between the polymers. is there. Further, the former composite particles have an advantage that the tactile sensation is better than the latter composite particles.
  • Patent Document 3 Composite particles in which the surface of polymer particles is covered with an inorganic substance are reported, for example, in JP-A-5-170924 (Patent Document 3).
  • Patent Document 3 describes composite particles in which a surface of a thermoplastic material is fixed with a material smaller than the thermoplastic material and having excellent heat resistance.
  • the method for producing composite particles described in this publication is a method in which a thermoplastic substance is heated to a temperature above the softening point, and a substance having excellent heat resistance and a thermoplastic substance are stirred to obtain mechanical shearing force. is there.
  • Patent Document 4 polymer particles derived from a polymerizable bule monomer and the surface of the polymer particles are exposed with an opening ratio of 0.1 to 1. Composite particles comprising a silica film covering polymer particles have been reported.
  • Patent Document 1 Japanese Patent Laid-Open No. 10-265580
  • Patent Document 2 JP 2005-126683 A
  • Patent Document 3 Japanese Patent Laid-Open No. 5-170924
  • Patent Document 4 Japanese Unexamined Patent Application Publication No. 2004-307837
  • the composite polymer particles described in the above publication have a structure in which the surface of the polymer particles is substantially uniformly covered with an inorganic substance or a silica film. For this reason, these particles have light diffusion reflectivity improved to some extent as compared with polymer particles alone. However, further improvements in diffuse reflectance are desired.
  • the inventors of the present invention have intensively studied to solve the above-mentioned problems.
  • a polymerization process of a polymerizable bull monomer in the presence of aqueous colloidal silica having a specific average particle size, and a polyalkoxy By producing silica composite polymer particles through a siloxane oligomer condensation step, silica composite polymer particles in which the silica component derived from the polyalkoxysiloxane oligomer is unevenly distributed inside and on the surface of the polymer component can be obtained. Surprisingly, it was found that the obtained particles were excellent in diffuse reflection of light, and the present invention was achieved.
  • aqueous suspension in which an aqueous colloidal silica having an average particle size of 90 nm or less is dispersed, 100 parts by weight of a polymerizable vinyl monomer and the polymerizable bull monomer are used. After adding a mixture containing 10 to 500 parts by weight of an inert polyalkoxysiloxane oligomer and 0.01 to 10 parts by weight of a polymerization initiator, an aqueous suspension polymerization is carried out, whereby the weight derived from the polymerizable bull monomer is added. Forming a coalescing component,
  • a silica composite containing the polymer component and the silica component is formed by adding an acid or base catalyst to the aqueous suspension after aqueous suspension polymerization to form a silica component by condensation of the polyalkoxysiloxane oligomer.
  • Production of silica composite polymer particles comprising obtaining polymer particles A manufacturing method is provided.
  • a silica composite polymer particle obtained by the above production method comprising a polymer component derived from a polymerizable vinyl monomer and a silica component,
  • the silica component force is a condensate derived from a polyalkoxysiloxane oligomer that is inactive with respect to the polymerizable bur monomer, and
  • the silica component is obtained by calcining the silica composite polymer particles and removing the polymer component so that the silica particles are in contact with a spherical or substantially spherical outer shell having a hollow structure and the outer shell.
  • silica composite polymer particles that are unevenly distributed in the silica composite polymer particles so as to have an inner shell portion that forms a convex portion toward the center.
  • a light diffusing plate comprising a transparent resin base material and silica composite polymer particles obtained by the above production method.
  • liquid crystal display panel having a display surface and a back surface, a light source disposed on the back surface side, and the light diffusion plate disposed between the liquid crystal display panel and the light source are provided.
  • a liquid crystal display device characterized by the above is provided.
  • the silica composite polymer particle of the present invention has a unique shape in which the silica component constituting the particle is unevenly distributed in the particle, and thus has excellent light diffuse reflectance.
  • the light diffusibility can be improved as compared to the case where the same amount of inorganic particles, acryl particles, styrene resin, or the like is used. Furthermore, since light diffusibility comparable to that obtained when inorganic particles and resin particles are used can be realized with a relatively small amount of use, if the light diffusibility is similar, the light transmittance expressed by the total light transmittance can be realized. Can be reduced.
  • the particles of the present invention are used for a light diffusion plate of a liquid crystal display, it is possible to provide a uniform light amount as a whole without observing an image of a fluorescent lamp or a cold cathode tube as a light source. . This uniform light quantity can be provided even when the LCD is thin and large.
  • blending into cosmetics not only suppresses reflection of light in the regular reflection direction, but also diffuses light in a wider range of directions.
  • the focus effect can be expected.
  • FIG. 1 is a schematic cross-sectional view of silica particles after firing of the silica composite polymer particles of the present invention.
  • FIG. 2 is a schematic view of silica composite polymer particles of the present invention.
  • FIG. 3 is a schematic view of a light diffusion plate of the present invention.
  • FIG. 4 is a schematic sectional view of a liquid crystal display device.
  • FIG. 5 is an electron micrograph of silica particles after firing the silica composite polymer particles of Example 1.
  • FIG. 6 is a graph of the reflected light intensity distribution of Example 1.
  • FIG. 7 is an electron micrograph of silica particles after firing the silica composite polymer particles of Example 2.
  • FIG. 8 is a graph of the reflected light intensity distribution of Example 2.
  • FIG. 9 is an electron micrograph of silica particles after firing the silica composite polymer particles of Example 3.
  • FIG. 10 is an electron micrograph of silica particles after firing the silica composite polymer particles of Example 7.
  • FIG. 11 is an electron micrograph of silica particles after firing the silica composite polymer particles of Example 11.
  • FIG. 12 is an electron micrograph of silica particles after firing the silica composite polymer particles of Example 12.
  • FIG. 13 is an electron micrograph of silica particles after firing the silica composite polymer particles of Example 13.
  • FIG. 14 is an electron micrograph of silica particles after firing the silica composite polymer particles of Example 14.
  • FIG. 15 is an electron micrograph of silica particles after firing the silica composite polymer particles of Example 15.
  • FIG. 16 is an electron micrograph of silica particles after firing the silica composite polymer particles of Comparative Example 2.
  • FIG. 17 is a graph of the reflected light intensity distribution of Comparative Example 4.
  • FIG. 18 is a graph of the reflected light intensity distribution of Comparative Example 6.
  • the silica composite polymer particles of the present invention are spherical or substantially spherical, and the silica component is unevenly distributed on a part of the surface thereof.
  • the uneven distribution can be confirmed by the shape of the silica particles derived from the silica component obtained by firing the silica composite polymer particles and removing the polymer components.
  • the silica component is composed of a spherical or substantially spherical outer shell portion having a hollow structure, and an inner shell portion that is in contact with the outer shell portion and forms a convex portion by directing force toward the center.
  • the silica composite polymer particles are unevenly distributed in a state corresponding to the silica particles having the following.
  • the silica composite polymer particle of the present invention has a structure in which the silica component 2 is unevenly distributed on the surface and inside of the spherical or substantially spherical polymer component 1 as shown in the schematic diagram of FIG. Conceivable.
  • reference numeral 3 means silica composite polymer particles.
  • the shape and size of the protrusion can be adjusted as appropriate by changing the type and amount of the raw material.
  • the silica component is unevenly distributed in the silica composite polymer particles so that the opening ratio of the outer shell portion of the silica particles after firing is 0.5 to 1.
  • the opening ratio of the silica particles is the same as the opening ratio of the silica component corresponding to the outer shell part due to shrinkage of the silica component during firing or lack of a thin region at the end of the silica component.
  • the values may differ, the inventor has confirmed that the opening ratio of the silica component of the silica composite polymer particles and the opening ratio of the outer shell of the silica particles are substantially the same.
  • the opening ratio is a value calculated by dividing the area of the opening by the projected area of the silica particles.
  • a more preferable aperture ratio is 0.5 to 0.8.
  • hZD is the silica particles shown in the schematic cross-sectional view of FIG. 1 by burning the silica composite polymer particles to burn out the polymer components, and the h / D of the silica particles is used. is doing.
  • the h / D of the silica particles is strictly different from the hZD of the silica composite polymer particles due to shrinkage of the silica component during firing or lack of a thin region at the end of the silica component.
  • the inventor has confirmed that the hZD of the silica component corresponding to the outer shell portion and the hZD of the silica particles are substantially the same.
  • a more preferable hZD is 0.5 to 0.9.
  • silica composite polymer particles of the present invention will be described with reference to the production method thereof.
  • a mixture containing a polymerizable vinyl monomer, a polyalkoxysiloxane oligomer, and a polymerization initiator is added to an aqueous suspension containing colloidal silica, and the polymerizable vinyl monomer is subjected to aqueous suspension polymerization.
  • a polymer component is obtained.
  • the polymerizable vinyl monomer that can be used in the present invention is not particularly limited.
  • Acrylic acid or methacrylic acid such as acrylonitrile, methacrylic acid-tolyl, acrylamide, methacrylamide, 2-hydroxychetyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate
  • acid derivatives Acrylic acid, methacrylic acid, maleic acid, fumaric acid and the like can also be used. Further, two or more of these may be used in combination.
  • hydrogen atoms in these monomers may be substituted with a halogen atom such as a fluorine atom. Examples of the substituted monomer include trifluoromethyl methacrylate.
