WO2009101974A1 - シリカコロイド粒子及びその製造方法、並びにその有機溶媒分散シリカゾル、重合性化合物分散シリカゾル及びジカルボン酸無水物分散シリカゾル - Google Patents
シリカコロイド粒子及びその製造方法、並びにその有機溶媒分散シリカゾル、重合性化合物分散シリカゾル及びジカルボン酸無水物分散シリカゾル Download PDFInfo
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- WO2009101974A1 WO2009101974A1 PCT/JP2009/052303 JP2009052303W WO2009101974A1 WO 2009101974 A1 WO2009101974 A1 WO 2009101974A1 JP 2009052303 W JP2009052303 W JP 2009052303W WO 2009101974 A1 WO2009101974 A1 WO 2009101974A1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/145—Preparation of hydroorganosols, organosols or dispersions in an organic medium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/146—After-treatment of sols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- 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
Definitions
- the present invention relates to silica colloidal particles and a production method thereof, and an organic solvent-dispersed silica sol, a polymerizable compound-dispersed silica sol, and a dicarboxylic acid anhydride-dispersed silica sol.
- Silica sol in which silica colloidal particles of several to about 100 nm are dispersed in a liquid has high transparency.
- silica colloid particles since silica colloid particles have high hardness, they are mixed with a resin or the like and used as a modifier for the purpose of imparting the hardness or heat resistance of the resin.
- aqueous silica sol may be used, but it is dispersed in organic solvent-dispersed silica sol or polymerizable compound that can be used as resin raw material in consideration of compatibility and reactivity with resin. In many cases, a sol obtained by dispersing silica colloidal particles in an organic compound is used.
- Patent Document 1 describes a method for producing an organic solvent-dispersed silica sol in which an aqueous silica sol and an organic solvent are mixed and then dehydrated with an ultrafiltration membrane.
- Patent Document 2 discloses a methanol silica sol in which metal ions contained in an aqueous silica sol are removed by ion exchange, an organic base is added, and then methanol is mixed, followed by concentration and dehydration by ultrafiltration. A manufacturing method is described.
- Patent Document 3 describes an organic solvent-dispersed silica sol in which alkaline earth metal ions are bonded to the surface of silica colloidal particles.
- Patent Document 4 describes an oxide sol in which 80 mol% or more of the dispersion medium is a reactive monomer having a polymerizable unsaturated bond in the molecule.
- alkali metal ions such as Na ions contained in the aqueous silica sol are previously removed by cation exchange to form an acidic aqueous silica sol.
- Alkaline aqueous silica sols containing alkali metal ions have poor compatibility with many organic solvents such as alcohols and ethers, and when these organic solvents are mixed, the colloidal silica particles cause aggregation or gelation.
- the acidic aqueous silica sol obtained by the above method has the property that the pH increases due to the elution of alkali metal ions present in the silica colloidal particles over time, and the viscosity of the silica sol increases and eventually gelation occurs. It is known. Therefore, after cation exchange of the alkaline aqueous silica sol, the obtained sol is aged as it is or in the presence of a small amount of acid to diffuse the alkali metal ions in the silica colloidal particles into the colloidal dispersion medium, and then further A method for stabilizing an acidic aqueous silica sol in which alkali metal ions are removed by cation exchange is disclosed (Patent Document 5).
- Patent Document 6 A method for producing an acidic aqueous silica sol is disclosed (Patent Document 6). JP 59-8614 A Japanese Patent Laid-Open No. 2-167813 JP 2007-63117 A JP-A-62-95130 US Pat. No. 3,342,747 JP-A-63-123807
- the organic solvent-dispersed silica sol is obtained by a solvent replacement method, it is desirable to increase the silica concentration of the acidic aqueous silica sol as a raw material as high as possible in order to increase the replacement efficiency of the organic solvent.
- the stability of the acidic aqueous silica sol is not sufficient as compared with the alkaline silica sol.
- the acidic aqueous silica sol produced by the method disclosed in Patent Document 6 has a strong electrostatic repulsion between the silica colloid particles due to the presence of the aluminum compound contained in the silica colloid particles, and it is easy to increase the silica concentration.
- there are many solid acid sites on the surface Due to the presence of this solid acid point, the catalytic action by the solid acid is increased, and when an organic solvent-dispersed silica sol is obtained, an organic solvent such as ketone, ester, amide or the like may decompose or discolor.
- the present invention does not cause decomposition or coloring of the organic compound, which occurs when the silica colloidal particles as described above are dispersed in the organic compound, and does not cause decomposition or coloring of the resin even when blended with the resin, and Disclosed are silica colloid particles having good dispersion stability in a dispersion medium, a method for producing the same, and organic solvent-dispersed silica sol, polymerizable compound-dispersed silica sol, and dicarboxylic anhydride-dispersed silica sol.
- the average content of the polyvalent metal element M which is at least one selected from the group consisting of iron, aluminum, zinc, zirconium, titanium, tin and lead, is 0.
- Silica colloidal particles having an average primary particle diameter of 5 to 40 nm, which is 001 to 0.02, wherein the content of the polyvalent metal element M present in the outermost layer of the colloidal particles is per 1 nm 2 of the surface area of the colloidal particles.
- silica colloidal particles As a second aspect, an organic solvent-dispersed silica sol in which the silica colloidal particles described in the first aspect are dispersed in an organic solvent, As a third aspect, the organic solvent according to the third aspect, wherein the organic solvent is at least one selected from the group consisting of alcohols, ethers, ketones, esters, amides, hydrocarbons, and nitriles.
- the silica colloidal particles described in the first aspect are a polymerizable compound having an ethylenically unsaturated bond, a polymerizable compound having an epoxy ring, a polymerizable compound having an oxetane ring, and a polymerizable compound having a vinyl ether structure
- the polymerizable compound having an epoxy ring is represented by the formula (1): (Where R 1 and R 2 each independently represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, a heterocyclic group, or a halogenated, aminated, or nitrated derivative thereof.
- the polymerizable compound-dispersed silica sol according to the fourth aspect which is an ester-modified epoxy compound containing the compound (i) having a functional group represented by (ii) in the molecule and the compound (ii) having a glycidyl group in the molecule
- the compound (i) is represented by the formula (1) wherein 1 or more and n or less of n (where n is an integer of 2 to 16) glycidyl groups in the molecule is represented.
- the polymerizable compound-dispersed silica sol according to the fifth aspect which is a compound substituted with a functional group
- the polymerizable compound-dispersed silica sol according to the fifth aspect wherein the compound (ii) is a compound having n glycidyl groups in the molecule (where n is an integer of 2 to 16).
- the polymerizable compound-dispersed silica sol according to the fifth aspect wherein the molar ratio of compound (i): compound (ii) is 1: 0.3 to 1.5
- the compound (i) is obtained by replacing the glycidyl group of tris- (2,3-epoxypropyl) -isocyanate with a functional group represented by the formula (1).
- the polymerizable compound-dispersed silica sol according to any one of the eighth aspect As a tenth aspect, the polymerizable compound-dispersed silica sol according to any one of the fifth, seventh, and eighth aspects, wherein the compound (ii) is tris- (2,3-epoxypropyl) -isocyanate ,
- a dicarboxylic acid anhydride-dispersed silica sol in which the silica colloidal particles described in the first aspect are dispersed in a liquid dicarboxylic acid anhydride at 30 ° C. As a twelfth aspect, according to the eleventh aspect, the dicarboxylic acid anhydride includes at least one selected from the group consisting of methylhexahydrophthalic anhydride, hydrogenated methylnadic acid anhydride, and hydrogenated trimellitic acid anhydride.
- Dicarboxylic anhydride-dispersed silica sol As a thirteenth aspect, the method for producing silica colloidal particles according to the first aspect including the following steps (I) and (II): (I): The average content of the polyvalent metal element M, which is at least one selected from the group consisting of iron, aluminum, zinc, zirconium, titanium, tin, and lead, is 0.001 to 0.00 as the M / Si molar ratio. A step of aging at 0 to 40 ° C.
- the average content of the polyvalent metal element M which is at least one selected from the group consisting of iron, aluminum, zinc, zirconium, titanium, tin and lead, is 0.
- the silica colloid particles of the present invention are silica colloid particles having a small action of solid acid on the surface of the silica colloid particles and a large electrostatic repulsion, such as various organic solvents, polymerizable compounds, dicarboxylic acid anhydrides, etc.
- Silica sol stably dispersed in an organic compound is obtained, and even when contacted with these organic compounds, decomposition, alteration, discoloration, etc. of the organic compounds hardly occur.
- the organic solvent-dispersed silica sol of the present invention comprises the colloidal silica particles of the present invention dispersed in an organic solvent such as alcohols, ethers, ketones, esters, amides, hydrocarbons, and nitriles. It is a stable silica sol that is unlikely to be decomposed, altered, or discolored.
- the polymerizable compound-dispersed silica sol of the present invention is a polymerizable compound such as a polymerizable compound having an ethylenically unsaturated bond, a polymerizable compound having an epoxy ring, a polymerizable compound having an oxetane ring, or a polymerizable compound having a vinyl ether structure.
- the silica colloidal particles of the present invention are dispersed, and it is a stable silica sol in which the polymerizable compound is hardly decomposed, altered, discolored, polymerized or the like.
- the silica colloidal particles of the present invention are dispersed in a dicarboxylic acid anhydride such as methylhexahydrophthalic acid anhydride, hydrogenated methylnadic acid anhydride, hydrogenated trimellitic acid anhydride or the like. It is a stable silica sol that is resistant to decomposition, alteration, discoloration and the like of dicarboxylic acid anhydride.
- the silica colloidal particles of the present invention or the organic solvent-dispersed silica sol thereof the polymerizable compound-dispersed silica sol, or the dicarboxylic acid-dispersed silica sol is used as a modifier for a resin or the like, imparting hardness without causing decomposition or coloring of the resin, It is useful for modifying resins such as imparting heat resistance.
- a polymerizable compound-dispersed silica sol having an epoxy ring or a dicarboxylic acid anhydride-dispersed silica sol can be obtained at a high silica concentration.
- the average content of the polyvalent metal element M which is at least one selected from the group consisting of iron, aluminum, zinc, zirconium, titanium, tin and lead, is 0.
- the silica colloidal particles of the present invention are well dispersed in various organic solvents, polymerizable compounds, dicarboxylic acid anhydrides and the like.
- the silica colloidal particles of the present invention are dense colloidal particles and have substantially no pores.
- the average content of the polyvalent metal element M which is at least one selected from the group consisting of iron, aluminum, zinc, zirconium, titanium, tin and lead, is 0 as the M / Si molar ratio. 0.001 to 0.02, and the polyvalent metal element M has a larger negative charge than silica colloidal particles having an M / Si molar ratio of less than 0.001.
- the polyvalent metal element M include iron, aluminum, zinc, zirconium, titanium, tin, and lead.
- Examples of the method for measuring the charge of the silica colloidal particles include zeta potential measurement.
- the silica colloidal particles of the present invention have a large negative charge of ⁇ 15 mV or less as the zeta potential measured at pH 3.5, for example, the dispersibility in the sol is good. Therefore, for example, a stable organic solvent-dispersed silica sol or polymerizable compound-dispersed silica sol can be obtained even at a high silica concentration of 30% by mass or more.
- the zeta potential of silica colloid particles having an M / Si molar ratio of less than 0.001 at pH 3.5 is about ⁇ 5 to 0 mV.
- the content of the polyvalent metal element M present in the outermost surface layer of the silica colloidal particles of the present invention is 0 to 0.003 per 1 nm 2 of the surface area of the silica colloidal particles, the surface solid acidity And the properties as a solid acid are very small.
- the silica colloidal particles of the present invention are dispersed in various organic solvents, polymerizable compounds, dicarboxylic acid anhydrides and other organic compounds, the organic compounds are not decomposed, altered, discolored, polymerized, or the like.
- the silica colloidal particles of the present invention are introduced into the cured epoxy resin, the heat resistance and strength of the cured body can be improved without causing coloring of the cured body.
- the average content of the polyvalent metal element M in the silica colloidal particles is less than 0.001 as the M / Si molar ratio, the charge of the silica colloidal particles becomes small, and the electrostatic repulsion between the silica particles decreases. Therefore, an organic solvent-dispersed silica sol or a polymerizable compound-dispersed silica sol having a high silica concentration may not be obtained.
- the average content of the polyvalent metal element M in the silica colloidal particles is larger than 0.02 as the M / Si molar ratio, the content of the polyvalent metal element M present in the outermost layer of the particles is silica colloid.
- the average content of the polyvalent metal element M in the silica colloid particles is the total silica colloid particles, that is, the number of moles of the polyvalent metal element M contained from the center of the silica colloid particles to the outermost layer and the total silica.
- the M / Si molar ratio is calculated from the number of moles of Si atoms in the colloidal particles.
- the polyvalent metal element M present in the outermost layer of the silica colloidal particles of the present invention means that a part of Si in the —O—Si—O—Si—O— layer present on the outermost surface of the colloidal particles is a polyvalent metal.
- the content of the polyvalent metal element M in the outermost layer of the silica colloid particles of the present invention can be analyzed by the following metal ion extraction method using an acid. From the specific gravity of silica colloid particles 2.2 and the molecular weight 60 of silica, the number of Si atoms present in the outermost layer of the silica colloid particles is calculated to be 7.9 per 1 nm 2 of the surface area of the silica colloid particles (THE COLORID CHEMISTRY). OF SILICA AND SILICATES, Chapter 6 Surface Chemistry p242 to p247, see Author: RALPH K. ILER).
- the polyvalent metal element M present in the surface layer is calculated as 7.9 ⁇ M / Si per 1 nm 2 .
- the inventor adjusted the pH of the aqueous sol containing colloidal silica particles to 1.9 with nitric acid and held it at 20 to 25 ° C. for 4.5 hours to cationize only the polyvalent metal element M on the outermost layer of the silica colloidal particles.
- the polyvalent metal element M present in the outermost layer of the silica colloid particles was quantified using this method.
- the content of the polyvalent metal element in the filtrate obtained by centrifugal filtration was measured.
- the polyvalent metal element M present in the outermost surface layer of the silica colloidal particle having a surface area of 1 nm 2 can be determined.
- the silica concentration of the aqueous silica sol adjusted to pH 1.9 is preferably 0.1 to 5% by mass.
- Centrifugal filtration is not particularly limited as long as the filtrate can be collected sufficiently, but it can be performed at about 1000 to 10000 rpm using an ultrafiltration membrane having a molecular weight cut off of 5000 to 50000.
- the polyvalent metal ion in the filtrate is measured by a general trace metal analysis method (for example, inductively coupled plasma emission spectroscopy). By dividing this measured value by the surface area of the silica colloid particles obtained by the nitrogen adsorption method, the content of the polyvalent metal element M present in the outermost surface layer of the silica colloid particles having a surface area of 1 nm 2 is calculated.
- a general trace metal analysis method for example, inductively coupled plasma emission spectroscopy
- the shape of the silica colloid particles of the present invention may be spherical, substantially spherical, or any other shape as long as the object of the present invention is achieved.
- the organic solvent-dispersed silica sol of the present invention is obtained by dispersing the colloidal silica particles of the present invention in an organic solvent such as alcohols, ethers, ketones, esters, amides, hydrocarbons, and nitriles.
