WO2012161191A1 - Procédé de fabrication de microparticules de blocage du rayonnement thermique, modifiées en surface et dispersion de microparticules de blocage du rayonnement thermique obtenues par le procédé - Google Patents

Procédé de fabrication de microparticules de blocage du rayonnement thermique, modifiées en surface et dispersion de microparticules de blocage du rayonnement thermique obtenues par le procédé Download PDF

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Publication number
WO2012161191A1
WO2012161191A1 PCT/JP2012/063067 JP2012063067W WO2012161191A1 WO 2012161191 A1 WO2012161191 A1 WO 2012161191A1 JP 2012063067 W JP2012063067 W JP 2012063067W WO 2012161191 A1 WO2012161191 A1 WO 2012161191A1
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heat ray
fine particles
resin
ray shielding
shielding fine
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PCT/JP2012/063067
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English (en)
Japanese (ja)
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藤本　修
智成 進士
欣也 小山
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日産化学工業株式会社
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Priority to JP2013516381A priority Critical patent/JPWO2012161191A1/ja
Publication of WO2012161191A1 publication Critical patent/WO2012161191A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/04—Compounds of zinc
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • C09D7/48—Stabilisers against degradation by oxygen, light or heat
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/69—Particle size larger than 1000 nm
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/32—Thermal properties

Definitions

  • the present invention relates to a method for producing surface-modified heat ray shielding fine particles, a heat ray shielding fine particle dispersion obtained by the method, a coating composition using the heat ray shielding fine particles, and a covering member using the coating composition. Involved.
  • heat ray shielding properties such as tin-doped indium oxide, antimony-doped tin oxide, anhydrous zinc antimonate that can absorb sunlight, especially infrared rays It is known that an increase in indoor temperature can be suppressed by containing a metal oxide. Such a heat ray shielding film is required to have high transparency and low haze. In order to realize this, it is known to use fine particles of heat ray shielding metal oxide.
  • Patent Documents 1 and 2 have a drawback that the original heat ray shielding ability is lowered because the heat ray shielding fine particles are coated with an insulating inert substance having no heat ray shielding ability.
  • a method for obtaining heat ray-shielding fine particles having high light resistance without using an insulating inert substance that has high transparency and causes a reduction in heat ray shielding ability, and heat ray shielding obtained by the method It is to provide a dispersion containing conductive fine particles, a coating composition, and a covering member using the coating composition.
  • the present inventors have found that the cause of the surface activity of the heat ray shielding fine particles is that the crystal structure of the fine particle surface is destroyed and becomes amorphous when pulverized for fine particle formation. . Then, the present inventors have found a method for suppressing the activity of the surface of the fine particles without using an insulating inactive substance having no heat ray shielding ability, and thereby a method for maintaining the heat ray shielding ability and improving the light resistance.
  • the present invention has, as a first aspect, a method for producing surface-modified heat ray shielding fine particles comprising the following steps (a) and (b): (A) Step: Dry pulverization and / or wet pulverization of crystalline heat ray shielding fine particles having a primary particle size of 5 to 100 nm, (B) step: a step of hydrothermally treating at 200 to 320 ° C.
  • the heat ray shielding fine particles are tin-doped indium oxide, antimony-doped tin oxide, aluminum-doped zinc oxide, indium-doped zinc oxide, gallium-doped zinc oxide, tungsten oxide, lanthanum hexaboride, cerium hexaboride, anhydrous
  • the surface-modified heat ray shielding fine particles obtained by the method described in the first aspect or the second aspect are any one selected from the group consisting of water, an organic solvent, or a mixed solvent of a plasticizer and an organic solvent.
  • a heat ray shielding fine particle dispersion dispersed in one As a fourth aspect, a coating composition comprising surface-modified heat ray shielding fine particles obtained by the method described in the first aspect or the second aspect and a resin binder, As a fifth aspect, the resin binder is an acrylic resin, polyester resin, urethane resin, epoxy resin, polyvinyl alcohol resin, melamine resin, gelatin and gelatin derivative, cellulose and cellulose derivative, polyimide resin, phenol resin, organosilicon compound, urea.
  • the resin binder is an acrylic resin, polyester resin, urethane resin, epoxy resin, polyvinyl alcohol resin, melamine resin, gelatin and gelatin derivative, cellulose and cellulose derivative, polyimide resin, phenol resin, organosilicon compound, urea.
  • the coating composition according to the fourth aspect which is at least one selected from the group consisting of a resin and an allyl phthalate resin;
  • a member having a film formed on the surface of the base material with the coating composition according to the fourth aspect or the fifth aspect As a seventh aspect, the member according to the sixth aspect, wherein the base material is plastic, rubber, glass, metal, ceramics, paper, or cloth, It is.
  • crystalline heat ray shielding fine particles in which an amorphous portion is generated near the particle surface by dry pulverization and / or wet pulverization are surface-modified by specific hydrothermal treatment. Therefore, the heat ray shielding fine particles obtained by the production method of the present invention do not impair the original heat ray shielding ability.
  • the present invention performs surface modification treatment on the amorphous structure of the fine particle surface that causes the surface activity of the heat ray shielding fine particles, so that the ratio of the amorphous portion of the obtained fine particles is untreated. The surface activity of the fine particles can be suppressed.
  • the coating containing the fine particles and the member having the coating on the surface it is possible to suppress the decrease in light resistance due to the surface activity described above.
  • the light transmittance as an index of light resistance 3.0 eV It is possible to suppress a decrease in transmittance, deterioration of the binder component, and yellowing before and after the above-described high-energy rays are applied to the coating film.
  • the crystalline heat ray shielding fine particles used in the production method of the present invention are tin-doped indium oxide, antimony-doped tin oxide, aluminum-doped zinc oxide, indium-doped zinc oxide, and gallium-doped that can absorb sunlight, particularly infrared rays.