  • butyl ethers such as butyl methyl ether, butyl ether, butyl isobutyl ether, vinyl ketones such as butyl methyl ketone, butyl hexyl ketone, and methyl isopropyl ketone, ⁇ -vinyl pyrrole, ⁇ ⁇ -butyl carbazole ⁇ -Bule indole, ⁇ -Bull pyrrolidone, etc.
  • ⁇ -Bull compounds, burnaphthalene salts, etc. may be used alone or in combination within a range that does not impede the effects of the present invention.
  • styrene or methyl methacrylate which is inexpensive in terms of cost, is preferable.
  • the polymer component is crosslinked with a monomer having two or more functional groups such as ethylene glycol dimetatalylate, polyethylene glycol dimethacrylate, and dibutenebenzene. May be.
  • the polyalkoxysiloxane oligomer which is a precursor of the silica component, is inactive (meaning that it does not copolymerize) to the polymerizable bur monomer, and has the structural formula shown below. Is preferred.
  • R may be the same or different.
  • oligomers such as polymethoxysiloxane, polyethoxysiloxane, polypropoxysiloxane, polybutoxysiloxane, and the like can be given.
  • polymethoxysiloxane oligomers and polybutoxysiloxane oligomers that are poorly water-soluble and have good phase separation from rosin are preferred.
  • Particularly preferred are a positive siloxane diol dimer and a positive siloxane siloxane oligomer having a weight average molecular weight of 300 to 3,000, and a girl with a weight of 300 to 2,000.
  • V is preferable because the deviation is difficult to form the silica composite polymer particles of the present invention!
  • the weight average molecular weight is measured under the following conditions using GPC.
  • TK GEL manufactured by Tosoh Corporation
  • n l-2
  • the water solubility becomes stronger due to hydrolysis of the functional group. For this reason, it is difficult and difficult for the monomer droplets to be stably present.
  • n is more preferably 3-20.
  • the addition amount of the polyalkoxysiloxane oligomer is preferably 10 to 500 parts by weight, more preferably 20 to 300 parts by weight, with respect to 100 parts by weight of the polymerizable butyl monomer. If it is less than 10 parts by weight or more than 500 parts by weight, it is not preferable because it is difficult to obtain a composite state of the present invention.
  • hydrolysable alkoxy metal compounds other than silicon-based compounds can be added to these polyalkoxysiloxane oligomers for the purpose of adding functions such as ultraviolet absorption.
  • a polymerization initiator is used for the polymerization of the polymerizable bur monomer.
  • the polymerization initiator include oil-soluble peroxide polymerization initiators and azo polymerization initiators that are generally used in aqueous suspension polymerization. Specific examples include benzoyl peroxide, lauroyl peroxide, otatanyl peroxide, orthochloroperoxide benzoyl, orthomethoxyperoxide benzoyl, methyl ethyl ketone peroxide, diisopropyl peroxide dicarbonate, cumene hydride peroxide. Peroxide-based polymerization initiators such as cyclohexanone peroxide, t-butyl hydride peroxide, and diisopropylbenzene hydroxide.
  • 2,2,1-azobisisobutyronitrile 2,2,1-azobis (2,4 dimethylvaleronitrile), 2,2, -azobis (2,3 dimethylbutyrate-tolyl), 2,2, -azobis (2-methylbutyral-tolyl), 2,2, -azobis (2,3,3 trimethylbutyral-tolyl), 2,2, -azobis (2-isopropylbutyral-tolyl), 1,1'-azobis (Cyclohexane 1-carbo-tolyl), 2, 2, -azobis (4-methoxy-2,4 dimethylvale-tolyl, (2-force rumomois) isobuty-mouth-tolyl, 4, 4'-azobis (4 cyanovaleric acid), azo-2 initiators such as dimethyl-2,2, monoazobisisobutyrate.
  • the polymerization initiator is preferably used in an amount of 0.01 to 10 parts by weight, more preferably 0.1 to 5.0 parts by weight, based on 100 parts by weight of the polymerizable vinyl monomer. If the polymerization initiator is less than 0.01 parts by weight, the function of initiating the polymerization is difficult to achieve, and if it is used in excess of 10 parts by weight, it is not preferable because it is not economical.
  • a metal oxide pigment such as titanium oxide, zinc oxide, magnesium oxide, chromium oxide, zirconium oxide or the like may be used.
  • the polymerizable bulle monomer, polyalkoxysiloxane oligomer, polymerization initiator, and other components are uniformly mixed by a known method to form a mixture.
  • examples of the aqueous medium for aqueous suspension polymerization of the mixture include water or a mixed medium of water and a water-soluble solvent such as alcohol (for example, methanol, ethanol).
  • the amount of the aqueous medium used is usually 100 to 1000 parts by weight with respect to a total of 100 parts by weight of the polymerizable vinyl monomer and the polyalkoxysiloxane oligomer in order to stabilize the suspension polymerized particles.
  • water-soluble polymerization inhibitors such as nitrites, sulfites, hydroquinones, ascorbic acids, water-soluble vitamin Bs, citrate, and polyphenols are used to suppress the generation of emulsified particles in water.
  • water-soluble polymerization inhibitors such as nitrites, sulfites, hydroquinones, ascorbic acids, water-soluble vitamin Bs, citrate, and polyphenols are used to suppress the generation of emulsified particles in water.
  • silica composite polymer particles having a structure in which the silica component is unevenly distributed on the surface and inside of the spherical or substantially spherical polymer component are obtained by using aqueous colloidal silica having a specific average particle size. It is done.
  • Aqueous colloidal silica having an average particle size of 90 nm or less is used. When it is larger than 90 nm, it is difficult to obtain silica composite polymer particles having a structure in which the silica component is unevenly distributed on the surface and inside of the polymer component. Further, it is preferable that the average particle size is as small as possible, and the more preferable average particle size is 0.1 to 70 nm.
  • the average particle diameter of the aqueous colloidal silica is a specific surface area diameter obtained by measurement by a nitrogen adsorption method (BET method).
  • aqueous colloidal silica examples include aqueous colloidal silica derived from precipitated silica powder, vapor phase silica powder, and the like, and stable dispersion of silica powder to the primary particle level in water. Dispersed aqueous colloidal silica can be used. Of these, the latter is preferred. Since aqueous colloidal silica uses an aqueous medium for the production of silica composite polymer particles, the dispersion stability of colloidal silica force can be improved. Aqueous colloidal silica is generally commercially available, and it is preferable to use an easily dispersed 5 to 50% by weight dispersed in water. The aqueous colloidal silica is preferably contained in the aqueous suspension at a concentration of 0.5 to 20% by weight.
  • colloidal silica sol-like organosilica in which colloidal silica is dispersed in an organic solvent is also known.
  • the inventors of the present invention have confirmed that organo-silica composite polymer particles having a special shape of the present invention cannot be obtained with organosilica. This means that in order to obtain the silica composite polymer particles of the present invention, it is important to select the kind of colloidal silica, not to use any kind.
  • a suspension stabilizer may be added as necessary.
  • phosphates such as calcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate
  • pyrophosphates such as calcium pyrophosphate, magnesium magnesium phosphate, aluminum pyrophosphate, zinc pyrophosphate, calcium carbonate, magnesium carbonate, water
  • dispersion stabilizers of poorly water-soluble inorganic compounds such as calcium oxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, and barium sulfate.
  • tribasic calcium phosphate is preferred because magnesium pyrophosphate and calcium pyrophosphate produced by the metathesis method can stably obtain the polymer component.
  • the suspension stabilizer is used in combination with a surfactant such as a ionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant. It is also possible.
  • a surfactant such as a ionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant. It is also possible.
  • surfactant surfactant examples include fatty acid oils such as sodium oleate and castor oil, alkyl sulfate esters such as sodium lauryl sulfate and ammonium lauryl sulfate, and sodium dodecylbenzenesulfonate.
  • nonionic surfactant examples include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenol ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxysorbitan fatty acid ester, and polyoxyethylene.
  • examples include alkylamines, glycerin fatty acid esters, and oxyethyleneoxypropylene block polymers.
  • Examples of the cationic surfactant include alkylamine salts such as laurylamine acetate and stearylamine acetate, and quaternary ammonium salts such as lauryltrimethylammonium chloride.
  • zwitterionic surfactant examples include lauryl dimethylamine oxide, phosphate ester-based or phosphite-based surfactant.
  • suspension stabilizers and surfactants may be used alone or in combination of two or more.
  • the stabilizer is used by appropriately selecting and using the stabilizer.
  • the addition amount of the suspension stabilizer is 0.5 to 15 parts by weight with respect to 100 parts by weight of the polymerizable beil monomer, and the addition amount of the surfactant is with respect to 100 parts by weight of the aqueous medium. 0.001 to 0.1 part by weight.
  • the mixture is added to the aqueous medium thus prepared to perform aqueous suspension polymerization.
  • a dispersion method of the mixture for example, a method in which the mixture is directly added to the aqueous medium and dispersed in the aqueous medium as monomer droplets by stirring force of a propeller blade or the like, dispersion using a high shear force constituted by a rotor and a stator force And a method of dispersing using a homomixer or an ultrasonic disperser.
  • the mixture is put into an aqueous medium through a high-pressure disperser or MPG (microporous glass) porous film that uses the collision force between monomer droplets such as microfluidizer and nanomizer and the collision force against the machine wall.
  • MPG microporous glass
  • suspension polymerization is initiated by heating the aqueous suspension in which the mixture is dispersed as spherical monomer droplets. During the polymerization reaction, it is preferred to stir the aqueous suspension. You can go loose.
  • the polymerization temperature is preferably about 30 to about LOO ° C, and more preferably about 40 to 80 ° C.
