WO2009098883A1 - Procédé pour produire une résine dispersée dans l'eau composite inorganique - Google Patents

Procédé pour produire une résine dispersée dans l'eau composite inorganique Download PDF

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WO2009098883A1
WO2009098883A1 PCT/JP2009/000449 JP2009000449W WO2009098883A1 WO 2009098883 A1 WO2009098883 A1 WO 2009098883A1 JP 2009000449 W JP2009000449 W JP 2009000449W WO 2009098883 A1 WO2009098883 A1 WO 2009098883A1
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weight
monomer
parts
emulsion
meth
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PCT/JP2009/000449
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Japanese (ja)
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Tomoya Naito
Mika Okada
Asami Kubo
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Nitto Denko Corporation
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/20—Aqueous medium with the aid of macromolecular dispersing agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/10—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to inorganic materials

Definitions

  • the present invention relates to a method for producing an inorganic composite water-dispersed resin, and more particularly to a method for producing an inorganic composite water-dispersed resin in which a hydrophilic inorganic compound having a specific shape is composited.
  • montmorillonite clay is hydrophobized and agglomerated with each other by blending dodecyltrimethylammonium bromide in the clay slurry. Therefore, when a monomer solution is added to the clay slurry, the monomer solution enters between the agglomerated montmorillonite clay.
  • the polymer latex When the monomer solution in the clay slurry is polymerized, the polymer latex partially encloses the montmorillonite clay. For this reason, agglomerated aggregates of the composite are generated, which may be settled or a film cannot be formed. Industrial products obtained from polymer latex have the disadvantage that their mechanical properties are not sufficiently improved.
  • the object of the present invention is to use a hydrophilic inorganic compound having a specific shape on the surface of a water-dispersed resin as a practical material having excellent characteristics and suppressing the generation of aggregates.
  • An object of the present invention is to provide an inorganic composite water-dispersed resin.
  • the method for producing an inorganic composite water-dispersed resin of the present invention comprises dispersing a hydrophilic inorganic compound having a bulk shape, needle shape, or plate shape in water, and water of the hydrophilic inorganic compound.
  • the step of preparing the dispersion, and the aqueous dispersion and the ethylenically unsaturated monomer are such that the blending ratio of the hydrophilic inorganic compound is 4 to 200 parts by weight with respect to 100 parts by weight of the ethylenically unsaturated monomer.
  • the method for producing an inorganic composite water-dispersed resin of the present invention further includes a step of blending a hydrophobic compound into at least one of the ethylenically unsaturated monomer and the monomer emulsion.
  • the maximum length of the hydrophilic inorganic compound is 1 to 400 nm.
  • a bulk, needle-like or plate-like hydrophobic inorganic compound is previously dispersed in the ethylenically unsaturated monomer. It is preferable to prepare a monomer dispersion of the hydrophobic inorganic compound, mix the monomer dispersion and the water dispersion, and emulsify the monomer dispersion.
  • the proportion of the hydrophobic inorganic compound is 0.1 to 15 parts by weight with respect to 100 parts by weight of the ethylenically unsaturated monomer. Is preferred.
  • the maximum length of the hydrophobic inorganic compound is preferably 1 to 200 nm.
  • the ethylenically unsaturated monomer is measured based on the volume of oil droplets measured by a laser diffraction particle size distribution analyzer. It is preferable to emulsify so that the median diameter is 100 ⁇ m or less.
  • a hydrophilic inorganic compound having a specific shape is dispersed in water to prepare an aqueous dispersion of the hydrophilic inorganic compound having a specific shape.
  • a monomer emulsion is prepared by blending with an unsaturated monomer, and the ethylenically unsaturated monomer is polymerized. Therefore, the obtained water-dispersed resin can be composited with a hydrophilic inorganic compound so that the hydrophilic inorganic compound is unevenly distributed on the surface thereof.
  • FIG. 1 shows a cross-sectional view of an example of an adhesive film using an inorganic composite water-dispersed resin obtained by the method for producing an inorganic composite water-dispersed resin of the present invention.
  • FIG. 2 is an image processing diagram of an SEM photograph of the inorganic composite water-dispersed resin of Example 2.
  • FIG. 3 is an image processing diagram of an SEM photograph of the inorganic composite water-dispersed resin of Example 3.
  • FIG. 4 is an image processing diagram of an SEM photograph of the inorganic composite water-dispersed resin of Example 4.
  • FIG. 5 shows an image processing diagram of an SEM photograph of the inorganic composite water-dispersed resin of Example 5.
  • FIG. 6 shows an image processing diagram of an SEM photograph of the inorganic composite water-dispersed resin of Example 6.
  • FIG. 7 shows an image processing diagram of an SEM photograph of the inorganic composite water-dispersed resin of Example 7.
  • FIG. 8 shows an image processing diagram of a TEM photograph of the inorganic composite water-dispersed resin of Example 8.
  • FIG. 9 shows an image processing diagram of an SEM photograph of the inorganic composite water-dispersed resin of Example 9.
  • FIG. 10 shows an image processing diagram of a TEM photograph of the inorganic composite water-dispersed resin of Example 9.
  • FIG. 11 is an image processing diagram of an SEM photograph of the inorganic composite water-dispersed resin of Example 10.
  • FIG. 12 shows an image processing diagram of an SEM photograph of the inorganic composite water-dispersed resin of Example 11.
  • FIG. 13 is an image processing diagram of an SEM photograph of the inorganic composite water-dispersed resin of Example 12.
  • FIG. 14 is an image processing diagram of an SEM photograph of the inorganic composite water-dispersed resin of Example 13.
  • FIG. 15 shows an image processing diagram of an SEM photograph of the inorganic composite water-dispersed resin of Example 14.
  • FIG. 16 shows an image processing diagram of an SEM photograph of the inorganic composite water-dispersed resin of Example 15.
  • FIG. 17 is an image processing diagram of an SEM photograph of the inorganic composite water-dispersed resin of Example 16.
  • FIG. 18 shows an image processing diagram of an SEM photograph of the inorganic composite water-dispersed resin of Example 17.
  • FIG. 19 shows an image processing diagram of an SEM photograph of the inorganic composite water-dispersed resin of Example 18.
  • FIG. 20 shows an image processing diagram of an SEM photograph of the inorganic composite water-dispersed resin of Example 19.
  • FIG. 21 shows an image processing diagram of a TEM photograph of the inorganic composite water-dispersed resin of Example 20.
  • FIG. 22 is an image processing diagram of a TEM photograph of the inorganic composite water-dispersed resin of Comparative Example 4.
  • FIG. 23 shows an image processing diagram of a TEM photograph of the inorganic composite water-dispersed resin of Comparative Example 5.
  • the method for producing an inorganic composite water-dispersed resin of the present invention comprises a step of dispersing a hydrophilic inorganic compound in water to prepare an aqueous dispersion of the hydrophilic inorganic compound (aqueous dispersion preparation step), an aqueous dispersion, A step of blending an ethylenically unsaturated monomer, emulsifying the ethylenically unsaturated monomer to prepare a monomer emulsion (monomer emulsion preparation step), and at least water, an aqueous dispersion, the ethylenically unsaturated monomer and the monomer emulsion A step of blending a surfactant (surfactant blending step) and a step of polymerizing an ethylenically unsaturated monomer in the monomer emulsion (polymerization step) are provided.
  • a surfactant surfactant blending step
  • polymerization step a step of polymerizing an
  • the hydrophilic inorganic compound has a bulk shape, a needle shape, or a plate shape (excluding a layer shape).
  • Examples of the hydrophilic inorganic compound having a bulk shape include a spherical inorganic shape, a rectangular parallelepiped shape, or an irregularly shaped hydrophilic inorganic compound thereof.
  • Examples of the bulk-form hydrophilic inorganic compound include hydrophilic silica, calcium carbonate, titanium oxide, tin oxide (including antimony-doped tin oxide), alumina, magnesium hydroxide, barium titanate, zinc oxide, and nitride. Examples thereof include silicon, silicon carbide, carbon (diamond), and metal fine particles.
  • the needle-shaped hydrophilic inorganic compound examples include potassium titanate, wollastonite, sepiolite, acicular tin oxide, acicular magnesium hydroxide, and alumina.
  • the plate-shaped hydrophilic inorganic compound is a plate-shaped hydrophilic inorganic compound excluding a layer-shaped inorganic compound (hydrophilic inorganic compound) such as a layered clay mineral, such as boron nitride, plate-like calcium carbonate, plate And aluminum hydroxide.