- organic solvent such as alcohols, ethers, ketones, esters, amides, hydrocarbons, and nitriles.
- Specific examples of the organic solvent used in the organic solvent-dispersed silica sol of the present invention are shown below.
- Alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, isobutyl alcohol, 2-butanol, ethylene glycol, glycerin, propylene glycol, triethylene glycol, polyethylene glycol, benzyl alcohol, 1,5 -Pentanediol, diacetone alcohol and the like.
- ethers include diethyl ether, dibutyl ether, tetrahydrofuran, dioxane, ethylene glycol monomethyl ether, ethylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, etc. Is mentioned.
- ketones include acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, methyl isobutyl ketone, 2-heptanone, and cyclohexanone.
- esters examples include ethyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate and the like.
- amides include acetamide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like.
- hydrocarbons examples include n-hexane, cyclohexane, benzene, toluene, xylene, solvent naphtha, and styrene.
- halogenated hydrocarbons examples include dichloromethane and trichloroethylene.
- nitriles include acetonitrile, glutaronitrile, methoxyacetonitrile, propionitrile, benzonitrile and the like.
- organic solvents include dimethyl sulfoxide.
- the organic solvent-dispersed silica sol of the present invention has a silica concentration of 5 to 70% by mass, preferably 15 to 60% by mass.
- the surface of the dispersed silica colloid particles may be subjected to a hydrophobic treatment.
- the hydrophobizing agent include silazane, siloxane or alkoxysilane and a partial hydrolyzate thereof, or a polymerized dimer or pentamer oligomer.
- silazane include hexamethyldisilazane and hexaethyldisilazane.
- siloxane examples include hexamethyldisiloxane, 1,3-dibutyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane, 1,3-divinyltetramethyldisiloxane, hexaethyldisiloxane, and 3-glycidoxy. And propylpentamethyldisiloxane.
- alkoxysilane examples include trimethylmethoxysilane, trimethylethoxysilane, trimethylpropoxysilane, phenyldimethylmethoxysilane, chloropropyldimethylmethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, Tetrabutoxysilane, ethyltrimethoxysilane, dimethyldiethoxysilane, propyltriethoxysilane, n-butyltrimethoxysilane, n-hexyltrimethoxysilane, n-octyltriethoxysilane, n-octylmethyldiethoxysilane, n- Octadecyltrimethoxysilane, phenyltrimethoxysilane, phenylmethyldime
- the hydrophobization treatment of the silica colloidal particle surface is particularly effective for an organic solvent-dispersed silica sol using a hydrophobic organic solvent such as ethers, ketones, esters and hydrocarbons.
- the organic solvent-dispersed silica sol of the present invention is a stable silica sol because the dispersed silica colloidal particles have a large negative charge and the properties as a solid acid are extremely weak, so that the organic solvent is not decomposed, altered or discolored. It is.
- the polymerizable compound-dispersed silica sol of the present invention is a polymerizable compound such as a polymerizable compound having an ethylenically unsaturated bond, a polymerizable compound having an epoxy ring, a polymerizable compound having an oxetane ring, or a polymerizable compound having a vinyl ether structure.
- the silica colloidal particles of the present invention are dispersed. Specific examples of the polymerizable compound used in the polymerizable compound-dispersed silica sol of the present invention are shown below.
- Examples of the polymerizable compound having an ethylenically unsaturated bond include unsaturated carboxylic acid compounds such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid and phthalic acid.
- derived from these unsaturated carboxylic acid compounds, an alcohol compound, or an amine compound can be mentioned.
- the alcohol compound is not particularly limited, and examples thereof include 2 to 6 hydroxyl groups such as ethylene glycol, triethylene glycol, tetraethylene glycol, tris (2-hydroxylethyl) isocyanuric acid, triethanolamine, and pentaerythritol.
- the polyol compound which has.
- the amine compound is not particularly limited, but ethylenediamine, diaminocyclohexane, diaminonaphthalene, 1,4-bis (aminomethyl) cyclohexane, 3,3 ′, 4,4′-tetraaminobiphenyl, tris (2-aminoethyl) And polyamine compounds having 2 to 6 primary or secondary amino groups, such as amines.
- polymerizable compound having an ethylenically unsaturated bond examples include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, nona Ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, nonapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate 2,2-bis [4-((meth) acryloxydiethoxy) phenyl] propane, 3-phenoxy-2-propanoyl acrylate, 1,6-bis (3-acrylate) Roxy-2-hydroxypropyl) -hexyl ether, trimethylolpropane tri (meth) acrylate, g
- a urethane compound, a polyvalent epoxy compound and a hydroxyalkyl unsaturated compound which can be obtained by reacting a polyvalent isocyanate compound with a hydroxyalkyl unsaturated carboxylic acid ester compound are also used. Mention may also be made of compounds obtainable by reaction with carboxylic acid ester compounds, diallyl ester compounds such as diallyl phthalate and divinyl compounds such as divinyl phthalate.
- a compound having 1 to 6 epoxy rings can be used as the polymerizable compound having an epoxy ring.
- a polymerizable compound having 1 to 6 epoxy rings is produced from a compound having two or more hydroxyl groups or carboxyl groups such as a diol compound, a triol compound, a dicarboxylic acid compound, or a tricarboxylic acid compound, and a glycidyl compound such as epichlorohydrin. Mention may be made of compounds having two or more glycidyl ether structures or glycidyl ester structures.
- polymerizable compound having an epoxy ring examples include 1,4-butanediol diglycidyl ether, 1,2-epoxy-4- (epoxyethyl) cyclohexane, glycerol triglycidyl ether, diethylene glycol diglycidyl ether, 2,6 Diglycidyl phenyl glycidyl ether, 1,1,3-tris [p- (2,3-epoxypropoxy) phenyl] propane, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, 4,4′-methylenebis (N, N -Diglycidylaniline), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, trimethylolethane triglycidyl ether, triglycidyl-p-aminophenol, tetraglycidylmetaxylenediamine, Tragly
- a compound having 1 to 6 oxetane rings can be used.
- a compound having 1 to 6 vinyl ether structures can be used.
- the polymerizable compound-dispersed silica sol of the present invention has a silica concentration of 5 to 70% by mass, preferably 15 to 60% by mass.
- the surface of the dispersed silica colloid particles may be subjected to a hydrophobic treatment.
- the hydrophobizing agent include silazane, siloxane or alkoxysilane and a partial hydrolyzate thereof, or a polymerized dimer or pentamer oligomer.
- hydrophobizing agent examples include the same hydrophobizing agents contained in the organic solvent-dispersed silica sol.
- the hydrophobizing agent containing a polymerizable group may improve the dispersibility in the polymerizable compound or may improve the resin performance by binding the silica colloid particles and the resin in the curing reaction. In some cases, it is preferably used.
- the polymerizable compound-dispersed silica sol of the present invention may contain a small amount of an organic solvent for the purpose of adjusting the viscosity.
- the dispersed silica colloid particles have a large negative charge, and the property as a solid acid is extremely weak, so that the polymerizable compound is not decomposed, discolored, polymerized, etc. It is a silica sol that is stable even in concentration.
- the polymerizable compound-dispersed silica sol having an epoxy ring is a particularly useful silica sol in that coloring of a cured product using the same hardly occurs depending on silica. .
- the cured product of the polymerizable compound having an epoxy ring has high transparency and strength
- a colorless material having higher heat resistance and strength by combining this resin with the colloidal silica particles of the present invention, a colorless material having higher heat resistance and strength.
- a transparent cured body can be obtained, and exhibits particularly excellent effects when used for sealing materials that require colorless transparency and heat resistance, such as LED sealing materials.
- the polymerizable compound having an epoxy ring used in the present invention has the following formula (1): (Where R 1 and R 2 each independently represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, a heterocyclic group, or a halogenated, aminated, or nitrated derivative thereof. It is preferable that it is an ester-modified epoxy compound containing the compound (i) having a functional group represented by () in the molecule and the compound (ii) having a glycidyl group in the molecule.
- the compound (i) is a compound in which n (where n is an integer of 2 to 16) glycidyl groups in the molecule are replaced with 1 or more and n or less functional groups represented by the formula (1). It is.
- Compound (ii) is a compound having n glycidyl groups in the molecule (where n is an integer of 2 to 16).
- n is preferably 3 in the epoxy compound used as the raw material of the compound (i) and the epoxy compound represented by the compound (ii).
- tris- (2,3-epoxypropyl) -isocyanurate can be preferably used as the epoxy compound used as the raw material of the compound (i) and the epoxy compound represented by the compound (ii).
- the compound (i) is preferably obtained by replacing the glycidyl group of tris- (2,3-epoxypropyl) -isocyanurate with a functional group represented by the formula (1).
- the compound (ii) is preferably tris- (2,3-epoxypropyl) -isocyanurate.
- tris- (2,3-epoxypropyl) -isocyanurate will be described in detail as a compound having a glycidyl group in the molecule.
- Tris- (2,3-epoxypropyl) -isocyanurate is a highly crystalline epoxy resin having three glycidyl groups in one molecule.
- the reason why the tris- (2,3-epoxypropyl) -isocyanurate has high crystallinity is considered to be because a hydrogen bond is formed between oxygen atoms of three epoxy groups present in the molecule and another molecule.
- the crystallinity can be lowered to make it liquid.
- an epoxy group is necessary for the epoxy resin to cure by causing a curing reaction with the curing agent. Therefore, the liquid ester-modified epoxy compound needs to be a mixture of the compound (i) in which the epoxy group is partially converted and the compound (ii) in which the epoxy group is not converted.
- a polymerizable compound having a liquid epoxy ring By containing -epoxypropyl) -isocyanurate, a polymerizable compound having a liquid epoxy ring can be obtained.
- the compound (i) is actually a compound obtained by adding one acid anhydride represented by the formula (2) to a glycidyl group of tris- (2,3-epoxypropyl) -isocyanurate, a compound obtained by adding two compounds, and It is a mixture of three added compounds.
- tris- (2,3-epoxypropyl) -isocyanurate and an acid anhydride are mixed with glycidyl of tris- (2,3-epoxypropyl) -isocyanurate.
- Those obtained by reacting at a molar ratio of group: acid anhydride of 1: 0.1 to 0.5 are preferred.
- the acid anhydride [formula (2)] used for the production of the compound (i) is an acid anhydride obtained from so-called two molecules of monocarboxylic acid. Unlike an acid anhydride obtained from a dicarboxylic acid used as a curing agent for an epoxy resin, it does not have a function as a curing agent for an epoxy resin.
- the sum total of the glycidyl group of the synthesized compound (i) and the glycidyl group of the compound (ii) is 2 or more in terms of average (converted to the total number of glycidyl groups). Is preferred. If the total of the glycidyl groups is less than 2, it is not preferable because the physical properties of the cured product, particularly heat resistance, is lowered.
- R 3 and R 4 are each independently an alkyl group, an alkenyl group, or an alkynyl group.
- the alkyl group is an alkyl group having 1 to 18 carbon atoms, for example, methyl group, ethyl group, n-propyl group, i-propyl group, cyclopropyl group, n-butyl group, i-butyl group, s-butyl.
- the alkenyl group is an alkenyl group having 2 to 6 carbon atoms, and examples thereof include a vinyl group, a 1-propenyl group, and a 2-propenyl group.
- the alkynyl group is an alkynyl group having 2 to 6 carbon atoms, and examples thereof include an ethynyl group and a propargyl group.
- the aryl group is an aryl group having 6 to 20 carbon atoms, and examples thereof include a phenyl group, a tolyl group, a naphthyl group, a methylnaphthyl group, an anthryl group, and an ethylanthryl group.
- the aralkyl group is an aralkyl group having 7 to 22 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, an anthryl group, and an anthrylmethyl group.
- the heterocyclic group include imidazole group, pyrazole group, pyridazine group, pyrimidine group, quinoline group, benzoxazole group, thiophene group, dithiol group, thiazole group, thiadiazole group, and benzothiazole group.
- alkyl groups, alkenyl groups, alkynyl groups, aryl groups, aralkyl groups, and heterocyclic groups may be used as halogenated (eg, fluorinated, chlorinated, brominated or iodinated), aminated or nitrated derivative groups. it can. Examples thereof include a chloromethyl group, a dichloromethyl group, a trichloromethyl group, a trifluoromethyl group, an aminophenyl group, and a nitrobenzyl group.
- R 3 and R 4 may be the same or different.
- Acid anhydrides of formula (2) containing R 3 and R 4 are, for example, acetic anhydride, propionic anhydride, n-butyric anhydride, n-valeric anhydride, n-hexanoic anhydride, trifluoroacetic anhydride, cinnamon An acid anhydride, a benzoic acid anhydride, etc. are mentioned.
- R 3 and R 4 in formula (2) are determined, and R 3 and R 4 are the number of carbon atoms from the viewpoint of the transparency of the resulting cured product. 1 to 5 linear hydrocarbon groups are preferred. Particularly preferred is propionic anhydride.
- tris- (2,3-epoxypropyl) -isocyanurate When tris- (2,3-epoxypropyl) -isocyanurate is used as the highly crystalline epoxy resin, tris- (2,3-epoxypropyl) -isocyanurate, which is a low melting point type ( ⁇ -type) stereoisomer, is used. It is preferable to use it.
- Tris- (2,3-epoxypropyl) -isocyanurate synthesized from isocyanuric acid and epichlorohydrin is a low-melting stereoisomer, tris- (2,3-epoxypropyl) -isocyanurate ( ⁇ -type crystal, 3) and a high melting point stereoisomer, tris- (2,3-epoxypropyl) -isocyanurate (which is a ⁇ -type crystal, called ⁇ -type) in a ratio of 3: 1 It is a mixture.
- tris- (2,3-epoxypropyl) -isocyanurate which forms crystals by the combination of RRR and SSS forms, is ⁇ -type tris- (2,3-epoxypropyl) -isocyanurate, and six others. Since tris- (2,3-epoxypropyl) -isocyanurate in combination forms ⁇ -type tris- (2,3-epoxypropyl) -isocyanurate to form crystals, Generated. By the way, ⁇ -type tris- (2,3-epoxypropyl) -isocyanurate has a melting point of 98 to 107 ° C.
- tris- (2,3-epoxypropyl) -isocyanurate when tris- (2,3-epoxypropyl) -isocyanurate is applied to the polymerizable compound having a liquid epoxy ring used in the present invention, unreacted tris- (2,3-epoxypropyl) -isocyanurate. It is preferable to use ⁇ -type tris- (2,3-epoxypropyl) -isocyanurate as a raw material because crystals are more difficult to precipitate when ⁇ is ⁇ -type.
- the solvent used in the reaction may be any one that is inert to the reaction.
- Typical examples of the solvent include ketones such as acetone and methyl ethyl ketone, nitriles such as acetonitrile, ethers such as tetrahydrofuran and dioxane, acetic acid.
- examples thereof include esters such as ethyl, aromatic hydrocarbons such as chlorobenzene and toluene, and halogenated hydrocarbons such as chloroform and dichloroethane.
- tris- (2,3-epoxypropyl) -isocyanurate may be used alone or as a mixed solvent to dissolve tris- (2,3-epoxypropyl) -isocyanurate.