  • examples thereof include zinc oxide, tungsten oxide, lanthanum hexaboride, cerium hexaboride, anhydrous zinc antimonate, and copper sulfide.
  • Tin-doped indium oxide is produced, for example, by co-precipitating In and Sn hydroxides by adding an alkaline aqueous solution such as sodium hydroxide or potassium hydroxide to a mixed aqueous solution of InCl 3 and SnCl 4 and thermally decomposing the precipitate. Is done.
  • Antimony-doped tin oxide is prepared by dissolving tin chloride and antimony chloride in a mixture of one or more of alcohol, aqueous hydrochloric acid and acetone in heated water, as described in, for example, JP-A-56-156606. It is manufactured by adding the prepared solution and hydrolyzing.
  • Anhydrous zinc antimonate is prepared, for example, by mixing a zinc compound and colloidal antimony oxide so as to obtain a ZnO / Sb 2 O 5 molar ratio of 0.8 to 1.2 as described in JP-A-6-219743. , And is fired at 500 to 1100 ° C.
  • the crystalline heat ray-shielding fine particles used in the present invention are fine particles having a primary particle diameter of 5 to 100 nm.
  • a secondary particle of about 1 to 100 ⁇ m is used. Aggregates are formed.
  • the primary particle diameter is observed by a transmission electron microscope, and the particle diameter of the secondary aggregate is measured by, for example, a particle size distribution measuring apparatus using a centrifugal sedimentation method, a laser diffraction method, or a dynamic light scattering method. It is to be measured.
  • the film obtained by mixing such a secondary aggregate having a large particle size with a resin binder does not become transparent.
  • step (a) crystalline heat ray shielding fine particles having a primary particle diameter of 5 to 100 nm are dry-ground and / or wet-ground.
  • the agglomerated particle diameter of the secondary aggregate of heat ray shielding fine particles is pulverized to about 20 to 200 nm, so that the fine particles are mixed with an appropriate resin binder described later to form a transparent film. It becomes possible to make a highly resistant film.
  • dry pulverization method known methods such as an impact pulverizer such as a hammer mill and a pin mill, a grinding pulverizer such as a pulverizer, and an airflow pulverizer such as a jet mill can be used.
  • wet pulverization is more effective for miniaturization of the secondary aggregate.
  • a wet pulverization method after preparing a slurry by dispersing the crystalline heat ray shielding fine particles in a dispersion medium such as water, a known method such as a bead mill, a sand mill, an attritor, a disper, a ball mill, a paint shaker or the like is used. Can be used.
  • the slurry used for wet pulverization preferably has a solid content concentration of 1 to 80% by mass, and more preferably 10 to 60% by mass.
  • beads having a diameter of about 0.03 to 10 mm such as alumina, zirconia, and glass are preferably used.
  • the wet pulverization is performed for 1 to 1000 hours, and the secondary aggregate can be refined to an aggregate particle diameter of about 20 to 200 nm.
  • performing the wet pulverization after the dry pulverization is more effective for refining the secondary aggregate.
  • the above-mentioned dry and / or wet pulverized crystalline heat ray shielding fine particles having a primary particle diameter of 5 to 100 nm have an amorphous portion near the surface of the heat ray shielding fine particles due to the impact of this pulverization. Has occurred.
  • the volume content of the amorphous part varies depending on the pulverization method and pulverization conditions, but is generally 10 to 70% by volume.
  • the volume fraction of the amorphous part is calculated by the following method.
  • a crystalline portion that connects the crystal lattice image to the central portion of the fine particles and an amorphous portion that does not connect the crystal lattice image to the periphery thereof Is observed.
  • a circle-equivalent diameter Rc is calculated from the area of the crystalline portion, and a sphere-reduced volume Vc is obtained.
  • a circle-equivalent diameter R a + c is calculated in the same manner from the combined area of the crystalline part and the amorphous part, and a sphere-equivalent volume V (a + c) is obtained.
  • the volume fraction of the amorphous part is calculated as (V (a + c) ⁇ V c ) / V (a + c) ⁇ 100 (volume%).
  • the heat ray shielding fine particles pulverized in the step (a) are dispersed in water, followed by hydrothermal treatment by heating at 200 to 320 ° C.
  • hydrothermal treatment is that the crystalline heat ray shielding fine particles in which an amorphous part is formed in the vicinity of the particle surface remain in an aqueous dispersion, and the surface modification by recrystallization of the amorphous part is performed while maintaining the particle diameter. There is something you can do. This surface modification (recrystallization) can suppress the activity of the surface of the fine particles and improve the light resistance.
  • the aqueous dispersion of the heat ray shielding fine particles to be hydrothermally treated has a heat ray shielding fine particle content of 1% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, and 70% by mass or less. Preferably it is 50 mass% or less.
  • the hydrothermal treatment temperature is 200 to 320 ° C. When the temperature of the hydrothermal treatment is less than 200 ° C., crystallization of the amorphous part does not occur at all or hardly occurs, which is not preferable. In the hydrothermal treatment, the time maintained at 200 to 320 ° C. is 5 minutes to 100 hours.
  • the apparatus for performing the hydrothermal treatment is not particularly limited, as long as it has a container and a structure having pressure resistance in the presence of high-temperature and high-pressure hot water, and a container made of stainless steel, titanium, nickel alloy, iron or the like is preferable. Used.
  • the surface-modified heat ray-shielding fine particles obtained by the production method of the present invention are obtained in the form of an aqueous dispersion.
  • the dispersion of an organic solvent described later or a mixed solvent of a plasticizer and an organic solvent described later is used. It can also be in the form of a dispersion liquid.