  • hydrophilic inorganic compounds can be used alone or in combination of two or more.
  • Preferred examples include antimony-doped tin oxide, titanium oxide, tin oxide, alumina, zinc oxide, boron nitride, silicon nitride, silicon carbide, and carbon (diamond).
  • antimony-doped tin oxide for example, SN-100S, SN-100P, SN manufactured by Ishihara Sangyo Co., Ltd.
  • titanium oxide for example, TTO series manufactured by Ishihara Sangyo Co., Ltd.
  • zinc oxide for example, SnO-310, SnO-350, SnO-410, manufactured by Sumitomo Osaka Cement Co.
  • alumina for example, the NANOBYK series manufactured by Big Chemie Japan, the alumina sol series manufactured by Nissan Chemical Industries, Ltd., the silicon carbide, for example, the SiC series manufactured by Sumitomo Osaka Cement Co., and the diamond, for example, the diamond powder series, etc. Can be mentioned.
  • the size of the hydrophilic inorganic compound is, for example, 1 to 400 nm, preferably 1 to 200 nm, more preferably 5 to 100 nm as the primary average particle diameter in the case of a bulk-shaped (spherical) hydrophilic inorganic compound. It is. If it is larger than the above range, oil droplets with the desired particle size may not be obtained. In the case of a needle-like hydrophilic inorganic compound or a plate-like hydrophilic inorganic compound, the maximum length is, for example, 1 to 400 nm, preferably 1 to 200 nm, more preferably 5 to 200 nm. If it is larger than the above range, oil droplets with the desired particle size may not be obtained.
  • these aspect ratios in the case of needles, the major axis length / minor axis length or the major axis length / thickness are expressed.
  • the diagonal length is also expressed.
  • Thickness or long side length / thickness is, for example, 5 to 200, preferably 10 to 100.
  • the hydrophilic inorganic compound described above is present at the interface between water and the oil droplets of the ethylenically unsaturated monomer in the monomer emulsion preparation step, and is unevenly distributed on the surface of the water-dispersed resin after the polymerization step. Need to be supported as follows. Therefore, if the hydrophilic inorganic compound is hydrophobic, it will be stably present in the oil phase in the monomer emulsion preparation process and cannot be present at the interface between water and oil droplets. Disappear.
  • the hydrophilicity of the hydrophilic inorganic compound is excessively high, it will exist stably in water, and again, it cannot exist at the interface between water and the oil droplets of the ethylenically unsaturated monomer. In some cases, it cannot be emulsified.
  • the surface of the hydrophilic inorganic compound is partially surface-treated with a surface treatment agent as necessary.
  • the surface treatment agent include general surface modifiers such as coupling agents and fatty acids.
  • the coupling agent include a silane coupling agent, a titanium coupling agent, and an aluminum coupling agent.
  • silane-based silane coupling agents include 3-methacryloxypropyl-trimethoxysilane, 3-acryloxypropyl-trimethoxysilane, 3-methacryloxypropyl-triethoxysilane, 3-acryloxypropyl-triethoxysilane 3-methacryloxypropylmethyl-dimethoxysilane, 3-acryloxypropylmethyl-dimethoxysilane, 3-methacryloxypropylmethyl-diethoxysilane, 3-acryloxypropylmethyl-diethoxysilane, vinyltrimethoxysilane, vinyltri Ethoxysilane, 4-vinylbutyltrimethoxysilane, 4-vinylbutyltriethoxysilane, 8-vinyloctyltrimethoxysilane, 8-vinyloctyltriethoxysilane, 10-meta Ryloxydecyltrimethoxysilane, 10-acryloxydecyltrimethoxysilane, 10-acryl
  • titanium coupling agents examples include isopropyl triisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite).
  • Titanate tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltri (dioctylphosphate) Titanate, isopropyl tricumylphenyl titanate, isopropyl tri (N-amidoethyl Minoechiru) such as titanate, and the like.
  • Examples of the aluminum coupling agent include acetoalkoxyaluminum diisopropylate.
  • Examples of the fatty acid include stearic acid, oleic acid, linoleic acid, linolenic acid, and eleostearic acid.
  • As the surface treatment with such a surface treatment agent for example, a dry method in which an aqueous alcohol solution, an organic solvent solution or an aqueous solution of a surface treatment agent is added while stirring a hydrophilic inorganic compound in a mixer, for example, a hydrophilic inorganic compound.
  • Examples include a wet method in which a compound is dispersed in an alcohol aqueous solution or an aqueous solution, and then a surface treatment agent is added, for example, a spray method in which a surface treatment agent is sprayed onto a hydrophilic inorganic compound.
  • the hydrophilic inorganic compound having excessively high hydrophilicity a commercially available product that has been surface-treated in advance can be used.
  • the ethylenically unsaturated monomer include (meth) acrylic acid alkyl ester.
  • the (meth) acrylic acid alkyl ester is, for example, a (meth) acrylic acid alkyl ester (methacrylic acid alkyl ester and / or acrylic acid alkyl ester) having an alkyl group having 1 to 18 carbon atoms.
  • alkyl (meth) acrylates can be used alone or in combination of two or more.
  • alkyl (meth) acrylates can be used alone or in combination of two or more.
  • the ethylenically unsaturated monomer include a copolymerizable polymer copolymerizable with (meth) acrylic acid alkyl ester.
  • copolymerizable vinyl monomer examples include aromatic vinyl monomers such as styrene and vinyl toluene, such as cyclopentyl di (meth) acrylate, cyclohexyl (meth) acrylate, bornyl (meth) acrylate, and (meth) acrylic acid.
  • (Meth) acrylic acid alicyclic hydrocarbon esters such as isobornyl, for example, (meth) acrylic aryl esters such as phenyl (meth) acrylate, such as methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate Alkoxy group-containing unsaturated monomers such as ethylene, propylene, isoprene, butadiene, isobutylene and other olefinic monomers, vinyl ether-based monomers such as vinyl ether, halogen atom-containing unsaturated monomers such as vinyl chloride, etc.
  • phenyl (meth) acrylate such as methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate
  • Alkoxy group-containing unsaturated monomers such as ethylene, propylene, isoprene, butadiene, isobutylene and other olefinic monomers
  • N-vinylpyrrolidone N- (1-methylvinyl) pyrrolidone
  • N-vinylpyridine N-vinylpiperidone
  • N-vinylpyrimidine N-vinylpiperazine
  • N-vinylpyrazine N-vinylpyrrole
  • N-vinylimidazole N-vinyl oxazole
  • N-vinyl morpholine vinyl group-containing heterocyclic compounds such as tetrahydrofurfuryl (meth) acrylate, for example, acrylate esters containing halogen atoms such as fluorine atoms such as fluorine (meth) acrylate And monomers.
  • copolymerizable vinyl monomer examples include functional group-containing vinyl monomers, for example, carboxyl group-containing monomers such as acrylic acid, methacrylic acid, fumaric acid, maleic acid, crotonic acid, and carboxyethyl (meth) acrylate.
  • functional group-containing vinyl monomers for example, carboxyl group-containing monomers such as acrylic acid, methacrylic acid, fumaric acid, maleic acid, crotonic acid, and carboxyethyl (meth) acrylate.
  • Carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate, for example, hydroxyl group-containing vinyl monomers such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-methylol (meta Acrylic net Amide group-containing unsaturated monomers such as N-methylolpropane (meth) acrylamide and N-vinylcarboxylic acid amide, such as aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, (meth ) Amino group-containing unsaturated monomers such as acrylic ter
  • Cyano group-containing unsaturated monomers for example, isocyanate group-containing unsaturated monomers such as 2-methacryloyloxyethyl isocyanate, such as styrene sulfonic acid, allyl sulfonic acid, 2- (meth) acrylamido-2-methylpropane sulfonic acid, (meth ) Acrylamide Sulfonic acid group-containing unsaturated monomers such as pansulfonic acid, sulfopropyl (meth) acrylate, (meth) acryloyloxynaphthalenesulfonic acid, such as N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, N-phenylmaleimide Maleimide monomers such as N-methyl itaconimide, N-ethyl itaconimide, N-butyl itaconimide, N-octyl itaconimide,
  • a polyfunctional monomer is mentioned as an above-described functional group containing vinyl monomer.
  • the multifunctional monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and tetraethylene glycol di (meth) acrylate.
  • (Mono or poly) alkylene glycol di (meth) such as (mono or poly) ethylene glycol di (meth) acrylate and (mono or poly) propylene glycol di (meth) acrylate such as propylene glycol di (meth) acrylate
  • neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol Examples include (meth) acrylic acid ester monomers of polyhydric alcohols such as tall tri (meth) acrylate and dipentaerythritol hexa (meth) acrylate, such as divinylbenzene.