  • the time for maintaining this polymerization temperature is preferably about 0.1 to 20 hours.
  • the polymerizable butyl monomer and the polyalkoxysiloxane oligomer do not volatilize. It is preferable to polymerize under pressure or pressure using a pressure-resistant polymerization facility such as an autoclave.
  • a silica component is formed by condensing a polyalkoxysiloxane oligomer, whereby the silica composite polymer particle of the present invention containing a polymer component and a silica component can be obtained.
  • the condensation method of the polyalkoxysiloxane oligomer include dehydration condensation using an acid catalyst or a base catalyst.
  • the acid catalyst and the base catalyst hydrochloric acid, sulfuric acid, nitric acid, ammonia, sodium hydroxide, potassium hydroxide, ammonium nitrate, sodium pyrophosphate and the like can be used.
  • the addition amount of the catalyst is preferably 0.01 to 30 parts by weight with respect to 100 parts by weight of the polyalkoxysiloxane oligomer. More preferably, it is 1 to 15 parts by weight.
  • the silica composite polymer particles are separated as a hydrous cake by a method such as suction filtration, centrifugal dehydration, centrifugal separation, and pressure dehydration, and the obtained hydrous cake is washed with water and dried. Silica composite polymer particles can be obtained.
  • the size and shape of the silica composite polymer particles of the present invention are not particularly limited. According to the manufacturing method of the above-mentioned silica composite polymer particles, it is possible to obtain particles having an average particle diameter of 1 to: LOO m.
  • the adjustment of the average particle diameter of the particles is to adjust the mixing conditions of the mixture and water, the addition amount of other suspension stabilizers, surfactants, and the like, and the stirring conditions and dispersion conditions of the agitator. It is possible.
  • the silica composite polymer particles of the present invention preferably contain 10 to 500 parts by weight of the silica component and more preferably 20 to 300 parts by weight with respect to 100 parts by weight of the polymer component.
  • the silica composite polymer particles of the present invention preferably have a luminous intensity of 70 or more when the peak luminous intensity in the regular reflection direction is 100 at a reflection angle of 0 ° with respect to 45 ° incident light with a three-dimensional photometer. . This luminous intensity indicates that the silica composite polymer particles of the present invention are excellent in light diffusibility, and light is diffused in a wider direction than just suppressing regular reflection light.
  • the luminous intensity is 70 or more
  • the use of silica composite polymer particles in the light diffusion plate can be expected to have an effect of uniformly diffusing incident light with sufficient light source power.
  • a soft focus effect can be expected, which is not possible with conventional particles. If it is less than 70, the reflection of light in the specular direction is strong and the diffusion is insufficient, and when it is added to cosmetics, a sufficient soft focus effect cannot be expected.
  • the luminous intensity is 75 ⁇ : L00.
  • the silica composite polymer particles of the present invention can be suitably used for applications where light diffusion is desired. Examples of such applications include light diffusion plates, cosmetics, paints, and the like.
  • the light diffusing plate 4 is composed of a transparent substrate resin 5 and silica composite polymer particles (light diffusing particles) 6 blended in the resin 5.
  • the light diffusing particles mean particles that can improve the light diffusibility as compared with the non-blended resin by blending with the transparent base resin.
  • the transparent base resin and silica composite polymer particles have a refractive index difference of 0.01 to 0.15 between the transparent base resin and the polymer particles in the silica composite polymer particles. It is preferable that the material strength be. When the difference in refractive index is less than 0.01, it is not preferable because excellent light diffusibility is hardly obtained. When it is larger than 0.15, it is difficult to obtain a light diffusing plate having a good balance between light diffusibility and light transmittance, which is preferable. More preferably, the refractive index difference is from 0.015 to 0.145.
  • silica composite polymer particles have the above-described structure, more complex light reflection and refraction occur than in the case of coated polymer particles in which the surface of inorganic particles or polymer particles is coated with silica or the like. The inventor has found that diffusibility can be expressed.
  • the mixing ratio of the silica composite polymer particles in the light diffusion plate of the present invention is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the transparent substrate resin. If particles having such a range and the silica component unevenly distributed in a specific shape as described above are used, a light diffusing plate having more excellent light diffusibility and less decrease in light transmittance can be obtained more reliably. . In addition A more preferable blending ratio is 0.3 to 15 parts by weight, and a still more preferable blending ratio is 0.5 to 10 parts by weight.
  • silica component in the silica composite polymer particles is 0.
  • the light diffusing plate It is preferable to be contained in the range of 01 to 15 parts by weight.
  • the silica component is included in this range and the silica component is unevenly distributed in the particles in a unique shape as described above, both light diffusibility and light transmittance can be achieved at a high level.
  • a more preferable content of the silica component is 0.1 to 5 parts by weight.
  • the content of the silica component means a value that also estimates the amount of the polyalkoxysiloxane oligomer used as a raw material.
  • the light diffusing plate usually comprises a light emitting surface, an opposite surface facing the light emitting surface, and a side surface defined by the light emitting surface and the opposite surface.
  • a light source for causing light to enter the light diffusing plate is disposed on the back surface of, for example, a luminaire or a liquid crystal display.
  • the wavelength of light diffused in the light diffusion plate may be shifted in the visible light region, the infrared region, and the ultraviolet region.
  • U which preferably includes at least visible light region.
  • the shape of the light diffusing plate is not particularly limited, and can be appropriately determined according to the intended use.
  • examples of the shape of the light emitting surface include a rectangle, a square, a polygon, a circle, and an ellipse.
  • the length of the side surface perpendicular to the light emitting surface is preferably 1: 1: 500 to 1: 4 with respect to the maximum length of the light emitting surface. More specifically, the maximum length of the light emitting surface is preferably 2 to 150 cm, preferably having a side length of 1 to 5 mm.
  • the light diffusing plate of the present invention is usually formed into a desired shape by extrusion molding, injection molding or the like from a kneaded product obtained by melt-kneading silica composite polymer particles and transparent substrate resin. Can be obtained.
  • the silica composite polymer particles have good dispersibility with respect to the transparent base resin, they can be uniformly mixed without particularly setting the kneading conditions severely.
  • thermoplastic resin can be usually used for the transparent substrate resin constituting the light diffusion plate.
  • transparent includes translucent. Further, the term “transparent” means that it is transparent to light having a desired wavelength and does not necessarily need to be transparent to light having all wavelengths.
  • thermoplastic resin examples include (meth) acrylic resin and alkyl (meth) acrylate.
  • examples include styrene copolymer resin, polycarbonate resin, polyester resin, polyethylene resin, polypropylene resin, and polystyrene resin.
  • the above-mentioned rosins may be used alone or in combination of two or more.
  • (Meth) acrylic means methacrylic or acrylic.
  • (meth) acrylic resin, (meth) acrylic acid-styrene copolymer resin, polycarbonate resin, polyester resin, and polystyrene resin have excellent transparency! / So I like it! /.
  • the size and shape of the silica composite polymer particles used for the light diffusion plate are not particularly limited.
  • silica composite polymer particles having an average particle size of 1 to: LOO m can be used.
  • the light diffusing plate of the present invention has a total light transmittance of 55% or more and is measured by an automatic goniophotometer to change the angle of the peak value on the incident optical axis of the light from the optical axis.
  • the angle at which 50% of the peak value is obtained can be 40 degrees or more. This angle indicates that the light diffusion plate of the present invention is excellent in light diffusibility. In the case of 40 degrees or more, even if it is used in an apparatus that has been enlarged recently such as a liquid crystal display, an image of a fluorescent lamp or a cold cathode tube as a light source is not visually observed, and a uniform light amount can be provided as a whole.
  • a liquid crystal display device provided with the light diffusing plate is provided.
  • the configuration of the liquid crystal display device is not particularly limited as long as it includes the light diffusion plate.
  • a liquid crystal display device is disposed between a liquid crystal display panel 10 having a display surface and a back surface, a light source 9 disposed on the back surface side of the panel, and the liquid crystal display panel and the light source. And at least a light diffusing plate 4.
  • This arrangement of light sources is called a direct type backlight arrangement.
  • the liquid crystal display panel has a configuration in which a liquid crystal layer 13 is sandwiched between a pair of substrates (11, 12). On the liquid crystal layer side of the substrate, electrodes (14, 15) and alignment films (16, 17) covering the electrodes are provided.
  • the electrode may include a thin film transistor.
  • the liquid crystal display panel may include a polarizing sheet, an antireflection sheet 18 and the like.
  • a prism sheet or the like may be disposed on the light emitting surface of the light diffusion plate on the liquid crystal panel side. Further, a reflective sheet may be disposed on the back surface of the light source.
  • silica composite polymer particles of the present invention may be used as a raw material for cosmetics and paints.
  • the average particle size is preferably 3 to 50; If it exceeds 50 m, the feeling of use may be poor. Particularly preferred is about 3 to 20 ⁇ m, which makes the feel smoother.
  • Specific cosmetics to which the silica composite polymer particles of the present invention are blended include solid cosmetics such as white! / Foam and foundation, powdered cosmetics such as baby powder and body powder, and cosmetics. Examples thereof include liquid cosmetics such as water, emulsion, cream, body lotion and the like.
  • the blending ratio in these cosmetics varies depending on the type of cosmetic, and in the case of solid cosmetics such as foundations, 1 to 20% by weight is preferred, and 3 to 15% by weight is particularly preferred. In the case of powdery cosmetics such as baby powder and body powder, 1 to 20% by weight is preferred, and 3 to 15% by weight is particularly preferred. Furthermore, in the case of liquid cosmetics such as skin lotions, emulsions, creams, liquid foundations, body lotions, and presci- sion broths, 1 to 15% by weight is preferred, and 3 to: LO weight%.
