Epoxy group-containing organosilica sol, epoxy resin composition, and method for producing the same

Abstract

[Problem] To provide a silica sol which, as the dispersoid, contains silica particles that include an epoxy group or an epoxy group-containing organic group and an alkoxy group, and that is stably dispersed in an organic solvent; and a cured body-forming composition or epoxy cured body containing these silica sols. [Solution] This silica sol contains, as the dispersoid, silica particles that include an epoxy group or an epoxy group-containing organic group (R2) and an alkoxy group (OR1), and that have a 5-100nm average primary particle diameter measured with nitrogen adsorption (the BET method), contains organic matter as the dispersion medium, and also contains a basic substance, wherein, when the average particle diameter of the silica particles measured with dynamic light scattering (DLS) is 5-200 nm, the ratio of (average particle diameter with DLS) / (average primary particle diameter with BET) is 1.05-2.00, the epoxy group or epoxy group-containing organic group (R2) and the alkoxy group (OR1) have a molar ratio (R2) / (OR1) of 0.1-2.0.

Description

[Technical Field]

[0001] This invention relates to an epoxy group-containing organosilica sol and a cured product-forming composition using the same. [Background technology]

[0002] The organic solvent-dispersed silica sol can be combined with an organic resin to obtain a silica-containing resin composition, which can then be used to form a resin molded article containing a curing agent, or as a coating composition for covering a film. By incorporating inorganic oxide particles such as silica into the resin, surface hardness, abrasion resistance, mechanical strength, heat resistance, corrosion resistance, thermal expansion coefficient, flexural strength, and flexural modulus are improved. Furthermore, if the silica particle diameter is 50 nm or less, a cured product can be formed without reducing transparency. Inorganic oxide particles such as silica contained in organic resins can achieve further improvements in physical properties by being present in the resin matrix via covalent bonds, depending on their compatibility with the organic resin and, in the case of polymerizable resins, by reacting with polymerizable groups in those resins. For this reason, a sol containing silica particles with polymerizable groups on their surface is desired. For example, a method for producing a polymerizable organic compound composition containing silica particles is disclosed, which involves mixing an amine-containing organic solvent-dispersed silica sol with a polymerizable organic compound (see Patent Document 1). Patent Document 1 describes that colloidal silica particles are treated to make them organically hydrophilic with an organosilane compound, and that the polymerizable organic compound is a liquid epoxy resin. Furthermore, a modified epoxy resin obtained by modifying tris-(2,3-epoxypropyl)-isocyanurate and a liquid epoxy resin composition containing silica particles are disclosed (see Patent Document 2). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] International public brochure WO2010 / 058754 [Patent Document 2] International Public Pamphlet WO2009 / 008509 [Overview of the project] [Problems that the invention aims to solve]

[0004] The present invention aims to provide a silica sol containing an epoxy group or an epoxy group-containing organic group and silica particles containing an alkoxy group as a dispersed phase, which is stably dispersed in an organic solvent, and a curing composition containing such silica sol and an epoxy cured product. [Means for solving the problem]

[0005] From a first perspective, the present invention relates to an epoxy group or an epoxy group-containing organic group (R 2 ) and alkoxy group (OR 1 A silica sol containing silica particles as a dispersed phase, wherein the average primary particle size determined by nitrogen gas adsorption (BET) method is 5 to 100 nm, an organic substance as a dispersion medium, and a basic substance, When the average particle diameter of the silica particles determined by dynamic light scattering (DLS) is 5 to 200 nm, the ratio of (average particle diameter by DLS) / (average primary particle diameter by BET) is 1.05 to 2.00. The silica particles are epoxy groups or epoxy group-containing organic groups (R 2 ) converted to 0.1 to 6.0 particles / nm per unit area of ​​the silica particle surface. 2 Including, Alkoxy group (OR 1 ) converted to 0.3 to 4.0 particles / nm per unit area of ​​the silica particle surface. 2 Including, (R 2 ) / (OR 1 ) The above silica sol having a molar ratio of 0.1 to 2.0, From a second perspective, the silica sol described in the first perspective, wherein the average particle size of the silica particles measured by the dynamic light scattering method after storage at 50°C for 7 days is in the range of 1.0 to 1.2 times compared to the value before storage. As a third aspect, the silica sol according to the first aspect or the second aspect, wherein the epoxy group is a glycidyl group or a 3,4-epoxycyclohexyl group, As a fourth aspect, the silica sol according to any one of the first to third aspects, wherein the dispersion medium is an organic substance having a carbonyl structure or an organic substance having an epoxy group, As a fifth aspect, the silica sol according to the fourth aspect, wherein the organic substance having a carbonyl structure in the dispersion medium is methyl ethyl ketone, methyl isobutyl ketone, diisopropyl ketone, diisobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, or propylene glycol monomethyl ether acetate, As a sixth aspect, the silica sol according to the fourth aspect, wherein the organic substance having an epoxy group in the dispersion medium is a bisphenol A liquid epoxy compound, a bisphenol F liquid epoxy compound, or 3',4'-epoxycyclohexylmethyl 3',4'-epoxycyclohexanecarboxylate, As a seventh aspect, the silica sol according to any one of the first to sixth aspects, wherein the basic substance is an amine, ammonia, an inorganic alkali compound, or a quaternary ammonium compound, As an eighth aspect, the silica sol according to the seventh aspect, wherein the amine is a secondary amine or a tertiary amine having a total number of carbon atoms of 5 to 35, As a ninth aspect, the silica particles further have the following formula (1) to formula (3):

Chemical Formula

[0006] This invention is a epoxy group or an epoxy group-containing organic group (R 2 ) and alkoxy group (OR 1 This silica sol contains silica particles as a dispersed phase, the average primary particle diameter measured by nitrogen gas adsorption (BET) is 5 to 100 nm, an organic substance as a dispersion medium, and a basic substance. Furthermore, when the average particle diameter of the silica particles measured by dynamic light scattering (DLS) is 5 to 200 nm, the ratio of (average particle diameter by DLS) / (average primary particle diameter by BET) is 1.05 to 2.00. Silica particles are epoxy groups or epoxy group-containing organic groups (R 2 ) converted to 0.1 to 6.0 particles / nm per unit area of ​​the silica particle surface. 2 Including, Alkoxy group (OR 1 ) converted to 0.3 to 4.0 particles / nm per unit area of ​​the silica particle surface. 2 Including, (R 2 ) / (OR 1This is a silica sol with a molar ratio of 0.1 to 2.0. In the present invention, the above (R 2 ) / (OR 1 It was found that silica particles can stably exist in an organic dispersion medium (i.e., an organic solvent) when the molar ratio is within a specific range.

[0007] In this invention, R 1 An epoxy group or an epoxy group-containing organic group (R) is dispersed in a silica sol with an OH-structured alcohol as the dispersion medium in the presence of a basic substance. 2 This method involves adding a silane compound having the specified structure, followed by solvent replacement with an organic dispersion medium (organic solvent). Alkoxy group (OR 1 ) uses aqueous silica sol R 1 When the solvent is replaced with an alcohol in the OH group, the silanol group of the silica particles becomes an alkoxy group (OR 1 ) is formed by changing to ), but in the presence of a basic substance, moisture causes the reverse reaction of the above reaction, forming an alkoxy group (OR 1 ) may revert to a silanol group. In this invention, R 1 The silica sol, with an alcohol of the OH structure as the dispersion medium, has a water content of 5% by mass or less, for example, 1.0 to 5.0% by mass, or 1.2 to 5.0% by mass, or 1.2 to 3.0% by mass, thereby containing epoxy groups or epoxy group-containing organic groups (R 2 (R 2 ) / (OR 1 The molar ratio can be set within the range of 0.1 to 2.0.

[0008] In the present invention, an epoxy group or an epoxy group-containing organic group (R 2 ) and alkoxy group (OR 1 ) means that the silica particles in the silica sol contain R 1 -OH structure alcohol is Si-OR 1 In its structure (Si represents Si in silica particles), it forms covalent bonds, and some of it is R 1 R derived from O- 1 This indicates that the -OH group is interacting with the silica particles through hydrogen bonding.

[0009] And similarly, the silica particles in the silica sol have epoxy groups or epoxy group-containing organic groups (R 2 ) via silicon atoms Si-O-Si-R 2 In the structure (the Si on the left represents Si in silica particles, and the Si on the right represents Si in a silane compound), covalent bonds are formed, and some are R 2 R derived from -Si-(OR)3 (where R is a methyl group or an ethyl group that forms a hydrolysis group of OR). 2 This indicates that the -Si-(OH)3 silane compound is interacting with silica particles via hydrogen bonding. [Modes for carrying out the invention]

[0010] This invention is a epoxy group or an epoxy group-containing organic group (R 2 ) and alkoxy group (OR 1 A silica sol containing silica particles as a dispersed phase, wherein the average primary particle size determined by nitrogen gas adsorption (BET) method is 5 to 100 nm, an organic substance as a dispersion medium, and a basic substance, When the average particle diameter of silica particles measured by dynamic light scattering (DLS) is 5 to 200 nm, the ratio of (average particle diameter by DLS) / (average primary particle diameter by BET) is 1.05 to 2.00. Silica particles are epoxy groups or epoxy group-containing organic groups (R 2 ) converted to 0.1 to 6.0 particles / nm per unit area of ​​the silica particle surface. 2 Including, Alkoxy group (OR 1 ) converted to 0.3 to 4.0 particles / nm per unit area of ​​the silica particle surface. 2 Including, (R 2 ) / (OR 1 The above silica sol has a molar ratio of 0.1 to 2.0.