  • the polyfunctional monomer include epoxy acrylate, polyester acrylate, and urethane acrylate.
  • examples of the copolymerizable vinyl monomer include alkoxysilyl group-containing vinyl monomers.
  • examples of the alkoxysilyl group-containing vinyl monomer include silicone-based (meth) acrylate monomers and silicone-based vinyl monomers.
  • silicone-based (meth) acrylate monomer examples include (meth) acryloyloxymethyl-trimethoxysilane, (meth) acryloyloxymethyl-triethoxysilane, 2- (meth) acryloyloxyethyl-trimethoxysilane, 2- ( (Meth) acryloyloxyethyl-triethoxysilane, 3- (meth) acryloyloxypropyl-trimethoxysilane, 3- (meth) acryloyloxypropyl-triethoxysilane, 3- (meth) acryloyloxypropyl-tripropoxysilane, 3 -(Meth) acryloyloxyalkyl-trialkoxysilanes such as (meth) acryloyloxypropyl-triisopropoxysilane, 3- (meth) acryloyloxypropyl-tributoxysilane, such as (meth) acryloyl
  • silicone-based vinyl monomer examples include vinyltrialkoxysilanes such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, vinyltributoxysilane, and vinyl corresponding to these.
  • Alkyldialkoxysilanes and vinyldialkylalkoxysilanes such as vinylmethyltrimethoxysilane, vinylmethyltriethoxysilane, ⁇ -vinylethyltrimethoxysilane, ⁇ -vinylethyltriethoxysilane, ⁇ -vinylpropyltrimethoxysilane, ⁇ -Vinyl alkyl such as vinylpropyltriethoxysilane, ⁇ -vinylpropyltripropoxysilane, ⁇ -vinylpropyltriisopropoxysilane, ⁇ -vinylpropyltributoxysilane Other trialkoxysilanes, these correspond and (vinyl) alkyl dialkoxy silanes, and the like (vinyl alkyl) dialkyl (mono) alkoxysilanes.
  • copolymerizable vinyl monomers can be used alone or in combination of two or more.
  • an alkoxysilyl group-containing vinyl monomer is preferable.
  • an alkoxysilyl group-containing vinyl monomer is introduced into the polymer chain, and a cross-linked structure can be formed by a reaction between them.
  • Such a copolymerizable vinyl monomer can be optionally used in combination with a (meth) acrylic acid alkyl ester if necessary, or can be used alone.
  • the blending ratio of the copolymerizable vinyl monomer is, for example, 40 parts by weight or less with respect to 100 parts by weight of the ethylenically unsaturated monomer. Preferably, it is 30 parts by weight or less, more preferably 20 parts by weight or less.
  • the blending ratio is, for example, 0.001 to 10 parts by weight, preferably 100 parts by weight of (meth) acrylic acid alkyl ester, preferably 0.01 to 5 parts by weight.
  • surfactant examples include known surfactants (surfactants listed in “Surfactant Physical Properties / Performance Manual, Noboru Moriyama, published by the Technical Information Society”), such as liquid and Dispersants that mainly act on the interface between the solids, for example emulsifiers that act mainly on the interface between the liquid and the liquid.
  • the dispersant examples include a phosphoric acid dispersant and a carboxylic acid dispersant.
  • the phosphate dispersant examples include sodium orthophosphate, sodium pyrophosphate, sodium tripolyphosphate, sodium tetraphosphate, sodium hexametaphosphate, and trisodium phosphate.
  • carboxylic acid-based dispersant examples include polymer dispersants such as polyacrylic acid-based, polymethacrylic acid-based, acrylic acid / maleic acid copolymer system, and styrene / maleic acid copolymer system.
  • polymer dispersant a general commercial product can be used.
  • Aquaric series polyacrylic acid type or acrylic acid / maleic acid copolymer system, manufactured by Nippon Shokubai Co., Ltd.
  • Aron series polyacrylic acid type
  • Series manufactured by Toagosei Co., Ltd., Charol series (polyacrylic acid, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Poise series (acrylic acid / maleic acid copolymer system, manufactured by Kao Corporation), SN Dispersant Series (polycarboxylic acid) Copolymer system, manufactured by San Nopco).
  • the emulsifier examples include sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, polyoxyethylene sodium lauryl sulfate, polyoxyethylene alkyl ether sodium sulfate, polyoxyethylene alkyl phenyl ether ammonium sulfate, and polyoxyethylene alkyl phenyl ether.
  • Anionic emulsifiers such as sodium sulfate and sodium polyoxyethylene alkyl sulfosuccinate, for example, nonionic emulsifiers such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene polyoxypropylene block polymer Etc.
  • the emulsifier examples include radical polymerizable (reactive) emulsifiers in which radical polymerizable functional groups (reactive groups) such as propenyl groups and allyl ether groups are introduced into these anionic emulsifiers and nonionic emulsifiers. .
  • These surfactants can be used alone or in combination of two or more.
  • the above-described hydrophilic inorganic compound and water are blended, and then these are stirred and mixed to disperse the hydrophilic inorganic compound in water.
  • An aqueous dispersion is prepared (aqueous dispersion preparation step).
  • the blending ratio of the hydrophilic inorganic compound is, for example, 0.1 to 50 parts by weight, preferably 0.2 to 40 parts by weight, and more preferably 0.5 to 30 parts by weight with respect to 100 parts by weight of water. is there.
  • the blending ratio of the hydrophilic inorganic compound exceeds the above range, the viscosity of the aqueous dispersion may be excessively increased or aggregation may occur in the polymerization process.
  • the blending ratio of the hydrophilic inorganic compound is less than the above range, the content ratio of the hydrophilic inorganic compound in the inorganic composite water-dispersed resin becomes excessively low, and the hydrophilic inorganic compound is placed on the surface of the water-dispersed resin. In some cases, it cannot be uniformly supported.
  • a known stirrer such as a disper or an ultrasonic homogenizer is used.
  • a partial surface treatment of the above-described hydrophilic inorganic compound can be performed.
  • an aqueous dispersion and an ethylenically unsaturated monomer are blended, followed by stirring and mixing to emulsify the ethylenically unsaturated monomer to prepare a monomer emulsion (monomer emulsion preparation step).
  • the blending ratio of the hydrophilic inorganic compound is 4 to 200 parts by weight, preferably 5 to 150 parts by weight, based on 100 parts by weight of the ethylenically unsaturated monomer. More preferably, it is 8 to 100 parts by weight. If the blending ratio of the hydrophilic inorganic compound is less than the above range, in the monomer emulsion preparation process, a stable emulsion form cannot be obtained, and the coverage of the hydrophilic inorganic compound in the inorganic composite water-dispersed resin is excessive. Lower.
  • the blending ratio of the hydrophilic inorganic compound exceeds the above range, the coverage of the hydrophilic inorganic compound in the inorganic composite water-dispersed resin becomes excessively high, the viscosity increases, and it may be necessary to adjust the viscosity.
  • a hydrophobic inorganic compound is previously dispersed in the ethylenically unsaturated monomer to prepare a monomer dispersion of the hydrophobic inorganic compound (monomer dispersion preparation step). It is also possible to emulsify a monomer dispersion of a functional inorganic compound. As a result, the hydrophobic inorganic compound can be encapsulated in the inorganic composite water-dispersed resin.
  • the hydrophobic inorganic compound has a bulk shape, a needle shape, or a plate shape (excluding a layer shape).
  • the bulk-form hydrophobic inorganic compound includes, for example, a spherical inorganic shape, a rectangular parallelepiped shape, or a hydrophobic inorganic compound having an irregular shape thereof.
  • Examples of the bulk-form hydrophobic inorganic compound include silica, calcium carbonate, titanium oxide, tin oxide (including antimony-doped tin oxide), alumina, magnesium hydroxide, barium titanate, zinc oxide, silicon nitride, and metal fine particles. Etc.
  • the needle-shaped hydrophobic inorganic compound examples include potassium titanate, wollastonite, sepiolite, acicular tin oxide, acicular magnesium hydroxide, and the like.
  • the plate-shaped hydrophobic inorganic compound is a plate-shaped hydrophobic inorganic compound excluding the layer-shaped hydrophobic inorganic compound, and examples thereof include boron nitride, plate-like calcium carbonate, and plate-like aluminum hydroxide.
  • hydrophobic inorganic compounds can be used alone or in combination of two or more.