  • the heat-ray shielding fine particles whose surface has been modified with an additive such as an alkali component, an acid component, or a surfactant can be stabilized as necessary.
  • additives are used in an addition amount of about 1.0 to 50% by mass with respect to the solid content of the heat ray shielding fine particles.
  • alkali component used as the additive examples include hydroxides of alkali metals such as lithium, sodium and potassium, hydroxides of alkaline earth metals such as calcium, magnesium and strontium, ammonia, ethylamine, n-propylamine, Fragrance of alkylamines such as isopropylamine, dipropylamine, diisopropylamine, dibutylamine, diisobutylamine, diamylamine, triethylamine, tripropylamine, tributylamine, triamylamine, n-octylamine, n-dodecylamine, and benzylamine Alkanolamines such as group amines, monoethanolamines and triethanolamines and quaternary ammonium hydroxides.
  • oxycarboxylic acids such as lactic acid, tartaric acid, malic acid, citric acid, glycolic acid, and mandelic acid
  • hydroxycarboxylic acids such as lactic acid, tartaric acid, malic acid, citric acid, glycolic acid, and mandelic acid
  • Formic acid, acetic acid, hydrochloric acid, Nitric acid, sulfuric acid and the like can also be used.
  • any of anionic, cationic and nonionic surfactants can be used, but nitrogen-containing polyoxyethylene derivatives having amino groups and anions having acid groups A surfactant is desirable.
  • the nitrogen-containing polyoxyethylene derivative having an amino group is not particularly limited.
  • Nimin (registered trademark) L-201, L-202, L-207, F-202, F manufactured by NOF Corporation may be used.
  • the acid group is not particularly limited, but those having a sulfone group, a carboxylic acid group, and a phosphoric acid group are preferable, and those having a phosphoric acid group are most preferable.
  • examples of the anionic surfactant having a phosphoric acid group include Disperbyk (registered trademark) -102, 103, 106, 110, 111, 142, 163, and 180 manufactured by Big Chemie Japan.
  • Examples of the organic solvent used in the heat ray shielding fine particle dispersion of the present invention include aliphatic hydrocarbons such as mineral spirits, aromatic hydrocarbons such as toluene and xylene, methanol, ethanol, 1-propanol, 2-propanol, Alcohols such as 1-butanol, 2-butanol and cyclohexanol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and isophorone, esters such as ethyl acetate, butyl acetate, isobutyl acetate and amyl acetate, ethyl cellosolve, Ether alcohols such as butyl cellosolve, carbitol, butyl carbitol, methoxypropanol, methoxybutanol, cellosolve acetate, butyl cellosolve acetate, carbitol acetate
  • an organic acid ester plasticizer is mentioned as a plasticizer used for the heat ray shielding fine particle dispersion of this invention.
  • the organic acid ester plasticizer is not particularly limited, but triethylene glycol di-2-ethylbutyrate, triethylene glycol di-2-ethylhexanoate, triethylene glycol dicaprylate, triethylene glycol di-n- Octanoate, triethylene glycol di-n-heptanoate, tetraethylene glycol di-n-heptanoate, dibutyl sebacate, dioctyl azelate, dibutyl carbitol adipate, ethylene glycol di-2-ethyl butyrate, 1,3-propylene glycol di -2-ethyl butyrate, 1,4-propylene glycol di-2-ethyl butyrate, 1,4-butylene glycol di-2-ethyl butyrate, 1,2-butylene glycol di-2-ethyl butyrate,
  • the aqueous dispersion of surface-modified heat ray shielding fine particles obtained by the present invention can be solvent-substituted by the above-mentioned organic solvent or a mixed solvent of a plasticizer and an organic solvent by a known solvent substitution method.
  • the content of the heat ray shielding fine particles is 1% by mass or more, preferably 10% by mass. % Or more, more preferably 20% by mass or more, and 70% by mass or less, preferably 50% by mass or less.
  • the present invention is also directed to a coating composition containing the above-mentioned surface-modified heat ray shielding fine particles and a resin binder.
  • the resin binder used here is not particularly limited to the description in the present specification, but acrylic resin, polyester resin, urethane resin, epoxy resin, polyvinyl alcohol resin, melamine resin, gelatin and gelatin derivative, cellulose and cellulose derivative, polyimide resin It is preferably at least one selected from the group consisting of a phenol resin, an organosilicon compound, a urea resin, and a diallyl phthalate resin.
  • acrylic resin examples include those having the following compounds (monomers) as constituent components, and these monomers can be used alone or in admixture of two or more. Moreover, it can be used in any state of a monomer, an oligomer and a polymer.
  • Trifluoroethyl acrylate Trifluoroethyl acrylate, trifluoromethyl acrylate, phenylglycidyl acrylate, hydroxyethyl (meth) acrylate, acryloylmorpholine, N-vinylpyrrolidone, N-vinyl- ⁇ -caprolactam, neopentyl glycol (meth) acrylate, 1,6- Hexanediol di (meth) acrylate, trimethylolpropane (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol (meth) acrylate, ethylene glycol Di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di
  • polyester resin examples include linear polyesters having a dicarboxylic acid component and a glycol component as constituent components.
  • dicarboxylic acid component and the glycol component are shown below. These can be used alone or in admixture of two or more.
  • Dicarboxylic acid component terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4-diphenyldicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, adipic acid, sebacic acid, phenylindanedicarboxylic acid and dimer Acid etc.
  • Glycol component ethylene glycol, 1,4-butanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, xylylene glycol, dimethylolpropionic acid, glycerin, Trimethylolpropane, poly (ethyleneoxy) glycol, poly (tetramethyleneoxy) glycol, alkylene oxide adduct of bisphenol A, alkylene oxide adduct of hydrogenated bisphenol A, and the like.