[0011] The present invention's alkoxy group (OR 1 ) uses aqueous silica sol R 1- When an alcohol with an OH structure is subjected to solvent substitution, an alkoxy group (OR) is formed on (on or near) silica particles. 1 These are functional groups derived from alcohols with 1 to 4 carbon atoms, such as methanol, ethanol, n-propanol, i-propanol, and propylene glycol monomethyl ether, and include methoxy, ethoxy, n-propanol, i-propanol, and 1-methoxy-2-propoxy groups. Some interact with silica particles in the form of alcohols.

[0012] Epoxy group or epoxy group-containing organic group (R 2 ) is a silica particle with an epoxy group or an epoxy group-containing organic group (R 2 ) is a functional group formed on (on or near) silica particles when a silane containing epoxy is added. Examples of epoxy groups include glycidyl groups or 3,4-epoxycyclohexyl groups, such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane.

[0013] Silica particles have alkoxy groups (OR 1 ) converted to 0.3 to 4.0 particles / nm per unit area of ​​the silica particle surface. 2 Includes epoxy groups or epoxy group-containing organic groups (R 2 ) converted to 0.1 to 6.0 particles / nm per unit area of ​​the silica particle surface. 2 Including, (R 2 ) / (OR 1 The molar ratio is 0.1 to 2.0. The above content is measured on a per-unit area basis of the silica particle surface, and this is the sum of the covalent and hydrogen bonding in the silica particles, (R 2 ) and (OR 1 ) This is caused by the addition of compounds containing this substance.

[0014] The sol of the present invention has a solid content of 0.1 to 70% by mass, or 1 to 60% by mass, or 10 to 55% by mass. Here, the solid content is the total components of the sol excluding the solvent component.

[0015] The silica particles of the present invention are obtained by nitrogen gas adsorption (BET) with an average primary particle diameter in the range of 5 to 200 nm, 5 to 150 nm, or 5 to 100 nm. Furthermore, the silica particles are obtained by dynamic light scattering (DLS) with an average particle diameter in the range of 5 to 200 nm, or 5 to 150 nm. The ratio of (average particle diameter by DLS) / (average primary particle diameter by BET) of the silica particles is 1.05 to 2.00. (R 2 ) has a group but (OR 1 Because the molar ratio with the ) group is 0.1 to 2.0, it exists in a near-spherical form without condensation even in organic solvents.

[0016] Furthermore, the average particle size of silica particles measured by the dynamic light scattering method after storage at 50°C for 7 days is in the range of 1.0 to 1.2 times compared to the value before storage. Since the value after storage is in the range of 1.0 to 1.2 times compared to the value before storage, the silica sol of the present invention has high storage stability and is stable.

[0017] The silica sol of the present invention uses an organic substance as a dispersion medium, wherein the dispersion medium is an organic substance having a carbonyl structure or an organic substance having an epoxy group.

[0018] Organic substances containing a carbonyl structure are ketone solvents, amide solvents, and ester solvents. Ketone solvents are linear or cyclic aliphatic ketones having 3 to 30 carbon atoms, such as methyl ethyl ketone, diethyl ketone, methyl propyl ketone, methyl isobutyl ketone, diisopropyl ketone, diisobutyl ketone, methyl amyl ketone, and cyclohexanone. Amide solvents are aliphatic amides having 4 to 30 carbon atoms, such as dimethylacetamide, dimethylformamide, N-methylpyrrolidone, and N-ethylpyrrolidone. Ester solvents include ethyl acetate, n-propyl acetate, isopropyl acetate, butyl acetate, or propylene glycol monomethyl ether acetate. Examples of organic materials having the above carbonyl structure include methyl isobutyl ketone, diisopropyl ketone, diisobutyl ketone, ethyl acetate, butyl acetate, or propylene glycol monomethyl ether acetate.

[0019] Organic substances containing epoxy groups are liquid epoxy compounds, such as 1,4-butanediol diglycidyl ether, 1,2-epoxy-4-(epoxyethyl)cyclohexane, glycerol triglycidyl ether, diethylene glycol diglycidyl ether, 2,6-diglycidylphenyl glycidyl ether, 1,1,3-tris[p-(2,3-epoxypropoxy)phenyl]propane, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, 4,4'-methylenebis(N,N-diglycidylaniline), and 3,4-epoxycyclohexyl Silmethyl-3,4-epoxycyclohexanecarboxylate, trimethylolethane triglycidyl ether, triglycidyl-p-aminophenol, tetraglycidyl metaxylenediamine, tetraglycidyl diaminodiphenylmethane, tetraglycidyl-1,3-bisaminomethylcyclohexane, bisphenol-A-diglycidyl ether, bisphenol-F-diglycidyl ether, bisphenol-S-diglycidyl ether, pentaerythritol tetraglycidyl ether, resorcinol diglycidyl ether, phthalate di Glycidyl esters, neopentyl glycol diglycidyl ether, polypropylene glycol diglycidyl ether, tetrabromobisphenol-A-diglycidyl ether, bisphenol hexafluoroacetone diglycidyl ether, pentaerythritol diglycidyl ether, hydrogenated bisphenol-A-diglycidyl ether, tris-(2,3-epoxypropyl) isocyanurate, 1-{2,3-di(propionyloxy)}-3,5-bis(2,3-epoxypropyl)-1,3,5-triazine-2,4,6·(1H,3 H,5H)-Trione, 1,3-Bis{2,3-di(propionyloxy)}-5-(2,3-epoxypropyl)-1,3,5-Triadine-2,4,6·(1H,3H,5H)-Trione, Monoallyl diglycidyl isocyanurate, Diglycerol polydiglycidyl ether, Pentaerythritol polyglycidyl ether, 1,4-Bis(2,3-epoxypropoxyperfluoroisopropyl)cyclohexane, Sorbitol polyglycidyl ether, Trimethylolpropane polyglycidyl ether, Resorcinol diglycidyl ether, 1,6-Hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, adipic acid diglycidyl ether, o-phthalate diglycidyl ether, dibromophenyl glycidyl ether, 1,2,7,8-diepoxyoctane, 1,6-dimethylol perfluorohexane diglycidyl ether, 4,4'-bis(2,3-epoxypropoxyperfluoroisopropyl)diphenyl ether, 2,2-bis(4-glycidyloxyphenyl)propane, 3,4-epoxycyclohexylmethyl-3',4'-epoxy Examples include chlorohexane carboxylate, 3,4-epoxycyclohexyloxirane, 2-(3,4-epoxycyclohexyl)-3',4'-epoxy-1,3-dioxan-5-spirocyclohexane, 1,2-ethylenedioxy-bis(3,4-epoxycyclohexylmethane), 4',5'-epoxy-2'-methylcyclohexylmethyl-4,5-epoxy-2-methylcyclohexane carboxylate, ethylene glycol-bis(3,4-epoxycyclohexane carboxylate), bis-(3,4-epoxycyclohexylmethyl) adipate, and bis(2,3-epoxycyclopentyl) ether. In particular, examples include bisphenol A liquid epoxy compounds, bisphenol F liquid epoxy compounds, or 3',4'-epoxycyclohexylmethyl 3',4'-epoxycyclohexanecarboxylate. Examples of bisphenol A liquid epoxy compounds include bisphenol-A-diglycidyl ether, and examples of bisphenol F liquid epoxy compounds include bisphenol-F-diglycidyl ether.

[0020] In this invention, it is preferable to use a silica sol in which dispersed silica particles contain aluminum atoms in a ratio of 800 to 10,000 ppm / SiO2, calculated as Al2O3. Using these silica sols improves stability.

[0021] The silica sol of the present invention is produced by the following steps (A) to (D): (A) Process: Silica particles with an average particle size of 5-200 nm are collected by dynamic light scattering (DLS) and then heated with alcohol R 1 OH (however R 1 This represents an organic group having 1 to 10 carbon atoms, which may have an oxygen atom. The process of obtaining the above silica sol is a silica sol dispersed in ( ), wherein the silica sol contains 5% by mass or less water. (B) Step: A step of adding a secondary or tertiary amine having a total of 5 to 35 carbon atoms to the silica sol obtained in step (A). (C) Step: Add epoxy groups or epoxy group-containing organic groups (R) to the silica sol obtained in step (B). 2 A step of coating silica particles by adding a silane compound having ) (D) Step: Dispersion medium is alcohol R 1 It can be produced by a method that includes a step of substituting the OH group with an organic substance having a carbonyl structure or an organic substance having an epoxy group.