- tertiary amines such as triethylamine, tripropylamine, 1,8-diazabicyclo-5,4,0-undecan-7-ene, and halogens such as triphenylethylphosphonium bromide are used as catalysts.
- Quaternary phosphonium salts such as triphenylmonoalkylphosphonium fluoride, imidazole compounds such as 2-ethyl-4-methylimidazole, quaternary ammonium salts such as tetraethylammonium bromide, and phosphorus compounds such as triphenylphosphine.
- the reaction is performed at the reflux temperature of the solvent until the epoxy group content titrated with a 0.1N-perchloric acid / acetic acid solution reaches a theoretical value (a value at which the added acid anhydride disappears by the reaction). . After completion of the reaction, the solvent is distilled off to obtain a liquid ester-modified epoxy compound.
- the obtained liquid ester-modified epoxy compound has an acid anhydride represented by the formula (2) on the glycidyl group of tris- (2,3-epoxypropyl) -isocyanurate.
- the obtained liquid ester-modified epoxy compound includes a compound in which one acid anhydride represented by the formula (2) is added to the glycidyl group of tris- (2,3-epoxypropyl) -isocyanurate and two additions.
- the obtained liquid ester-modified epoxy compound is a compound (compound i) in which one acid anhydride represented by the formula (2) is added to the glycidyl group of tris- (2,3-epoxypropyl) -isocyanurate.
- the viscosity of the liquid ester-modified epoxy compound is about 500 to 5000 mPa ⁇ s as measured at 60 ° C.
- the polymerizable compound-dispersed silica sol having an epoxy ring has a large negative charge and the property as a solid acid is extremely weak because the dispersed silica colloidal particles of the present invention have an epoxy cured composition.
- the cured product can be filled with silica at a high concentration, and the cured product is hardly colored.
- the cured product of the polymerizable compound having an epoxy ring itself has high transparency and strength, and by combining this resin with the colloidal silica particles of the present invention, extremely high heat resistance and colorless transparency.
- a cured product having the properties and strength is obtained, and exhibits particularly excellent effects when used in applications requiring colorless transparency and heat resistance such as LED sealing materials.
- the dicarboxylic acid anhydride-dispersed silica sol of the present invention is obtained by dispersing the silica colloidal particles of the present invention in a liquid dicarboxylic acid anhydride at 30 ° C.
- the liquid state at 30 ° C. means a liquid state at an atmospheric pressure of 30 ° C.
- dicarboxylic acid anhydride which is liquid at 30 ° C. used in the dicarboxylic acid anhydride-dispersed silica sol of the present invention include methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic acid anhydride, hydrogenation Examples thereof include methylnadic acid anhydride, hydrogenated trimellitic acid, trialkylhydrophthalic acid anhydride, dodecenyl succinic acid anhydride, and the like.
- dicarboxylic acid anhydrides from the viewpoint of colorless transparency, heat resistance, and high light resistance when cured into epoxy, methylhexahydrophthalic anhydride, hydrogenated methylnadic acid anhydride, hydrogenated trimellit Acid is particularly preferred. Moreover, if the mixture of solid dicarboxylic anhydrides, such as hexahydrophthalic anhydride, and the said liquid dicarboxylic anhydride is liquid at 30 degreeC, it can be used for this invention.
- the dicarboxylic acid anhydride-dispersed silica sol of the present invention has a silica concentration of 5 to 70% by mass, preferably 15 to 60% by mass.
- the surface of the dispersed silica colloid particles may be subjected to a hydrophobic treatment.
- the hydrophobizing agent include silazane, siloxane or alkoxysilane and a partial hydrolyzate thereof, or a polymerized dimer or pentamer oligomer.
- the hydrophobizing agent include the same hydrophobizing agents contained in the organic solvent-dispersed silica sol.
- the dispersed silica colloidal particles have a large negative charge and the property as a solid acid is extremely weak. Therefore, when the silica sol is blended in an epoxy cured composition, The cured product can be filled with silica at a high concentration, and the cured product is hardly colored.
- the silica colloidal particles are filled in the epoxy cured product with a high filling rate and while maintaining the colorless transparency of the resin. Therefore, when used in applications requiring colorless transparency and heat resistance, such as an LED encapsulant, it exhibits particularly excellent effects.
- the average content of the polyvalent metal element M which is at least one selected from the group consisting of iron, aluminum, zinc, zirconium, titanium, tin and lead, is 0.
- the average content of the polyvalent metal element M which is at least one selected from the group consisting of iron, aluminum, zinc, zirconium, titanium, tin and lead is 0.
- An aqueous silica sol in which colloidal silica particles having an average primary particle diameter of 5 to 40 nm, which is 001 to 0.02, is dispersed can be obtained, for example, by the method disclosed in Japanese Patent Application Laid-Open No. 63-123807. For example, a method is described in which silica sol is sized using as a raw material an aqueous solution obtained by mixing an aqueous solution of an aluminum compound with an aqueous solution of an alkali metal silicate such as sodium silicate.
- an aluminum compound aqueous solution is added at the time of silica sol sizing, specifically, a silica-containing alkaline aqueous solution or an alkali metal hydroxide aqueous solution is mixed with an acidic silicate solution and an aluminum compound aqueous solution simultaneously or alternately.
- the aluminum compound used is an aluminate represented by sodium aluminate, or an acidic aluminum salt represented by aluminum sulfate or aluminum chloride.
- tin compounds, zinc compounds, lead compounds, and the like can be used. Specifically, sodium stannate, sodium zincate, sodium naminate, and the like can be used.
- an acid is added to the obtained aqueous silica sol.
- the silica concentration is extremely dilute (for example, less than 5% by mass), the production efficiency is lowered, so concentration is performed using an ultrafiltration membrane or the like, and the silica concentration is adjusted to 5% by mass or more. It is preferable to add.
- the aqueous silica sol that can be used when the acid is added may be an alkaline silica sol, or an acidic silica sol obtained by removing alkali metal ions of the alkaline silica sol with a cation exchange resin or the like.
- the kind of acid to be added is preferably a strong acid such as an inorganic acid or an organic acid in view of the effect of eluting polyvalent metal ions from silica colloidal particles. Specifically, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, benzenesulfonic acid and the like are selected.
- the acid When the acid is added to the aqueous silica sol, it is preferable to add the acid in an aqueous solution having an acid concentration of 1 to 20% by mass.
- the acid is added so that the pH of the aqueous silica sol is in the range of 0 to 2.0.
- the pH exceeds 2.0 the effect of eluting the polyvalent metal element as polyvalent metal ions from the vicinity of the surface of the silica colloidal particles becomes insufficient.
- aging is performed at 0 ° C. to 40 ° C. for 30 minutes to 100 hours. When the aging temperature is below this range, the effect of eluting polyvalent metal ions from the vicinity of the surface of the silica colloidal particles becomes insufficient.
- step (II) first, a hydrogen type strong acidic cation exchange resin is brought into contact with the acidic silica sol obtained in step (I) to remove polyvalent metal ions eluted from the vicinity of the surface of the silica colloid particles. At this time, it is confirmed that the pH of the acidic silica sol is 2.0 or less. When the pH exceeds 2.0, the elution of polyvalent metal ions is not sufficient, and some of the eluted polyvalent metal ions are not sufficiently adsorbed on the cation exchange resin, and the surface of the silica colloid particles May remain. Next, a hydroxyl group type strongly basic anion exchange resin is brought into contact to remove excess anion components.
- Hydroxyl-type strongly basic anion exchange resins are usually regenerated with a strong base such as sodium hydroxide, so a trace amount of sodium ions, etc. remain, and after contact with the acidic silica sol, a trace amount in the acidic silica sol May leak sodium ions. In this case, it is preferable to remove sodium ions and the like again by contacting with a strong acid cation exchanger. Moreover, before making it contact with a hydrogen type strong acidic cation exchange resin and a hydroxyl group type strong basic anion exchange resin, you may adjust a silica concentration by adding a pure water to aqueous silica sol.
- the silica colloidal particles of the present invention can be obtained by the method including the steps (I) and (II).
- the organic solvent-dispersed silica sol of the present invention is produced by a method in which water contained in the aqueous silica sol in which the silica colloidal particles of the present invention obtained by the production method are dispersed is replaced with an organic solvent.
- organic solvent substitution of the aqueous silica sol any method known in the art may be used, and examples thereof include a distillation substitution method and an ultrafiltration method.
- the organic solvent is a hydrophobic organic solvent such as methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, or toluene
- a method of hydrophobizing the surface of the colloidal silica particles of the aqueous silica sol and then substituting with the desired solvent can be applied.
- a method for hydrophobizing treatment a method of esterifying silanol groups on the surface of colloidal silica particles by heating aqueous silica sol in the presence of excess alcohol (Japanese Patent Laid-Open No. 57-196717), silylating agent or silane Methods for treating the silica surface with a coupling agent (Japanese Patent Laid-Open Nos. 58-145614, 03-187913, 11-43319) are known.
- the polymerizable compound-dispersed silica sol of the present invention is produced by substituting an organic solvent, which is a dispersion medium of the organic solvent-dispersed silica sol in which the silica colloidal particles of the present invention obtained by the above production method are dispersed, with a polymerizable compound. .
- a polymerizable compound is added to the organic solvent-dispersed silica sol, and at least a part of the organic solvent is distilled off at room temperature or under reduced pressure or normal pressure while stirring to obtain the polymerizable compound-dispersed silica sol of the present invention.
- the conditions for replacing the organic solvent with the polymerizable compound may be any conditions that allow the organic solvent to be distilled off without causing polymerization or decomposition of the polymerizable compound, and may be performed by appropriately adjusting the pressure and liquid temperature in the container to be replaced. Just do it.
- the organic solvent may be distilled off or the organic solvent of the organic solvent-dispersed silica sol may be retained. While leaving, the polymerizable compound may be gradually added to the organic solvent-dispersed silica sol for substitution.
- the polymerizable compound-dispersed silica sol of the present invention may be a silica sol in which almost all of the organic solvent of the organic solvent-dispersed silica sol of the present invention is distilled off to make only the polymerizable compound only a dispersion medium, and prevents an increase in viscosity.
- a part of the organic solvent may be left and a sol of a mixed dispersion medium of the polymerizable compound and the organic solvent may be used.
- the mass ratio of the polymerizable compound and the organic solvent in the mixed dispersion medium is preferably in the range of 100: 0 to 50:50.
- the polymerizable compound-dispersed silica sol of the present invention can also be produced by directly substituting the polymerizable compound for water, which is a dispersion medium of the aqueous silica sol in which the silica colloidal particles of the present invention obtained by the production method are dispersed. be able to.
- the dicarboxylic acid anhydride-dispersed silica sol of the present invention is an organic solvent-dispersed silica sol in which the silica colloidal particles of the present invention obtained by the above production method are dispersed. It can manufacture by substituting with an acid anhydride.
- a dicarboxylic acid anhydride is added to the non-alcoholic organic solvent-dispersed silica sol, and at least a part of the organic solvent is distilled off at room temperature or under heating under reduced pressure or normal pressure while stirring to obtain a dicarboxylic acid anhydride-dispersed silica sol.
- the organic solvent may be distilled off, While distilling off the organic solvent of the non-alcoholic organic solvent-dispersed silica sol, dicarboxylic acid anhydride may be gradually added to the organic solvent-dispersed silica sol for substitution.
- dicarboxylic acid anhydride may be gradually added to the organic solvent-dispersed silica sol for substitution.
- the dicarboxylic acid anhydride-dispersed silica sol of the present invention may be a silica sol in which almost all of the organic solvent of the non-alcoholic organic solvent-dispersed silica sol is distilled off to make only the dicarboxylic anhydride only a dispersion medium, or the viscosity increases.
- a non-alcoholic organic solvent may be left and a mixed dispersion medium sol of a dicarboxylic anhydride and a non-alcoholic organic solvent may be used.
- the mass ratio of the dicarboxylic acid anhydride and the non-alcoholic organic solvent in the mixed dispersion medium is preferably in the range of 100: 0 to 50:50.
- the non-alcoholic organic solvent preferably has a low reactivity with a dicarboxylic anhydride, and examples thereof include ethers, esters, ketones and hydrocarbons.
- ethers include diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran and dioxane.
- Esters include ethyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate and ethylene glycol monobutyl ether acetate.
- ketones include acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, methyl isobutyl ketone, 2-heptanone, and cyclohexanone.
- hydrocarbons include n-hexane, cyclohexane, benzene, toluene, xylene, solvent naphtha, dichloromethane and trichloroethylene.
- Other organic solvents include acetonitrile, acetamide, N, N-dimethylformamide, dimethyl sulfoxide, N, N-dimethylacetamide and N-methylpyrrolidone.
- the content of the polyvalent metal element in the filtrate obtained by centrifuging the silica sol adjusted to pH 1.9 with nitric acid was measured to determine the quantification of the polyvalent metal element present in the outermost layer of the silica colloid particles.
- the acidic silica sol 1a was adjusted to pH 1.9 with nitric acid, held at 20 to 25 ° C. for 4.5 hours, and the content of polyvalent metal in the filtrate obtained by centrifugal filtration was determined to be 0.00 per 1 nm 2 by plasma emission spectroscopy. It was measured to be 020 and almost coincided with the calculated value.
- a specific method for measuring the polyvalent metal element content in the outermost layer of the silica colloidal particles was as follows. 1.0 g of acidic silica sol was collected as SiO 2 , diluted to 50 g with pure water, adjusted to pH 1.9 with 10% by mass nitric acid (EL grade), and maintained at 23 ° C. for 4.5 hours.
- the sol was charged into a centrifugal filter (Amicon Ultra-15, manufactured by MILLIPORE, molecular weight cut off 10,000), and centrifuged at 5000 rpm for 30 minutes.
- the metal analysis was carried out.
- the polyvalent metal element measured by this method is a polyvalent metal element present in the outermost layer of the silica colloidal particle, and this is divided by the surface area of the silica colloidal particle obtained by the nitrogen adsorption method.
- the content of the polyvalent metal element M present in the outermost layer of 1 nm 2 was calculated.
- Reference example 1 In a 100 L polycontainer, sodium silicate solution (manufactured by Fuji Chemical Co., Ltd., No. 3 sodium silicate, SiO 2 concentration 29.1% by mass, SiO 2 / Na 2 O molar ratio 3.2, Al 2 O 3 / SiO 2 mol (0.0003) 9.6 kg of pure water and 60.2 kg of pure water were charged and stirred to be uniform. 1.98 kg of sodium aluminate aqueous solution (Al 2 O 3 concentration 1.0 mass%, Na 2 O concentration 0.77 mass%) was added to the diluted sodium silicate solution while stirring with a disper, and the mixture was stirred for 30 minutes. Went.
- sodium silicate solution manufactured by Fuji Chemical Co., Ltd., No. 3 sodium silicate, SiO 2 concentration 29.1% by mass, SiO 2 / Na 2 O molar ratio 3.2, Al 2 O 3 / SiO 2 mol (0.0003) 9.6 kg of pure water and 60.2 kg of pure water were charged and stirred to be uniform. 1.98 kg of
- aqueous solution was passed through a column filled with 24 L of a hydrogen-type strongly acidic cation exchange resin (Amberlite (registered trademark) IR-120B, manufactured by Organo Corp.) to obtain an active silicic acid solution (SiO 2 concentration of 3. 7 mass%, pH 2.8) 70.0 kg was obtained.