  • Examples of the urethane resin include those obtained by polyaddition reaction of a polyisocyanate and an active hydrogen-containing compound.
  • Examples of the polyisocyanate and the active hydrogen-containing compound are shown below. These can be used alone or in admixture of two or more.
  • Polyisocyanate ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), tolylene diisocyanate (TDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, Lysine diisocyanate, 2,6-diisocyanatomethyl caproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate , Isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene dii Socyanate, bis (2-isocyanato
  • Active hydrogen-containing compounds dihydric alcohol (ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, etc.), diol having a branched chain (Propylene glycol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,2-diethyl-1,3-propanediol, 1,2-, 1,3- or 2,3-butanediol, etc.) Diols having a cyclic group (1,4-bis (hydroxymethyl) cyclohexane, m- or p-xylylene glycol, etc.), dihydric phenols (bisphenol A, etc.), polyhydric alcohols (glycerin, trimethylolpropane, pentaerythritol) , Sorbitol, etc.), sugars and their derivatives
  • the epoxy resin examples include various liquid epoxy resins such as bisphenol A type, bisphenol F type, hydrogenated bisphenol A type, bisphenol AF type, phenol novolac type, and derivatives thereof, liquid epoxy resins derived from polyhydric alcohol and epichlorohydrin, and examples thereof include various glycidyl type liquid epoxy resins such as glycidylamine type, hydantoin type, aminophenol type, aniline type, and toluidine type, and derivatives thereof.
  • liquid epoxy resins such as bisphenol A type, bisphenol F type, hydrogenated bisphenol A type, bisphenol AF type, phenol novolac type, and derivatives thereof
  • liquid epoxy resins derived from polyhydric alcohol and epichlorohydrin examples include various glycidyl type liquid epoxy resins such as glycidylamine type, hydantoin type, aminophenol type, aniline type, and toluidine type, and derivatives thereof.
  • polyvinyl alcohol resin examples include those obtained by saponifying a polyvinyl ester polymer obtained by radical polymerization of a vinyl ester monomer such as vinyl acetate.
  • vinyl ester monomer examples include vinyl ester monomers: vinyl formate, vinyl acetate, vinyl propionate, vinyl valelate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl pivalate and vinyl versatate.
  • the polyvinyl ester polymer may be a copolymer obtained by copolymerizing a comonomer copolymerizable with the above vinyl ester monomers.
  • Examples of the comonomer include olefins such as ethylene, propylene, 1-butene, and isobutene, acrylic acid and salts thereof, methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, and n-acrylate.
  • olefins such as ethylene, propylene, 1-butene, and isobutene
  • acrylic acid and salts thereof methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, and n-acrylate.
  • -Acrylic esters such as butyl, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, octadecyl acrylate, methacrylic acid and its salts, methyl methacrylate, ethyl methacrylate, methacryl Methacrylic acid esters such as n-propyl acid, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, acrylic Amide, hydroxyalkylamide, N-methylacrylamide, N-ethylacrylamide, N, N-dimethylacrylamide, diacetoneacrylamide, acrylamidepropanesulfonic acid and its salt,
  • melamine resin examples include methylated melamine resin, butylated melamine resin, and methylbutyl mixed melamine resin.
  • gelatin and gelatin derivatives examples include phthalated gelatin, succinated gelatin, trimellitated gelatin, pyromellitic gelatin, esterified gelatin, amidated gelatin, and formylated gelatin.
  • cellulose and cellulose derivatives include diacetyl cellulose, triacetyl cellulose, hydroxypropyl cellulose, triacetyl cellulose, diacetyl cellulose, acetyl cellulose, cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate phthalate, and cellulose acetate trimellitate. , And cellulose nitrate.
  • Component C an organosilicon compound represented by the general formula (I) or a hydrolysis-condensation product thereof.
  • R 2 represents an organic group selected from the group consisting of a group and a cyano group
  • R 2 represents an organic group selected from the group consisting of an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an acyl group and a phenyl group
  • b represents an integer of 0 or 1.
  • Component D an organosilicon compound represented by the general formula (II) or a hydrolysis-condensation product thereof.
  • ⁇ (OX) 3-a Si (R 4 ) ⁇ 2 Y (II) (In the formula, R 4 represents an organic group having 1 to 5 carbon atoms, X represents an alkyl group having 1 to 4 carbon atoms or an acyl group having 1 to 4 carbon atoms, and Y represents 2 to 2 carbon atoms) 20 represents an organic group, and a represents an integer of 0 or 1.)
  • organosilicon compound represented by the general formula (I) or a hydrolysis condensate thereof include the following. : Methyl silicate, ethyl silicate, n-propyl silicate, isopropyl silicate, n-butyl silicate, tetraacetoxysilane, methyltrimethoxysilane, methyltripropoxysilane, methyltriacetoxysilane, methyltributoxysilane, methyltripropoxysilane, methyl Triamyloxysilane, methyltriphenoxysilane, methyltribenzyloxysilane, methyltriphenethyloxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, ⁇ -glycidoxyethyltrimethoxysilane, ⁇ - Glycidoxyethyltriethoxysilane, ⁇ -glycidoxyethyltrime
  • organosilicon compound represented by the general formula (II) or a hydrolysis condensate thereof include the following. : Methylene bis (methyldimethoxysilane), ethylene bis (ethyldimethoxysilane), propylene bis (ethyldiethoxysilane), butylene bis (methyldiethoxysilane), etc., and their hydrolysis condensates.
  • the organosilicon compound of component C and component D or a hydrolysis-condensation product thereof can be used alone or in combination with component C or component D, respectively. It is also possible to use two or more C components and two or more D components. Hydrolysis condensation reaction of organosilicon compound of component C and / or component D is carried out by using an acid component such as hydrochloric acid aqueous solution, sulfuric acid aqueous solution, acetic acid aqueous solution or the like as a catalyst in organic silicon compound of C component and / or D component. It is carried out by adding about 0.1 to 10% by mass to the silicon compound and stirring.