[0022] (A) In step (A), a silica sol can be used with an alcohol having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, as the dispersion medium. Examples of this alcohol include methanol, ethanol, n-propanol, i-propanol, and propylene glycol monomethyl ether. Methanol is particularly preferred among the above alcohols. 1 The silica sol, which uses an alcohol with an OH structure as the dispersion medium, preferably has a water content of 5% by mass or less, for example, 1.0 to 5.0% by mass, or 1.2 to 5.0% by mass, or 1.2 to 3.0% by mass.

[0023] Alcohol R having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms 1Silica sols using OH as a dispersion medium can be obtained using aqueous silica sol as a starting material. Aqueous silica sols can be obtained using water glass as a starting material through a) a process of obtaining activated silicic acid by cation exchange of water glass, and b) a process of obtaining silica particles by heating the activated silicic acid. In step a), mineral acid (e.g., hydrochloric acid, nitric acid, or sulfuric acid) can be added to purify the activated silicic acid to dissolve metal impurities other than silica, and activated silicic acid from which metal impurities and unwanted anions have been removed by cation exchange and anion exchange can be used. In step b), alkaline components (e.g., NaOH, KOH) are added to the activated silicic acid to promote particle growth of silica particles. To promote particle growth of silica particles, a seed solution and a feed solution can be prepared by adding alkali to the activated silicic acid obtained in step a), and by supplying the feed solution while heating the seed solution, the particle size of the silica particles can be increased to obtain aqueous silica sol with a desired particle size. More preferably, of the aqueous silica sol obtained in step b), an acidic silica sol from which alkali ions present outside the particles have been removed is suitable as the starting material for the present invention.

[0024] In step (A) of the present invention, the aqueous medium of the aqueous silica sol is preferably an alcohol R having 1 to 4 carbon atoms. 1 OH (however R 1 This represents an alkyl group having 1 to 4 carbon atoms. By substituting this alcohol (particularly methanol) with other solvents, a silica sol can be obtained in which silica particles with an average particle size of 5 to 200 nm, determined by dynamic light scattering, are dispersed, and the alcohol having 1 to 4 carbon atoms is used as the dispersion medium.

[0025] Step (B) is the process of adding a basic substance to the silica sol obtained in step (A). The amount of basic substance added is preferably such that the pH of the silica sol is 6.0 to 11.0, or 7.0 to 11.0. The amount of basic substance added is present as content in the silica sol. The pH of the silica sol of this invention is measured using a pH meter on a liquid mixture of silica sol, methanol, and pure water in a mass ratio of 1:1:1 or 1:2:1.

[0026] Examples of the basic substances mentioned above include amines, ammonia, inorganic alkali compounds, and quaternary ammonium compounds.

[0027] Examples of amines include secondary and tertiary amines with a total number of carbon atoms ranging from 5 to 35. Examples of the above secondary amines include ethyl-n-propylamine, ethylisopropylamine, dipropylamine, diisopropylamine, ethylbutylamine, n-propylbutylamine, dibutylamine, ethylpentylamine, n-propylpentylamine, isopropylpentylamine, dipentylamine, ethyloctylamine, i-propyloctylamine, butyloctylamine, and dioctylamine. Examples of the above-mentioned tertiary amines include triethylamine, ethyldi-n-propylamine, diethyl-n-propylamine, tri-n-propylamine, triisopropylamine, ethyldibutylamine, diethylbutylamine, isopropyldibutylamine, diisopropylethylamine, diisopropylbutylamine, tributylamine, ethyldipentylamine, diethylpentylamine, tri-n-pentylamine, methyldioctylamine, dimethyloctylamine, ethyldioctylamine, diethyloctylamine, trioctylamine, benzyldibutylamine, and diazabicycloundecene. Among the above amines, secondary and tertiary amines having an alkyl group with a total number of carbon atoms of 5 to 35 are preferred, for example, diisopropylamine, tri-n-pentylamine, triisopropylamine, dimethyloctylamine, trioctylamine, diisopropylethylamine, and the like.

[0028] Ammonia can be used as gaseous ammonia or aqueous ammonia.

[0029] As the quaternary ammonium hydroxide, tetraalkylammonium hydroxide with a total number of carbon atoms of 4 to 40 is preferred. Examples include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetran-propylammonium hydroxide, tetrai-propylammonium hydroxide, tetrabutylammonium hydroxide, and ethyltrimethylammonium hydroxide.

[0030] Examples of inorganic alkali compounds include alkali metal hydroxides, such as sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate.

[0031] (C) Step (B) involves adding epoxy groups or epoxy group-containing organic groups (R 2 This is a step of coating silica particles by adding a silane compound having ). Epoxy group or epoxy group-containing organic group (R 2 ) is a silica particle with an epoxy group or an epoxy group-containing organic group (R 2 This refers to a functional group formed on (on or near) silica particles when a silane containing silane is added. The epoxy group is a glycidyl group or a 3,4-epoxycyclohexyl group, and examples include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane. In particular, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane or 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltrimethoxysilane can be preferably used.

[0032] This is a step in which a hydroxy group on or near the surface of silica particles, for example, a silanol group in the case of silica particles, reacts with the silane compound, and the surface of the silica particles is coated with the silane compound via a siloxane bond. The reaction can be carried out at a temperature ranging from 20°C to the boiling point of the dispersion medium, and for example, can be carried out within a range of 20°C to 100°C. The reaction time can be about 0.1 to 6 hours.

[0033] Water is required for the hydrolysis of the above silane compound, but alcohol R having 1 to 4 carbon atoms 1 In the case of an OH solvent sol, moisture remaining in the alcohol solvent when an aqueous medium is solvent-substituted with alcohol can be used. The residual moisture is moisture remaining when a sol of an aqueous medium is solvent-substituted to a sol of an alcohol solvent having 1 to 4 carbon atoms, and for example, the moisture can be used when the silica sol dispersed in the alcohol has a moisture content of 5% by mass or less, for example 1.0 to 5.0% by mass, alternatively 1.2 to 5.0% by mass, or alternatively 1.2 to 3.0% by mass. As a catalyst, the above basic substance also serves as a hydrolysis catalyst.

[0034] In step (C), in addition to adding the silane containing an epoxy group or an epoxy group-containing organic group (R 2 ), at least one silane compound selected from the group consisting of formula (1) to formula (3) can also be added. In formula (1), R 3 each represents an organic group having an alkyl group, a halogenated alkyl group, an alkenyl group, an aryl group, a (meth)acryloyl group, a mercapto group, an amino group, a ureido group, or a cyano group, and is bonded to a silicon atom via a Si-C bond, R 4 each represents an alkoxy group, an acyloxy group, or a halogen group, a represents an integer of 1 to 3, In formula (2) and formula (3), R 5 and R 7 each represent an alkyl group having 1 to 3 carbon atoms, or an aryl group having 6 to 30 carbon atoms, and are bonded to a silicon atom via a Si-C bond, R 6 and R8 Each of the following groups represents an alkoxy group, an acyloxy group, or a halogen group; Y represents an alkylene group, an NH group, or an oxygen atom; b is an integer from 1 to 3; c is an integer of 0 or 1; and d is an integer from 1 to 3.

[0035] The alkyl groups mentioned above are alkyl groups 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 group, t-butyl group, cyclobutyl group, 1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl- n-propyl group, cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2-ethyl-cyclopropyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group , 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl Group, 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group, 1-i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group, 2,2,Examples of such groups include, but are not limited to, 3-trimethylcyclopropyl group, 1-ethyl-2-methylcyclopropyl group, 2-ethyl-1-methylcyclopropyl group, 2-ethyl-2-methylcyclopropyl group and 2-ethyl-3-methylcyclopropyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, etc. Furthermore, alkylene groups can be derived from the alkyl groups mentioned above.

[0036] The aryl group mentioned above is an aryl group having 6 to 30 carbon atoms, and examples include the phenyl group, naphthyl group, anthracene group, and pyrene group.

[0037] Alkenyl groups are alkenyl groups having 2 to 10 carbon atoms, including ethenyl group, 1-propenyl group, 2-propenyl group, 1-methyl-1-ethenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-ethylethenyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-n-propylethenyl group, 1-methyl-1-butenyl group, 1-methyl-2-butenyl group, 1-methyl-3-butenyl group, 2-ethyl-2-propenyl group, 2-methyl-1-butenyl group, 2-methyl-2-butenyl group, 2-methyl-3-butenyl group, and 3 Examples of but not limited to the following are methyl-1-butenyl group, 3-methyl-2-butenyl group, 3-methyl-3-butenyl group, 1,1-dimethyl-2-propenyl group, 1-i-propylethenyl group, 1,2-dimethyl-1-propenyl group, 1,2-dimethyl-2-propenyl group, 1-cyclopentenyl group, 2-cyclopentenyl group, 3-cyclopentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 1-methyl-1-pentenyl group, 1-methyl-2-pentenyl group, 1-methyl-3-pentenyl group, 1-methyl-4-pentenyl group, 1-n-butylethenyl group, 2-methyl-1-pentenyl group, 2-methyl-2-pentenyl group, etc.