- a hydrogen-type strongly acidic cation exchange resin Amberlite (registered trademark) IR-120B, manufactured by Organo Corp.
- the obtained alkaline silica sol 1 was packed with 1.5 L of a hydrogen type strongly acidic cation exchange resin (Amberlite (registered trademark) IR-120B, manufactured by Organo Corp.), a hydroxyl type strongly basic anion exchange resin ( Amberlite (registered trademark) IR-410, manufactured by Organo Co., Ltd.) 1.0 L packed column, hydrogen-type strongly acidic cation exchange resin (Amberlite IR-120B) 300 mL packed in order, Acidic silica sol 1a (SiO 2 concentration 25.0% by mass, average primary particle diameter 12 nm, pH 2.8, at least one selected from the group consisting of iron, aluminum, zinc, zirconium, titanium, tin and lead in silica colloidal particles) Average content of polyvalent metal element M: M / Si molar ratio 0.0028, present in the outermost layer of silica colloidal particles M0.020 one polyvalent metal element / nm 2, to obtain a zeta potential -24mV) 1
- Example 1 Acidic silica sol 1a obtained in Reference Example 1 (average primary particle diameter 12 nm, SiO 2 25.0 mass%, pH 2.8, average content of the polyvalent metal element M: M / Si molar ratio 0.0028, particles 2000 g of polyvalent metal element M0.020 / nm 2 on the surface, zeta potential ⁇ 24 mV) was collected in a 3 L polyethylene jar, and 96.0 g of 10 mass% sulfuric acid was added while stirring at 1000 rpm using a disper. The mixture was then stirred for 10 minutes. The resulting silica sol had a pH of 1.2. The sol was allowed to stand at 23 ° C.
- Example 2 Acidic silica sol 2a obtained in Reference Example 2 (SiO 2 concentration 25.0 mass%, average primary particle size 22 nm, pH 2.5, average content of the polyvalent metal element M: M / Si molar ratio 0.0027, 2000 g of polyvalent metal element M0.038 particles / nm 2 on the particle surface, zeta potential ⁇ 28 mV) was collected in a 3 L polyethylene wide-mouthed bottle, and 96.0 g of 10 mass% sulfuric acid was added while stirring at 1000 rpm using a disper. Thereafter, the mixture was stirred for 10 minutes. The resulting silica sol had a pH of 1.2. The sol was allowed to stand at 23 ° C.
- a column packed with 250 mL and a column packed with 50 mL of hydrogen-type strongly acidic cation exchange resin (Amberlite IR-120B) were passed in the order of 2 hours to pass acidic silica sol 2A (SiO 2 concentration 23.0% by mass, Average primary particle size 22 nm, pH 2.6, average content of polyvalent metal element M: M / Si molar ratio 0.0019, polyvalent metal element M0.001 present in the outermost layer of silica colloidal particles / nm 2 Less, zeta potential -28 mV) was obtained.
- Comparative Example 1 Except that sulfuric acid was not added, the same procedure as in Example 1 was performed, and acidic silica sol 1C (average primary particle size 12 nm, SiO 2 23.4% by mass, pH 2.7, average content of polyvalent metal element M: M / Si molar ratio 0.0020, polyvalent metal element M0.018 / nm 2 present in the outermost layer of the silica colloidal particles, zeta potential ⁇ 23 mV).
- acidic silica sol 1C average primary particle size 12 nm, SiO 2 23.4% by mass, pH 2.7, average content of polyvalent metal element M: M / Si molar ratio 0.0020, polyvalent metal element M0.018 / nm 2 present in the outermost layer of the silica colloidal particles, zeta potential ⁇ 23 mV.
- Example 3 Charge 2000 g of acidic silica sol 1A into a 3 L glass reactor equipped with a stirrer, condenser, thermometer and two inlets, and in a separate boiler with the sol in the reactor boiled. The generated methanol vapor was continuously blown into the silica sol in the reactor, and the water was replaced with methanol while keeping the liquid level almost constant. The substitution was terminated when the volume of the distillate reached 20 L, and 1840 g of methanol-dispersed silica sol 1A was obtained.
- the obtained methanol-dispersed silica sol has a SiO 2 concentration of 25.0% by mass, methanol 74.4% by mass, water 0.6% by mass, viscosity 2 mPa ⁇ s, pH 3.0 when the sol is diluted with an equal mass of water. there were.
- Example 4 Except having used 2000 g of acidic silica sol 2A, it carried out similarly to Example 3 and obtained 1840g of methanol dispersion
- the obtained methanol-dispersed silica sol has an SiO 2 concentration of 25.0% by mass, methanol 74.4% by mass, water 0.6% by mass, viscosity 2 mPa ⁇ s, and pH 3.2 when the sol is diluted with an equal mass of water. there were.
- Comparative Example 2 Except having used 2000 g of acidic silica sol 1a, it carried out like Example 3 and obtained 1840g of methanol dispersion
- the obtained methanol-dispersed silica sol has a SiO 2 concentration of 25.0% by mass, methanol 74.4% by mass, water 0.6% by mass, viscosity 2 mPa ⁇ s, pH 3.0 when the sol is diluted with an equal mass of water. there were.
- Comparative Example 3 Except having used 2000 g of acidic silica sol 2a, it carried out like Example 4 and obtained 1840g of methanol dispersion
- the obtained methanol-dispersed silica sol has an SiO 2 concentration of 25.0% by mass, methanol 74.4% by mass, water 0.6% by mass, viscosity 2 mPa ⁇ s, and pH 3.2 when the sol is diluted with an equal mass of water. there were.
- Comparative Example 4 Except having used 2000 g of acidic silica sol 1C, it carried out similarly to Example 4 and obtained 1840g of methanol dispersion
- the obtained methanol-dispersed silica sol has a SiO 2 concentration of 25.0% by mass, methanol 74.4% by mass, water 0.6% by mass, viscosity 2 mPa ⁇ s, pH 3.0 when the sol is diluted with an equal mass of water. there were.
- Example 5 280 g of methanol-dispersed silica sol 1A was collected in a 500 mL eggplant-shaped flask, 7.6 g of phenyltrimethoxysilane was added while stirring with a magnetic stirrer, and the liquid temperature was maintained at 55 ° C. for 2 hours. Thereafter, under the conditions of 500 to 400 Torr and a bath temperature of 70 ° C.
- methyl ethyl ketone is added to the sol while gradually lowering the liquid level, and the dispersion medium is replaced with methyl ethyl ketone, whereby transparent methyl ethyl ketone dispersed silica sol 1A (SiO 2 2 40.0% by mass, methyl ethyl ketone 59.7% by mass, methanol 0.2% by mass, moisture 0.1% by mass, viscosity 2 mPa ⁇ s).
- transparent methyl ethyl ketone dispersed silica sol 1A SiO 2 2 40.0% by mass, methyl ethyl ketone 59.7% by mass, methanol 0.2% by mass, moisture 0.1% by mass, viscosity 2 mPa ⁇ s.
- Comparative Example 5 A transparent methyl ethyl ketone dispersed silica sol 1a (SiO 2 40.0% by mass, methyl ethyl ketone 59.7% by mass, methanol 0.5% by mass) was carried out in the same manner as in Example 5 except that the methanol dispersed silica sol 1a was used instead of the methanol dispersed silica sol 1A. 2 mass%, water content 0.1 mass%, viscosity 2 mPa ⁇ s). When this sol was sealed in a 100 mL narrow glass bottle and kept at 50 ° C. for 1 month, the viscosity did not change, but the appearance turned yellow.
- Example 6 200 g of methanol-dispersed silica sol 1A was collected in a 500 mL eggplant-shaped flask, 7.2 g of methacryloxypropyltrimethoxysilane was added while stirring with a magnetic stirrer, and the liquid temperature was maintained at 55 ° C. for 2 hours. Thereafter, 113 g of tetrahydrofurfuryl acrylate was added, and methanol and water were removed by a rotary evaporator under conditions of 200 to 40 Torr and a bath temperature of 50 ° C., whereby colorless and transparent tetrahydrofurfuryl acrylate-dispersed silica sol 1A (SiO 2 30.
- Comparative Example 6 Although it carried out similarly to Example 6 except having used methanol dispersion
- Comparative Example 7 The same procedure as in Example 6 was performed except that methanol-dispersed silica sol 1C was used instead of methanol-dispersed silica sol 1A. However, when about 60 g of methanol was distilled off, tetrahydrofurfuryl acrylate was polymerized to form a jelly. No tetrahydrofurfuryl acrylate-dispersed silica sol could be obtained.
- the reaction solution was concentrated to confirm that the epoxy value was 5.65 eq / kg or less (theoretical value was 5.48 eq / kg), and then toluene was distilled off to obtain 1208 g of a liquid ester-modified epoxy resin. .
- the composition of the obtained liquid ester-modified epoxy resin (2) was as follows.
- Tris- (2,3-epoxypropyl) -isocyanurate obtained by adding one propionic anhydride to one epoxy group of compound (ii), tris- (2,3-epoxypropyl) -isocyanurate ( Compound (i-1), tris- (2,3-epoxypropyl) -isocyanurate having two epoxy groups added with two propionic anhydrides (two-adduct)
- Compound (i-3) is a compound (i-3) obtained by adding three propionic anhydrides to three epoxy groups of i-2) and tris- (2,3-epoxypropyl) -isocyanurate.
- the molar ratio of (ii) :( i-1) :( i-2) :( i-3) in the epoxy resin (2) was 35%: 45%: 17%: 3%.
- the viscosity of the ester-modified epoxy resin (2) was 1300 mPa ⁇ s at 60 ° C.
- Example 7 1000 g of methanol-dispersed silica sol 2A was charged into an eggplant-shaped flask having an internal volume of 2 L, and the solvent was distilled off while adding acetonitrile at 500 Torr and a bath temperature of 70 ° C. using a rotary evaporator. Evaporation and distillation was performed until the sol liquid level was substantially constant and the supply amount of acetonitrile was 750 g, and acetonitrile / methanol mixed solvent sol (SiO 2 26 mass%, acetonitrile 49 mass%, methanol 24 mass%, moisture 0.3 Mass%).
- the solvent was evaporated and distilled while supplying 1500 g of acetonitrile, and acetonitrile-dispersed silica sol 2A (SiO 2 28 mass%, acetonitrile 72 mass%, methanol less than 0.1 mass%, 900 g of water (0.03% by mass) was obtained.
- 80 g of the ester-modified epoxy resin (2) prepared in Reference Example 3 was charged into a separable flask having an internal volume of 500 mL, and 286 g of acetonitrile-dispersed silica sol 2A was added and stirred to make a uniform solution.
- Comparative Example 8 The same procedure as in Example 7 was carried out except that methanol-dispersed silica sol 2a was used instead of methanol-dispersed silica sol 2A, and colorless and transparent ester-modified epoxy resin-dispersed silica sol 2a (SiO 2 46 mass%, ester-modified epoxy resin 46 mass%, acetonitrile 8% by mass and a B-type viscosity at 40 ° C. of 1150 mPa ⁇ s) was obtained.
- methanol-dispersed silica sol 2a was used instead of methanol-dispersed silica sol 2A, and colorless and transparent ester-modified epoxy resin-dispersed silica sol 2a (SiO 2 46 mass%, ester-modified epoxy resin 46 mass%, acetonitrile 8% by mass and a B-type viscosity at 40 ° C. of 1150 mPa ⁇ s) was obtained.
- Example 8 1000 g of methanol-dispersed silica sol 2A was charged into an eggplant-shaped flask having an internal volume of 2 L, and the solvent was distilled off while adding acetonitrile at 500 Torr and a bath temperature of 70 ° C. using a rotary evaporator. Evaporation and distillation were performed until the sol liquid level was substantially constant and the supply amount of acetonitrile was 750 g, and acetonitrile / methanol mixed solvent sol (SiO 2 26 mass%, acetonitrile 49 mass%, methanol mass 24%, moisture 0.3 Mass%).
- the solvent was evaporated and distilled while supplying 1500 g of acetonitrile, and acetonitrile-dispersed silica sol 2A (SiO 2 28 mass%, acetonitrile 72 mass%, methanol less than 0.1 mass%, 900 g of water (0.03% by mass) was obtained.
- 100 g of methylhexahydrophthalic anhydride (reagent manufactured by Tokyo Chemical Industry Co., Ltd.) was charged into a separable flask having an internal volume of 500 mL, and 153 g of acetonitrile-dispersed silica sol 2A was added and stirred to make a uniform solution.
- Comparative Example 9 A colorless and transparent methylhexahydrophthalic anhydride was obtained in the same manner as in Example 8 except that the methanol-dispersed silica sol 2a was used instead of the methanol-dispersed silica sol 2A and that the hexahydrophthalic anhydride was changed from 100 g to 117 g. Dispersed silica sol 2a (SiO 2 29 mass%, methyl hexahydrophthalic anhydride 67 mass%, acetonitrile 4 mass%, B-type viscosity at 30 ° C. of 310 mPa ⁇ s) was obtained.
- Example 9 40.5 g of the ester-modified epoxy resin-dispersed silica sol 2A obtained in Example 7 and 15.03 g of methylhexahydrophthalic anhydride were placed in a 300 mL four-necked flask and mixed and stirred at 80 ° C. for 40 minutes. . Next, 209 mg of tetrabutylphosphonium O, O′-diethyldithiophosphate (manufactured by Nippon Chemical Industry Co., Ltd., product name: Hishicolin PX-4ET) as a curing accelerator is dissolved in 2.0 g of methylhexahydrophthalic anhydride.
- tetrabutylphosphonium O, O′-diethyldithiophosphate manufactured by Nippon Chemical Industry Co., Ltd., product name: Hishicolin PX-4ET
- the resulting epoxy resin curing composition was poured into a casting plate (3 mm thick glass plate treated with a release agent SR-2410 (manufactured by Toray / Daushi Recorning)), and the mixture was heated at 100 ° C. for 2 hours, 150 Heat treatment was performed at 5 ° C. for 5 hours to obtain a cured epoxy resin.
- the physical properties of the obtained cured epoxy resin are shown in Tables 5 and 6.
- MeHHPA is methylhexahydrophthalic anhydride
- PX is tetrabutylphosphonium O, O'-diethyldithiophosphate
- PX / MeHHPA is methylhexahydrophthalate containing tetrabutylphosphonium O, O'-diethyldithiophosphate.
- the phthalic anhydride was shown and indicated by mass.
- Example 10 and Comparative Examples 10 to 12 The same operation as in Example 9 was performed to obtain an epoxy resin composition.
- Table 5 shows the blending ratio of the epoxy resin and the epoxy curing agent or the epoxy curing agent-dispersed silica sol and the curing accelerator.
- the resulting epoxy resin curing composition was poured into a casting plate (3 mm thick glass plate treated with a release agent SR-2410 (manufactured by Toray / Daushi Recorning)), and the mixture was heated at 100 ° C. for 2 hours, 150 Heat treatment was performed at 5 ° C. for 5 hours to obtain a cured epoxy resin.
- SR-2410 manufactured by Toray / Daushi Recorning
- MeHHPA is methylhexahydrophthalic anhydride
- PX is tetrabutylphosphonium O, O'-diethyldithiophosphate
- PX / MeHHPA is methylhexahydrophthalate containing tetrabutylphosphonium O, O'-diethyldithiophosphate.