  • an acid component such as hydrochloric acid aqueous solution, sulfuric acid aqueous solution, acetic acid aqueous solution or the like
  • organosilicon compound examples include modified silicone varnishes such as silicone varnish, silicone alkyd varnish, silicone epoxy varnish, silicone acrylic varnish, and silicone polyester varnish in addition to the silicon compounds mentioned as the component (C) and the component (D). Can be used. These can be used alone or in admixture of two or more.
  • diallyl phthalate resins examples include diallyl phthalate, diallyl isophthalate, and diallyl terephthalate.
  • a cationic, anionic or nonionic surfactant can be further added for the purpose of improving the dispersibility, storage stability and wettability of the coated substrate.
  • the mixing ratio of the surface-modified heat ray-shielding fine particles and the resin binder component is 99: 1 as a mass ratio of the solid content. ⁇ 1: 99.
  • the mass ratio of the solid content is preferably in the range of 95: 5 to 50:50.
  • the member of the present invention has a film formed by the coating composition on the surface of the substrate.
  • the member of the present invention can be obtained by applying the coating composition on a substrate and curing it to form a film.
  • the base material used for the member of the present invention is plastic, rubber, glass, metal, ceramics, paper, or cloth.
  • the method of applying the coating composition onto the substrate may be any known method, for example, bar coating method, reverse method, gravure printing method, micro gravure printing method, dipping method, spin coating method, spraying method. Law.
  • a hardening process can be performed by hot-air drying or active energy ray irradiation. When hot air drying is used, it is preferably performed in hot air at 70 to 200 ° C.
  • the thickness of the coating formed on the member of the present invention is not particularly limited, but is preferably about 0.1 to 10 ⁇ m.
  • the particle diameter (major axis) was 10 to 20 nm, and the specific surface area by the BET method was 57.0 m 2 / g.
  • the Sb 2 O 5 concentration became 13.3 mass%
  • basic zinc carbonate (manufactured by Sakai Chemical Industry Co., Ltd., 3ZnCO 3 .4Zn) (OH) 2 , containing 70% by mass in terms of ZnO) 16.9 kg was added and stirred for 6 hours to obtain a slurry.
  • This slurry contained 3.1% by mass in terms of ZnO and 12.7% by mass in terms of Sb 2 O 5 , respectively, and the molar ratio of ZnO / Sb 2 O 5 was 0.97.
  • This slurry was dried with a spray dryer to obtain a dry powder.
  • the result of X-ray diffraction measurement of this dried powder coincided with the peak of hydrous antimony pentoxide (Sb 2 O 5 / xH 2 O).
  • a mixed gas (0.47 as a partial pressure ratio of water vapor / nitrogen gas) obtained by charging 72 kg of this dry powder into a fluidized bed of 450 mm ⁇ and bubbling air through a warm bath at 85 ° C.
  • the reflectance of the obtained powder was measured from a wavelength of 250 nm to 2500 nm using a spectrophotometer using an integrating sphere (manufactured by Shimadzu Corporation, UV-3150). As a result, a decrease in reflectance was observed at 800 to 2500 nm. It was confirmed that it absorbs infrared light and has heat ray shielding properties.
  • Example 1 Grinding treatment of anhydrous zinc antimonate powder
  • the pH of the sol after cation / anion exchange was 3.1. 400 g of diisopropylamine was added to this aqueous sol, and this aqueous sol was concentrated to 258 kg using an ultrafiltration apparatus.
  • the obtained anhydrous zinc antimonate aqueous sol has a transparent deep blue color, specific gravity 1.353, pH 6.9, viscosity 2.8 mPa ⁇ s, conductivity 409 ⁇ S / cm, ZnSb 2 O 6 concentration 30.6% by mass. Met.
  • the particle size of anhydrous zinc antimonate contained in this sol is 10 to 20 nm in the primary particle size (major axis) observed with a transmission electron microscope (JEM-1010 manufactured by JEOL Ltd.), and the particle size of dynamic light scattering method
  • the particle diameter of the aggregate was 87 nm as measured by a distribution measuring device.
  • the specific surface area by BET method of this dried sol was 63.9 m 2 / g, and the particle diameter calculated from the specific surface area was 15 nm.
  • Example 1-1 Hydrothermal treatment of anhydrous zinc antimonate aqueous sol and preparation of dispersion
  • the anhydrous zinc antimonate aqueous sol obtained in Example 1 was diluted with pure water so that the ZnSb 2 O 6 concentration was 15% by mass, and this was diluted in a 3 liter autoclave container (manufactured by Pressure Glass Industrial Co., Ltd.). Then, the liquid temperature was raised to 200 ° C. over 2.0 hours, held at 200 ° C. for 5 hours, and then hydrothermally treated to cool to room temperature over 2 hours.
  • the obtained hydrothermally treated anhydrous zinc antimonate aqueous sol had a pH of 7.2, and the aggregate particle size was 80 nm as measured by a dynamic light scattering particle size distribution analyzer.
  • the aqueous solvent of the obtained hydrothermally treated anhydrous zinc antimonate aqueous sol was concentrated while blowing methanol vapor under normal pressure, and replaced with a methanol solvent.
  • the obtained methanol sol contains 60.5% by mass of ZnSb 2 O 6 , the pH of the solution in which water and the sol are mixed at 1: 1 (mass ratio) is 6.2, and the particle size distribution of dynamic light scattering method
  • the particle diameter of the aggregate was 81 nm as measured by a measuring machine.
  • Example 1-2 Production of coating composition and film having film made of the composition
  • KAYARAD registered trademark
  • DPHA manufactured by Nippon Kayaku Co., Ltd.