[0038] The alkoxy groups mentioned above include, but are not limited to, alkoxy groups having 1 to 10 carbon atoms, such as methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, s-butoxy group, t-butoxy group, n-pentyloxy group, 1-methyl-n-butoxy group, 2-methyl-n-butoxy group, 3-methyl-n-butoxy group, 1,1-dimethyl-n-propoxy group, 1,2-dimethyl-n-propoxy group, 2,2-dimethyl-n-propoxy group, 1-ethyl-n-propoxy group, and n-hexyloxy group.

[0039] The above-mentioned acyloxy groups, which have 2 to 10 carbon atoms, include, but are not limited to, methyl carbonyloxy group, ethyl carbonyloxy group, n-propyl carbonyloxy group, i-propyl carbonyloxy group, n-butyl carbonyloxy group, i-butyl carbonyloxy group, s-butyl carbonyloxy group, t-butyl carbonyloxy group, n-pentyl carbonyloxy group, 1-methyl-n-butyl carbonyloxy group, 2-methyl-n-butyl carbonyloxy group, 3-methyl-n-butyl carbonyloxy group, 1,1-dimethyl-n-propyl carbonyloxy group, 1,2-dimethyl-n-propyl carbonyloxy group, 2,2-dimethyl-n-propyl carbonyloxy group, 1-ethyl-n-propyl carbonyloxy group, n-hexyl carbonyloxy group, 1-methyl-n-pentyl carbonyloxy group, and 2-methyl-n-pentyl carbonyloxy group. Examples of the halogen groups mentioned above include fluorine, chlorine, bromine, and iodine.

[0040] The above term "(meth)acryloyl group" refers to both an acryloyl group and a methacryloyl group. Examples of organic groups having a (meth)acryloyl group include 3-methacryloxypropyl group and 3-acryloxypropyl group.

[0041] An example of an organic group containing a mercapto group is the 3-mercaptopropyl group. Examples of organic groups having an amino group include 2-aminoethyl group, 3-aminopropyl group, N-2-(aminoethyl)-3-aminopropyl group, N-(1,3-dimethylbutylidene)aminopropyl group, N-phenyl-3-aminopropyl group, and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyl group.

[0042] An example of an organic group having a ureido group is the 3-ureidopropyl group.

[0043] An example of an organic group having a cyano group is the 3-cyanopropyl group.

[0044] The silica compounds represented by the above formula (2) and formula (3) are preferably compounds capable of forming trimethylsilyl groups on the surface of silica particles. These compounds can be exemplified as follows.

Chemical Formula

[0045] Preferred functional groups include a trimethylsilyl group, a monomethylsilyl group, a dimethylsilyl group, a methacryloxypropylsilyl group, and a phenyl group. Corresponding silane compounds include hexamethyldisilazane, hexamethylsiloxane, hexamethyldisiloxane, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane, acryloxypropyltrimethoxysilane, acryloxypropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, and the like.

[0046] The above silane compound is preferably a silane compound represented by formula (1) (wherein R 3 is an organic group having an aryl group and is bonded to a silicon atom via a Si-C bond, each R 4 independently represents an alkoxy group, an acyloxy group, or a halogen group, and a represents an integer of 1 to 3), and examples thereof include phenyltriethoxysilane and phenyltrimethoxysilane.

[0047] Step (D) is a step of replacing the dispersion medium of the silica sol obtained in step (C) from alcohol R 1 OH with an organic substance having a carbonyl structure or an organic substance having an epoxy group. The organic substances having a carbonyl structure are ketone solvents, amide solvents, and ester solvents, and the organic substances having an epoxy group are liquid epoxy compounds, and the compounds exemplified above may be mentioned. (D) In ​​step (D), the dispersion medium is alcohol R 1 After substituting the OH group with an organic compound having a carbonyl structure, it can be further substituted with an organic compound having an epoxy group.

[0048] In this invention, silica sols can be obtained using an organic substance having a carbonyl structure as a dispersion medium, and silica sols can be obtained using an organic substance having an epoxy group as a dispersion medium. Either silica sol can be cured by containing a curing agent such as an amine-based curing agent, an acid anhydride-based curing agent, or an acid-generating agent (thermal acid generator or photoacid generator). A cured product can be formed by applying a cured product composition containing silica sol and curing agent to a substrate and then heating, irradiating with light, or a combination thereof. The cured product composition may further contain an epoxy resin.

[0049] In the case of a thermosetting cured product-forming composition, the thermosetting agent can be contained in an amount of 0.5 to 1.5 equivalents, preferably 0.8 to 1.2 equivalents, relative to the epoxy groups. The equivalent amount of the thermosetting agent relative to the epoxy compound is expressed as the equivalent ratio of the curable groups of the thermosetting agent to the epoxy groups.

[0050] Examples of thermosetting agents include phenolic resins, amine-based curing agents, polyamide resins, imidazoles, polymer mercaptans, acid anhydrides, and thermoacid generators. Acid anhydride-based curing agents and amine-based curing agents are particularly preferred. Although these thermosetting agents can be used by dissolving them in a solvent even if they are solid, evaporation of the solvent can lead to a decrease in density of the cured product, the formation of pores, a decrease in strength, and a decrease in water resistance. Therefore, it is preferable that the curing agent itself be liquid at room temperature and atmospheric pressure.

[0051] Examples of phenolic resins include phenol novolac resins and cresol novolac resins.

[0052] Examples of amine-based curing agents include piperidine, N,N-dimethylpiperazine, triethylenediamine, 2,4,6-tris(dimethylaminomethyl)phenol, benzyldimethylamine, 2-(dimethylaminomethyl)phenol, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine, di(1-methyl-2-aminocyclohexyl)methane, mensendiamine, isophoronediamine, diaminodicyclohexylmethane, 1,3-diaminomethylcyclohexane, xylenediamine, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, 3,3'-diethyl-4,4'-diaminodiphenylmethane, and diethyltoluenediamine. Among these, liquid diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine, di(1-methyl-2-aminocyclohexyl)methane, mensendiamine, isophoronediamine, diaminodicyclohexylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, diethyltoluenediamine, etc., can be preferably used.

[0053] Polyamide resins are produced by the condensation of dimer acid and polyamine, and are polyamidoamines having a primary amine and a secondary amine in their molecules.

[0054] Examples of imidazoles include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, and epoxyimidazole adduct.

[0055] Polymercaptans are, for example, those in which mercaptan groups are present at the ends of polypropylene glycol chains or polyethylene glycol chains, and are preferably in liquid form.

[0056] As acid anhydride-based curing agents, anhydrides of compounds having multiple carboxyl groups in one molecule are preferred. Examples of these acid anhydride-based curing agents include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, ethylene glycol bistrimellitate, glycerol trimellitate, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, succinic anhydride, methylcyclohexendicarboxylic anhydride, and chloride anhydride.

[0057] Examples of thermal acid generators include sulfonium salts and phosphonium salts, but sulfonium salts are preferred. The following compounds are examples. [ka]

[0058] R can be an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 20 carbon atoms, with alkyl groups having 1 to 12 carbon atoms being particularly preferred.

[0059] Among these, methyltetrahydrophthalic anhydride, methyl-5-norbornene-2,3-dicarboxylic acid anhydride (methylnadic anhydride, methylhymic anhydride), hydrogenated methylnadic anhydride, methylbutenyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, methylhexahydrophthalic anhydride, and mixtures of methylhexahydrophthalic anhydride and hexahydrophthalic anhydride are preferred, as they are liquid at room temperature and atmospheric pressure. These liquid acid anhydrides have a viscosity of approximately 10 mPas to 1000 mPas when measured at 25°C.

[0060] Furthermore, when obtaining the above-mentioned cured product, a curing aid may be used in combination as appropriate. Examples of curing aids include organophosphorus compounds such as triphenylphosphine and tributylphosphine, quaternary phosphonium salts such as ethyltriphenylphosphonium bromide and methyltriphenylphosphonium diethyl phosphate, 1,8-diazabicyclo(5,4,0)undecane-7-ene, a salt of 1,8-diazabicyclo(5,4,0)undecane-7-ene and octic acid, zinc octyolate, and quaternary ammonium salts such as tetrabutylammonium bromide. These curing aids can be included in a ratio of 0.001 to 0.1 parts by mass per 1 part by mass of the curing agent.

[0061] Epoxy group or epoxy group-containing organic group (R 2 ) and alkoxy group (OR 1 A silica sol containing silica particles, or a composition further containing an epoxy resin, can be mixed with a curing agent and optionally a curing aid to obtain a thermosetting composition (a thermosetting composition that forms a cured body). These mixing can be carried out in a reaction vessel using a stirring blade or a kneader. Mixing is carried out by a heated mixing method, at a temperature of 60°C to 100°C for 0.5 to 1 hour.