- the phthalic anhydride was shown and indicated by mass.
- the thickness of the test piece was measured accurately and measured with TMA (Thermal Mechanical Analysis) at a load of 0.05 N and a heating rate of 1 ° C./min.
- the epoxy resin-dispersed silica sol and the dicarboxylic acid anhydride-dispersed silica sol in which the silica colloidal particles of the present invention are dispersed are less likely to cause discoloration during curing of the epoxy resin and hardly cause light scattering of the silica. There is almost no reduction in the colorless transparency of the film. Moreover, the thermal characteristics and physical characteristics of the cured resin body are improved by filling the silica particles in the resin.
- the epoxy resin-dispersed silica sol and dicarboxylic anhydride-dispersed silica sol in which the silica colloidal particles of the present invention are dispersed are used for sealing materials such as LEDs (light emitting devices) that require high colorless transparency and heat resistance.
- sealing materials such as LEDs (light emitting devices) that require high colorless transparency and heat resistance.
- peeling and cracking due to a difference in coefficient of thermal expansion between the element and the resin can be prevented, which is very effective.
- the silica colloidal particles of the present invention or the organic solvent-dispersed silica sol thereof, the polymerizable compound component silica sol, and the dicarboxylic acid-dispersed silica sol are used as a modifier such as a resin, the resin is not decomposed, colored, etc. Resin modification such as imparting heat resistance is possible. Added to the transparent resin hard coat film to impart hardness to the hard coat film, and internally added to the transparent resin to improve the bending strength, scratch resistance, heat resistance, etc. Useful for.
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Abstract
Description
第2観点として、第1観点に記載のシリカコロイド粒子が有機溶媒に分散された有機溶媒分散シリカゾル、
第3観点として、前記有機溶媒が、アルコール類、エーテル類、ケトン類、エステル類、アミド類、炭化水素類及びニトリル類からなる群から選ばれる少なくとも1種である第3観点に記載の有機溶媒分散シリカゾル、
第4観点として、第1観点に記載のシリカコロイド粒子が、エチレン性不飽和結合を有する重合性化合物、エポキシ環を有する重合性化合物、オキセタン環を有する重合性化合物及びビニルエーテル構造を有する重合性化合物からなる群から選ばれる少なくとも1種の化合物に分散された重合性化合物分散シリカゾル、
第5観点として、前記エポキシ環を有する重合性化合物が、式(1):
R1及びR2は、それぞれ独立して、アルキル基、アルケニル基、アルキニル基、アリール基、アラルキル基、複素環基、又はそれらのハロゲン化、アミノ化、若しくはニトロ化誘導体を表す。)で示される官能基を分子内に有する化合物(i)及び分子内にグリシジル基を有する化合物(ii)とを含むエステル変性エポキシ化合物である第4観点に記載の重合性化合物分散シリカゾル、
第6観点として、前記化合物(i)が、分子内のn個(但し、nは2ないし16の整数である。)のグリシジル基の1個以上n個以下を、式(1)で示される官能基で置き換えた化合物である第5観点に記載の重合性化合物分散シリカゾル、
第7観点として、前記化合物(ii)が、分子内のn個(但し、nは2ないし16の整数である。)のグリシジル基を有する化合物である第5観点に記載の重合性化合物分散シリカゾル、
第8観点として、化合物(i):化合物(ii)のモル比が、1:0.3ないし1.5である第5観点に記載の重合性化合物分散シリカゾル、
第9観点として、前記化合物(i)が、トリス-(2,3-エポキシプロピル)-イソシアネートのグリシジル基を式(1)で示される官能基で置き換えたものである第5観点、第6観点及び第8観点のいずれか1つに記載の重合性化合物分散シリカゾル、
第10観点として、前記化合物(ii)が、トリス-(2,3-エポキシプロピル)-イソシアネートである第5観点、第7観点及び第8観点のいずれか1つに記載の重合性化合物分散シリカゾル、
第11観点として、第1観点に記載のシリカコロイド粒子が、30℃で液状のジカルボン酸無水物に分散されたジカルボン酸無水物分散シリカゾル、
第12観点として、前記ジカルボン酸無水物がメチルヘキサヒドロフタル酸無水物、水素化メチルナジック酸無水物及び水素化トリメリット酸無水物からなる群から選ばれる少なくとも1種を含む第11観点に記載のジカルボン酸無水物分散シリカゾル、
第13観点として、下記工程(I)及び(II)を含む第1観点に記載のシリカコロイド粒子の製造方法:
(I):鉄、アルミニウム、亜鉛、ジルコニウム、チタン、スズ及び鉛からなる群から選ばれる少なくとも1種である多価金属元素Mの平均含有率がM/Siモル比として0.001ないし0.02である5ないし40nmの平均一次粒子径を有するシリカコロイド粒子を含むシリカゾルに、酸を加えてpH0ないし2.0とし、0ないし40℃で0.5ないし100時間熟成する工程、
(II):(I)で得られた酸性シリカゾルをpH0ないし2.0において水素型強酸性陽イオン交換樹脂と接触させ、更に水酸基型強塩基性陰イオン交換樹脂に接触させる工程。
特に、本発明のシリカコロイド粒子を用いるとエポキシ環を有する重合性化合物分散シリカゾルやジカルボン酸無水物分散シリカゾルを高いシリカ濃度で得ることができる。そして、これらを用いてエポキシ硬化組成物を調製して硬化体にした場合、該硬化体中に高濃度でシリカを導入することができるためにエポキシ硬化体の耐熱性や強度を大幅に向上させることが可能であり、且つ本発明のシリカコロイド粒子の固体酸の作用が極めて低いために、硬化体の着色をほとんど起こさないのである。
アルコール類としては、メタノール、エタノール、1-プロパノール、2-プロパノール、1-ブタノール、イソブチルアルコール、2-ブタノール、エチレングリコール、グリセリン、プリピレングリコール、トリエチレングリコール、ポリエチレングリコール、ベンジルアルコール、1,5-ペンタンジオール、ジアセトンアルコール等が挙げられる。
エーテル類としては、ジエチルエーテル、ジブチルエーテル、テトラヒドロフラン、ジオキサン、エチレングリコールモノメチルエーテル、エチレングリコールモノプロピルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル等が挙げられる。
ケトン類としては、アセトン、メチルエチルケトン、2-ペンタノン、3-ペンタノン、メチルイソブチルケトン、2-ヘプタノン、シクロヘキサノン等が挙げられる。
エステル類としては、ギ酸エチル、酢酸メチル、酢酸エチル、酢酸プロピル、酢酸ブチル、エチレングリコールモノエチルエーテルアセタート、エチレングリコールモノブチルエーテルアセタート、プロピレングリコールモノメチルエーテルアセタート等が挙げられる。
アミド類としては、アセトアミド、N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド、N-メチルピロリドン等が挙げられる。
炭化水素類としては、n-ヘキサン、シクロヘキサン、ベンゼン、トルエン、キシレン、ソルベントナフサ、スチレン等があげられ、更にハロゲン化炭化水素類としてはジクロロメタン、トリクロロエチレン等が挙げられる。
ニトリル類としては、アセトニトリル、グルタロニトリル、メトキシアセトニトリル、プロピオニトリル、ベンゾニトリル等が挙げられる。
その他の有機溶媒としては、ジメチルスルホキシドが挙げられる。
シラザンとしては、例えばヘキサメチルジシラザン及びヘキサエチルジシラザンが挙げられる。
シロキサンとしては、例えばヘキサメチルジシロキサン、1,3-ジブチルテトラメチルジシロキサン、1,3-ジフェニルテトラメチルジシロキサン、1,3-ジビニルテトラメチルジシロキサン、ヘキサエチルジシロキサン及び3-グリシドキシプロピルペンタメチルジシロキサンが挙げられる。
アルコキシシランとしては、例えばトリメチルメトキシシラン、トリメチルエトキシシラン、トリメチルプロポキシシラン、フェニルジメチルメトキシシラン、クロロプロピルジメチルメトキシシラン、ジメチルジメトキシシラン、メチルトリメトキシシラン、テトラメトキシシラン、テトラエトキシシラン、テトラプロポキシシラン、テトラブトキシシラン、エチルトリメトキシシラン、ジメチルジエトキシシラン、プロピルトリエトキシシラン、n-ブチルトリメトキシシラン、n-ヘキシルトリメトキシシラン、n-オクチルトリエトキシシラン、n-オクチルメチルジエトキシシラン、n-オクタデシルトリメトキシシラン、フェニルトリメトキシシラン、フェニルメチルジメトキシシラン、フェネチルトリメトキシシラン、ドデシルトリメトキシシラン、n-オクタデシルトリエトキシシラン、フェニルトリメトキシシラン、ジフェニルジメトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス(βメトキシエトキシ)シラン、γ-メタアクリルオキシプロピルトリメトキシシラン、γ-アクリルオキシプロピルトリメトキシシラン、γ-(メタアクリルオキシプロピル)メチルジメトキシシラン、γ-メタアクリルオキシプロピルメチルジエトキシシラン、γ-メタアクリルオキシプロピルトリエトキシシラン、β-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン、γ-グリシドキシプロピルトリメトキシシラン、γ-グリシドキシプロピルメチルジエトキシシラン、γ-グリシドキシプロピルトリエトキシシラン、N-β(アミノエチル)γ-(アミノプロピル)メチルジメトキシシラン、N-β(アミノエチル)γ-(アミノプロピル)トリメトキシシラン、N-β(アミノエチル)γ-(アミノプロピル)トリエトキシシラン、γ-アミノプロピルトリメトキシシラン、γ-アミノプロピルトリエトキシシラン、N-フェニル-γ-アミノプロピルトリメトキシシラン、γ-メルカプトプロピルトリメトキシシラン、3-イソシアネートプロピルトリエトキシシラン、トリフルオロプロピルトリメトキシシラン、ヘプタデカトリフルオロプロピルトリメトキシシラン、n-デシルトリメトキシシラン、ジメトキシジエトキシシラン、ビス(トリエトキシシリル)エタン及びヘキサエトキシジシロキサンが挙げられる。
エポキシ環を有する重合性化合物の具体例としては、1,4-ブタンジオールジグリシジルエーテル、1,2-エポキシ-4-(エポキシエチル)シクロヘキサン、グリセロールトリグリシジルエーテル、ジエチレングリコールジグリシジルエーテル、2,6-ジグリシジルフェニルグリシジルエーテル、1,1,3-トリス[p-(2,3-エポキシプロポキシ)フェニル]プロパン、1,2-シクロヘキサンジカルボン酸ジグリシジルエステル、4,4’-メチレンビス(N,N-ジグリシジルアニリン)、3,4-エポキシシクロヘキシルメチル-3,4-エポキシシクロヘキサンカルボキシレート、トリメチロールエタントリグリシジルエーテル、トリグリシジル-p-アミノフェノール、テトラグリシジルメタキシレンジアミン、テトラグリシジルジアミノジフェニルメタン、テトラグリシジル-1,3-ビスアミノメチルシクロヘキサン、ビスフェノール-A-ジグリシジルエーテル、ビスフェノール-S-ジグリシジルエーテル、ペンタエリスリトールテトラグリシジルエーテルレゾルシノールジグリシジルエーテル、フタル酸ジグリシジルエステル、ネオペンチルグリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル、テトラブロモビスフェノール-A-ジグリシジルエーテル、ビスフェノールヘキサフルオロアセトンジグリシジルエーテル、ペンタエリスリトールジグリシジルエーテル、水素化ビスフェノール-A-ジグリシジルエーテル、トリス-(2,3-エポキシプロピル)イソシアヌレート、1-{2,3-ジ(プロピオニルオキシ)}-3,5-ビス(2,3-エポキシプロピル)-1,3,5-トリアジン-2,4,6・(1H,3H,5H)-トリオン、1,3-ビス{2,3-ジ(プロピオニルオキシ)}-5-(2,3-エポキシプロピル)-1,3,5-トリアジン-2,4,6・(1H,3H,5H)-トリオン、モノアリルジグリシジルイソシアヌレート、ジグリセロールポリジグリシジルエーテル、ペンタエリスリトールポリグリシジルエーテル、1,4-ビス(2,3-エポキシプロポキシパーフルオロイソプロピル)シクロヘキサン、ソルビトールポリグリシジルエーテル、トリメチロールプロパンポリグリシジルエーテル、レゾルシンジグリシジルエーテル、1,6-へキサンジオールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、フェニルグリシジルエーテル、p-ターシャリーブチルフェニルグリシジルエーテル、アジピン酸ジグリシジルエーテル、o-フタル酸ジグリシジルエーテル、ジブロモフェニルグリシジルエーテル、1,2,7,8-ジエポキシオクタン、1,6-ジメチロールパーフルオロヘキサンジグリシジルエーテル、4,4’-ビス(2,3-エポキシプロポキシパーフルオロイソプロピル)ジフェニルエーテル、2,2-ビス(4-グリシジルオキシフェニル)プロパン、3,4-エポキシシクロヘキシルメチル-3’,4’-エポキシシクロヘキサンカルボキシレート、3,4-エポキシシクロヘキシルオキシラン、2-(3,4-エポキシシクロヘキシル)-3’,4’-エポキシ-1,3-ジオキサン-5-スピロシクロヘキサン、1,2-エチレンジオキシ-ビス(3,4-エポキシシクロヘキシルメタン)、4’,5’-エポキシ-2’-メチルシクロヘキシルメチル-4,5-エポキシ-2-メチルシクロヘキサンカルボキシレート、エチレングリコール-ビス(3,4-エポキシシクロヘキサンカルボキシレート)、ビス-(3,4-エポキシシクロヘキシルメチル)アジペート、ビス(2,3-エポキシシクロペンチル)エーテル等を挙げることができる。
R1及びR2は、それぞれ独立して、アルキル基、アルケニル基、アルキニル基、アリール基、アラルキル基、複素環基、又はそれらのハロゲン化、アミノ化、若しくはニトロ化誘導体を表す。)で示される官能基を分子内に有する化合物(i)及び分子内にグリシジル基を有する化合物(ii)とを含むエステル変性エポキシ化合物であることが好ましい。