  • silica, titanium oxide, antimony-doped tin oxide, zinc oxide, boron nitride, and silicon nitride are used.
  • the hydrophobic inorganic compound hydrophobized by surface-treating using a surface treating agent can also be used.
  • the surface treatment agent the same ones as described above are used, and examples thereof include metal hydroxides such as aluminum hydroxide, and metal oxides such as zirconium oxide.
  • the surface treatment method is the same as described above.
  • hydrophobic inorganic compound a general commercial product can be used.
  • silica Aerosil series (manufactured by Nippon Aerosil Co., Ltd.), for example, as titanium oxide, TTO series (manufactured by Ishihara Sangyo Co., Ltd.), etc.
  • examples of the Aerosil series include Aerosil R8200 (primary average particle diameter 12 nm, hexamethyldisilazane treatment), Aerosil R104 (primary average particle diameter 12 nm, octamethylcyclotetrasiloxane treatment), Aerosil R974 (primary average particle diameter).
  • TTO-51 C
  • TTO-55 C
  • TTO-55 D
  • TTO-55 D
  • the size of the hydrophobic inorganic compound is, for example, 1 to 200 nm, preferably 5 to 150 nm, more preferably 5 to 100 nm, as the primary average particle diameter (maximum length in the case of needles and plates). Preferably, it is 5 to 50 nm. If the primary average particle size of the hydrophobic inorganic compound is larger than the above range, the hydrophobic inorganic compound may not be encapsulated in oil droplets having a desired particle size and may aggregate during polymerization.
  • the hydrophobic inorganic compound and the ethylenically unsaturated monomer are blended, and the mixture is stirred and mixed with the above-described known stirrer, whereby the hydrophobic inorganic compound is mixed with the ethylenically unsaturated monomer.
  • the blending ratio of the hydrophobic inorganic compound is, for example, 0.1 to 15 parts by weight, preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the ethylenically unsaturated monomer. When the blending ratio of the hydrophobic inorganic compound exceeds the above range, the hydrophobic inorganic compound may not be completely encapsulated in the oil droplets and may aggregate during the polymerization.
  • an aqueous dispersion and an oil phase liquid containing the ethylenically unsaturated monomer are blended, and then these are emulsified, for example.
  • the oil phase liquid contains, for example, an ethylenically unsaturated monomer as an essential component, and an initiator and a hydrophobic compound (or a hydrophobic inorganic compound) as an optional component as necessary.
  • the initiator for example, a polymerization initiator usually used for emulsion polymerization is used, and for example, an oil-soluble initiator or a water-soluble initiator is used.
  • oil-soluble initiator include oil-soluble peroxide-based initiators such as benzoyl peroxide and lauroyl peroxide, such as dimethyl 2,2′-azobis (2-methylpropionate) (commercially available products such as V-601, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyldimethylvaleronitrile), 2,2′-azobis (2-methyl-butyronitrile), 1,1′-azobis (cyclohexane-1-carbononitrile), 2,2′-azobisisobutyronitrile (AIBN), azobis (2-methyl) And oil-soluble azo initiators such as butyronitrile).
  • water-soluble initiator examples include 2,2′-azobis (2-methylpropionamidine) disulfate, 2,2′-azobis (2-methylpropionamidine) dihydrochloride, 2,2′-azobis ( 2-Amidinopropane) dihydrochloride, 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate, 2,2′-azobis (N, N′-dimethyleneisobutyl) Amidine), 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride and the like azo initiators (excluding oil-soluble azo initiators), such as potassium persulfate, Persulfate-based initiators such as ammonium persulfate, for example, peroxide-based initiators (excluding oil-soluble peroxide-based initiators) such as t-butyl hydroperoxide, hydrogen peroxide, etc.
  • azo initiators excluding oil-soluble azo initiators
  • Substituted ethane initiators such as substituted ethanes, for example, carbonyl initiators such as aromatic carbonyl compounds, for example, redox systems such as a combination of persulfate and sodium bisulfite, a combination of peroxide and sodium ascorbate An initiator etc. are mentioned.
  • the initiators are suitably used alone or in combination.
  • an oil-soluble initiator is preferably used, and an oil-soluble azo initiator is more preferably used.
  • the mixing ratio of the initiator is appropriately selected, and is, for example, 0.005 to 1 part by weight with respect to 100 parts by weight of the ethylenically unsaturated monomer.
  • the hydrophobic compound is a hydrophobic organic compound excluding the above-described hydrophobic inorganic compound, for example, higher alkanes having 8 to 30 carbon atoms such as dodecane, hexadecane, and octadecane, such as lauryl alcohol, cetyl alcohol, and stearyl alcohol.
  • alkyl (meth) acrylates having an alkyl group having 8 to 30 carbon atoms such as lauryl (meth) acrylate, stearyl (meth) acrylate, etc.
  • alkyl (meth) acrylates having an alkyl group having 8 to 30 carbon atoms such as lauryl (meth) acrylate, stearyl (meth) acrylate, etc.
  • examples include thiols having an alkyl group having 8 to 30 carbon atoms such as lauryl mercaptan, cetyl mercaptan, stearyl mercaptan, and polymers such as polystyrene and polymethyl (meth) acrylate.
  • These hydrophobic compounds can be used alone or in combination of two or more. Preferably, higher alkanes are used.
  • the alkyl (meth) acrylate when using an alkyl (meth) acrylate having an alkyl group having 8 to 30 carbon atoms as the ethylenically unsaturated monomer, the alkyl (meth) acrylate may function as a hydrophobic compound. , There is a case where it is not necessary to blend.
  • the blending ratio of the hydrophobic compound is, for example, 1 to 80 parts by weight, preferably 1 to 60 parts by weight with respect to 100 parts by weight of the ethylenically unsaturated monomer. If a hydrophobic compound is added to the oil phase liquid, the oil droplets in the monomer emulsion can be maintained at a median diameter in a specific range. In order to include an optional component in the oil phase liquid, an initiator and a hydrophobic compound are added to the ethylenically unsaturated monomer and dissolved.
  • the optional component is blended in the oil phase liquid, but it can also be added directly to the monomer emulsion, for example.
  • the emulsifier include an ultrasonic homogenizer, a high-pressure homogenizer (PANDA 2K, manufactured by NIRO-SOAVI), a microfluidizer (manufactured by Microfluidics), a nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.), and a TK homomixer (manufactured by Primics). TK film mix (manufactured by Primics) is used.
  • the frequency of the ultrasonic wave used is not particularly limited, and is, for example, 20 to 40 kHz.
  • the oil droplets of the ethylenically unsaturated monomer are refined to the above-mentioned median diameter by the cavitation effect by ultrasonic irradiation.
  • the pressure applied is not particularly limited, and is, for example, 10 to 300 MPa.
  • the TK homomixer and the TK fill mix are emulsifiers that utilize the high-speed rotation of the rotating body.
  • a high shear force is added to the mixed solution, and oil droplets are generated. It is miniaturized to the median diameter described above.
  • These emulsifiers can be used alone or in combination of two or more.
  • the volume-based median diameter of the oil droplets of the ethylenically unsaturated monomer to be emulsified is, for example, 100 ⁇ m or less, preferably 40 ⁇ m or less, more preferably 4 ⁇ m or less, and usually 0.05 ⁇ m or more. If the median diameter of the oil droplets exceeds the above range, aggregates may be generated in the polymerization step.
  • the volume-based median diameter of oil droplets in this monomer emulsion is measured with a laser diffraction particle size distribution analyzer.
  • a laser diffraction type particle size distribution measuring device a general commercial product is usually used. Specifically, LS13 320 (manufactured by Beckman Coulter) or the like is used, and the measurement conditions are a laser light source using a laser diode and a tungsten lamp. The wavelength is 450 to 900 nm.
  • the monomer emulsion is then polymerized, for example, by heating, to polymerize the ethylenically unsaturated monomer in the monomer emulsion.
  • the heating temperature (polymerization temperature) is set to 40 to 90 ° C., for example, and the polymerization time is set to 1 to Set to 10 hours.
  • the monomer emulsion can be polymerized at a time under the reaction conditions described above, and after the polymerization of a part of the monomer emulsion, the remaining monomer emulsion can be polymerized, for example, dropwise, and further, the reaction It is also possible to charge water in advance in a container and raise the temperature to the above-described temperature, and then add the monomer emulsion dropwise or dividedly.
  • surfactant is mix
  • the blending ratio of the surfactant is, for example, 0.01 to 20 parts by weight, preferably 0.05 to 15 parts by weight with respect to 100 parts by weight of the hydrophilic inorganic compound.