[0062] The obtained liquid epoxy resin composition (thermosetting composition) is a thermosetting composition and has an appropriate viscosity for use as a liquid encapsulant, for example. The liquid thermosetting composition can be adjusted to any viscosity and can be partially encapsulated at any point on an LED or the like for use as a transparent encapsulant by casting, potting, dispensing, printing, etc. An epoxy resin cured body can be obtained by directly mounting the liquid thermosetting composition onto an LED or the like in liquid form using the method described above, and then drying and curing it. A thermosetting composition is applied to a substrate and heated at a temperature of 80 to 200°C to obtain a cured product.

[0063] In the case of a photocurable composition (a photocurable cured product forming composition), the photocuring agent (photoacid generator) can be contained in a ratio of 0.5 to 20% by mass, preferably 0.8 to 10% by mass, relative to the epoxy group. The photoacid generator is not particularly limited as long as it generates acid directly or indirectly upon light irradiation. Specific examples of photoacid generators include triazine compounds, acetophenone derivative compounds, disulfone compounds, diazomethane compounds, sulfonic acid derivative compounds, iodonium salts, sulfonium salts, phosphonium salts, selenium salts and other onium salts, metallocene complexes, and iron arene complexes.

[0064] The onium salt used as the above-mentioned photoacid generator is an iodonium salt such as diphenyliodonium chloride, diphenyliodonium trifluoromethanesulfate, diphenyliodonium mesylate, diphenyliodonium tosylate, diphenyliodonium bromide, diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluoroarsenate, bis(p-tert-butylphenyl)iodonium hexafluorophosphate, bis(p-tert-butylphenyl)iodonium mesylate, bis(p-tert-butylphenyl)iodonium tosylate, bis(p-tert-butylphenyl)iodonium trifluoromethanesulfate, bis(p-tert-butylphenyl)iodonium Examples include bis(alkylphenyl)iodonium salts such as bis(4-t-butylphenyl)iodonium tetrafluoroborate, bis(p-tert-butylphenyl)iodonium chloride, bis(p-chlorophenyl)iodonium chloride, bis(p-chlorophenyl)iodonium tetrafluoroborate, and bis(alkylphenyl)iodonium salts such as bis(4-t-butylphenyl)iodonium hexafluorophosphate, alkoxycarbonylalkoxy-trialkylaryliodonium salts (e.g., 4-[(1-ethoxycarbonyl-ethoxy)phenyl]-(2,4,6-trimethylphenyl)-iodonium hexafluorophosphate), and bis(alkoxyaryl)iodonium salts (e.g., bis(alkoxyphenyl)iodonium salts such as (4-methoxyphenyl)phenyliodonium hexafluoroantimonate).

[0065] Examples of sulfonium salts include triphenylsulfonium chloride, triphenylsulfonium bromide, tri(p-methoxyphenyl)sulfonium tetrafluoroborate, tri(p-methoxyphenyl)sulfonium hexafluorophosphonate, tri(p-ethoxyphenyl)sulfonium tetrafluoroborate, triphenylsulfonium triflate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluorophosphate, and other triphenylsulfonium salts, as well as sulfonium salts such as (4-phenylthiophenyl)diphenylsulfonium hexafluoroantimonate, (4-phenylthiophenyl)diphenylsulfonium hexafluorophosphate, bis[4-(diphenylsulfonio)phenyl]sulfide-bis-hexafluoroantimonate, bis[4-(diphenylsulfonio)phenyl]sulfide-bis-hexafluorophosphate, and (4-methoxyphenyl)diphenylsulfonium hexafluoroantimonate.

[0066] Examples of phosphonium salts include triphenylphosphonium chloride, triphenylphosphonium bromide, tri(p-methoxyphenyl)phosphonium tetrafluoroborate, tri(p-methoxyphenyl)phosphonium hexafluorophosphonate, tri(p-ethoxyphenyl)phosphonium tetrafluoroborate, 4-chlorobenzenediazonium hexafluorophosphate, and benzyltriphenylphosphonium hexafluoroantimonate.

[0067] Examples include selenium salts such as triphenylselenium hexafluorophosphate and metallocene complexes such as (η5 or η6-isopropylbenzene)(η5-cyclopentadienyl)iron(II) hexafluorophosphate.

[0068] In addition, the following compounds can also be used as photoacid generators. [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0069] Sulfonium salt compounds and iodonium salt compounds are preferred as photoacid generators. The anionic species is CF3SO3. - , C4F9SO3 - , C8F 17 SO3 - Camphor sulfonate anion, tosylate anion, BF4 - PF6 - AsF6 - and SbF6 - These are some examples. Anionic species such as phosphorus hexafluoride and antimony hexafluoride, which exhibit strong acidity, are particularly preferred.

[0070] The curing composition of the present invention may optionally contain conventional additives. Examples of such additives include pigments, colorants, thickeners, sensitizers, defoamers, leveling agents, coatability improvers, lubricants, stabilizers (such as antioxidants, heat stabilizers, and light stabilizers), plasticizers, surfactants, dissolution accelerators, fillers, antistatic agents, and curing agents. These additives may be used individually or in combination of two or more.

[0071] Examples of coating methods include flow coating, spin coating, spray coating, screen printing, casting, bar coating, curtain coating, roll coating, gravure coating, dipping, and slitting. In this invention, a photocurable curing composition can be applied to a substrate and cured by light irradiation. Heating can also be performed before and after light irradiation.

[0072] The thickness of the coating film can be selected from a range of approximately 0.01 μm to 10 mm, depending on the application of the cured material. For example, when used for photoresists, it can be approximately 0.05 to 10 μm (especially 0.1 to 5 μm); when used for printed circuit boards, it can be approximately 5 μm to 5 mm (especially 100 μm to 1 mm); and when used for optical thin films, it can be approximately 0.1 to 100 μm (especially 0.3 to 50 μm).

[0073] When using a photoacid generator, the light used for irradiation or exposure may be, for example, gamma rays, X-rays, ultraviolet light, or visible light, and is usually visible light or ultraviolet light, especially ultraviolet light. The wavelength of the light is, for example, 150 to 800 nm, preferably 150 to 600 nm, more preferably 200 to 400 nm, and especially around 300 to 400 nm. The amount of irradiation light varies depending on the thickness of the coating film, but is, for example, 2 to 20,000 mJ / cm². 2 Preferably 5 to 5000 mJ / cm² 2 The degree can be adjusted accordingly. The light source can be selected according to the type of light to be exposed; for example, in the case of ultraviolet light, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, deuterium lamps, halogen lamps, laser light (helium-cadmium laser, excimer laser, etc.) can be used. The curing reaction of the composition proceeds upon such light irradiation.

[0074] When using a thermal acid generator, or when using a photoacid generator and heating the coating film after light irradiation as needed, the heating is performed at, for example, 60 to 250°C, preferably around 100 to 200°C. The heating time can be selected from a range of 3 seconds or more (for example, 3 seconds to 5 hours), for example, 5 seconds to 2 hours, preferably 20 seconds to 30 minutes, and usually 1 minute to 3 hours (for example, 5 minutes to 2.5 hours).

[0075] Furthermore, when forming patterns or images (for example, when manufacturing printed circuit boards), the coating film formed on the substrate may be pattern-exposed. This pattern exposure may be performed by scanning with a laser beam or by irradiating with light through a photomask. The un-irradiated areas (unexposed parts) generated by such pattern exposure can be developed (or dissolved) with a developer to form a pattern or image.

[0076] Alkaline aqueous solutions or organic solvents can be used as developing solutions. Examples of alkaline aqueous solutions include aqueous solutions of alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, potassium carbonate, and sodium carbonate; aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline; and aqueous solutions of amines such as ethanolamine, propylamine, and ethylenediamine.

[0077] The aforementioned alkaline developer is generally an aqueous solution of 10% by mass or less, preferably an aqueous solution of 0.1 to 3.0% by mass. Furthermore, alcohols and surfactants can be added to the developer, preferably in amounts of 0.05 to 10 parts by mass per 100 parts by mass of the developer. Among these, a 0.1 to 2.38% by mass aqueous solution of tetramethylammonium hydroxide can be used.

[0078] Furthermore, as the developing solution, general organic solvents can be used, such as acetone, acetonitrile, toluene, dimethylformamide, methanol, ethanol, isopropanol, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, ethyl lactate, cyclohexanone, etc., and one or more of these can be used as a mixture. Propylene glycol methyl ether, propylene glycol methyl ether acetate, ethyl lactate, etc., are particularly preferred.

[0079] In this invention, surfactants may be added to improve the applicability. Such surfactants are not particularly limited and include fluorine-based surfactants, silicone-based surfactants, nonionic surfactants, etc. One or more of the above surfactants can be used in combination.

[0080] Among these surfactants, fluorinated surfactants are preferred due to their high effectiveness in improving coating properties. Specific examples of fluorinated surfactants include, but are not limited to, F-Top EF301, EF303, EF352 (product names manufactured by Tochem Products Co., Ltd.), Megafac F171, F173, R-30, R-08, R-90, BL-20, F-482 (product names manufactured by Dainippon Ink and Chemicals, Inc.), Florard FC430, FC431 (product names manufactured by Sumitomo 3M Co., Ltd.), Asahiguard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (product names manufactured by Asahi Glass Co., Ltd.).