アルキル基としては炭素原子数1ないし18のアルキル基であり、例えばメチル基、エチル基、n-プロピル基、i-プロピル基、シクロプロピル基、n-ブチル基、i-ブチル基、s-ブチル基、t-ブチル基、シクロブチル基、1-メチル-シクロプロピル基、2-メチル-シクロプロピル基、n-ペンチル基、1-メチル-n-ブチル基、2-メチル-n-ブチル基、3-メチル-n-ブチル基、1,1-ジメチル-n-プロピル基、1,2-ジメチル-n-プロピル基、2,2-ジメチル-n-プロピル基、1-エチル-n-プロピル基、シクロペンチル基、1-メチル-シクロブチル基、2-メチル-シクロブチル基、3-メチル-シクロブチル基、1,2-ジメチル-シクロプロピル基、2,3-ジメチル-シクロプロピル基、1-エチル-シクロプロピル基、2-エチル-シクロプロピル基、n-ヘキシル基、1-メチル-n-ペンチル基、2-メチル-n-ペンチル基、3-メチル-n-ペンチル基、4-メチル-n-ペンチル基、1,1-ジメチル-n-ブチル基、1,2-ジメチル-n-ブチル基、1,3-ジメチル-n-ブチル基、2,2-ジメチル-n-ブチル基、2,3-ジメチル-n-ブチル基、3,3-ジメチル-n-ブチル基、1-エチル-n-ブチル基、2-エチル-n-ブチル基、1,1,2-トリメチル-n-プロピル基、1,2,2-トリメチル-n-プロピル基、1-エチル-1-メチル-n-プロピル基、1-エチル-2-メチル-n-プロピル基、シクロヘキシル基、1-メチル-シクロペンチル基、2-メチル-シクロペンチル基、3-メチル-シクロペンチル基、1-エチル-シクロブチル基、2-エチル-シクロブチル基、3-エチル-シクロブチル基、1,2-ジメチル-シクロブチル基、1,3-ジメチル-シクロブチル基、2,2-ジメチル-シクロブチル基、2,3-ジメチル-シクロブチル基、2,4-ジメチル-シクロブチル基、3,3-ジメチル-シクロブチル基、1-n-プロピル-シクロプロピル基、2-n-プロピル-シクロプロピル基、1-i-プロピル-シクロプロピル基、2-i-プロピル-シクロプロピル基、1,2,2-トリメチル-シクロプロピル基、1,2,3-トリメチル-シクロプロピル基、2,2,3-トリメチル-シクロプロピル基、1-エチル-2-メチル-シクロプロピル基、2-エチル-1-メチル-シクロプロピル基、2-エチル-2-メチル-シクロプロピル基、2-エチル-3-メチル-シクロプロピル基、n-ヘプチル基、シクロヘキシル基等が挙げられる。
アルケニル基としては炭素原子数2ないし6のアルケニル基であり、例えばビニル基、1-プロペニル基、2-プロペニル基等が挙げられる。
アルキニル基としては炭素原子数2ないし6のアルキニル基であり、例えばエチニル基、プロパルギル基等が挙げられる。
アリール基としては炭素原子数6ないし20のアリール基であり、例えばフェニル基、トリル基、ナフチル基、メチルナフチル基、アントリル基、エチルアントリル基等が挙げられる。
アラルキル基としては炭素原子数7ないし22のアラルキル基であり、例えばベンジル基、フェネチル基、ナフチルメチル基、ナフチルエチル基、アントリル基、アントリルメチル基等が挙げられる。
複素環基としては、例えばイミダゾール基、ピラゾール基、ピリダジン基、ピリミジン基、キノリン基、ベンゾオキサゾール基、チオフェン基、ジチオール基、チアゾール基、チアジアゾール基、ベンゾチアゾール基等が挙げられる。
これらのアルキル基、アルケニル基、アルキニル基、アリール基、アラルキル基、複素環基は、ハロゲン化(例えばフッ素化、塩素化、臭素化又はヨウ素化)、アミノ化又はニトロ化誘導体基として用いることもできる。例えば、クロロメチル基、ジクロロメチル基、トリクロロメチル基、トリフルオロメチル基、アミノフェニル基、ニトロベンジル基等が挙げられる。
上記液状のエステル変性エポキシ化合物の粘度は、60℃の測定で約500ないし5000mPa・sである。
上記疎水化処理剤としては、前記した有機溶媒分散シリカゾルに含有される疎水化処理剤と同じものが例示される。
(I):鉄、アルミニウム、亜鉛、ジルコニウム、チタン、スズ及び鉛からなる群から選ばれる少なくとも1種である多価金属元素Mの平均含有率がM/Siモル比として0.001ないし0.02である5ないし40nmの平均一次粒子径を有するシリカコロイド粒子を含むシリカゾルに、酸を加えてpH0ないし2.0とし、0ないし40℃で0.5ないし100時間熟成する工程、
(II):(I)で得られた酸性シリカゾルをpH0ないし2.0において水素型強酸性陽イオン交換樹脂と接触させ、更に水酸基型強塩基性陰イオン交換樹脂に接触させる工程。
〔SiO2濃度〕
シリカゾルを坩堝に取り、130℃で乾燥後、得られたゲルを800℃焼成し、焼成残分を計量して算出した。
〔平均一次粒子径(窒素吸着法粒子径)〕
酸性シリカゾルの300℃乾燥粉末の比表面積を比表面積測定装置モノソーブ(登録商標)MS-16(ユアサアイオニクス(株)製)を用いて測定した。
〔ゼータ電位〕
酸性シリカゾルを純水で希釈し、0.1N塩酸水溶液でpHを3.5に調製した後、シリカコロイド粒子のゼータ電位をレーザーゼータ電位計ELS-6000(大塚電子(株)製)を用いて測定した。
〔水分〕
カールフィッシャー滴定法にて求めた。
〔有機溶媒含有量〕
ガスクロマトグラフィーにて求めた。
ガスクロマトグラフィー条件:
カラム:3mm×1mガラスカラム、充填剤:ポーラパックQ、カラム温度:130ないし230℃(昇温8℃/min)、キャリアー:N2 40mL/min、 検出器:FID注入量:1μL、内部標準:メチルエチルケトン又はアセトニトリルを採用した。
〔粘度〕
シリカゾルの粘度はB型回転粘度計(東機産業(株)製)を用いて測定した。
〔シリカコロイド粒子の最表層の多価金属元素含有量の分析〕
シリカコロイド粒子最表層に存在するSi原子を1nm2当たり7.9個として、多価金属元素Mの平均含有率がモル比M/Siの場合、シリカコロイド粒子の最表層に存在する多価金属元素Mは1nm2当たり7.9×M/Si個と計算される。シリカコロイド粒子最表層の多価金属元素を定量するため鋭意検討の結果、シリカコロイド粒子を含む水性ゾルを硝酸でpH1.9に調製し、20ないし25℃で4.5時間保持することで最表層の多価金属元素のみが陽イオン化されることが分かった。硝酸でpH1.9に調整された該シリカゾルを遠心分離した濾液中の多価金属元素含有量を測定して、シリカコロイド粒子の最表層に存在する多価金属元素を定量が決定された。例えば、参考例1のシリカコロイド粒子中には、多価金属元素が粒子中にほぼ均一に存在しているといえ、M/Siモル比は0.0028である。この値から、最表層の多価金属元素は1nm2当たり7.9×0.0028=0.022個と算出された。一方、酸性シリカゾル1aを硝酸でpH1.9に調製し、20ないし25℃で4.5時間保持し、遠心濾過した濾液の多価金属元素含有量をプラズマ発光分光分析法で1nm2当たり0.020個と測定され、計算値とほぼ一致した。
シリカコロイド粒子の最表層の多価金属元素含有量の具体的な測定方法は以下の通り行った。
酸性シリカゾルをSiO2として1.0g採取し純水で50gに希釈した後、10質量%硝酸(ELグレード)でpH1.9に調製し、23℃で4.5時間保持した。このゾルを遠心濾過器(Amicon Ultra-15,MILLIPORE社製、分画分子量1万)に仕込み、5000rpmで30分間遠心分離し、得られた濾液をプラズマ発光分光分析装置(SPS7800、セイコーインスツルメンツ(株)製)にて金属分析を行った。この方法によって測定された多価金属元素は、シリカコロイド粒子の最表層に存在する多価金属元素であり、これを窒素吸着法によって得られるシリカコロイド粒子の表面積で除することにより、シリカコロイド粒子1nm2の最表層に存在する多価金属元素Mの含有量を算出した。
100Lポリ容器に、珪酸ソーダ溶液(富士化学(株)製、3号珪酸ソーダ、SiO2濃度29.1質量%、SiO2/Na2Oモル比3.2、Al2О3/SiO2モル比0.0003)9.6kgと純水60.2kgとを仕込み、均一になるよう攪拌した。この希釈珪酸ソーダ溶液に、ディスパーにて攪拌を行いながらアルミン酸ソーダ水溶液(Al2O3濃度1.0質量%、Na2O濃度0.77質量%)1.98kgを添加し、30分間攪拌を行った。得られた水溶液を水素型強酸性陽イオン交換樹脂(アンバーライト(登録商標)IR-120B、オルガノ(株)製)24Lが充填されたカラムに通過させて、活性珪酸溶液(SiO2濃度3.7質量%、pH2.8)70.0kgを得た。還流器、攪拌機、加熱部及び一つの注液口を供えた100Lのステンレス製容器に、0.31kgの前記珪酸ソーダ溶液と9.1kgの純水とを仕込み、これを90℃に加熱してヒール液とした。該ヒール液を90℃に維持しつつ、これに注液口から前記活性珪酸溶液69.6kgを一定流量で6時間かけて添加した。添加終了後、90℃で4時間保持した後、限外濾過法により濃縮を行い、SiO2濃度28.5質量%のアルカリ性シリカゾル1(平均一次粒子径(窒素吸着法粒子径)12nm、pH9.8)9.0kgを得た。得られたアルカリ性シリカゾル1を水素型強酸性陽イオン交換樹脂(アンバーライト(登録商標)IR-120B、オルガノ(株)製)1.5Lを充填したカラム、水酸基型強塩基性陰イオン交換樹脂(アンバーライト(登録商標)IR-410、オルガノ(株)製)1.0Lを充填したカラム、水素型強酸性陽イオン交換樹脂(アンバーライトIR-120B)300mLを充填したカラムの順に通液し、酸性シリカゾル1a(SiO2濃度25.0質量%、平均一次粒子径12nm、pH2.8、シリカコロイド粒子中における鉄、アルミニウム、亜鉛、ジルコニウム、チタン、スズ及び鉛からなる群から選ばれる少なくとも1種である多価金属元素Mの平均含有率:M/Siモル比0.0028、シリカコロイド粒子の最表層に存在する多価金属元素M0.020個/nm2、ゼータ電位-24mV)10.0kgを得た。
参考例1で得られた酸性シリカゾル1aの4000gに10質量%水酸化ナトリウム水溶液74.0gを添加して、ゾルをアルカリ性(pH9.2)とした後、3Lステンレス製オートクレーブ容器を用いて、205℃で2.5時間水熱処理を行って、アルカリ性シリカゾル2を製造した。水熱処理は、前記アルカリ性にしたゾルを2000gづつ2回に分けて行った。得られたアルカリ性シリカゾル2は、SiO2濃度25.0質量%、平均一次粒子径22nm、pH10.3であった。アルカリ性シリカゾル2の4000gを、水素型強酸性陽イオン交換樹脂(アンバーライトIR-120B)500mLを充填したカラムに通液し、酸性シリカゾル2a(SiO2濃度25.0質量%、平均一次粒子径22nm、pH2.5、前記多価金属元素Mの平均含有率:M/Siモル比0.0027、シリカコロイド粒子の最表層に存在する多価金属元素M0.038個/nm2、ゼータ電位-28mV)4000gを得た。
参考例1ないし2で得られたシリカゾルの物性を表1に示した。
参考例1で得られた酸性シリカゾル1a(平均一次粒子径12nm、SiO225.0質量%、pH2.8、前記多価金属元素Mの平均含有率:M/Siモル比0.0028、粒子表面の多価金属元素M0.020個/nm2、ゼータ電位-24mV)2000gを3Lポリエチレン製広口瓶に採取し、ディスパーを用いて1000rpmで攪拌しながら10質量%硫酸96.0gを添加し、その後10分間攪拌した。得られたシリカゾルのpHは1.2であった。このゾルを23℃で24時間静置した後、水素型強酸性陽イオン交換樹脂(アンバーライトIR-120B)100mLを充填したカラム、水酸基型強塩基性陰イオン交換樹脂(アンバーライトIR-410)250mLを充填したカラム、水素型強酸性陽イオン交換樹脂(アンバーライトIR-120B)50mLを充填したカラムの順に2時間をかけて通液して酸性シリカゾル1A(平均一次粒子径12nm、SiO223.0質量%、pH2.8、前記多価金属元素Mの平均含有率:M/Siモル比0.0020、シリカコロイド粒子の最表層に存在する多価金属元素M0.001個/nm2未満、ゼータ電位-23mV)が得られた。
参考例2で得られた酸性シリカゾル2a(SiO2濃度25.0質量%、平均一次粒子径22nm、pH2.5、前記多価金属元素Mの平均含有率:M/Siモル比0.0027、粒子表面の多価金属元素M0.038個/nm2、ゼータ電位-28mV)2000gを3Lポリエチレン製広口瓶に採取し、ディスパーを用いて1000rpmで攪拌しながら10質量%硫酸96.0g添加し、その後10分攪拌した。得られたシリカゾルのpHは1.2であった。このゾルを23℃で24時間静置した後、水素型強酸性陽イオン交換樹脂(アンバーライトIR-120B)100mLを充填したカラム、水酸基型強塩基性陰イオン交換樹脂(アンバーライトIR-410)250mLを充填したカラム、水素型強酸性陽イオン交換樹脂(アンバーライトIR-120B)50mLを充填したカラムの順に2時間をかけて通液して酸性シリカゾル2A(SiO2濃度23.0質量%、平均一次粒子径22nm、pH2.6、前記多価金属元素Mの平均含有率:M/Siモル比0.0019、シリカコロイド粒子の最表層に存在する多価金属元素M0.001個/nm2未満、ゼータ電位-28mV)が得られた。
硫酸を添加しなかった以外は実施例1と同様に行い、酸性シリカゾル1C(平均一次粒子径12nm、SiO223.4質量%、pH2.7、前記多価金属元素Mの平均含有率:M/Siモル比0.0020、シリカコロイド粒子の最表層に存在する多価金属元素M0.018個/nm2、ゼータ電位-23mV)が得られた。
酸性シリカゾル1Aの2000gを撹拌機、コンデンサー、温度計及び注入口2個を備えた内容積3Lのガラス製反応器に仕込み、反応器内のゾルを沸騰させたままの状態で、別のボイラーで発生させたメタノールの蒸気を反応器内のシリカゾル中に連続的に吹き込んで、液面をほぼ一定に保ちながらメタノールによる水の置換を行った。留出液の体積が20Lになったところで置換を終了して、メタノール分散シリカゾル1Aを1840g得た。得られたメタノール分散シリカゾルはSiO2濃度25.0質量%、メタノール74.4質量%、水分0.6質量%、粘度2mPa・s、ゾルを等質量の水で希釈したときのpH3.0であった。
酸性シリカゾル2Aの2000gを用いた以外は実施例3と同様に行い、メタノール分散シリカゾル2Aを1840g得た。得られたメタノール分散シリカゾルはSiO2濃度25.0質量%、メタノール74.4質量%、水分0.6質量%、粘度2mPa・s、ゾルを等質量の水で希釈したときのpH3.2であった。
酸性シリカゾル1aの2000gを用いた以外は実施例3と同様に行い、メタノール分散シリカゾル1aを1840g得た。得られたメタノール分散シリカゾルはSiO2濃度25.0質量%、メタノール74.4質量%、水分0.6質量%、粘度2mPa・s、ゾルを等質量の水で希釈したときのpH3.0であった。
酸性シリカゾル2aの2000gを用いた以外は実施例4と同様に行い、メタノール分散シリカゾル2aを1840g得た。得られたメタノール分散シリカゾルはSiO2濃度25.0質量%、メタノール74.4質量%、水分0.6質量%、粘度2mPa・s、ゾルを等質量の水で希釈したときのpH3.2であった。
酸性シリカゾル1Cの2000gを用いた以外は実施例4と同様に行い、メタノール分散シリカゾル1Cを1840g得た。得られたメタノール分散シリカゾルはSiO2濃度25.0質量%、メタノール74.4質量%、水分0.6質量%、粘度2mPa・s、ゾルを等質量の水で希釈したときのpH3.0であった。
メタノール分散シリカゾル1Aの280gを500mLナス型フラスコに採取し、マグネチックスターラーで攪拌しながらフェニルトリメトキシシラン7.6gを添加し、液温を55℃で2時間保持した。その後、ロータリーエバポレーターにて500ないし400Torr、浴温70℃の条件で、液面を徐々に下げながらゾルにメチルエチルケトンを添加して分散媒をメチルエチルケトンに置換することにより、透明なメチルエチルケトン分散シリカゾル1A(SiO240.0質量%、メチルエチルケトン59.7質量%、メタノール0.2質量%、水分0.1質量%、粘度2mPa・s)を得た。このゾルを100mL細口ガラス瓶に密閉し、50℃で1ヶ月間保持したところ、粘度及び外観に変化は無かった。
メタノール分散シリカゾル1Aの代わりにメタノール分散シリカゾル1aを用いた以外は実施例5と同様に行って、透明なメチルエチルケトン分散シリカゾル1a(SiO240.0質量%、メチルエチルケトン59.7質量%、メタノール0.2質量%、水分0.1質量%、粘度2mPa・s)を得た。このゾルを100mL細口ガラス瓶に密閉し、50℃で1ヶ月間保持したところ、粘度は変化しなかったが、外観が黄色に変色した。
メタノール分散シリカゾル1A200gを500mLナス型フラスコに採取し、マグネチックスターラーで攪拌しながらメタクリロキシプロピルトリメトキシシラン7.2gを添加し、液温を55℃で2時間保持した。その後、テトラヒドロフルフリルアクリレート113gを投入し、ロータリーエバポレーターにて200ないし40Torr、浴温50℃の条件でメタノールと水を除去することにより、無色透明のテトラヒドロフルフリルアクリレート分散シリカゾル1A(SiO230.0質量%、テトラヒドロフルフリルアクリレート68.9質量%、メタノール1.0質量%、水分0.1質量%、粘度12mPa・s)を得た。このゾルを100mL細口褐色ガラス瓶中に密閉し、23℃で1ヶ月保持したところ、外観、粘度に変化は無かった。
メタノール分散シリカゾル1Aの代わりにメタノール分散シリカゾル1aを用いた以外は実施例6と同様に行ったが、メタノールを約50g留去した時点でテトラヒドロフルフリルアクリレートが重合してゼリー状になったため、安定なテトラヒドロフルフリルアクリレート分散シリカゾルを得ることができなかった。