  • these cosmetics are colored with inorganic compounds such as my strength and tar, iron oxide, titanium oxide, ultramarine, bitumen, and carbon black in order to improve optical functions and touch.
  • Pigment or azo-based synthetic dyes can be added.
  • the liquid medium is not particularly limited, but water, alcohol, hydrocarbons, silicone oil, vegetable or animal oils and the like can also be used.
  • moisturizers, anti-inflammatory agents, whitening agents, UV care agents, bactericides, antiperspirants, refreshing agents, fragrances, etc. commonly used in cosmetics are added. Therefore, it is possible to add various functions.
  • the silica composite polymer particles can be suitably used as a raw material for liquid cosmetics.
  • Examples of the moisturizing material used in the present invention include polyethylene glycol, propylene glycol, glycerin, 1,3-butylene glycol, xylitol, sorbitol, maltitol, chondroitin sulfate, hyaluronic acid, mucoytin sulfate, caronic acid, atelocollagen, Cholesteryl mono- 12-hydroxystearate, sodium lactate, bile salt, d, 1-pyrrolidone carboxylate, short-chain soluble collagen, diglycerin (EO) PO adduct, Isaiyobara extract, sorghum extract , But not limited to these.
  • EO diglycerin
  • Oils used in liquid cosmetics include liquid fats such as apogado oil, camellia oil, turtle oil, macadamia nut oil, corn oil, mink oil, olive oil, rapeseed oil, egg yolk oil, sesame oil, Persic oil, wheat germ oil, southern power oil, castor oil, flax oil, safflower oil, cottonseed oil, eno oil, soybean oil, peanut oil, tea seed oil, oyster oil, rice bran oil, cinnagiri oil, Nippon Kiri Oil Jojoba oil, germ oil, triglycerin, glyceryl trioctanoate, glycerin triisopalmitate and the like.
  • liquid fats such as apogado oil, camellia oil, turtle oil, macadamia nut oil, corn oil, mink oil, olive oil, rapeseed oil, egg yolk oil, sesame oil, Persic oil, wheat germ oil, southern power oil, castor oil, flax
  • Solid fats and oils include cocoa butter, palm oil, horse fat, hardened pear oil, palm oil, beef tallow, sheep fat, hardened beef tallow, palm kernel oil, pork tallow, beef bone fat, owl kernel oil, hardened oil, beef leg fat , Mole, hardened castor oil, and the like.
  • waxes beeswax, power ndelilla wax, cotton wax, carnauba wax, beberry wax, ipotarou, whale wax, montan mouth, nuka wax, lanolin, kapok wax, lanolin acetate, liquid lanolin, sugarcane wax, lanolin fatty acid isopropyl, lauryl hexyl , Reduced lanolin, jojopa wax, hard lanolin, shellac wax, POE lanolin alcohol ether, POE lanolin alcohol acetate, POE cholesterol ether, lanolin fatty acid polyethylene glycol, POE hydrogenated carolanoline alcohol ether, and the like.
  • the hydrocarbon oil include liquid paraffin, ozokerite, squalene, pristane, paraffin, ceresin, petrolatum, microcrystalline wax, and the like. The oil components are not limited to these.
  • surfactants used in liquid cosmetics include sorbitan monooleate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquiole Ate, sorbitan trioleate, pentater 2-ethylhexylhexyl diglycerol sorbitan, tetra-2-ethylhexyl Sorbitan fatty acid esters such as diglycerol sorbitan formic acid, mono cottonseed oil fatty acid glycerin, monoergic acid glycerin, glyceryl sesquioleate, glyceryl monostearate, ⁇ , ⁇ , glyceryl monostearate, glyceryl monostearate, etc.
  • Glycerin polyglycerin fatty acids propylene glycol fatty acid esters such as propylene glycol monostearate, hydrogenated castor oil derivative, glycerin alkyl ether, ⁇ ⁇ sorbitan monooleate, ⁇ sorbitan monostearate, ⁇ ⁇ sorbitan tetraoleate, etc.
  • Sorbitan fatty acid esters ⁇ Sorbit monolaurate, ⁇ ⁇ Sorbit monooleate, ⁇ ⁇ Sorbit pentaoleate, ⁇ Sorbit monostearate ⁇ Sorbit fatty acid esters such as ⁇ ⁇ ⁇ , ⁇ Glycerin monostearate, ⁇ ⁇ Glycerol monoisostearate, ⁇ Glycerin fatty acid esters such as glycerol tristearate, ⁇ Monooleate, ⁇ Distearate, ⁇ Monodiolate, ethylene glycol stearate ⁇ fatty acid esters such as ⁇ lauryl ether, ⁇ oleyl ether, ⁇ stearyl ether, ⁇ behether ether, ⁇ 2-octyldodecyl ether, ⁇ cholestanol ether, etc.
  • PAB A aminobenzoic acid
  • PAB A PABA
  • Drugs used in liquid cosmetics include nonyl acid ⁇ renylamide, nicotinic acid benzyl ester, nicotinic acid butoxetyl ester, capsaicin, gingerone, strength tantalis tincture, ictamol, caffeine, tannic acid, a borneol, Tocopherol nicotinate, inositol hexa-cotinate, cyclandelate, cinnarizine, trazoline, acetylcholine, verapamil, cephalanthin, ⁇ oryzanol, clotrimazo mononor, pentachrono enoenore, trichrono enoenore force proate, tribromophenone Nore Strength Proate, Lauryl Triphenyl Phospho-umpromide, Dianthazole Hydrochloride, Paracetylaminophenol Rhodan, Methylosal, Undecy
  • colorants used in liquid cosmetics include inorganic white pigments such as titanium dioxide and zinc oxide, inorganic red pigments such as iron oxide (Bengara) iron titanate, y inorganic brown pigments such as iron monoxide, Inorganic yellow pigments such as yellow iron oxide and ocher, inorganic black pigments such as black iron oxide, carbon black and low-order titanium oxide, inorganic purple pigments such as mango violet and cobalt violet, acid chrome chrome, chromium hydroxide , Green pigments such as cobalt titanate, blue pigments such as ultramarine and bitumen, acid-titanium coated my strength, acid-titanium-coated oxide salt, bismuth, acid-titanium-coated talc, colored acid Titanium coated My power, oxy salt, bismuth, pearl pigment such as fish scale foil, metal powder pigment such as aluminum powder, kappa powder, red 201, red 202, red 204, red 205, red 220, red 226, red 22
  • salts used in the liquid cosmetics include natural salts such as rock salt, sea salt, and mineral spring water salt.
  • polymer compounds used in liquid cosmetics include gum arabic, gum tragacanth, galactan, guar gum, jarop gum, cara gum, carrageenan, pectin, agar, quince seed (malt mouth), alge colloid (cutlet extract), starch ( Rice, corn, potato, wheat), plant polymers such as glycyrrhizic acid, microbial polymers such as xanthan gum, dextran, succinoglucan, pullulan, animal polymers such as collagen, casein, albumin, gelatin, carboxy Starch-based polymers such as methyl starch and methylhydroxypropyl starch, methylcellulose, nitrocellulose, ethinoresenorelose, methinorehydroxypropinoresenorelose, hydroxyethinoresenorelose, Cellulose polymers such as sodium cellulose sulfate, hydroxypropyl cellulose, carboxymethyl cellulose sodium (CMC), crystalline cellulose, cellulose powder, alginic acid poly
  • fragrance component used in the liquid cosmetics animal-based, plant-based and mineral-based natural fragrances and synthetic fragrances can be used.
  • stabilizers used in liquid cosmetics include 1-hydroxyethane-1,1,1-diphosphonic acid, 1-hydroxyethane-1,1,1-diphosphonic acid tetrasodium salt, and edetic acid nitric acid.
  • buffer used in the liquid cosmetics examples include phosphates such as sodium phosphate and potassium phosphate, and organic acid salts such as sodium ascorbate and sodium benzoate. It is not limited.
  • the silica composite polymer particles of the present invention can be used as a raw material for a light guide plate.
  • the light guide plate includes a transparent substrate resin and silica composite polymer particles dispersed in the transparent substrate resin.
  • the transparent substrate resin and the silica composite polymer particles also have a material force that the difference in refractive index between the transparent substrate resin and the polymer particles in the silica composite polymer particles is less than 0.01. It is preferable. If the refractive index difference is 0.01 or more, the light diffusibility of the light guide plate is increased (the total light transmittance is decreased), and the luminance of the emitted light is decreased, which is not preferable. A more preferable refractive index difference is less than 0.006. The lower limit of the refractive index difference is 0.
  • the light guide plate containing the silica composite polymer particles is more uniform and higher than conventional light guide plates containing inorganic particles such as alumina and transparent resin particles! The inventor has found that the brightness can be expressed.
  • the blending ratio of the silica composite polymer particles is preferably 0.01 to 20 parts by weight with respect to 100 parts by weight of the transparent base resin. If the blending ratio is 0.01 parts by weight or more and the particles in which the silica component is unevenly distributed in a specific shape as described above are used, the effect of improving the luminance is satisfactorily exhibited. In addition, if particles with a compounding ratio of up to 20 parts by weight and the silica component are unevenly distributed in a unique shape as described above, the light incident from the light source is perpendicular to the light emitting surface in the vicinity of the light source. It is possible to reduce the rate of conversion toward the light, and to sufficiently reach the center of the light guide plate.