[0081] The amount of surfactant added to the cured body-forming composition of the present invention is 0.0008 to 4.5% by mass, preferably 0.0008 to 2.7% by mass, and more preferably 0.0008 to 1.8% by mass, relative to the solid content.

[0082] In the present invention, adhesion promoters can be added to improve adhesion to the substrate after development. These adhesion promoters include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane; alkoxysilanes such as trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylvinylethoxysilane, diphenyldimethoxysilane, and phenyltriethoxysilane; silazanes such as hexamethyldisilazane, N,N'-bis(trimethylsilyl)urea, dimethyltrimethylsilylamine, and trimethylsilylimidazole; vinyltrichlorosilane, γ-chloropropyltrimethoxysilane, and γ- Examples of adhesion promoters include silanes such as aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-(N-piperidinyl)propyltrimethoxysilane; heterocyclic compounds such as benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urazole, thiouracil, mercaptoimidazole, and mercaptopyrimidine; and ureas such as 1,1-dimethylurea and 1,3-dimethylurea, or thiourea compounds. One or more of the above adhesion promoters can be used in combination. The amount of these adhesion promoters added is usually 18% by mass or less, preferably 0.0008 to 9% by mass, and more preferably 0.04 to 9% by mass, in terms of solid content.

[0083] The present invention may include a sensitizer. Examples of usable sensitizers include anthracene, phenothiazene, perylene, thioxanthone, and benzophenonethioxanthone. Furthermore, examples of sensitizing dyes include thiopyrillium salt dyes, merocyanine dyes, quinoline dyes, styrylquinoline dyes, ketocoumarin dyes, thioxanthene dyes, xanthene dyes, oxonol dyes, cyanine dyes, rhodamine dyes, and pyrylium salt dyes. Particularly preferred are anthracene-based sensitizers, which, when used in combination with a cationic curing catalyst (radiosensitive cationic polymerization initiator), dramatically improve sensitivity and also possess radical polymerization initiation capabilities. In the hybrid type of the present invention that uses both the cationic curing system and the radical curing system, the catalyst species can be simplified. Specific anthracene compounds that are effective include dibutoxyanthracene and dipropoxyanthraquinone. The amount of sensitizer added is 0.01 to 20% by mass, preferably 0.01 to 10% by mass, relative to the solid content.

[0084] The present invention aims to photo-cur or thermo-cur a curing composition containing an epoxy compound using a photo-acid generator or a thermo-acid generator. Because a photo-acid generator or thermo-acid generator is used, conventional epoxy curing agents (e.g., amines or acid anhydrides) are not used, or if they are used, their content is extremely low, thus improving the storage stability of the epoxy compound-containing composition.

[0085] We have found that compositions containing the above-mentioned liquid epoxy compound exhibit photocationic polymerization properties. They have a higher curing rate than conventional liquid epoxy compounds (e.g., alicyclic epoxy compounds having an epoxycyclohexyl ring). Due to the fast curing rate, it is possible to reduce the amount of acid generator added, or to use a weak acid-based acid generator. Reducing the amount of acid generator is important for preventing metal corrosion, as acid-active species may remain even after UV irradiation. The fast curing rate also allows for thick-film curing. Curing by UV irradiation can be applied to materials (equipment) that are sensitive to heat.

[0086] The thermosetting and photocuring materials using the epoxy compound-containing curing composition of this invention have characteristics such as rapid hardening, transparency, and low curing shrinkage, and can be used for coating and bonding electronic components, optical components, and precision mechanical components. For example, they can be used for bonding optical elements such as lenses in mobile phones and cameras, light-emitting diodes (LEDs) and semiconductor lasers (LDs), liquid crystal panels, biochips, camera lenses and prisms, magnetic components in hard disks of personal computers, pickups in CD and DVD players (the part that captures light information reflected from the disc), speaker cones and coils, motor magnets, circuit boards, electronic components, and internal engine components of automobiles.

[0087] For hard coat materials used for surface protection of automobile bodies, lamps and electrical appliances, building materials, and plastics, it can be applied to, for example, automobile and motorcycle bodies, headlight lenses and mirrors, plastic lenses for eyeglasses, mobile phones, game consoles, optical films, ID cards, etc.

[0088] For ink materials used to print on metals such as aluminum and plastics, applications include inks for printing on cards such as credit cards and membership cards, switches and keyboards in electrical appliances and office equipment, and inkjet printer inks for CDs, DVDs, etc. Examples of applications include the creation of complex three-dimensional objects by curing resin in combination with 3D CAD, applications to stereolithography for the production of industrial product models, and applications to optical fiber coating, bonding, optical waveguides, and thick film resists.

[0089] Furthermore, the curing composition containing the epoxy compound of the present invention can be suitably used as an insulating resin for electronic materials such as semiconductor encapsulating materials, adhesives for electronic materials, printed circuit board materials, interlayer insulating film materials, and encapsulating materials for power modules, as well as an insulating resin used in high-voltage equipment such as generator coils, transformer coils, and gas-insulated switchgear. [Examples]

[0090] (Analysis method) [Measurement of SiO2 concentration] The silica sol was placed in a crucible, dried at 130°C, and the resulting gel was calcined at 1000°C. The calcination residue was then weighed and calculated. [Measurement of average primary particle diameter (particle diameter by nitrogen adsorption method)] The specific surface area of ​​acidic silica sol powder dried at 300°C was measured using a specific surface area measuring device, Monosorb® MS-16 (manufactured by Yuasa Ionics Co., Ltd.). [Measurement of moisture content] The result was obtained by Karl Fischer titration. [Measurement of average particle diameter] Average particle size was measured using dynamic light scattering by diluting an organic solvent-dispersed silica sol with a dispersion solvent and measuring the average particle size using a dynamic light scattering particle size analyzer (ZETASIZER Nano series, Malvern Instruments LTD). When the dispersion medium was an organic substance having a carbonyl structure, the measurement was performed after diluting it to a predetermined concentration with that dispersion medium. When the dispersion medium was an organic substance having an epoxy group, the measurement was performed after diluting it to a predetermined concentration with methyl ethyl ketone. [Measuring viscosity] The viscosity of the organic solvent-dispersed silica sol (organic material having a carbonyl structure as the dispersion medium) was measured using an Ostwald viscometer. The viscosity of the resin monomer-dispersed sol (organic material having an epoxy group as the dispersion medium) was measured using a Type B rotational viscometer (manufactured by Toki Sangyo Co., Ltd.). [Analysis method for alkoxy group content] Four mL of silica sol was vacuum-dried at 60°C for four hours to obtain a gel. The resulting gel was pulverized in a mortar and pestle, and then dried at 150°C under atmospheric pressure for two hours to obtain a dry powder. 0.2 g of the powder obtained above was mixed with 10 mL of 0.05 N sodium hydroxide aqueous solution and dispersed in an ultrasonic cleaner (40 kHz) for 20 minutes. After being left at room temperature for one day, the solution portion was measured by gas chromatography to determine the alkoxy group content per unit area of ​​the silica surface (groups / nm). 2 ) was measured. [Measurement of GI] A liquid mixture of silica sol, methanol, and pure water in a weight ratio of 1:1:1 was measured using a pH meter. [Measurement of methanol] The measurement was performed using gas chromatography. [Measurement of epoxy equivalent] 0.3 g of resin monomer dispersion (dispersion medium being an organic substance with epoxy groups) sol was weighed and added to a glass beaker, and then 10 mL of chloroform was added and the mixture was stirred using a magnetic stirrer. 20 mL of acetic acid was added to the solution, followed by 20 mL of tetraethylammonium bromide acetic acid solution (0.25 g / mL acetic acid), and the mixture was stirred. The solution was potentiometrically titrated with perchloric acid-acetic acid standard solution (0.1 mol / L) using an automatic titrator COM-1700A (manufactured by HIRANUMA Co., Ltd.), and the epoxy equivalent was calculated according to JIS K7236 (2001). [Analytical method for the content of activated epoxy groups] 10 g of silica sol was weighed and added to a glass beaker, and then 10 mL of acetone or chloroform was added and the mixture was stirred using a magnetic stirrer. 20 mL of acetic acid was added to the solution, followed by 20 mL of tetraethylammonium bromide acetic acid solution (0.25 g / mL acetic acid), and the mixture was stirred. The solution was potentiometrically titrated with perchloric acid-acetic acid standard solution (0.1 mol / L) using an automatic titrator COM-1700A (manufactured by HIRANUMA Co., Ltd.), and the epoxy equivalent D (g / eq) was calculated according to JIS K7236 (2001). Active epoxy group content (pcs / nm 2 The following formula was used to calculate ). Activated epoxy groups (number / nm) 2 ) = NA / [D(g / eq) × S(m 2 ( / g) × 10 18 ×SiO2 content in silica sol (%) / 100 NA: Avogadro's number S: Specific surface area of ​​the particle (m²) 2 / g)=2720 / average primary particle diameter (nm) [Evaluation of physical properties of epoxy cured products] The resulting silica-containing epoxy resin cured product was subjected to a three-point bending strength test, glass transition temperature, coefficient of thermal expansion, and transmittance. [Measurement of three-point bending strength] The measurements were taken using a tensile testing machine in accordance with JIS K-6911. The height and width of the test specimen were measured, the specimen was supported, and a load was applied to its center using a pressure wedge. The load at which the specimen broke was measured, and the bending strength (σ) was calculated. Bending strength σ: (MPa) {kgf / mm 2}, P: load (N) {kgf} when the test specimen broke, L: distance between supports (mm), W: width of the test specimen (mm), h: height of the test specimen (mm). σ = (3PL) / (2Wh) 2 ) Flexural modulus (E): (MPa) {kgf / mm 2 If} is defined as F / Y: the gradient of the straight portion of the load-deflection curve (N / mm) {kgf / mm}, E = [L 3 / (4Wh 3 )〕×〔F / Y〕 [Measurement of glass transition temperature] The glass transition temperature was determined from the DSC curve obtained using a differential scanning calorimetry system (DSC3500: manufactured by Netch Japan Co., Ltd.) over a temperature range of 30°C to 250°C at a heating rate of 5°C / min. [Measurement of linear thermal expansion coefficient] The coefficient of thermal expansion was measured according to JIS K-6911. The thickness of the test specimen was accurately measured and measured using TMA (Thermal Mechanical Analysis) with a load of 0.05 N and a heating rate of 1 °C / min. The coefficient of thermal expansion α1 was calculated as the change in the length of the test specimen at 30-80 °C (ΔL1) / the initial length of the test specimen (L) × 50 = α1. [Measurement of transmittance] The transmittance at 520 nm was measured using a spectrophotometer (model UV-3600, manufactured by Shimadzu Corporation).