  • Irgacure Registered Trademark
  • a propylene glycol monomethyl ether 7.0 g mixed UV curable resin composition
  • a resin composition containing anhydrous zinc antimonate Got
  • the dispersion state of the obtained resin composition was good. This was applied to the upper surface of a PET film (Toyobo Co., Ltd. Cosmo Shine A4300, film thickness 125 ⁇ m). After coating using a 12 (thickness 27.4 ⁇ m) wire bar, ultraviolet rays were irradiated with an ultraviolet irradiator to obtain a PET film having a coating containing anhydrous zinc antimonate fine particles. The film thickness was 2 ⁇ m. The optical properties of the obtained coated PET film were measured using a spectral haze meter TC-H3DPK-MKII (manufactured by Tokyo Denshoku). As a result, the total light transmittance (Tt 0 ) was 86.1%. It was.
  • Example 1-3 Light resistance evaluation
  • the coated PET film obtained in Example 1-2 was subjected to a high-pressure mercury lamp (80 W / cm) containing high energy of 3.0 eV or more with a UV irradiation apparatus (Handy UV-800, Oak Manufacturing Co., Ltd.) for 10 hours. Irradiated.
  • a UV irradiation apparatus Haps UV-800, Oak Manufacturing Co., Ltd.
  • the total light transmittance (Tt) after irradiation was 83.0%.
  • the decrease rate (Tt 0 -Tt) / Tt 0 of the total light transmittance before and after UV irradiation was 3.6%.
  • Example 2-1 Hydrothermal treatment of anhydrous zinc antimonate aqueous sol and preparation of dispersion
  • the anhydrous zinc antimonate aqueous sol obtained in Example 1 was diluted with pure water so that the ZnSb 2 O 6 concentration was 15% by mass, and this was diluted in a 3 liter autoclave container (manufactured by Pressure Glass Industrial Co., Ltd.). The solution was heated to 220 ° C. over 2.0 hours, held at 220 ° C. for 5 hours, and then hydrothermally treated to cool to room temperature over 3 hours.
  • the obtained hydrothermally treated anhydrous zinc antimonate aqueous sol had a pH of 7.2 and a particle size of the aggregate of 86 nm as measured by a dynamic light scattering particle size distribution analyzer.
  • the aqueous solvent of the obtained hydrothermally treated anhydrous zinc antimonate aqueous sol was concentrated while blowing methanol vapor under normal pressure, and replaced with a methanol solvent.
  • the obtained methanol sol contains 61.1% by mass of ZnSb 2 O 6 , the pH of the solution in which water and the sol are mixed at 1: 1 (mass ratio) is 6.1, and the particle size distribution of dynamic light scattering method
  • the particle diameter of the aggregate was 80 nm as measured by a measuring machine.
  • Example 2-2 Preparation of a coating composition and a film having a film made of the composition
  • the dispersion state of the obtained resin composition was good. This was applied to the upper surface of a PET film (Toyobo Co., Ltd. Cosmo Shine A4300, film thickness 125 ⁇ m). After coating using a 12 (thickness 27.4 ⁇ m) wire bar, ultraviolet rays were irradiated with an ultraviolet irradiator to obtain a PET film having a coating containing anhydrous zinc antimonate fine particles. The film thickness was 2 ⁇ m. As a result of measuring the optical properties of the obtained coated PET film using a spectral haze meter TC-H3DPK-MKII (manufactured by Tokyo Denshoku), the total light transmittance (Tt 0 ) was 87.2%. It was.
  • Example 2-3 Light resistance evaluation
  • the coated PET film obtained in Example 2-2 was subjected to a high-pressure mercury lamp (80 W / cm) containing high energy of 3.0 eV or more with a UV irradiation apparatus (Handy UV-800, Oak Manufacturing Co., Ltd.) for 10 hours. Irradiated.
  • a UV irradiation apparatus Haps UV-800, Oak Manufacturing Co., Ltd.
  • the total light transmittance (Tt) after irradiation was 85.3%.
  • the decrease rate of the total light transmittance before and after UV irradiation (Tt 0 -Tt / Tt 0 ) was 2.2%.
  • Example 3-1 Hydrothermal treatment of anhydrous zinc antimonate aqueous sol and preparation of dispersion
  • the anhydrous zinc antimonate aqueous sol obtained in Example 1 was diluted with pure water so that the ZnSb 2 O 6 concentration was 15% by mass, and this was diluted in a 3 liter autoclave container (manufactured by Pressure Glass Industrial Co., Ltd.). The solution was heated to 250 ° C. over 2.5 hours, held at 250 ° C. for 5 hours, and then subjected to hydrothermal treatment to cool to room temperature over 3 hours.
  • the obtained hydrothermally treated anhydrous zinc antimonate aqueous sol had a pH of 5.5 and a particle size of the aggregate of 63 nm as measured by a dynamic light scattering particle size distribution analyzer.
  • the aqueous solvent of the obtained hydrothermally treated anhydrous zinc antimonate aqueous sol was concentrated while blowing methanol vapor under normal pressure, and replaced with a methanol solvent.
  • the obtained methanol sol contains 58.9% by mass of ZnSb 2 O 6 , the pH of the solution in which water and the sol are mixed at 1: 1 (mass ratio) is 6.0, and the particle size distribution of dynamic light scattering method
  • the particle diameter of the aggregate was 67 nm as measured by a measuring machine.
  • Example 3-2 Production of coating composition and film having film formed from the composition
  • Example 3-3 Light resistance evaluation
  • the PET film with a coating obtained in Example 3-2 was subjected to a high-pressure mercury lamp (80 W / cm) containing high energy of 3.0 eV or more with a UV irradiation apparatus (Handy UV-800, Oak Manufacturing Co., Ltd.) for 10 hours. Irradiated.