  • the emission distribution on the light emitting surface can be appropriately balanced.
  • Such an appropriate balance is desired especially for large liquid crystal display devices of 15 inches or more.
  • the mixing ratio is up to 20 parts by weight and the particles in which the silica component is unevenly distributed in a unique shape as described above, there is little change in the color tone in the vicinity of the light source of the light guide plate due to scattering. The color tone distribution of the emitted light at can be suppressed.
  • a more preferable blending ratio is 0.03 to 15 parts by weight.
  • the silica component in the silica composite polymer particles is preferably contained in the light guide plate in the range of 0.01 to 15 parts by weight with respect to 100 parts by weight of the light guide plate.
  • the silica component is included, and the silicic force component is unevenly distributed in the particles in a unique shape as described above, so that both light guiding properties and light diffusing properties can be achieved in both dimensions.
  • the light guide plate usually includes a light emitting surface, an opposite surface facing the light emitting surface, and a side surface defined by the light emitting surface and the opposite surface.
  • the light source for making light incident on the light guide plate is disposed on the side surface of, for example, a notebook computer liquid crystal display device or a thin liquid crystal TV.
  • the light emitting surface is a square and there are four corresponding side surfaces
  • the light source may be arranged on at least one side surface.
  • a pair of light sources may be disposed on two opposing side surfaces, or a light source may be disposed on all four side surfaces.
  • the wavelength of light guided and diffused in the light guide plate may be in the visible light region, the infrared region, or the ultraviolet region.
  • the liquid crystal display device preferably includes at least a visible light region.
  • the shape of the light guide plate is not particularly limited, and can be determined as appropriate according to the intended use.
  • the shape of the light emitting surface includes a rectangle, a square, a polygon, a circle, an ellipse, and the like.
  • the length of the side surface perpendicular to the light emitting surface is preferably 1: 500 to 1: 4 with respect to the maximum length of the light emitting surface. More specifically, it is preferable that the length of the side surface is 1 to 5 mm, and the maximum length of the light emitting surface is preferably 2 to 50 cm.
  • the light guide plate is usually obtained by molding a kneaded product obtained by melt-kneading silica composite polymer particles and transparent base resin resin into a desired shape by extrusion molding, injection molding or the like. Is possible.
  • the silica composite polymer particles have good dispersibility with respect to the transparent base resin, both can be mixed uniformly without particularly setting the kneading conditions severely.
  • the same kind of resin as that of the light diffusion plate can be used.
  • the light guide plate is usually used for a liquid crystal display device.
  • the configuration of the liquid crystal display device is not particularly limited as long as it includes the light guide plate.
  • the liquid crystal display device includes at least a liquid crystal display panel having a display surface and a back surface, a light guide plate disposed on the back surface side of the panel, and a light source that makes light incident on the side surface of the light guide plate.
  • the liquid crystal of the light guide plate A reflective sheet is provided on the opposite surface side of the display panel. This arrangement of light sources is generally referred to as an edge light type backlight arrangement.
  • the liquid crystal display panel has a configuration in which a liquid crystal layer is sandwiched between a pair of substrates. An electrode and an alignment film covering the electrode are provided on the liquid crystal layer side of the substrate.
  • the electrode may include a thin film transistor.
  • the liquid crystal display panel may include a polarizing sheet, an antireflection sheet, and the like.
  • a diffusion sheet, a prism sheet, or the like may be disposed on the light emitting surface of the light guide plate on the liquid crystal panel side.
  • a reflective sheet may be disposed on the back surface facing the light emitting surface.
  • the average particle diameter is a value measured with Multisizer II (manufactured by Beckman Coulter). Values are Reference MANUAL FOR TH published by Coulter Electronics Limited
  • Affix double-sided tape on black-and-white concealment test paper so that air does not enter. Apply to the adhesive side of the double-sided tape while spreading the particles uniformly with a cosmetic puff. Excess particles are thoroughly swept away using a brush to obtain a sample. Measure the reflected light intensity distribution at a reflection angle of 90 to 90 ° with an incident angle of 45 ° using a three-dimensional photometer (Go-off otometer GP-200, manufactured by Murakami Color Research Laboratory).
  • the light intensity at the reflection angle of 0 ° is calculated with the peak light intensity in the regular reflection direction (45 °) as 100. This means that the closer the luminous intensity is to 100, the luminous intensity of the reflected light does not change in the specular reflection direction or in the diffuse reflection direction, and the diffusibility of the reflected light is greater.
  • each sample plate is set in an optical microscope and observed using a sodium lamp as a light source, and it is confirmed that the outline of particles becomes invisible at a temperature where the refractive index of each liquid organic compound is known.
  • the refractive index of the liquid organic compound is used as the refractive index of the particles.
  • the above-mentioned publication includes, for example, “Frifurylamine (17.C)... Refractive index 1.4900,
  • the refractive index is rounded off to the fourth decimal place.
  • silica particles Particles having only the silica portion of the coalesced particles (hereinafter referred to as silica particles) are obtained.
  • the silica particles are gently taken out from the inside of the magnetic crucible with a spatula, and a photograph is taken with a scanning electron microscope (manufactured by JEOL Ltd .: GMS-820-A). Furthermore, 50 arbitrary images with silica particle openings on the top were selected from the photographed images, and each of them was manually selected using the trace measurement of the image analysis device (Image: Ana LITE). Specify the contour of the silica particle and the contour of the opening, and measure the projected area (S2) and the area of the opening (S 1).
  • the aperture ratio of each silica particle is obtained by the following formula.
  • the aperture ratio is an average value of 50 silica particles.
  • Opening ratio area of the silica particle opening (Sl) ⁇ projected area of the silica particle (S2)
  • the hZD value is measured by the following method when the diameter of the silica particles is D and the height of the silica particles is h.
  • hZD means an average value of 50 hZDs.
  • the total light transmittance of the molded product is measured according to JIS K7105 using a haze meter (“NDH-2000” manufactured by Nippon Denshoku).
  • the light diffusivity (D50) is obtained by the following procedure using an automatic goniophotometer (Goniophotometer GP-1R manufactured by Murakami Color Research Laboratory).
  • a straight ray of the light source power of the automatic goniophotometer is applied from the normal direction of the compact placed at a distance of 75 cm.
  • This intensity is converted into transmittance, and the transmittance is plotted on a graph corresponding to the angle from the normal direction. From this graph, find the angle at which the transmittance is 50% of the light transmittance in the normal direction (straight light transmittance). This angle is referred to as the degree of dispersion D50, and the unit is “degree”.
  • the larger D50 the better the diffusibility.
  • a dispersion medium (aqueous suspension) in which 250 g of 1750 g of water was mixed with SNOWTEX O-40 (Nissan Chemical Co., Ltd .: 40% by weight aqueous colloidal silica with an average particle size of 20 to 30 nm) as a colloidal silica was stirred. Placed in polymerization vessel with equipment.
  • This mixture was added to the above dispersion medium and stirred with a homomixer at 7, OOOrpm for about 10 minutes to finely disperse the mixture.
  • the reaction solution in the polymerization vessel is cooled to room temperature (about 30 ° C.) with stirring, and the surface of the polymer component is locally coated with the silica component derived from the polyalkoxysiloxane oligomer.
  • Composite polymer particles were obtained.
  • the target particles were taken out by dehydrating and drying the obtained particles.
  • the average particle diameter of the obtained silica composite polymer particles is 8.6 m.
  • Table 1 shows the measurement results of luminous intensity at a reflection angle of 0 °.
  • silica composite polymer particles The core was baked in an electric furnace at 500 ° C. to remove the polymer component, and silica particles were obtained. The shape of the obtained silica particles was observed with an electron micrograph. The silica particles had a shape with spherical protrusions (seeds) inside the hemisphere.
  • the silica component is unevenly distributed in the silica composite polymer particles, in other words, the first silica component corresponding to the outer shell portion of the silica particles located on the surface of the silica composite polymer particles; It was confirmed that it was composed of a second silica component corresponding to the inner shell portion of the silica particle that was in contact with this surface layer and directed toward the center of the silica composite polymer particle to form a convex portion.
  • An electron micrograph is shown in Fig. 5.
  • Table 1 also shows the types and amounts of the polymerizable vinyl monomers, polyalkoxysiloxane oligomers and colloidal silica used, the silica particle opening ratio, and hZD.
  • the amount of colloidal silica used means weight% with respect to the dispersion medium (the same applies hereinafter).
  • Figure 6 shows a graph of the reflectance distribution.
  • Table 1 also shows the types and amounts of the polymerizable vinyl monomers, polyalkoxysiloxane oligomers and colloidal silica used, the silica particle opening ratio and hZD.
  • Fig. 8 shows a graph of the reflected light intensity distribution.
  • Example 1 silica composite polymer particles were used in the same manner as in Example 1 except that Snowtex OL (manufactured by Nissan Chemical Co., Ltd .: 20% by weight aqueous colloidal silica solution having an average particle size of 40 to 50 nm) was used as colloidal silica. Got. The average particle size of the obtained particles was 8.2 m. Table 1 shows the measurement results of luminous intensity at a reflection angle of 0 °. When fired in the same manner as in Example 1, the shape of the silica particles has a shape with spherical protrusions inside the hemisphere bowl, and the silica component is unevenly distributed in the silica composite polymer particles as in Example 1. I was able to confirm that it was.