[0091] I [Production of organosols containing epoxy group-containing silica particles] (Example 1) A water-dispersible silica sol (average primary particle size 12 nm, pH 3, silica concentration 33% by mass, manufactured by Nissan Chemical Corporation) was prepared. 1000g of the above silica sol was placed in a 2L glass reactor equipped with a stirrer, condenser, thermometer, and two inlets. While the sol in the reactor was kept boiling, methanol vapor generated in a separate boiler was continuously blown into the silica sol in the reactor, gradually raising the liquid level and replacing the water with methanol. The replacement was stopped when the volume of the distillate reached 9L, yielding 1100g of methanol-dispersed silica sol. The obtained methanol-dispersed silica sol had an SiO2 concentration of 30.5% by mass, a water content of 1.6% by mass, and a viscosity of 2 mPa·s. 600 g of the above methanol-dispersed silica sol was placed in a 1 L round-bottom flask. While stirring the sol with a magnetic stirrer, 0.9 g of tri-n-pentylamine was added, followed by 17.5 g of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., trade name KBM-303). The solution temperature was then maintained at 60°C for 2 hours. Next, 32.4 g of phenyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., trade name KBM-103) was added, and the solution temperature was then maintained at 60°C for 2 hours. Subsequently, distillation is performed in a rotary evaporator under reduced pressure of 500-350 Torr at a bath temperature of 80°C while supplying methyl ethyl ketone, resulting in a methyl ethyl ketone-dispersed silica sol (SiO2 30.5% by mass, viscosity (20°C) 1.13 mPa·s, water content 0.05% by mass, methanol 0.05% by mass, pH 8.46, dynamic light scattering particle size 14.8 nm, active epoxy content 0.80 particles / nm). 2 Methoxy group content: 1.2 groups / nm 2 The obtained methyl ethyl ketone-dispersed silica sol showed a change of less than 20% from the initial particle size after storage at 50°C for 7 days, as measured by dynamic light scattering.

[0092] Similarly, compositions were prepared using the formulation ratios of Examples 2 to 7 and Comparative Examples 1 to 3, and their physical properties were evaluated. The results are shown in Tables 1 to 3.

[0093] [Table 1] A-1: The mass (g) of methanol-dispersed silica sol in step (A) is shown. A-2: The SiO2 content (%) in the methanol-dispersed silica sol of step (A) is shown. A-3: The average particle size (nm) of SiO2 particles in methanol-dispersed silica sol from step (A) is shown by the BET method. A-4: The moisture content (%) of the methanol-dispersed silica sol in step (A) is shown. A-5: This is the pH of the methanol-dispersed silica sol from step (A), which was measured by mixing the silica sol with pure water in a 1:1 mass ratio. B-1: The type of basic substance added in step (B). TnPnA indicates tri-n-pentylamine, DiPA indicates diisopropylamine, and DiPEA indicates diisopropylmonoethylamine. B-2: The amount (g) of basic substance added in step (B) is shown. B-3: The pH of the methanol-dispersed silica sol after adding a basic substance in step (B), and the pH of the liquid obtained by mixing the silica sol, methanol, and pure water in a mass ratio of 1:1:1 were measured. (B-3) in Comparative Example 1 is the result of re-measuring (A-5).

[0094] [Table 2] C-1: The amount (g) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane added in step (C) is shown for Examples 1-6 and the comparative example. For Example 7, the amount (g) of 3-glycidoxypropyltrimethoxysilane added in step (C) is shown. C-2: The reaction conditions after adding 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane or 3-glycidoxypropyltrimethoxysilane in step (C) are shown. C-3: The amount (g) of phenyltrimethoxysilane added in step (C) is shown. C-4: The reaction conditions after adding phenyltrimethoxysilane in step (C) are shown.

[0095] [Table 3] D-1: This shows the types of organic substances with a carbonyl structure used as dispersion media in step (D). MEK represents methyl ethyl ketone, and MIBK represents methyl isobutyl ketone. D-2: The yield (g) of silica sol using the organic material having a carbonyl structure obtained in step (D) as the dispersion medium is shown. D-3: This shows the SiO2 content (%) in the silica sol containing the organic material having a carbonyl structure obtained in step (D) as a dispersion. D-4: This shows the water content (%) in the silica sol containing the organic material having a carbonyl structure obtained in step (D) as a dispersion. D-5: This shows the methanol content (%) in the silica sol containing the organic material having a carbonyl structure obtained in step (D) as a dispersion. D-6: The viscosity (mPa·s) of the silica sol containing the carbonyl structure-containing organic material obtained in step (D) as measured by an Ostwald viscometer is shown. D-7: This is the pH of the silica sol using the organic material having a carbonyl structure from step (D) as the dispersion medium. The pH was measured by mixing the silica sol, pure water, and methanol in a mass ratio of 1:1:1. D-8: The silica particle size (nm) measured by dynamic light scattering of silica sol using an organic substance with a carbonyl structure as the dispersion medium in step (D) is shown. D-9: Active epoxy content (particles / nm) of silica sol using an organic substance having a carbonyl structure as a dispersion medium in step (D) 2 ) was shown. D-10: Number of methoxy groups (groups / nm) in silica sol using an organic substance having a carbonyl structure as the dispersion medium in step (D). 2 ) was shown. D-11: The aluminum content (ppm / SiO2) in silica sol using an organic substance with a carbonyl structure as the dispersion medium in step (D) is shown, converted to Al2O3. D-12: The viscosity (mPa·s) measured with an Ostwald viscometer after storing a silica sol containing an organic substance with a carbonyl structure from step (D) as the dispersion medium at 50°C for 7 days was shown. D-13: The silica particle size (nm) measured by dynamic light scattering after storing the silica sol containing an organic substance with a carbonyl structure from step (D) as a dispersion medium at 50°C for 7 days is shown. D-14: The active epoxy content (particles / nm) of the silica sol containing an organic substance with a carbonyl structure from step (D) as the dispersion medium after storage at 50°C for 7 days. 2 ) was shown.

[0096] II [Preparation of silica sol in which epoxy group-containing silica particles are dispersed in epoxy monomer] 400 g of silica sol (methyl ethyl ketone dispersed silica sol) using an organic material having a carbonyl structure as the dispersion medium in step (D) of Example 1 was mixed with 255 g of a mixed monomer of bisphenol A type epoxy resin and bisphenol F type epoxy resin (DIC Corporation, trade name EXA-830LVP). Desolvation was carried out at a bath temperature of 100°C and 200-30 Torr to obtain a silica sol dispersed with a mixed resin monomer of bisphenol A type epoxy resin and bisphenol F type epoxy resin. The obtained silica sol had an SiO2 concentration of 30.7% by mass, methanol and methyl ethyl ketone content of less than 0.1% by mass, a B-type viscosity of 7820 mPa·s at 25°C, and a particle size of 18.8 nm measured by dynamic light scattering after dilution with methyl ethyl ketone. The change in particle size from the initial value measured by dynamic light scattering after storage of the obtained mixed resin monomer dispersed silica sol at 50°C for 7 days and dilution with methyl ethyl ketone was within 20%. Furthermore, an alicyclic epoxy resin monomer (trade name Celoxide 2021P: Daicel Corporation) was added to the silica sol (methyl ethyl ketone dispersed silica sol) using an organic substance having a carbonyl structure as a dispersion medium in step (D) of Example 1, and the same treatment was carried out to obtain an alicyclic epoxy resin monomer dispersed silica sol.