メタノール分散シリカゾル1Aの代わりにメタノール分散シリカゾル1Cを用いた以外は実施例6と同様に行ったが、メタノールを約60g留去した時点でテトラヒドロフルフリルアクリレートが重合してゼリー状になったため、安定なテトラヒドロフルフリルアクリレート分散シリカゾルを得ることができなかった。
α型トリス-(2,3-エポキシプロピル)-イソシアヌレート(日産化学工業(株)製、エポキシ価は9.95eq/kg)894.7gとトルエン400gを冷却管、温度計、攪拌装置付きの反応フラスコに仕込み、リフラックス温度まで加熱して完全に溶解した。次に反応触媒としてトリフェニルホスホニウムブロマイド0.38gを溶解させた無水プロピオン酸溶液313.3gを上記反応系に60分間かけて滴下した。滴下終了後、リフラックス温度で2時間反応させた。反応液を濃縮してエポキシ価が5.65eq/kg以下(理論値は5.48eq/kg)になったことを確認してからトルエンを留去して液状のエステル変性エポキシ樹脂を1208g得た。得られた液状のエステル変性エポキシ樹脂(2)の組成は次のとおりであった。トリス-(2,3-エポキシプロピル)-イソシアヌレートを化合物(ii)、トリス-(2,3-エポキシプロピル)-イソシアヌレートの1個のエポキシ基に1個の無水プロピオン酸が付加したもの(1付加体)を化合物(i-1)、トリス-(2,3-エポキシプロピル)-イソシアヌレートの2個のエポキシ基に2個の無水プロピオン酸が付加したもの(2付加体)を化合物(i-2)、トリス-(2,3-エポキシプロピル)-イソシアヌレートの3個のエポキシ基に3個の無水プロピオン酸が付加したもの(3付加体)を化合物(i-3)とすると、エポキシ樹脂(2)における(ii):(i-1):(i-2):(i-3)のモル比は35%:45%:17%:3%であった。このエステル変性エポキシ樹脂(2)の粘度は60℃で1300mPa・sであった。
メタノール分散シリカゾル2Aの1000gを内容積2Lのナス型フラスコに仕込み、ロータリーエバポレーターにて500Torr、浴温70℃でアセトニトリルを添加しながら溶媒を蒸発留去した。ゾルの液面をほぼ一定でアセトニトリルの供給量が750gになるまで蒸発留去を行い、アセトニトリル・メタノール混合溶媒ゾル(SiO226質量%、アセトニトリル49質量%、メタノール24質量%、水分0.3質量%)を得た。次いで大気圧下で攪拌しながら、得られたゾルにフェニルトリメトキシシラン5.0g添加し、浴温65℃で5時間加熱した。このゾルに5.0質量%ジアザビシクロウンデセンメタノール溶液を5.0g添加し、2時間攪拌した。その後、ロータリーエバポレーターで500ないし350Torr、浴温70℃でアセトニトリルを添加しながら溶媒を蒸発留去した。ゾルの液面をほぼ一定に保つように、アセトニトリル1500gを供給しながら溶媒の蒸発留去を行い、アセトニトリル分散シリカゾル2A(SiO228質量%、アセトニトリル72質量%、メタノール0.1質量%未満、水分0.03質量%)900gを得た。内容積500mLのセパラブルナス型フラスコに参考例3で調製したエステル変性エポキシ樹脂(2)80gを仕込み、アセトニトリル分散シリカゾル2Aの286gを添加、攪拌して均一な溶液にした。これを、ロータリーエバポレーターで200ないし100Torr、浴温60℃で脱溶媒を行い、無色透明のエステル変性エポキシ樹脂分散シリカゾル2A(SiO247質量%、エステル変性エポキシ樹脂47質量%、アセトニトリル6質量%、40℃におけるB型粘度3760mPa・s)を得た。
メタノール分散シリカゾル2Aの代わりにメタノール分散シリカゾル2aを用いた以外は実施例7と同様に行い、無色透明のエステル変性エポキシ樹脂分散シリカゾル2a(SiO246質量%、エステル変性エポキシ樹脂46質量%、アセトニトリル8質量%、40℃におけるB型粘度1150mPa・s)を得た。
メタノール分散シリカゾル2Aの1000gを内容積2Lのナス型フラスコに仕込み、ロータリーエバポレーターにて500Torr、浴温70℃でアセトニトリルを添加しながら溶媒を蒸発留去した。ゾルの液面をほぼ一定でアセトニトリルの供給量が750gになるまで蒸発留去を行い、アセトニトリル・メタノール混合溶媒ゾル(SiO226質量%、アセトニトリル49質量%、メタノール質量24%、水分0.3質量%)を得た。次いで大気圧下で攪拌しながら、得られたゾルにフェニルトリメトキシシラン5.0g添加し、浴温65℃で5時間加熱した。このゾルに5.0質量%ジアザビシクロウンデセンメタノール溶液を7.5g添加し、攪拌した。その後、ロータリーエバポレーターで500ないし350Torr、浴温70℃でアセトニトリルを添加しながら溶媒を蒸発留去した。ゾルの液面をほぼ一定に保つように、アセトニトリル1500gを供給しながら溶媒の蒸発留去を行い、アセトニトリル分散シリカゾル2A(SiO228質量%、アセトニトリル72質量%、メタノール0.1質量%未満、水分0.03質量%)900gを得た。内容積500mLのセパラブルナス型フラスコにメチルヘキサヒドロフタル酸無水物(東京化成(株)製試薬)100gを仕込み、アセトニトリル分散シリカゾル2Aの153gを添加、攪拌して均一な溶液にした。これを、ロータリーエバポレーターで200ないし40Torr、浴温60℃で脱溶媒を行い、無色透明のメチルヘキサヒドロフタル酸無水物分散シリカゾル2A(SiO239質量%、メチルヘキサヒドロフタル酸無水物59質量%、アセトニトリル2質量%、30℃におけるB型粘度120mPa・s)を得た。
メタノール分散シリカゾル2Aの代わりにメタノール分散シリカゾル2aを用いたことと、ヘキサヒドロフタル酸無水物を100gから117gに変更した以外は実施例8と同様に行い、無色透明のメチルヘキサヒドロフタル酸無水物分散シリカゾル2a(SiO229質量%、メチルヘキサヒドロフタル無水物67質量%、アセトニトリル4質量%、30℃におけるB型粘度310mPa・s)を得た。
300mLの四つ口フラスコに実施例7で得られたエステル変性エポキシ樹脂分散シリカゾル2Aの40.5gとメチルヘキサヒドロフタル酸無水物15.03gを入れ、80℃で40分間の混合攪拌を行った。次いでこの混合物に硬化促進剤としてテトラブチルホスホニウムO,O'-ジエチルジチオホスフェート(日本化学工業(株)製、製品名:ヒシコーリンPX-4ET)209mgをメチルヘキサヒドロフタル酸無水物2.0gに溶解したものを加えて更に減圧下で2分間脱泡を行い、エポキシ樹脂硬化用組成物を得た。得られたエポキシ樹脂硬化用組成物には残留溶媒は検出されなかった。得られたエポキシ樹脂硬化用組成物を注型板(離型剤SR-2410(東レ・ダウシリコーニング(株)製)で処理されたガラス板3mm厚)に流し込み、100℃で2時間、150℃で5時間の硬化条件で加熱処理を行い、エポキシ樹脂硬化体を得た。得られたエポキシ樹脂硬化体の物性は表5及び表6に示した。表5においてMeHHPAはメチルヘキサヒドロフタル酸無水物を、PXはテトラブチルホスホニウムO,O'-ジエチルジチオホスフェートを、PX/MeHHPAはテトラブチルホスホニウムO,O'-ジエチルジチオホスフェートを含有したメチルヘキサヒドロフタル酸無水物を示し、それぞれの質量で示した。
実施例9と同様の操作を行って、エポキシ樹脂組成物を得た。表5にはエポキシ樹脂とエポキシ硬化剤又はエポキシ硬化剤分散シリカゾル、硬化促進剤の配合割合を示した。得られたエポキシ樹脂硬化用組成物を注型板(離型剤SR-2410(東レ・ダウシリコーニング(株)製)で処理されたガラス板3mm厚)に流し込み、100℃で2時間、150℃で5時間の硬化条件で加熱処理を行い、エポキシ樹脂硬化体を得た。表5においてMeHHPAはメチルヘキサヒドロフタル酸無水物を、PXはテトラブチルホスホニウムO,O'-ジエチルジチオホスフェートを、PX/MeHHPAはテトラブチルホスホニウムO,O'-ジエチルジチオホスフェートを含有したメチルヘキサヒドロフタル酸無水物を示し、それぞれの質量で示した。
(曲げ特性の測定)
引張り試験機によりJIS K-6911に基づき測定した。
試験片の高さ及び幅を測定し、試験片を支え、その中央に加圧くさびで荷重を加え、試験片が折れたときの荷重を測定し、曲げ強度(σ)を算出した。曲げ強度σ:(MPa){kgf/mm2}、P:試験片が折れたときの荷重(N){kgf}、L:支点間距離(mm)、W:試験片の幅(mm)、h:試験片の高さ(mm)とした。
σ=(3PL)/(2Wh2)
曲げ弾性率(E):(MPa){kgf/mm2}は、F/Y:荷重-たわみ曲線の直線部分のこう配(N/mm){kgf/mm}とすると、
E=〔L3/(4Wh3)〕×〔F/Y〕
(透過率の測定)
分光光度計(型式UV-3600、(株)島津製作所製)を用いて200-800nmの透過率を測定した。
(線膨張率の測定)
線膨張率の測定の測定は、JIS K-6911に基づき測定した。試験片の厚みを正確に測定してTMA(Thermal Mechanical Analysis)で荷重0.05N、昇温速度1℃/分で測定した。線膨張係数α1は30-80℃の長さの変化量(ΔL1)/試験片の初期の長さ(L)×50=α1で求めた。
一方、比較例10及び11のように、シリカコロイド粒子表面に前記多価金属元素がコロイド粒子の表面積1nm2当たり0.003個を超えて含有するシリカコロイド粒子では、エポキシ樹脂分散シリカゾルやジカルボン酸無水物分散シリカゾルは得られるものの、それらを用いたエポキシ樹脂硬化体が黄色に着色したため、光線透過率が低下した。結果として、実施例9及び10の硬化物は、比較例12のシリカコロイド粒子を含まない硬化物に比べて、光線透過率の低下を殆ど起こさせずに、且つ、線膨張率の低下や曲げ強度の向上をさせることができた。
Claims (13)
- 鉄、アルミニウム、亜鉛、ジルコニウム、チタン、スズ及び鉛からなる群から選ばれる少なくとも1種である多価金属元素Mの平均含有率がM/Siモル比として0.001ないし0.02である5ないし40nmの平均一次粒子径を有するシリカコロイド粒子であって、前記コロイド粒子の最表層に存在する多価金属元素Mの含有量が前記コロイド粒子の表面積1nm2当たり0ないし0.003個であるシリカコロイド粒子。
- 請求項1に記載のシリカコロイド粒子が有機溶媒に分散された有機溶媒分散シリカゾル。
- 前記有機溶媒が、アルコール類、エーテル類、ケトン類、エステル類、アミド類、炭化水素類及びニトリル類からなる群から選ばれる少なくとも1種である請求項2に記載の有機溶媒分散シリカゾル。
- 請求項1に記載のシリカコロイド粒子が、エチレン性不飽和結合を有する重合性化合物、エポキシ環を有する重合性化合物、オキセタン環を有する重合性化合物及びビニルエーテル構造を有する重合性化合物からなる群から選ばれる少なくとも1種の化合物に分散された重合性化合物分散シリカゾル。
- 前記化合物(i)が、分子内のn個(但し、nは2ないし16の整数である。)のグリシジル基の1個以上n個以下を、式(1)で示される官能基で置き換えた化合物である請求項5に記載の重合性化合物分散シリカゾル。
- 前記化合物(ii)が、分子内にn個(但し、nは2ないし16の整数である。)のグリシジル基を有する化合物である請求項5に記載の重合性化合物分散シリカゾル。
- 前記化合物(i):化合物(ii)のモル比が、1:0.3ないし1.5である請求項5に記載の重合性化合物分散シリカゾル。
- 前記化合物(i)が、トリス-(2,3-エポキシプロピル)-イソシアネートのグリシジル基を式(1)で示される官能基で置き換えたものである請求項5、6及び8のいずれか1項に記載の重合性化合物分散シリカゾル。
- 前記化合物(ii)が、トリス-(2,3-エポキシプロピル)-イソシアネートである請求項5、7及び8のいずれか1項に記載の重合性化合物分散シリカゾル。
- 請求項1に記載のシリカコロイド粒子が、30℃で液状のジカルボン酸無水物に分散されたジカルボン酸無水物分散シリカゾル。
- 前記ジカルボン酸無水物が、メチルヘキサヒドロフタル酸無水物、水素化メチルナジック酸無水物及び水素化トリメリット酸無水物からなる群から選ばれる少なくとも1種を含む請求項11に記載のジカルボン酸無水物分散シリカゾル。
- 下記工程(I)及び(II)を含む請求項1に記載のシリカコロイド粒子の製造方法:
(I):鉄、アルミニウム、亜鉛、ジルコニウム、チタン、スズ及び鉛からなる群から選ばれる少なくとも1種である多価金属元素Mの平均含有率がM/Siモル比として0.001ないし0.02である5ないし40nmの平均一次粒子径を有するシリカコロイド粒子を含むシリカゾルに、酸を加えてpH0ないし2.0とし、0ないし40℃で0.5ないし100時間熟成する工程、
(II):(I)で得られた酸性シリカゾルをpH0ないし2.0において水素型強酸性陽イオン交換樹脂と接触させ、更に水酸基型強塩基性陰イオン交換樹脂に接触させる工程。
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CN200980104988.3A CN102066252B (zh) | 2008-02-12 | 2009-02-12 | 胶体二氧化硅粒子及其制造方法、以及该粒子的有机溶剂分散二氧化硅溶胶、聚合性化合物分散二氧化硅溶胶和二羧酸酐分散二氧化硅溶胶 |
US14/851,863 US9376322B2 (en) | 2008-02-12 | 2015-09-11 | Process for producing colloidal silica particles |
US15/011,001 US9527749B2 (en) | 2008-02-12 | 2016-01-29 | Colloidal silica particles, process for producing the same, and organic solvent-dispersed silica sol, polymerizable compound-dispersed silica sol, and dicarboxylic anhydride-dispersed silica sol each obtained from the same |
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US14/851,863 Division US9376322B2 (en) | 2008-02-12 | 2015-09-11 | Process for producing colloidal silica particles |
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JP2009197078A (ja) * | 2008-02-20 | 2009-09-03 | Jgc Catalysts & Chemicals Ltd | ハードコート層形成用塗料組成物および光学物品 |
WO2012096172A1 (ja) * | 2011-01-11 | 2012-07-19 | 日本板硝子株式会社 | 金属酸化物を含む粒体の製造方法および金属酸化物コロイド粒子の凝集体の製造方法 |
WO2012124390A1 (ja) * | 2011-03-17 | 2012-09-20 | 日産化学工業株式会社 | シリカ含有エポキシ硬化剤の製造方法 |
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KR101276763B1 (ko) * | 2010-12-14 | 2013-06-19 | 금호석유화학 주식회사 | 소수성 실리카의 제조 방법 |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8952119B2 (en) | 2010-11-18 | 2015-02-10 | Aspen Aerogels, Inc. | Organically modified hybrid aerogels |
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Citations (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3342747A (en) | 1961-04-17 | 1967-09-19 | Nalco Chemical Co | Method of stabilizing silica sols |
JPS57196717A (en) | 1981-05-25 | 1982-12-02 | Shokubai Kasei Kogyo Kk | Powdered silica dispersible homogeneously in organic solvent and its manufacture |
JPS58145614A (ja) | 1982-02-23 | 1983-08-30 | Shokubai Kasei Kogyo Kk | 有機溶剤に均質に分散可能な粉末状シリカとその製造法 |
JPS598614A (ja) | 1982-06-30 | 1984-01-17 | Shokubai Kasei Kogyo Kk | 有機溶剤を分散媒とするシリカゾルの製造方法 |