  • Snowtex OL manufactured by Nissan Chemical Co., Ltd .: 20% by weight aqueous colloidal silica solution having an average particle size of 40 to 50 nm
  • the average particle size of the obtained particles was 8.2 m.
  • Table 1 shows the measurement results of
  • Table 1 also shows the types and amounts of the polymerizable vinyl monomers, polyalkoxysiloxane oligomers and colloidal silica used, the silica particle opening ratio and hZD.
  • Example 1 the same as Example 1 except that MKC silicate MS5 1 (Mitsubishi Chemical Corporation: average molecular weight 500 to 700, R-catyl, n average is 5 to LO) was used as the polyalkoxysiloxane oligomer.
  • MKC silicate MS5 1 Mitsubishi Chemical Corporation: average molecular weight 500 to 700, R-catyl, n average is 5 to LO
  • silica composite polymer particles were obtained.
  • the average particle size of the obtained particles was 8.6 m.
  • Table 1 shows the measurement results of luminous intensity at a reflection angle of 0 °.
  • the shape of the silica particles had a spherical protrusion inside the hemisphere bowl, and as in Example 1, the silica component was contained in the silica composite polymer particles. I was able to confirm that it was unevenly distributed.
  • Table 1 also shows the types and amounts of the polymerizable vinyl monomers, polyalkoxysiloxane oligomers and colloidal silica used, the silica particle opening ratio and hZD.
  • Example 1 MKC silicate MS5 8B15 (manufactured by Mitsubishi Chemical Co., Ltd .: average molecular weight 1600 to 1800, R is butyl, n average is 11 to 13) is used as Example 1 except that polyalkoxysiloxane oligomer is used.
  • silica composite polymer particles were obtained. The average particle size of the obtained particles was 8.5 m.
  • Table 1 shows the measurement results of luminous intensity at a reflection angle of 0 °. When fired in the same manner as in Example 1, the shape of the silica particles is spherical inside the hemisphere bowl. In the same manner as in Example 1, it was confirmed that the silica component was unevenly distributed in the silica composite polymer particles.
  • Table 1 also shows the types and amounts of the polymerizable vinyl monomers, polyalkoxysiloxane oligomers and colloidal silica used, the silica particle opening ratio and hZD.
  • Silicic force composite polymer particles were obtained in the same manner as in Example 1 except that Quatron PL-3 (manufactured by Fuso-Igaku Kogyo Co., Ltd .: 20% by weight aqueous colloidal silica solution having an average particle size of 35 nm) was used as colloidal silica. It was. The average particle diameter of the obtained particles was 7.5 m.
  • Table 1 shows the measurement results of luminous intensity at a reflection angle of 0 °. When fired in the same manner as in Example 1, the shape of the silica particles has a shape with spherical protrusions inside the hemisphere bowl, and the silica component is unevenly distributed in the silica composite polymer particles as in Example 1. I was able to confirm. Fig. 10 shows an electron micrograph.
  • Table 1 also shows the types and amounts of the polymerizable vinyl monomers, polyalkoxysiloxane oligomers and colloidal silica used, the silica particle opening ratio and hZD.
  • Silicic force composite polymer particles were obtained in the same manner as in Example 1 except that Quatlon PL-7 (manufactured by Fuso Kai Sangaku Kogyo Co., Ltd .: 20% by weight aqueous colloidal silica solution having an average particle size of 70 nm) was used as colloidal silica. It was. The average particle diameter of the obtained particles was 8.9 m.
  • Table 1 shows the measurement results of luminous intensity at a reflection angle of 0 °. When fired in the same manner as in Example 1, the shape of the silica particles has a shape with spherical protrusions inside the hemisphere bowl, and the silica component is unevenly distributed in the silica composite polymer particles as in Example 1. I was able to confirm.
  • Table 1 also shows the types and amounts of the polymerizable vinyl monomers, polyalkoxysiloxane oligomers and colloidal silica used, the silica particle opening ratio and hZD.
  • Silica composite polymer particles were obtained in the same manner as in Example 1 except that 25 g of acetic acid was used instead of sodium pyrophosphate. The average particle diameter of the obtained particles was 8.3 m.
  • Table 1 shows the measurement results of luminous intensity at a reflection angle of 0 °. When fired in the same manner as in Example 1, the shape of the siri force particles is a shape having a spherical protrusion inside the hemisphere bowl. Similarly, it was confirmed that the silica component was unevenly distributed in the silica composite polymer particles. Table 1 also shows the types and amounts of the polymerizable vinyl monomers, polyalkoxysiloxane oligomers and colloidal silica used, the silica particle opening ratio and hZD.
  • Silica composite polymer particles were obtained in the same manner as in Example 1, except that 500 g of styrene and 500 g of MKC siliquette MS57 were used instead of 700 g of methyl methacrylate.
  • the average particle size of the obtained particles was 8.7 m.
  • Table 1 shows the measurement results of luminous intensity at a reflection angle of 0 °.
  • the shape of the silica particles has a shape with spherical protrusions inside the hemispherical bowl, and the silica component is unevenly distributed in the silica composite polymer particles as in Example 1. I was able to confirm that.
  • Table 1 also shows the types and amounts of the polymerizable vinyl monomers, polyalkoxysiloxane oligomers and colloidal silica used, the silica particle opening ratio and hZD.
  • Silica composite polymer particles were obtained in the same manner as in Example 1 except that Snowtex O-40 was used for 1OOOOg V for 1400 g of water.
  • the average particle size of the obtained particles was 8.
  • Table 1 shows the measurement results of luminous intensity at a reflection angle of 0 °.
  • the shape of the silica particles has a shape with spherical protrusions inside the hemispherical bowl, and as in Example 1, the silica component is contained in the silica composite polymer particles. It was confirmed that it was unevenly distributed.
  • Fig. 11 shows an electron micrograph.
  • Table 1 also shows the types and amounts of the polymerizable vinyl monomers, polyalkoxysiloxane oligomers and colloidal silica used, the silica particle opening ratio and hZD.
  • Silica composite polymer particles were obtained in the same manner as in Example 1 except that the rotation speed of the homomixer was lOOOOrpm. The average particle diameter of the obtained particles was 3 m.
  • Table 1 shows the measurement results of luminous intensity at a reflection angle of 0 °. When fired in the same manner as in Example 1, the shape of the silica particles has a shape with spherical protrusions inside the hemisphere bowl, and the silica component is unevenly distributed in the silica composite polymer particles as in Example 1. I was able to confirm.
  • Figure 12 shows an electron micrograph. Table 1 also shows the types and amounts of the polymerizable vinyl monomers, polyalkoxysiloxane oligomers and colloidal silica used, the silica particle opening ratio and hZD.
  • Silica composite polymer particles were obtained in the same manner as in Example 12, except that 490 g of styrene and 10 g of ethylene glycol dimetatalylate 2 were used as the polymerizable bull monomer.
  • the average particle size of the obtained particles was 4 ⁇ m.
  • Table 1 shows the measurement results of luminous intensity at a reflection angle of 0 °. When fired in the same manner as in Example 1, the shape of the silica particles has a spherical protrusion inside the hemisphere bowl, and the silica component is unevenly distributed in the silica composite polymer particles as in Example 1. I was able to confirm. An electron micrograph is shown in FIG. Table 1 also shows the types and amounts of the polymerizable vinyl monomers, polyalkoxysiloxane oligomers and colloidal silica used, the silica particle opening ratio and hZD.
  • Silica composite polymer particles were obtained in the same manner as in Example 12 except that MKC silicate MS51 was used as the polyalkoxysiloxane oligomer.
  • the average particle size of the obtained particles was 3.5 m.
  • Table 1 shows the measurement results of luminous intensity at a reflection angle of 0 °.
  • the shape of the silica particles has a shape with spherical protrusions inside the hemisphere bowl, and the silica component is unevenly distributed in the silica composite polymer particles as in Example 1. I was able to confirm. An electron micrograph is shown in FIG.
  • Table 1 also shows the types and amounts of the polymerizable vinyl monomers, polyalkoxysiloxane oligomers and colloidal silica used, the silica particle opening ratio and hZD.
  • Silica composite polymer particles were prepared in the same manner as in Example 12, except that 165 g of methyl methacrylate, 90 g of ethylene glycol dimethacrylate and 45 g of styrene were used as the polymerizable bull monomer, and 700 g of the polyalkoxysiloxane oligomer was used. Obtained. The average particle size of the obtained particles was 3.2 m. Table 1 shows the measurement results of luminous intensity at a reflection angle of 0 °. When calcined in the same manner as in Example 1, the shape of the silica particles has a shape with spherical protrusions inside the hemisphere bowl, and the silica component is unevenly distributed in the silica composite polymer particles as in Example 1.
  • Table 1 also shows the types and amounts of the polymerizable vinyl monomers, polyalkoxysiloxane oligomers and colloidal silica used, the silica particle opening ratio and hZD.
  • Silica composite polymer particles were obtained in the same manner as in Example 12 except that 300 g of trifluoroethyl methacrylate and 175 g of ethylene glycol dimethacrylate were used as the polymerizable butyl monomer.
  • the average particle size of the obtained particles was 3.
  • Table 1 shows the measurement results of luminous intensity at a reflection angle of 0 °.
  • the shape of the silica particles has a shape with spherical protrusions inside the hemisphere bowl, and the silica component is unevenly distributed in the silica composite polymer particles as in Example 1. I was able to confirm.
  • Table 1 also shows the types and amounts of the polymerizable vinyl monomers, polyalkoxysiloxane oligomers and colloidal silica used, the silica particle opening ratio and hZD.