  • a UV irradiation apparatus Haps UV-800, Oak Manufacturing Co., Ltd.
  • the total light transmittance (Tt) after irradiation was 87.5%.
  • the decrease rate of total light transmittance before and after UV irradiation (Tt 0 -Tt / Tt 0 ) was 0.6%.
  • Example 1-1 Preparation of anhydrous zinc antimonate aqueous sol (dispersion)
  • the anhydrous zinc antimonate aqueous sol obtained in Example 1 was concentrated while blowing methanol vapor under normal pressure, and replaced with a methanol solvent.
  • the obtained methanol sol contains 60.9% by mass of ZnSb 2 O 6 , the pH of the solution in which water and the sol are mixed at 1: 1 (mass ratio) is 7.1, and the particle size distribution of dynamic light scattering method The particle diameter of the aggregate was 87 nm as measured by a measuring machine.
  • PET film Cosmo Shine (registered trademark) A4300 manufactured by Toyobo Co., Ltd., film thickness 125 ⁇ m.
  • a high pressure mercury lamp 80 W / cm was irradiated for 30 seconds with a UV irradiation device (Handy UV-800, Oak Manufacturing Co., Ltd.), and anhydrous antimony A PET film having a coating containing zinc acid fine particles was obtained.
  • the film thickness was 2 ⁇ m.
  • the haze of the obtained coated PET film was measured using a spectral haze meter TC-H3DPK-MKII (manufactured by Tokyo Denshoku). As a result, the total light transmittance (Tt 0 ) was 86.0%. .
  • Comparative Example 1-3 Light resistance evaluation
  • the coated PET film obtained in Comparative Example 1-2 was subjected to a high-pressure mercury lamp (80 W / cm) containing high energy of 3.0 eV or more with a UV irradiation apparatus (Handy UV-800, Oak Manufacturing Co., Ltd.) for 10 hours. Irradiated.
  • a UV irradiation apparatus Haps UV-800, Oak Manufacturing Co., Ltd.
  • the total light transmittance (Tt) after irradiation was 76.1%.
  • the decrease rate (Tt 0 -Tt / Tt 0 ) of the total light transmittance before and after UV irradiation was 11.5%.
  • Example 2-1 Hydrothermal treatment of anhydrous zinc antimonate aqueous sol and preparation of dispersion
  • the anhydrous zinc antimonate aqueous sol obtained in Example 1 was diluted with pure water so that the ZnSb 2 O 6 concentration was 15% by mass, and this was diluted in a 3 liter autoclave container (manufactured by Pressure Glass Industrial Co., Ltd.). Then, the temperature was raised to 150 ° C. over 2.0 hours, held at 150 ° C. for 5 hours, and then hydrothermally treated to cool to room temperature over 2 hours.
  • the obtained hydrothermally treated anhydrous zinc antimonate aqueous sol had a pH of 7.3 and a particle size of the aggregate of 84 nm as measured by a dynamic light scattering particle size distribution analyzer.
  • the aqueous solvent of the obtained hydrothermally treated anhydrous zinc antimonate aqueous sol was concentrated while blowing methanol vapor under normal pressure, and replaced with a methanol solvent.
  • the obtained methanol sol contains 60.8% by mass of ZnSb 2 O 6 , the pH of the solution in which water and the sol are mixed at 1: 1 (mass ratio) is 6.8, and the particle size distribution of dynamic light scattering method
  • the particle diameter of the aggregate was 84 nm as measured by a measuring machine.
  • Example 3-1 Hydrothermal treatment of anhydrous zinc antimonate aqueous sol and preparation of dispersion
  • the anhydrous zinc antimonate aqueous sol obtained in Example 1 was diluted with pure water so that the ZnSb 2 O 6 concentration was 15% by mass, and this was diluted in a 3 liter autoclave container (manufactured by Pressure Glass Industrial Co., Ltd.). The solution was heated to 180 ° C. over 2.0 hours, held at 180 ° C. for 5 hours, and then subjected to hydrothermal treatment to cool to room temperature over 3 hours.
  • the obtained hydrothermally treated anhydrous zinc antimonate aqueous sol had a pH of 7.6, and the aggregate particle size was 75 nm as measured by a dynamic light scattering particle size distribution analyzer.
  • the aqueous solvent of the obtained hydrothermally treated anhydrous zinc antimonate aqueous sol was concentrated while blowing methanol vapor under normal pressure, and replaced with a methanol solvent.
  • the obtained methanol sol contains 49.2% by mass of ZnSb 2 O 6 , the pH of the solution in which water and the sol are mixed at 1: 1 (mass ratio) is 6.1, and the particle size distribution of dynamic light scattering method
  • the particle diameter of the aggregate was 75 nm as measured by a measuring machine.
  • Comparative Example 3-3 Light resistance evaluation
  • the PET film with a coating obtained in Comparative Example 3-2 was subjected to a high-pressure mercury lamp (80 W / cm) containing high energy of 3.0 eV or more with a UV irradiation apparatus (Handy UV-800, Oak Manufacturing Co., Ltd.) for 10 hours. Irradiated.
  • a UV irradiation apparatus Handy UV-800, Oak Manufacturing Co., Ltd.
  • the total light transmittance (Tt) after irradiation was 78.0%.
  • the decrease rate (Tt 0 -Tt / Tt 0 ) of the total light transmittance before and after UV irradiation was 9.5%.