JPS6295130A (ja) | 1985-10-18 | 1987-05-01 | Sumitomo Chem Co Ltd | 反応性モノマ−を分散媒とする酸化物ゾル |
JPS63123807A (ja) | 1986-11-13 | 1988-05-27 | Catalysts & Chem Ind Co Ltd | 酸性シリカゾルの製造法 |
JPH02167813A (ja) | 1988-12-21 | 1990-06-28 | Mitsubishi Monsanto Chem Co | コロイダルシリカメタノールゾルの製造方法 |
JPH03187913A (ja) | 1989-12-15 | 1991-08-15 | Shin Etsu Chem Co Ltd | シリカ粉末の製造方法 |
JPH0710522A (ja) * | 1993-06-17 | 1995-01-13 | Catalysts & Chem Ind Co Ltd | 複合酸化物ゾルの製造方法 |
JPH1143319A (ja) | 1997-05-26 | 1999-02-16 | Nissan Chem Ind Ltd | 疎水性オルガノシリカゾルの製造方法 |
WO2000034396A1 (fr) * | 1998-12-09 | 2000-06-15 | Nippon Kayaku Kabushiki Kaisha | Materiau de revetement dur et film obtenu au moyen de celui-ci |
JP2000169133A (ja) * | 1998-12-09 | 2000-06-20 | Nissan Chem Ind Ltd | シリカ−フッ化マグネシウム水和物複合ゾル及びその製造法 |
WO2000037359A1 (fr) * | 1998-12-21 | 2000-06-29 | Catalysts & Chemicals Industries Co., Ltd. | Particules fines, sol de particules fines dispersees, procede de preparation dudit sol et substrat revetu |
JP2002302617A (ja) * | 2001-04-06 | 2002-10-18 | Tokuyama Corp | 変性乾式シリカ分散液 |
JP2007063117A (ja) | 2005-08-02 | 2007-03-15 | Nissan Chem Ind Ltd | 有機溶媒分散シリカゾル及びその製造方法 |
JP2007217228A (ja) * | 2006-02-16 | 2007-08-30 | Tokuyama Corp | カチオン性樹脂変性シリカ分散液 |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4284580A (en) * | 1980-01-02 | 1981-08-18 | The Procter & Gamble Company | Fractionation of triglyceride mixture |
US5010207A (en) * | 1990-01-10 | 1991-04-23 | Amoco Corporation | Process for the production of trimellitic anhydride with superior color properties |
JP3753192B2 (ja) * | 1994-08-05 | 2006-03-08 | 日産化学工業株式会社 | シリカプロパノールゾルの製造法 |
IL153338A0 (en) * | 2000-06-22 | 2003-07-06 | Akzo Nobel Nv | Construction material |
US6857824B2 (en) * | 2001-10-18 | 2005-02-22 | Akzo Nobel N.V. | Sealing composition and its use |
US20050048291A1 (en) * | 2003-08-14 | 2005-03-03 | General Electric Company | Nano-filled composite materials with exceptionally high glass transition temperature |
US20040101822A1 (en) * | 2002-11-26 | 2004-05-27 | Ulrich Wiesner | Fluorescent silica-based nanoparticles |
KR20070102713A (ko) * | 2005-02-15 | 2007-10-19 | 미쓰이 가가쿠 가부시키가이샤 | 광촉매, 그 제조 방법, 광촉매를 함유하는 분산액 및광촉매 도료 조성물 |
JP5067942B2 (ja) * | 2005-09-28 | 2012-11-07 | Jx日鉱日石エネルギー株式会社 | 触媒及びその製造方法 |
-
2009
- 2009-02-12 KR KR1020107020315A patent/KR101565513B1/ko active IP Right Grant
- 2009-02-12 JP JP2009553439A patent/JP5505620B2/ja active Active
- 2009-02-12 TW TW098104496A patent/TWI457283B/zh active
- 2009-02-12 US US12/867,289 patent/US9284197B2/en active Active
- 2009-02-12 EP EP09710977.1A patent/EP2251304B1/en active Active
- 2009-02-12 WO PCT/JP2009/052303 patent/WO2009101974A1/ja active Application Filing
- 2009-02-12 CN CN200980104988.3A patent/CN102066252B/zh active Active
-
2014
- 2014-01-31 JP JP2014017963A patent/JP2014144908A/ja not_active Withdrawn
-
2015
- 2015-09-11 US US14/851,863 patent/US9376322B2/en active Active
-
2016
- 2016-01-29 US US15/011,001 patent/US9527749B2/en active Active
Patent Citations (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3342747A (en) | 1961-04-17 | 1967-09-19 | Nalco Chemical Co | Method of stabilizing silica sols |
JPS57196717A (en) | 1981-05-25 | 1982-12-02 | Shokubai Kasei Kogyo Kk | Powdered silica dispersible homogeneously in organic solvent and its manufacture |
JPS58145614A (ja) | 1982-02-23 | 1983-08-30 | Shokubai Kasei Kogyo Kk | 有機溶剤に均質に分散可能な粉末状シリカとその製造法 |
JPS598614A (ja) | 1982-06-30 | 1984-01-17 | Shokubai Kasei Kogyo Kk | 有機溶剤を分散媒とするシリカゾルの製造方法 |
JPS6295130A (ja) | 1985-10-18 | 1987-05-01 | Sumitomo Chem Co Ltd | 反応性モノマ−を分散媒とする酸化物ゾル |
JPS63123807A (ja) | 1986-11-13 | 1988-05-27 | Catalysts & Chem Ind Co Ltd | 酸性シリカゾルの製造法 |
JPH02167813A (ja) | 1988-12-21 | 1990-06-28 | Mitsubishi Monsanto Chem Co | コロイダルシリカメタノールゾルの製造方法 |
JPH03187913A (ja) | 1989-12-15 | 1991-08-15 | Shin Etsu Chem Co Ltd | シリカ粉末の製造方法 |
JPH0710522A (ja) * | 1993-06-17 | 1995-01-13 | Catalysts & Chem Ind Co Ltd | 複合酸化物ゾルの製造方法 |
JPH1143319A (ja) | 1997-05-26 | 1999-02-16 | Nissan Chem Ind Ltd | 疎水性オルガノシリカゾルの製造方法 |
WO2000034396A1 (fr) * | 1998-12-09 | 2000-06-15 | Nippon Kayaku Kabushiki Kaisha | Materiau de revetement dur et film obtenu au moyen de celui-ci |
JP2000169133A (ja) * | 1998-12-09 | 2000-06-20 | Nissan Chem Ind Ltd | シリカ−フッ化マグネシウム水和物複合ゾル及びその製造法 |
WO2000037359A1 (fr) * | 1998-12-21 | 2000-06-29 | Catalysts & Chemicals Industries Co., Ltd. | Particules fines, sol de particules fines dispersees, procede de preparation dudit sol et substrat revetu |
JP2002302617A (ja) * | 2001-04-06 | 2002-10-18 | Tokuyama Corp | 変性乾式シリカ分散液 |
JP2007063117A (ja) | 2005-08-02 | 2007-03-15 | Nissan Chem Ind Ltd | 有機溶媒分散シリカゾル及びその製造方法 |
JP2007217228A (ja) * | 2006-02-16 | 2007-08-30 | Tokuyama Corp | カチオン性樹脂変性シリカ分散液 |
Cited By (27)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2009197078A (ja) * | 2008-02-20 | 2009-09-03 | Jgc Catalysts & Chemicals Ltd | ハードコート層形成用塗料組成物および光学物品 |
KR101276763B1 (ko) * | 2010-12-14 | 2013-06-19 | 금호석유화학 주식회사 | 소수성 실리카의 제조 방법 |
WO2012096172A1 (ja) * | 2011-01-11 | 2012-07-19 | 日本板硝子株式会社 | 金属酸化物を含む粒体の製造方法および金属酸化物コロイド粒子の凝集体の製造方法 |
WO2012096171A1 (ja) * | 2011-01-11 | 2012-07-19 | 日本板硝子株式会社 | フレーク状のメソポーラス粒体とその製造方法 |
CN103313939A (zh) * | 2011-01-11 | 2013-09-18 | 日本板硝子株式会社 | 含有金属氧化物的颗粒的制造方法和金属氧化物胶体颗粒的凝聚体的制造方法 |
US9656874B2 (en) | 2011-01-11 | 2017-05-23 | Nippon Sheet Glass Company, Limited | Method for producing metal oxide-containing particles, and method for producing aggregates of metal oxide colloidal particles |
JP5870041B2 (ja) * | 2011-01-11 | 2016-02-24 | 日本板硝子株式会社 | フレーク状のメソポーラス粒体とその製造方法 |
JP5870042B2 (ja) * | 2011-01-11 | 2016-02-24 | 日本板硝子株式会社 | 金属酸化物を含む粒体の製造方法および金属酸化物コロイド粒子の凝集体の製造方法 |
US9272915B2 (en) | 2011-01-11 | 2016-03-01 | Nippon Sheet Glass Company, Limited | Flaky mesoporous particles, and method for producing the same |
WO2012124390A1 (ja) * | 2011-03-17 | 2012-09-20 | 日産化学工業株式会社 | シリカ含有エポキシ硬化剤の製造方法 |
WO2012161157A1 (ja) * | 2011-05-24 | 2012-11-29 | 日産化学工業株式会社 | 有機溶媒分散シリカゾル |
JPWO2012161157A1 (ja) * | 2011-05-24 | 2014-07-31 | 日産化学工業株式会社 | 有機溶媒分散シリカゾル |
CN104487383B (zh) * | 2012-07-10 | 2016-04-27 | 日本板硝子株式会社 | 含有金属氧化物的颗粒的制造方法 |
CN104487383A (zh) * | 2012-07-10 | 2015-04-01 | 日本板硝子株式会社 | 含有金属氧化物的颗粒的制造方法 |
KR20160068750A (ko) | 2013-09-27 | 2016-06-15 | 다이이치 고교 세이야쿠 가부시키가이샤 | 경화성 수지 조성물, 및 경질 코팅용 조성물 |
US9982162B2 (en) | 2013-09-27 | 2018-05-29 | Dai-Ichi Kogyoseiyaku Co., Ltd. | Curable resin composition, and composition for hard coat |
JPWO2019050008A1 (ja) * | 2017-09-07 | 2020-11-05 | 日産化学株式会社 | シリカ含有絶縁性組成物 |
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US11708273B2 (en) | 2020-11-04 | 2023-07-25 | Nissan Chemical Corporation | Aluminum-containing silica sol dispersed in nitrogen-containing solvent and resin composition |
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WO2024117228A1 (ja) * | 2022-11-30 | 2024-06-06 | 日産化学株式会社 | 遷移金属ドープシリカゾル及びその製造方法 |
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TW200948716A (en) | 2009-12-01 |
CN102066252A (zh) | 2011-05-18 |
EP2251304A1 (en) | 2010-11-17 |
KR20100138920A (ko) | 2010-12-31 |
US20160145110A1 (en) | 2016-05-26 |
JP5505620B2 (ja) | 2014-05-28 |
KR101565513B1 (ko) | 2015-11-03 |
JP2014144908A (ja) | 2014-08-14 |
EP2251304B1 (en) | 2017-07-19 |
US20100311871A1 (en) | 2010-12-09 |
US9527749B2 (en) | 2016-12-27 |
EP2251304A4 (en) | 2012-07-25 |
TWI457283B (zh) | 2014-10-21 |
US9376322B2 (en) | 2016-06-28 |
US20150376018A1 (en) | 2015-12-31 |
JPWO2009101974A1 (ja) | 2011-06-09 |
CN102066252B (zh) | 2014-08-06 |
US9284197B2 (en) | 2016-03-15 |
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