  • Silica composite polymer particles were obtained in the same manner as in Example 12, except that 300 g of trifluoroethyl methacrylate and 700 g of MKC silicate were used as the polymerizable butyl monomer.
  • the average particle size of the obtained particles was 3.5 m.
  • Table 1 shows the measurement results of luminous intensity at a reflection angle of 0 °.
  • the shape of the silica particles had a spherical protrusion inside the hemisphere, and as in Example 1, the silica component was unevenly distributed in the silica composite polymer particles. I was able to confirm that.
  • Table 1 also shows the types and amounts of the polymerizable vinyl monomers, polyalkoxysiloxane oligomers and colloidal silica used, the silica particle opening ratio and hZD.
  • Example 2 The same method as in Example 1 except that ⁇ -methacryloxypropyltrimethoxysilane (manufactured by Toray Dow Coung Silicone Co., Ltd .: SZ6030) having a polymerizable property with a polymerizable bur monomer was used instead of the polyalkoxysiloxane oligomer.
  • ⁇ -methacryloxypropyltrimethoxysilane manufactured by Toray Dow Coung Silicone Co., Ltd .: SZ6030
  • the polymer component was uniformly dispersed in the particles.
  • Table 2 shows the measurement results of luminous intensity at a reflection angle of 0 °.
  • Table 2 also shows the types and amounts of polymerizable vinyl monomers, siloxanes and colloidal silica used. [0119] Comparative Example 2
  • Particles were obtained in the same manner as in Example 1 except that 950 g of methyl methacrylate and 50 g of MKC silicate MS57 were used (average particle size 7.8 m).
  • Table 2 shows the types and amounts of the polymerizable vinyl monomers, siloxanes and colloidal silica used.
  • Particles were obtained in the same manner as in Example 1 except that 50 g of methyl methacrylate and 950 g of MKC silicate MS57 were used. The obtained particles were not spherical but had an irregular shape. When calcined in the same manner as in Example 1, there was no evidence that the silica component was unevenly distributed in the particles.
  • Table 2 shows the types and amounts of the polymerizable vinyl monomers, siloxanes and colloidal silica used.
  • Particles were obtained in the same manner as in Example 1 except that Snowtex MP1040 (manufactured by Nissan Chemical Co., Ltd .: 40 wt% aqueous colloidal silica solution having an average particle size of lOOnm) was used as colloidal silica (average particle size 20. Reflection angle).
  • Table 2 shows the measurement results of luminous intensity at 0 °.
  • Table 2 also shows the types and amounts of polymerizable vinyl monomers, siloxanes and colloidal silica used, the silica particle opening ratio and hZD.
  • Figure 17 shows the reflected light intensity distribution.
  • Hybridizer manufactured by Nara Machinery Co., Ltd. 21 g of acrylic resin particles with an average particle diameter of 8 ⁇ m (MB-8, manufactured by Sekisui Plastics Co., Ltd.) and 9 g of Aerosil R972 (manufactured by Nippon Aerosil Co., Ltd., average particle diameter of 16 nm) And processed at 50 ° C for 5 minutes at 14000 rpm to obtain composite polymer particles whose surface was coated with silica particles (average particle size 8.). The results are shown in Table 2.
  • a dispersion medium in which 50 g of magnesium pyrophosphate by metathesis method is mixed with 2000 g of water as a suspension stabilizer is placed in a polymerization vessel having a stirrer, 0.4 g of sodium lauryl sulfate as a surfactant, and Sodium nitrate (0.2 g) was dissolved in the dispersion medium.
  • This mixture was added to the above dispersion medium and stirred with a homomixer at 7, OOOrpm for about 10 minutes to finely disperse the mixture.
  • Table 2 also shows the types and amounts of polymerizable vinyl monomers and siloxanes used, the silica particle opening ratio, and hZD. Furthermore, a graph of the reflected light intensity distribution is shown in FIG.
  • Particles were obtained in the same manner as in Example 5 except that 125 g of methyl methacrylate and 875 g of MKC silicate MS57 were used. The obtained particles were not spherical but had an irregular shape. Fruit When calcined in the same manner as in Example 1, no evidence of the silica component being unevenly distributed in the particles was found.
  • Table 2 shows the types and amounts of the polymerizable vinyl monomers, siloxanes and colloidal silica used.
  • Particles were prepared in the same manner as in Comparative Example 6 except that 560 g of methyl methacrylate and 240 g of ethylene glycol dimetatalylate were used as the monofunctional polymerizable bule monomer and the rotation speed of the homomixer was changed to lOOOOrpm.
  • Average particle diameter 4. Measurement results of luminous intensity at a reflection angle of 0 ° are shown in Table 2.
  • the shape of the silica particles is a bowl shape without protrusions inside. It can be seen that the silica component covered the polymer component.
  • Table 2 also shows the types and amounts of polymerizable vinyl monomers and siloxanes used, the silica particle opening ratio, and hZD.
  • Example 12 The same method as in Example 12 except that ⁇ -methacryloxypropyltrimethoxysilane (manufactured by Toray Dow Cowing Silicone Co., Ltd .: SZ6030) having a polymerizable property with a polymerizable bur monomer was used instead of the polyalkoxysiloxane oligomer.
  • the obtained particles had polymer components uniformly dispersed in the particles.
  • Table 2 shows the measurement results of luminous intensity at a reflection angle of 0 °.
  • Table 2 also shows the types and amounts of polymerizable vinyl monomers, siloxanes and colloidal silica used.
  • the inside of the polymerization vessel is heated to 65 ° C and subjected to suspension polymerization with stirring, and then cooled. It was.
  • the suspension was filtered, washed and dried to obtain particles having a true spherical polymer force (average particle diameter 5 ⁇ m).
  • Table 2 shows the measurement results of luminous intensity at 0 reflection angle.
  • Comparative Example 11 A silica composite polymer particle was obtained in the same manner as in Example 1 except that a 15% by weight silica solution with an average particle size of 15 nm was used (average particle size of 8. 2; ⁇ ⁇ ). Table 2 shows the measurement results of luminous intensity at a reflection angle of 0 °.
  • Table 2 also shows the types and amounts of polymerizable vinyl monomers, siloxanes and colloidal silica used, the silica particle opening ratio and hZD.
  • Table 2 also shows the types and amounts of polymerizable vinyl monomers, siloxanes and colloidal silica used, the silica particle opening ratio and hZD.
  • EG-ST manufactured by Nissan Chemical Industries, Ltd .: ethylene glycol solution having an average particle size of 15 nm and a silica content of 30% by weight
  • Example 2 In the same manner as in Example 1, except that MEK-ST (manufactured by Nissan Chemical Industries, Ltd .: methyl ethyl ketone solution having an average particle size of 15 nm and a silica content of 30% by weight) was used as colloidal silica.
  • MEK-ST manufactured by Nissan Chemical Industries, Ltd .: methyl ethyl ketone solution having an average particle size of 15 nm and a silica content of 30% by weight
  • the force that attempted to produce coalesced particles The force that could not provide particles that lacked the dispersion stability of the monomer mixture in the suspension.
  • Table 2 also shows the types and amounts of polymerizable vinyl monomers, siloxanes and colloidal silica used.
  • MMA means methyl methacrylate
  • ST means styrene
  • EGDMA means ethylene glycol dimetatalate
  • TFEMA trifluoroethyl methacrylate
  • the silica composite polymer particles of Examples 1 to 17 have a luminous intensity at a reflection angle of 0 °, compared to the silica composite polymer particles obtained by simply coating the silica component on the inorganic particles or the polymer particles. High power, I was able to help.
  • the luminous intensity at a reflection angle of 20 ° obtained from FIGS. 6, 8, 17 and 18 is 95.0 in Example 1, 98.7 in Example 2, 72.4 in Comparative Example 4, and 75 in Comparative Example 6. 8 was. From these results, Examples 1 and 2 have a small difference in luminous intensity at reflection angles of 20 ° and 0 °, while Comparative Examples 4 and 6 have a large difference. Therefore, it was found that the silica composite polymer particles of Examples 1 and 2 were less biased in the light diffusion direction than the particles of Comparative Examples 4 and 6.
  • a light diffusing plate was obtained in the same manner as in Example A except that the amount of the light diffusing particles added was 9 g with respect to 300 g of the alkyl (meth) acrylate-styrene copolymer resin. Further, in the same manner as in Example A, the total light transmittance and dispersion degree of this light diffusion plate were measured. The results are shown in Table 3 below.
  • a light diffusing plate was obtained in the same manner as in Example A except that 6 g of the light diffusing particles of Example 13 was used with respect to 300 g of methyl methacrylate resin (Sumitex EX A manufactured by Sumitomo Chemical Co., Ltd.). Further, in the same manner as in Example A, the total light transmittance and the degree of dispersion of this light diffusion plate were measured. The results are shown in Table 3 below.
  • a light diffusing plate was obtained in the same manner as in Example A except that the light diffusing particles of Example 14 were used. Further, in the same manner as in Example A, the total light transmittance and the degree of dispersion of this light diffusion plate were measured. The results are shown in Table 3 below.
  • a light diffusing plate was obtained in the same manner as in Example A except that the light diffusing particles of Example 15 were used. . Further, in the same manner as in Example A, the total light transmittance and the degree of dispersion of this light diffusion plate were measured. The results are shown in Table 3 below.