  • the surfactant when added to the aqueous dispersion, the surfactant is added to the prepared aqueous dispersion in the monomer emulsion preparation step (after the aqueous dispersion preparation step).
  • a dispersant is added.
  • blending surfactant with an oil phase liquid in a monomer emulsion preparation process, surfactant is added to the prepared oil phase liquid (specifically ethylenically unsaturated monomer).
  • an emulsifier is blended. By blending the surfactant into the oil phase liquid, a stable emulsion form of the monomer emulsion can be obtained.
  • blending surfactant with a monomer emulsion surfactant is added to the prepared monomer emulsion in a superposition
  • an emulsifier is blended. By blending the surfactant into the monomer emulsion, high polymerization stability can be obtained.
  • surfactant when preparing a monomer emulsion from a monomer dispersion liquid, surfactant is mix
  • surfactant By adding the surfactant to the monomer dispersion, a stable emulsion form of the monomer emulsion can be obtained.
  • An emulsion of an inorganic composite water-dispersed resin can be obtained by such polymerization.
  • the solid content concentration of the inorganic composite water-dispersed resin emulsion is, for example, 5 to 50% by weight, preferably 6 to 45% by weight, and more preferably 8 to 40% by weight.
  • the solid content concentration of the emulsion exceeds the above range, the viscosity of the emulsion in the polymerization step becomes excessively high, handling properties may be lowered, and control of the polymerization temperature may be difficult. If the solid content concentration of the emulsion is less than the above range, productivity may be reduced.
  • the volume-based median diameter of the water-dispersed resin of the inorganic composite water-dispersed resin is, for example, 100 ⁇ m or less, preferably 40 ⁇ m or less, more preferably 4 ⁇ m or less, and usually 0.05 ⁇ m or more. It is almost the same as the volume-based median diameter of the droplet.
  • a pH adjuster such as an acetic acid aqueous solution
  • a crosslinking agent isocyanate-based, epoxy-based, oxazoline-based, aziridine-based, metal chelate-based
  • chain transfer agent for example, if necessary, a pH adjuster (such as an acetic acid aqueous solution), a crosslinking agent (isocyanate-based, epoxy-based, oxazoline-based, aziridine-based, metal chelate-based), chain transfer agent.
  • additives such as (thiols), viscosity modifiers, release modifiers, plasticizers, softeners, fillers, colorants (pigments, dyes, etc.), anti-aging agents, surfactants, etc. can do. These additives may be added after the polymerization step, or may be added to each liquid in the aqueous dispersion preparation step, the monomer dispersion preparation step, the monomer emulsion preparation step, and the polymerization step.
  • an aqueous dispersion is prepared so that a hydrophobizing agent such as a swelling agent (specifically, dodecyltrimethylammonium bromide or the like) is not added to the aqueous dispersion.
  • a hydrophobizing agent such as a swelling agent (specifically, dodecyltrimethylammonium bromide or the like)
  • the hydrophobizing agent is added, the hydrophilic inorganic compound is reduced in hydrophilicity and the dispersibility in the aqueous dispersion is lowered, and is not uniformly supported on the surface of the water-dispersed resin.
  • a hydrophilic inorganic compound is dispersed in water to prepare an aqueous dispersion of the hydrophilic inorganic compound, and the aqueous dispersion, the ethylenically unsaturated monomer, Is added to prepare a monomer emulsion, and an ethylenically unsaturated monomer is polymerized.
  • the obtained water-dispersed resin can be composited with a hydrophilic inorganic compound so that the hydrophilic inorganic compound is unevenly distributed on the surface thereof. That is, the inorganic composite water-dispersed resin can carry the hydrophilic inorganic compound on the outer surface without encapsulating the hydrophilic inorganic compound.
  • the inorganic composite water-dispersed resin of the present invention can form a path in which the hydrophilic inorganic compound is continuous in the water-dispersed resin, and is therefore suitable as a heat-dissipating material or a conductive material in various industrial fields. Can be used.
  • a hydrophilic inorganic compound is formed on the outer surface while encapsulating the hydrophobic inorganic compound, not the hydrophilic inorganic compound, in the resulting inorganic composite water-dispersed resin.
  • FIG. 1 shows a cross-sectional view of an example of an adhesive film using an inorganic composite water-dispersed resin obtained by the method for producing an inorganic composite water-dispersed resin of the present invention.
  • a method for producing an adhesive film using the inorganic composite water dispersion obtained by the method for producing an inorganic composite water dispersion resin of the present invention will be described. In this method, first, a substrate 1 is prepared.
  • Examples of the material for forming the substrate 1 include polyolefin films such as polyethylene, polypropylene, and ethylene / propylene copolymers, polyester films such as polyethylene terephthalate, plastic films such as polyvinyl chloride, kraft paper, and Japanese paper. Examples thereof include papers, cotton cloths, cloths such as soft cloths, textiles such as polyester nonwoven fabrics and vinylon cloths, and metal foils.
  • polyethylene is used.
  • the base material 1 is formed in a sheet (film) shape or a tape shape, for example.
  • the base material 1 can be subjected to known processes such as undercoating, sealing, corona and back processes, if necessary.
  • the thickness of the substrate 1 is appropriately selected according to its use and purpose, and is, for example, 20 to 150 ⁇ m, preferably 30 to 100 ⁇ m.
  • the pressure-sensitive adhesive layer 2 is laminated on one side of the substrate 1.
  • the above-mentioned inorganic composite water-dispersed resin emulsion is directly applied to one side of the substrate 1 by a known coating method such as roll coating, screen coating, gravure coating, and the like. For example, it is dried by heating at 50 to 180 ° C. Further, the pressure-sensitive adhesive layer 2 can be transferred to the substrate 1 from the release sheet on which the pressure-sensitive adhesive layer 2 is laminated.
  • the release sheet laminated with the pressure-sensitive adhesive layer 2 is, for example, an inorganic composite water-dispersed resin emulsion is directly applied to a known release sheet by a known application method, and dried by heating. Formed by forming layer 2.
  • a release sheet on which the pressure-sensitive adhesive layer 2 is laminated is bonded to the base material 1 so that one side of the base material 1 and the pressure-sensitive adhesive layer 2 are in contact with each other. Then, the release sheet is peeled off from the pressure-sensitive adhesive layer 2.
  • the thickness of the pressure-sensitive adhesive layer 2 thus formed is appropriately selected according to its use and purpose, and is, for example, in the range of about 1.0 to 100 ⁇ m, preferably about 3.0 to 50 ⁇ m.
  • the pressure-sensitive adhesive layer 2 is provided on one side of the substrate 1, but it can also be provided on both sides of the substrate 1, for example.
  • the pressure-sensitive adhesive layer has a high loss elastic modulus G ′′ and loss tangent tan ⁇ obtained by dynamic viscoelasticity measurement. Therefore, it is presumed that the pressure-sensitive adhesive layer has excellent vibration damping properties. Furthermore, since this adhesive film is excellent in the adhesive strength, heat resistance and moisture resistance of the pressure-sensitive adhesive layer, it is excellent in adhesive strength, heat resistance and moisture resistance.
  • Example 1 Water dispersion preparation process
  • 20 parts by weight of hydrophilic boron nitride particles BN-20, bulk shape, primary average particle diameter 20 nm
  • BN-20 hydrophilic boron nitride particles
  • this monomer pre-emulsion was treated with a high-pressure homogenizer (PANDA 2K) for 2 passes at a pressure of 100 MPa, and 20 wt% dispersant liquid (polymer dispersant, trade name: Charol AN-103P, Daiichi 5 parts by weight (manufactured by Kogyo Seiyaku Co., Ltd.) (1 part by weight in solid content) was added to obtain a monomer emulsion.
  • PANDA 2K high-pressure homogenizer
  • 20 wt% dispersant liquid polymer dispersant, trade name: Charol AN-103P, Daiichi 5 parts by weight (manufactured by Kogyo Seiyaku Co., Ltd.) (1 part by weight in solid content) was added to obtain a monomer emulsion.
  • Polymerization process Charge the prepared monomer emulsion into a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer and a stirrer, and then
  • Example 2 In the aqueous dispersion preparation step, a monomer emulsion was prepared in the same manner as in Example 1 except that the blending number of water was changed to 942 parts by weight and the blending number of boron nitride particles was changed to 60 parts by weight. This was polymerized to obtain an emulsion of an inorganic composite water-dispersed resin having a solid content concentration of 20%.