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Abstract

L'invention a pour but de pourvoir à un procédé pour obtenir des microparticules de blocage du rayonnement thermique, ayant une résistance à lumière élevée sans utiliser de substance inerte isolante, une dispersion contenant les microparticules de blocage du rayonnement thermique obtenues par le procédé, une composition de revêtement et un élément revêtu qui utilise la composition de revêtement. A cet effet, selon l'invention, le procédé de fabrication de microparticules de blocage du rayonnement thermique, modifiées en surface, comprend (a) une étape d'écrasement à sec et/ou d'écrasement par voie humide de microparticules cristallines de blocage du rayonnement thermique ayant une dimension de grain primaire de 5 à 10 nm et (b) une étape pour soumettre les microparticules de blocage du rayonnement thermique, pulvérisées, obtenues par l'étape (a) à une dispersion dans l'eau, puis à un traitement hydrothermal à 200 à 320°C.
PCT/JP2012/063067 2011-05-24 2012-05-22 Procédé de fabrication de microparticules de blocage du rayonnement thermique, modifiées en surface et dispersion de microparticules de blocage du rayonnement thermique obtenues par le procédé WO2012161191A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103468094A (zh) * 2013-09-26 2013-12-25 陈理敬 一种壳体外表面密封、隔热涂层材料及其制备方法
JP2015105325A (ja) * 2013-11-29 2015-06-08 住友大阪セメント株式会社 透明樹脂組成物及び塗膜並びに熱線遮蔽フィルム
WO2017090489A1 (fr) * 2015-11-26 2017-06-01 株式会社Adeka Composition de revêtement de résine aqueuse, film de protection contre un rayonnement thermique la mettant en œuvre, et procédés de production associés
JP2018111787A (ja) * 2017-01-13 2018-07-19 株式会社Adeka 水系樹脂塗料組成物およびこれを用いた熱線遮蔽フィルム

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JPH04184839A (ja) * 1990-11-20 1992-07-01 Asahi Glass Co Ltd 帯電防止膜及びその製造方法
JPH0931238A (ja) * 1995-07-20 1997-02-04 Mitsubishi Materials Corp 導電性分散液、導電性塗料及びその製造方法
JP2003049083A (ja) * 2001-08-09 2003-02-21 Dokai Chemical Industries Co Ltd 鱗片状シリカ粒子を含有する硬化性組成物の製造方法
JP2005060263A (ja) * 2003-08-08 2005-03-10 Dokai Chemical Industries Co Ltd 化粧品配合用シリカ系微粒子の製造方法
JP2005179096A (ja) * 2003-12-17 2005-07-07 Hitachi Maxell Ltd アルミニウム置換スズ含有酸化インジウム粒子とその製造方法、ならびに該粒子を用いた導電性塗料、導電性塗膜および導電性シート
JP2005194125A (ja) * 2004-01-06 2005-07-21 Hitachi Maxell Ltd 銀添加スズ含有酸化インジウム粒子とその製造方法、ならびに導電性塗料、導電性塗膜および導電性シート
JP2007016153A (ja) * 2005-07-08 2007-01-25 Konoshima Chemical Co Ltd 高い耐熱性を有する水酸化マグネシウム系難燃剤、難燃性樹脂組成物および成型体
JP2008050253A (ja) * 2006-06-22 2008-03-06 Nissan Chem Ind Ltd 導電性酸化スズゾル及びその製造方法

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Publication number Priority date Publication date Assignee Title
JPS55158132A (en) * 1979-05-30 1980-12-09 Titan Kogyo Kk Antimony-containing heat-resistant yellow iron oxide pigment and its manufacture
JPH04184839A (ja) * 1990-11-20 1992-07-01 Asahi Glass Co Ltd 帯電防止膜及びその製造方法
JPH0931238A (ja) * 1995-07-20 1997-02-04 Mitsubishi Materials Corp 導電性分散液、導電性塗料及びその製造方法
JP2003049083A (ja) * 2001-08-09 2003-02-21 Dokai Chemical Industries Co Ltd 鱗片状シリカ粒子を含有する硬化性組成物の製造方法
JP2005060263A (ja) * 2003-08-08 2005-03-10 Dokai Chemical Industries Co Ltd 化粧品配合用シリカ系微粒子の製造方法
JP2005179096A (ja) * 2003-12-17 2005-07-07 Hitachi Maxell Ltd アルミニウム置換スズ含有酸化インジウム粒子とその製造方法、ならびに該粒子を用いた導電性塗料、導電性塗膜および導電性シート
JP2005194125A (ja) * 2004-01-06 2005-07-21 Hitachi Maxell Ltd 銀添加スズ含有酸化インジウム粒子とその製造方法、ならびに導電性塗料、導電性塗膜および導電性シート
JP2007016153A (ja) * 2005-07-08 2007-01-25 Konoshima Chemical Co Ltd 高い耐熱性を有する水酸化マグネシウム系難燃剤、難燃性樹脂組成物および成型体
JP2008050253A (ja) * 2006-06-22 2008-03-06 Nissan Chem Ind Ltd 導電性酸化スズゾル及びその製造方法

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103468094A (zh) * 2013-09-26 2013-12-25 陈理敬 一种壳体外表面密封、隔热涂层材料及其制备方法
JP2015105325A (ja) * 2013-11-29 2015-06-08 住友大阪セメント株式会社 透明樹脂組成物及び塗膜並びに熱線遮蔽フィルム
WO2017090489A1 (fr) * 2015-11-26 2017-06-01 株式会社Adeka Composition de revêtement de résine aqueuse, film de protection contre un rayonnement thermique la mettant en œuvre, et procédés de production associés
JPWO2017090489A1 (ja) * 2015-11-26 2018-09-13 株式会社Adeka 水系樹脂塗料組成物、これを用いた熱線遮蔽フィルムおよびこれらの製造方法
JP2018111787A (ja) * 2017-01-13 2018-07-19 株式会社Adeka 水系樹脂塗料組成物およびこれを用いた熱線遮蔽フィルム

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