  • a light diffusing plate was obtained in the same manner as in Example A, except that 30 g of the light diffusing particles of Example 13 was used with respect to 300 g of polystyrene resin (Toyostyrene GP HRM40 manufactured by Toyo Styrene Co., Ltd.). Further, in the same manner as in Example A, the total light transmittance and the degree of dispersion of this light diffusion plate were measured. The results are shown in Table 3 below.
  • a light diffusing plate was obtained in the same manner as in Example A, except that 3 g of the light diffusing particles of Example 16 was used with respect to 300 g of polystyrene resin (Toyostyrene GP HRM40 manufactured by Toyo Styrene Co., Ltd.). Further, in the same manner as in Example A, the total light transmittance and the degree of dispersion of this light diffusion plate were measured. The results are shown in Table 3 below.
  • a light diffusing plate was obtained in the same manner as in Example A except that the light diffusing particles of Comparative Example 8 were used. Further, in the same manner as in Example A, the total light transmittance and the degree of dispersion of this light diffusion plate were measured. The results are shown in Table 3 below.
  • a light diffusing plate was obtained in the same manner as in Example A except that 9 g of the light diffusing particles of Comparative Example 9 were used. Further, in the same manner as in Example A, the total light transmittance and the degree of dispersion of this light diffusion plate were measured. The results are shown in Table 3 below.
  • a light diffusing plate was obtained in the same manner as in Example A, except that 30 g of the light diffusing particles of Comparative Example 10 was used with respect to 300 g of methyl methacrylate resin (Sumitex EX A manufactured by Sumitomo Chemical Co., Ltd.). Further, in the same manner as in Example A, the total light transmittance and the degree of dispersion of this light diffusion plate were measured. The results are shown in Table 3 below.
  • a light diffusing plate was obtained in the same manner as Example A, except that no light diffusing particles were blended and only methyl methacrylate resin (Sumitex EXA manufactured by Sumitomo Chemical Co., Ltd.) was used. The same as in Example A In the same manner, the total light transmittance and dispersion degree of this light diffusion plate were measured. The results are shown in Table 3 below [Table 3]
  • a light diffusing plate containing light diffusing particles having a specific shape has a high total light transmittance and degree of dispersion.
  • Example A and Comparative Examples A and B it can be seen that the dispersity can be further improved when the silica component has an inner shell portion.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Optical Elements Other Than Lenses (AREA)
  • Silicon Compounds (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

Particule de polymère combiné à de la silice comprenant un ingrédient polymère dérivé d'un monomère vinylique polymérisable et un ingrédient silice, l'ingrédient silice étant un produit de condensation dérivé d'un oligomère de type polyalcoxysiloxane inerte vis-à-vis du monomère vinylique polymérisable et l'ingrédient silice étant présent de façon non uniforme dans la particule de polymère combiné à de la silice de façon à ce que, lorsque la particule de polymère combiné à de la silice est brûlée pour enlever l'ingrédient polymère, alors la particule de silice résultante comprenne une partie enveloppe externe sphérique ou pratiquement sphérique qui a une structure creuse et une partie enveloppe interne qui est en contact avec la partie enveloppe externe et forme une partie saillante vers le centre.
PCT/JP2006/318971 2005-09-28 2006-09-25 Particule de polymère combiné à de la silice, procédé servant à produire celle-ci et utilisation de celle-ci WO2007037202A1 (fr)

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JP2011132087A (ja) * 2009-12-25 2011-07-07 Ube Nitto Kasei Co Ltd 中空無機粒子の製造方法、及び中空無機粒子
WO2012029643A1 (fr) * 2010-08-30 2012-03-08 東レ・ダウコーニング株式会社 Particules composites, leur procédé de fabrication et leur utilisation
JP2012211222A (ja) * 2011-03-30 2012-11-01 Aica Kogyo Co Ltd 複合微粒子
EP3124112A1 (fr) * 2015-07-30 2017-02-01 DWI - Leibniz-Institut für Interaktive Materialien e.V. Procédé pour l'encapsulation de substances dans des capsules à base de silice et produits ainsi obtenus
JPWO2016104055A1 (ja) * 2014-12-24 2017-04-27 Ｊｘエネルギー株式会社 透明フィルム、それを備えた透明スクリーン、およびそれを備えた画像投影装置
JP6185217B1 (ja) * 2016-02-29 2017-08-23 積水化成品工業株式会社 シリカ内包マイクロカプセル樹脂粒子、その製造方法及びその用途
WO2017150423A1 (fr) * 2016-02-29 2017-09-08 積水化成品工業株式会社 Particules de résine en microcapsule contenant de la silice, procédé de production de celles-ci, et application de celles-ci
RU2701030C1 (ru) * 2018-12-29 2019-09-24 Федеральное государственное бюджетное учреждение науки Институт элементоорганических соединений им. А.Н. Несмеянова Российской академии наук (ИНЭОС РАН) Способ получения полых кремнеземных нанокапсул
CN110603223A (zh) * 2017-05-31 2019-12-20 日挥触媒化成株式会社 中空粒子和化妆品
CN111100333A (zh) * 2019-12-24 2020-05-05 上海师范大学 中空PMMA@SiO2光扩散剂、PC光扩散板及制备方法

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JP2005240006A (ja) * 2004-01-29 2005-09-08 Sekisui Plastics Co Ltd 塗布用組成物、塗布物、光学部材及び液晶ディスプレイ

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JP2011132087A (ja) * 2009-12-25 2011-07-07 Ube Nitto Kasei Co Ltd 中空無機粒子の製造方法、及び中空無機粒子
WO2012029643A1 (fr) * 2010-08-30 2012-03-08 東レ・ダウコーニング株式会社 Particules composites, leur procédé de fabrication et leur utilisation
JPWO2012029643A1 (ja) * 2010-08-30 2013-10-28 東レ・ダウコーニング株式会社 複合粒子、その製造方法およびその用途
JP2012211222A (ja) * 2011-03-30 2012-11-01 Aica Kogyo Co Ltd 複合微粒子
JPWO2016104055A1 (ja) * 2014-12-24 2017-04-27 Ｊｘエネルギー株式会社 透明フィルム、それを備えた透明スクリーン、およびそれを備えた画像投影装置
JP2018526433A (ja) * 2015-07-30 2018-09-13 ディーダブリューアイ − ライプニッツ−インスティチュート フュア インタラクティブ マテリアーリエン エー．ファオ． シリカベースのカプセル内における物質のカプセル化方法、及びそれにより得られる製品
EP3124112A1 (fr) * 2015-07-30 2017-02-01 DWI - Leibniz-Institut für Interaktive Materialien e.V. Procédé pour l'encapsulation de substances dans des capsules à base de silice et produits ainsi obtenus
US10906018B2 (en) 2015-07-30 2021-02-02 Dwi - Leibniz-Institut Für Interaktive Materialien E.V. Method for the encapsulation of substances in silica-based capsules and the products obtained thereof
WO2017016636A1 (fr) 2015-07-30 2017-02-02 Dwi - Leibniz-Institut Für Interaktive Materialien E.V. Procédé d'encapsulation de substances dans des capsules à base de silice et produits ainsi obtenus
KR102090986B1 (ko) * 2016-02-29 2020-03-19 세키스이가세이힝코교가부시키가이샤 실리카 내포 마이크로 캡슐 수지 입자, 그 제조 방법 및 그 용도
JP6185217B1 (ja) * 2016-02-29 2017-08-23 積水化成品工業株式会社 シリカ内包マイクロカプセル樹脂粒子、その製造方法及びその用途
CN108697595A (zh) * 2016-02-29 2018-10-23 积水化成品工业株式会社 内含二氧化硅的微胶囊树脂颗粒、其生产方法及其用途
US11806414B2 (en) 2016-02-29 2023-11-07 Sekisui Plastics Co., Ltd. Silica-including microcapsule resin particles, method for producing same, and application thereof
CN108697595B (zh) * 2016-02-29 2022-01-14 积水化成品工业株式会社 内含二氧化硅的微胶囊树脂颗粒、其生产方法及其用途
WO2017150423A1 (fr) * 2016-02-29 2017-09-08 積水化成品工業株式会社 Particules de résine en microcapsule contenant de la silice, procédé de production de celles-ci, et application de celles-ci
US10952938B2 (en) 2016-02-29 2021-03-23 Sekisui Plastics Co., Ltd. Silica-including microcapsule resin particles, method for producing same, and application thereof
KR20180088424A (ko) * 2016-02-29 2018-08-03 세키스이가세이힝코교가부시키가이샤 실리카 내포 마이크로 캡슐 수지 입자, 그 제조 방법 및 그 용도
EP3632849A4 (fr) * 2017-05-31 2020-05-06 JGC Catalysts And Chemicals Ltd. Particules creuses et produit cosmétique
US11020326B2 (en) 2017-05-31 2021-06-01 Jgc Catalysts And Chemicals Ltd. Hollow particles and cosmetic
CN110603223A (zh) * 2017-05-31 2019-12-20 日挥触媒化成株式会社 中空粒子和化妆品
RU2701030C1 (ru) * 2018-12-29 2019-09-24 Федеральное государственное бюджетное учреждение науки Институт элементоорганических соединений им. А.Н. Несмеянова Российской академии наук (ИНЭОС РАН) Способ получения полых кремнеземных нанокапсул
CN111100333A (zh) * 2019-12-24 2020-05-05 上海师范大学 中空PMMA@SiO2光扩散剂、PC光扩散板及制备方法
CN111100333B (zh) * 2019-12-24 2022-01-14 上海师范大学 中空PMMA@SiO2光扩散剂、PC光扩散板及制备方法

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