  • Example 3 Water dispersion preparation process 20 parts by weight of hydrophilic titanium oxide (TTO-55D, bulk shape, primary average particle size 30-50 nm, manufactured by Ishihara Sangyo Co., Ltd.) is added to 517 parts by weight of water, and this is treated with an ultrasonic homogenizer for 3 minutes to form titanium oxide. An aqueous dispersion was obtained.
  • TTO-55D hydrophilic titanium oxide
  • Isostearyl acrylate 100 parts by weight, hexadecane 5 parts by weight, 3-methacryloyloxypropyl-trimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.05 parts by weight, initiator (dimethyl 2,2′-azobis (2 -Methylpropionate), oil-soluble azo initiator, trade name: V-601, manufactured by Wako Pure Chemical Industries, Ltd.) 0.25 parts by weight were mixed to prepare an oil phase solution.
  • initiator dimethyl 2,2′-azobis (2 -Methylpropionate
  • V-601 oil-soluble azo initiator
  • the oil phase liquid and the aqueous dispersion were mixed, and stirred and forcedly emulsified at 6000 (1 / min) for 1 minute using a TK homomixer (manufactured by Primex) to prepare a monomer pre-emulsion.
  • this monomer pre-emulsion was treated for 2 passes at a pressure of 100 MPa using a high-pressure homogenizer (PANDA 2K), and 20 wt% dispersant liquid (polymer dispersant, trade name: SN Dispersant 5045, manufactured by San Nopco) ) 25 parts by weight (5 parts by weight solids) was added to obtain a monomer emulsion.
  • PANDA 2K high-pressure homogenizer
  • the prepared monomer emulsion was charged into a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirrer, and then the reaction vessel was purged with nitrogen, then heated to 70 ° C. and polymerized for 3 hours to form a solid.
  • An inorganic composite water-dispersed resin having a partial concentration of 20% was obtained.
  • Example 4 Preparation of aqueous dispersion
  • ATO antimony-doped tin oxide
  • aqueous dispersion (SN-100S, solid content concentration 17.9%, bulk shape, primary average particle size 20 nm, manufactured by Ishihara Sangyo Co., Ltd.) 84 parts by weight (solid content 15 parts by weight)
  • 368 parts by weight of water and 4.5 parts by weight of 3-methacryloyloxypropyl-trimethoxysilane KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.
  • this monomer pre-emulsion was subjected to one pass treatment at a pressure of 150 MPa using a high-pressure homogenizer (Nanomizer, manufactured by Yoshida Kikai Kogyo Co., Ltd.) to obtain a monomer emulsion.
  • a high-pressure homogenizer Nenomizer, manufactured by Yoshida Kikai Kogyo Co., Ltd.
  • the prepared monomer emulsion was charged into a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirrer, and then the reaction vessel was purged with nitrogen, then heated to 70 ° C. and polymerized for 3 hours to form a solid.
  • An emulsion of an inorganic composite water-dispersed resin having a partial concentration of 20% was obtained.
  • Example 5 In the aqueous dispersion preparation step, the blending part of the ATO aqueous dispersion was changed to 50 parts by weight in solid content, the blending part of water was changed to 486 parts by weight, and 3-methacryloyloxypropyl-trimethoxysilane Except that the blending amount was changed to 9.1 parts by weight, an aqueous dispersion was prepared in the same manner as in Example 4, and then a monomer emulsion was prepared, followed by polymerization to obtain a solid content concentration. An emulsion of 18% inorganic composite water-dispersed resin was obtained.
  • Example 6 In the aqueous dispersion preparation step, the blending number of the ATO aqueous dispersion was changed to 70 parts by weight in solid content, the blending number of water was changed to 486 parts by weight, and the pH was adjusted to 4.0 with a 5% aqueous acetic acid solution. After that, 2.2 parts by weight of the dispersant liquid (polycarboxylic acid type dispersant, trade name: Charol AN-103P, solid content concentration 45%, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was added.
  • the dispersant liquid polycarboxylic acid type dispersant, trade name: Charol AN-103P, solid content concentration 45%, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
  • an aqueous dispersion was prepared in the same manner as in Example 4 and then a monomer emulsion was prepared and then polymerized to obtain an inorganic composite water-dispersed resin having a solid content concentration of 18%. An emulsion was obtained.
  • Example 7 In the aqueous dispersion preparation step, after adjusting the pH to 4.0 with a 5% aqueous acetic acid solution, 5 parts by weight of a 20% by weight dispersant liquid (polymer dispersant, trade name: Charol AN-103P, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) (1 part by weight in solid content) was further added, and in the monomer emulsion preparation step, a monomer emulsion was prepared in the same manner as in Example 4 except that butyl acrylate was used instead of methyl methacrylate. Was polymerized to obtain a water-dispersed nanoparticle polymer composite composition having a solid content concentration of 20%.
  • a 20% by weight dispersant liquid polymer dispersant, trade name: Charol AN-103P, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
  • a monomer emulsion was prepared in the same manner as in Example 4 except that butyl acryl
  • Example 8 After adjusting the pH to 4.0 with 5% aqueous acetic acid in the aqueous dispersion preparation step, the aqueous dispersion was further stirred and mixed for 20 hours. In the monomer emulsion preparation step, butyl acrylate was used instead of methyl methacrylate. In the same manner as in Example 4, a monomer emulsion was prepared, and then polymerized to obtain an emulsion of an inorganic composite water-dispersed resin having a solid content concentration of 20%.
  • Example 9 Preparation of aqueous dispersion 168 parts by weight of ATO (antimony-doped tin oxide) aqueous dispersion (SN-100D, solid concentration 29.7%, bulk shape, primary average particle size 20 nm, manufactured by Ishihara Sangyo Co., Ltd.) 167 parts by weight of water and 3.8 parts by weight of 3-methacryloyloxypropyl-trimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) were added, and the pH was adjusted to 4.0 with a 5% aqueous acetic acid solution.
  • ATO antimony-doped tin oxide
  • SN-100D solid concentration 29.7%, bulk shape, primary average particle size 20 nm, manufactured by Ishihara Sangyo Co., Ltd.
  • KBM-503 3-methacryloyloxypropyl-trimethoxysilane
  • this monomer pre-emulsion was subjected to one pass treatment at a pressure of 150 MPa using a high-pressure homogenizer (Nanomizer, manufactured by Yoshida Kikai Kogyo Co., Ltd.) to obtain a monomer emulsion.
  • a high-pressure homogenizer Nenomizer, manufactured by Yoshida Kikai Kogyo Co., Ltd.
  • the prepared monomer emulsion was charged into a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirrer, and then the reaction vessel was purged with nitrogen, then heated to 70 ° C. and polymerized for 3 hours to form a solid.
  • An emulsion of an inorganic composite water-dispersed resin having a partial concentration of 35% was obtained.
  • Example 10 (Preparation of aqueous dispersion)
  • a monomer emulsion was prepared in the same manner as in Example 9 except that 100 parts by weight of 2-ethylhexyl acrylate was used instead of 100 parts by weight of butyl acrylate, and this was then polymerized.
  • an emulsion of an inorganic composite water-dispersed resin having a solid content concentration of 35% was obtained.
  • Example 11 In the monomer emulsion preparation step, a monomer emulsion was prepared in the same manner as in Example 9 except that 100 parts by weight of lauryl methacrylate (dodecyl methacrylate) was used instead of 100 parts by weight of butyl acrylate.
  • lauryl methacrylate dodecyl methacrylate
  • butyl acrylate was used instead of 100 parts by weight of butyl acrylate.
  • Example 12 In the monomer emulsion preparation step, a monomer emulsion was prepared in the same manner as in Example 9, except that 100 parts by weight of isostearyl acrylate (2-methylheptadecyl acrylate) was used instead of 100 parts by weight of 2-ethylhexyl acrylate. This was then polymerized to obtain an inorganic composite water-dispersed resin emulsion having a solid content of 35%.
  • Example 13 In the aqueous dispersion preparation process, the number of blended parts of 3-methacryloyloxypropyl-trimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) was changed to 15.2 parts by weight, and the number of blended parts of water was changed to 111 parts by weight. In the same manner as in Example 9, an aqueous dispersion was prepared, and then a monomer emulsion was prepared, followed by polymerization to obtain an emulsion of an inorganic composite water-dispersed resin having a solid content concentration of 35%. Obtained.
  • KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd. the number of blended parts of 3-methacryloyloxypropyl-trimethoxysilane
  • Example 14 (Preparation of aqueous dispersion) Titanium oxide aqueous dispersion (TTO-W-5, solid content concentration 30.7%, bulk shape, primary average particle size 50 nm, manufactured by Ishihara Sangyo Co., Ltd.) 163 parts by weight (solid content 50 parts by weight) and water 172 Part by weight and 3.8 parts by weight of 3-methacryloyloxypropyl-trimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) were added, and the pH was adjusted to 4.0 with a 5% aqueous acetic acid solution.
  • TTO-W-5 solid content concentration 30.7%, bulk shape, primary average particle size 50 nm, manufactured by Ishihara Sangyo Co., Ltd.
  • KBM-503 3-methacryloyloxypropyl-trimethoxysilane
  • this monomer pre-emulsion was subjected to one pass treatment at a pressure of 150 MPa using a high-pressure homogenizer (Nanomizer, manufactured by Yoshida Kikai Kogyo Co., Ltd.) to obtain a monomer emulsion.
  • a high-pressure homogenizer Nenomizer, manufactured by Yoshida Kikai Kogyo Co., Ltd.
  • the prepared monomer emulsion was charged into a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirrer, and then the reaction vessel was purged with nitrogen, then heated to 70 ° C. and polymerized for 3 hours to form a solid.
  • An emulsion of an inorganic composite water-dispersed resin having a partial concentration of 35% was obtained.
  • Example 15 (Preparation of aqueous dispersion) 100 parts by weight of alumina aqueous dispersion (NANOBYK-3600, alumina solid content concentration 50%, bulk shape, primary average particle size 40 nm, manufactured by Big Chemie Japan Co., Ltd.) and 235 parts by weight of water Then, 3.8 parts by weight of 3-methacryloyloxypropyl-trimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) was added, and the pH was adjusted to 4.0 with a 5% aqueous acetic acid solution.
  • alumina aqueous dispersion NANOBYK-3600, alumina solid content concentration 50%, bulk shape, primary average particle size 40 nm, manufactured by Big Chemie Japan Co., Ltd.
  • KBM-503 3-methacryloyloxypropyl-trimethoxysilane
  • this monomer pre-emulsion was subjected to one pass treatment at a pressure of 150 MPa using a high-pressure homogenizer (Nanomizer, manufactured by Yoshida Kikai Kogyo Co., Ltd.) to obtain a monomer emulsion.
  • a high-pressure homogenizer Nenomizer, manufactured by Yoshida Kikai Kogyo Co., Ltd.
  • the prepared monomer emulsion was charged into a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirrer, and then the reaction vessel was purged with nitrogen, then heated to 70 ° C. and polymerized for 3 hours to form a solid.
  • An emulsion of an inorganic composite water-dispersed resin having a partial concentration of 35% was obtained.
  • Example 16 (Preparation of aqueous dispersion) 285 parts by weight of alumina aqueous dispersion (alumina sol 100, alumina solid content concentration 10.3%, needle shape, maximum length 300 nm, manufactured by Nissan Chemical Industries, Ltd.), 67 parts by weight of water, 15.3 parts by weight of 3-methacryloyloxypropyl-trimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) was added, and the pH was adjusted to 4.0 with a 5% aqueous acetic acid solution.
  • alumina aqueous dispersion alumina sol 100, alumina solid content concentration 10.3%, needle shape, maximum length 300 nm, manufactured by Nissan Chemical Industries, Ltd.
  • KBM-503 3-methacryloyloxypropyl-trimethoxysilane
  • this monomer pre-emulsion was subjected to one pass treatment at a pressure of 150 MPa using a high-pressure homogenizer (Nanomizer, manufactured by Yoshida Kikai Kogyo Co., Ltd.) to obtain a monomer emulsion.
  • a high-pressure homogenizer Nenomizer, manufactured by Yoshida Kikai Kogyo Co., Ltd.
  • the prepared monomer emulsion was charged into a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirrer, and then the reaction vessel was purged with nitrogen, then heated to 70 ° C. and polymerized for 3 hours to form a solid.
  • An inorganic composite water-dispersed resin emulsion having a partial concentration of 35% was obtained.
  • EXAMPLE 17 (Preparation of aqueous dispersion) Alumina water dispersion (NANOBYK-3600, alumina solid content concentration 50%, bulk shape, primary average particle size 40 nm, manufactured by Big Chemie Japan) 100 parts by weight (solid content 50 parts by weight) and alumina water dispersion (alumina sol 100, alumina solid content concentration 10.3%, needle shape, maximum length 300 nm, manufactured by Nissan Chemical Industries, Ltd.) 485 parts by weight (solid part 50 parts by weight), water 70 parts by weight, 3-methacryloyloxypropyl- 16.2 parts by weight of trimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) was added, and the pH was adjusted to 4.0 with a 5% aqueous acetic acid solution.
  • Alumina water dispersion NANOBYK-3600, alumina solid content concentration 50%, bulk shape, primary average particle size 40 nm, manufactured by Big Chemie Japan
  • this monomer pre-emulsion was subjected to one pass treatment at a pressure of 150 MPa using a high-pressure homogenizer (Nanomizer, manufactured by Yoshida Kikai Kogyo Co., Ltd.) to obtain a monomer emulsion.
  • a high-pressure homogenizer Nenomizer, manufactured by Yoshida Kikai Kogyo Co., Ltd.
  • the prepared monomer emulsion was charged into a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirrer, and then the reaction vessel was purged with nitrogen, then heated to 70 ° C. and polymerized for 3 hours to form a solid.
  • An emulsion of an inorganic composite water-dispersed resin having a partial concentration of 35% was obtained.
  • Example 18 (Preparation of aqueous dispersion) 50 parts by weight of silicon carbide powder ( ⁇ -SiC, bulk shape, primary average particle size 30 nm, manufactured by Sumitomo Osaka Cement Co., Ltd.), 282 parts by weight of water, 20% by weight dispersant liquid (polymer dispersant, trade name) : Charol AN-103P, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 15.0 parts by weight (3 parts by weight in solids), treated with an ultrasonic homogenizer for 5 minutes, and then 3-methacryloyloxypropyl-trimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) 1.9 parts by weight was added, and the pH was adjusted to 4.0 with 5% acetic acid aqueous solution.
  • silicon carbide powder ⁇ -SiC, bulk shape, primary average particle size 30 nm, manufactured by Sumitomo Osaka Cement Co., Ltd
  • this monomer pre-emulsion was subjected to one pass treatment at a pressure of 150 MPa using a high-pressure homogenizer (Nanomizer, manufactured by Yoshida Kikai Kogyo Co., Ltd.) to obtain a monomer emulsion.
  • a high-pressure homogenizer Nenomizer, manufactured by Yoshida Kikai Kogyo Co., Ltd.
  • the prepared monomer emulsion was charged into a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirrer, and then the reaction vessel was purged with nitrogen, then heated to 70 ° C. and polymerized for 3 hours to form a solid.
  • An emulsion of an inorganic composite water-dispersed resin having a partial concentration of 35% was obtained.
  • Example 19 (Preparation of aqueous dispersion) 50 parts by weight of diamond powder (trade name: HHM-A-1 / 10 ⁇ m, bulk shape, primary average particle size 100 nm, manufactured by Techno Rise), 279 parts by weight of water, and 20% by weight dispersant liquid (polymer dispersion) Agent, trade name: Charol AN-103P, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 15.0 parts by weight (3 parts by weight in solids), treated with an ultrasonic homogenizer for 5 minutes, and then 3-methacryloyloxypropyl -Trimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) (0.5 part by weight) was added, and the pH was adjusted to 4.0 with a 5% aqueous acetic acid solution.
  • diamond powder trade name: HHM-A-1 / 10 ⁇ m, bulk shape, primary average particle size 100 nm, manufactured by Techno Rise
  • this monomer pre-emulsion was subjected to one pass treatment at a pressure of 150 MPa using a high-pressure homogenizer (Nanomizer, manufactured by Yoshida Kikai Kogyo Co., Ltd.) to obtain a monomer emulsion.
  • a high-pressure homogenizer Nenomizer, manufactured by Yoshida Kikai Kogyo Co., Ltd.
  • the prepared monomer emulsion was charged into a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirrer, and then the reaction vessel was purged with nitrogen, then heated to 70 ° C. and polymerized for 3 hours to form a solid.
  • An emulsion of an inorganic composite water-dispersed resin having a partial concentration of 35% was obtained.
  • Example 20 (Preparation of aqueous dispersion) 168 parts by weight of ATO (antimony-doped tin oxide) aqueous dispersion (SN-100D, solid concentration 29.7%, bulk shape, primary average particle size 20 nm, manufactured by Ishihara Sangyo Co., Ltd.) 183 parts by weight of water and 3.8 parts by weight of 3-methacryloyloxypropyl-trimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) were added, and the pH was adjusted to 4.0 with a 5% aqueous acetic acid solution.
  • ATO antimony-doped tin oxide
  • SN-100D solid concentration 29.7%, bulk shape, primary average particle size 20 nm, manufactured by Ishihara Sangyo Co., Ltd.
  • KBM-503 3-methacryloyloxypropyl-trimethoxysilane
  • this monomer pre-emulsion was subjected to one pass treatment at a pressure of 150 MPa using a high-pressure homogenizer (Nanomizer, manufactured by Yoshida Kikai Kogyo Co., Ltd.) to obtain a monomer emulsion.
  • a high-pressure homogenizer Nenomizer, manufactured by Yoshida Kikai Kogyo Co., Ltd.
  • the prepared monomer emulsion was charged into a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirrer, and then the reaction vessel was purged with nitrogen, then heated to 70 ° C. and polymerized for 3 hours to form a solid.
  • An emulsion of an inorganic composite water-dispersed resin having a partial concentration of 35% was obtained.
  • Comparative Example 1 In the monomer emulsion preparation step, the monomer emulsion was prepared in the same manner as in Example 1 except that 20% by weight dispersant liquid (polymer dispersant, trade name: Charol AN-103P, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was not used. This was then polymerized to obtain an inorganic composite water-dispersed resin emulsion having a solid content of 20%.
  • dispersant liquid polymer dispersant, trade name: Charol AN-103P, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
  • Comparative Example 2 In the aqueous dispersion preparation step, an aqueous dispersion was prepared in the same manner as in Example 1 except that the blending number of boron nitride particles was changed to 250 parts by weight and the blending number of water was changed to 1438 parts by weight. A monomer emulsion was prepared and subsequently polymerized to obtain an emulsion of an inorganic composite water-dispersed resin having a solid content concentration of 20%.
  • Comparative Example 3 In the aqueous dispersion preparation step, an aqueous dispersion was prepared in the same manner as in Example 1, except that the blending number of boron nitride particles was changed to 3 parts by weight and the blending number of water was changed to 450 parts by weight. A monomer emulsion was prepared and subsequently polymerized to obtain an emulsion of an inorganic composite water-dispersed resin having a solid content concentration of 20%.
  • Comparative Example 4 100 parts by weight of butyl acrylate, 3 parts by weight of hexadecane, 0.2 parts by weight of initiator (azobisisobutyronitrile), 20% by weight emulsifier liquid (anionic non-reactive emulsifier, trade name: Haitenol LA-16, 1 part by weight (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 1 part by weight (0.2 part by weight in solids), 309 parts by weight of water, and 1 minute at 6000 (1 / min) using a TK homomixer (manufactured by Primex) A monomer pre-emulsion was prepared by stirring and forcibly emulsifying.
  • initiator azobisisobutyronitrile
  • emulsifier liquid anionic non-reactive emulsifier, trade name: Haitenol LA-16, 1 part by weight (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
  • this monomer pre-emulsion was subjected to one pass treatment at a pressure of 150 MPa using a high-pressure homogenizer (Nanomizer, manufactured by Yoshida Kikai Kogyo Co., Ltd.) to obtain a monomer emulsion.
  • a high-pressure homogenizer Nenomizer, manufactured by Yoshida Kikai Kogyo Co., Ltd.
  • Polymerization process By charging the prepared monomer dispersion in a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer and a stirrer, and then substituting the reaction vessel with nitrogen, the temperature was raised to 70 ° C. and polymerization was performed for 3 hours. An emulsion of a water-dispersed resin having a solid content concentration of 23% was obtained.
  • aqueous dispersion 75 parts by weight (15 parts by weight of solids) of an aqueous dispersion (SN-100S, solid content 17.9%, manufactured by Ishihara Sangyo Co., Ltd.) was added to the emulsion and stirred to obtain an inorganic composite water-dispersed resin. An emulsion was obtained.
  • Comparative Example 5 Water dispersion preparation process 10 parts by weight of Lucentite SWN (layered clay mineral, manufactured by Co-op Chemical) was added to 372 parts by weight of water, allowed to stand for 24 hours, and further stirred for 24 hours to prepare an aqueous dispersion.
  • Lucentite SWN layered clay mineral, manufactured by Co-op Chemical
  • Aggregate rate (%) ⁇ (A + B) / C ⁇ ⁇ 100
  • A Weight of aggregate remaining on nylon mesh
  • B Weight of aggregate adhered to reaction vessel and stirring blade
  • C Total weight of oil phase liquid component, hexadecane and clay mineral, hydrophilic inorganic compound and hydrophobic inorganic compound
  • FIGS. 2 to 7, 9, and 11 to 20 Image processing diagrams of these SEM photographs are shown in FIGS. 2 to 7, 9, and 11 to 20.
  • FIG. 5 TEM observation The emulsion of the inorganic composite water-dispersed resin obtained in Examples 8, 9, 20, Comparative Example 4 and Comparative Example 5 was diluted with water, and one drop thereof was dropped on a sample table for a TEM with a carbon film. After drying, the film was observed at an acceleration voltage of 100 kV using a Hitachi transmission electron microscope Hitachi H-7650.
  • the inorganic composite water-dispersed resin obtained by the method for producing an inorganic composite water-dispersed resin of the present invention is suitably used as a heat-dissipating material or a conductive material in various industrial fields, and as an adhesive layer of an adhesive film, Preferably used.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
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Abstract

L'invention concerne un procédé pour produire une résine dispersée dans l'eau composite inorganique, lequel procédé comprend une étape consistant à préparer une dispersion aqueuse d'un composé inorganique hydrophile par dispersion d'un composé inorganique hydrophile de type aciculaire ou lamellaire en vrac dans de l'eau, une étape consistant à préparer une émulsion de monomère par mélange de la dispersion aqueuse et d'un monomère à insaturation éthylénique en proportion telle que 4 à 200 parties en poids du composé inorganique hydrophile est mélangé pour 100 parties en poids du monomère à insaturation éthylénique, ce qui permet ainsi d'émulsifier le monomère à insaturation éthylénique, une étape consistant à mélanger un tensioactif dans au moins l'eau, la dispersion aqueuse, le monomère à insaturation éthylénique ou l'émulsion de monomère, et une étape consistant à polymériser le monomère à insaturation éthylénique dans l'émulsion de monomère.
PCT/JP2009/000449 2008-02-07 2009-02-05 Procédé pour produire une résine dispersée dans l'eau composite inorganique WO2009098883A1 (fr)

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WO2017159253A1 (fr) * 2016-03-18 2017-09-21 株式会社ダイセル Composition de résine durcissable et élément optique
CN109251281A (zh) * 2018-09-17 2019-01-22 西安天亿胶粘材料有限公司 一种耐高温易剥离印刷水乳型树脂的制备方法
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JP5302089B2 (ja) * 2008-12-26 2013-10-02 日東電工株式会社 無機多孔質体の製造方法
JP5474854B2 (ja) * 2010-03-16 2014-04-16 積水化成品工業株式会社 有機無機複合粒子およびその製造方法、熱伝導性フィラー、並びに、熱伝導性樹脂組成物およびその製造方法
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TWI710606B (zh) * 2016-03-18 2020-11-21 日商大賽璐股份有限公司 硬化性樹脂組成物及光學構件
WO2017159253A1 (fr) * 2016-03-18 2017-09-21 株式会社ダイセル Composition de résine durcissable et élément optique
CN108884176A (zh) * 2016-03-18 2018-11-23 株式会社大赛璐 固化性树脂组合物及光学部件
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CN108884176B (zh) * 2016-03-18 2021-03-02 株式会社大赛璐 固化性树脂组合物及光学部件
JP2019048448A (ja) * 2017-09-08 2019-03-28 株式会社ダイセル 反射防止フィルム
CN111051930A (zh) * 2017-09-08 2020-04-21 株式会社大赛璐 防反射膜
WO2019049578A1 (fr) * 2017-09-08 2019-03-14 株式会社ダイセル Film antireflet
US11372138B2 (en) 2017-09-08 2022-06-28 Daicel Corporation Anti-reflection film
JP7224106B2 (ja) 2017-09-08 2023-02-17 株式会社ダイセル 反射防止フィルム
CN109251281A (zh) * 2018-09-17 2019-01-22 西安天亿胶粘材料有限公司 一种耐高温易剥离印刷水乳型树脂的制备方法

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