[0097] Then, an epoxy resin monomer-dispersed silica sol was obtained by changing the silica sol (methyl ethyl ketone-dispersed silica sol) using an organic substance having a carbonyl structure as the dispersion medium in step (D) of Example 1 and Example 5 to a liquid epoxy resin monomer (product name YDF-8170C, manufactured by Nippon Steel Chemical & Material Co., Ltd.). Table 4 shows the results for epoxy resin monomer-dispersed silica sols No. 1 to 4 obtained. [Table 4] D-15: The silica sols in step (D) of Examples 1 and 5, which used an organic substance having a carbonyl structure as the dispersion medium, were subjected to solvent replacement with silica sols using an organic substance having an epoxy group as the dispersion medium, and the types of epoxy monomers were shown. D-16: The trade names of the epoxy monomers used in D-15 are listed. D-17: Shows the epoxy monomer content (g). D-18: The content (g) of silica sol using an organic substance having a carbonyl structure as the dispersion medium in step (D) of Example 1 and Example 5 is shown. D-19: The conditions for solvent replacement in step (D) of Examples 1 and 3, where a silica sol containing an organic substance with a carbonyl structure is used as the dispersion medium, is shown, and the silica sol containing an organic substance with an epoxy group is used as the dispersion medium. D-20: The temperature (°C) of the heating bath in D-19 is shown. D-21: The SiO2 content (%) of the silica sol using an organic substance having epoxy groups as the dispersion medium in step (D) of Example 1 and Example 5 is shown. D-22: The moisture content (%) of the silica sol using an organic substance having epoxy groups as the dispersion medium in step (D) of Example 1 and Example 5 is shown. D-23: The percentage content (%) of methanol and organic substances having a carbonyl structure in the silica sol containing an organic substance having an epoxy group as the dispersion medium in step (D) of Example 1 and Example 5. D-24: The viscosity (mPa·s) of the silica sol using an epoxy-group-containing organic material as the dispersion medium in step (D) of Example 1 and Example 5 is shown on a type B rotational viscometer. D-25: The average particle size (nm) of silica particles in a silica sol using an epoxy-group-containing organic material as the dispersion medium, as measured by dynamic light scattering, is shown for step (D) of Examples 1 and 5. D-26: The epoxy equivalent (g / eq) in the silica sol containing an organic substance with epoxy groups as the dispersion medium in step (D) of Example 1 and Example 5 is shown. D-27: The viscosity (mPa·s) of the silica sols using the epoxy group-containing organic material as the dispersion medium in step (D) of Example 1 and Example 5, measured using a type B rotational viscometer after storage at 50°C for 7 days, is shown. D-28: The silica particle size (nm) measured by dynamic light scattering after storing the silica sol containing an epoxy group-containing organic material as the dispersion medium in step (D) of Example 1 and Example 5 at 50°C for 7 days is shown. D-29: This shows the epoxy equivalent (g / eq) in the silica sol after storing the silica sol containing an epoxy-containing organic material as a dispersion medium in step (D) of Example 1 and Example 5 at 50°C for 7 days.

[0098] III [Thermosetting product containing epoxy group-containing silica particles] In Example 1, a silica sol (methyl ethyl ketone dispersed silica sol) using an organic substance having a carbonyl structure as a dispersion medium was prepared in step (D). An alicyclic epoxy resin monomer (trade name Celoxide 2021P: Daicel Corporation) was added, and desolvation was carried out under reduced pressure of 200 to 10 Torr at a bath temperature of 100°C to obtain an alicyclic epoxy resin monomer dispersed silica sol (SiO2 concentration 20% by mass, methanol and methyl ethyl ketone content less than 0.1% by mass). A curing agent (a mixture of methyl hexahydrophthalic anhydride and hexahydrophthalic anhydride) was added to the alicyclic epoxy resin monomer dispersed silica sol, and the mixture was stirred using a vacuum degasser V-mini300 (manufactured by EME) to obtain a mixture. Next, dimethylbenzylamine was added to this mixture as a curing accelerator, and the mixture was stirred using a vacuum degasser to obtain a silica-containing epoxy resin curing composition. The obtained silica-containing epoxy resin curing composition was poured into a casting plate (a glass plate treated with a fluorine-based release agent, with a 3 mm thickness between the two glass plates), and heat-treated at 90°C for 2 hours, followed by 150°C for 8 hours, to obtain a silica-containing epoxy resin thermoset product.

[0099] In Example 1, a silica sol (methyl ethyl ketone dispersed silica sol) using an organic material having a carbonyl structure as a dispersion medium was added to a bisphenol F type liquid epoxy resin (trade name YDF-8170C, manufactured by Nippon Steel Chemical & Material Co., Ltd.). A similarly treated epoxy resin monomer dispersed silica sol was then mixed with a liquid epoxy resin monomer (trade name YDF-8170C, manufactured by Nippon Steel Chemical & Material Co., Ltd.) and a curing agent (3,3-diethyl-4,4'-diaminodiphenylmethane (trade name Kayahard AA, manufactured by Nippon Kayaku Co., Ltd.) and diethyltoluenediamine (trade name EtaCure 100, manufactured by Albamer Corporation)) and stirred to obtain a silica-containing epoxy resin thermoset product.

[0100] In Example 5, step (D), a bisphenol F type liquid epoxy resin (trade name YDF-8170C, manufactured by Nippon Steel Chemical & Material Co., Ltd.) was added to a silica sol containing an organic substance with a carbonyl structure as a dispersion medium. A liquid epoxy resin monomer (trade name YDF-8170C, manufactured by Nippon Steel Chemical & Material Co., Ltd.) and a curing agent (3,3'-diethyl-4,4'-diaminodiphenylmethane (trade name Kayahard AA, manufactured by Nippon Kayaku Co., Ltd.) and diethyltoluenediamine (trade name EtaCure 100, manufactured by Albamer Corporation)) were added to the epoxy resin monomer-dispersed silica sol treated in the same manner, and after stirring, a silica-containing epoxy resin thermoset was obtained in the same manner.

[0101] As a reference example (1), an alicyclic epoxy resin monomer (Celoxide 2021P: Daicel Corporation), methylhexahydrophthalic anhydride as a curing agent, and dimethylbenzylamine as a curing accelerator were mixed to obtain a silica sol-free epoxy resin thermosetting product. Thermosetting was performed in the same manner.

[0102] Table 5 shows the composition and thermosetting properties of the epoxy resin compositions using silica sols with organic materials having a carbonyl structure as a dispersion medium, as in Examples 1 and 5, and the epoxy resin compositions without silica sols, as in Reference Examples 1 and 2. [Table 5] E-1: Shows the added mass (g) of epoxy resin monomer-dispersed silica sols (No. 2, 3, 4) in Examples 1 and 5. E-2: The added mass (g) of alicyclic epoxy resin monomer (product name Celoxide 2021P: Daicel Corporation) is shown. E-3: The added mass (g) of liquid epoxy resin monomer (product name YDF-8170C, manufactured by Nippon Steel Chemical & Material Co., Ltd.) is shown. E-4: Indicates the SiO2 content (g) in the composition. E-5: The thermosetting agent is a mixture of Me-HHPA (methylhexahydrophthalic anhydride) and HHPA (hexahydrophthalic anhydride), and the amount added (g) is indicated. E-6: The thermosetting agent was 3,3'-diethyl-4,4'-diaminodiphenylmethane (trade name Kayahard AA, manufactured by Nippon Kayaku Co., Ltd.), and the amount added (g) is shown. E-7: The thermosetting agent was diethyltoluenediamine (trade name EtaCure 100, manufactured by Albamere Corporation), and the amount added (g) is shown. E-8: The thermosetting accelerator was dimethylbenzylamine, and its added mass (g) is indicated. E-9: The thermosetting conditions are shown. E-10: Indicates the glass transition temperature (°C). E-11: Linear thermal expansion coefficient below the glass transition temperature (10 -6 This indicates / K). E-12: Linear thermal expansion coefficient above the glass transition temperature (10 -6 This indicates / K). E-13: Bending strength (MPa) is shown. E-14: Shows the flexural modulus (MPa). E-15: Transmittance (%) of a 3mm thick cured material

[0103] IV [Photocurable film containing epoxy group-containing silica particles] In the silica sols using the carbonyl structure-containing organic material dispersed as the dispersion medium in step (D) of Examples 3 and 5, an alicyclic epoxy resin monomer (Celoxide 2021P: Daicel Corporation) and a triarylsulfonium SbF6 salt-based photocationic polymerization initiator (manufactured by Sunapro Co., Ltd., trade name CPI101A, structure is formula (A-2)) were mixed as a photoacid generator to obtain silica-containing epoxy resin curing compositions. The obtained silica-containing epoxy resin curing compositions were applied to a substrate (made of polyethylene terephthalate, 125 μm thick) using a bar coater, dried at 70°C for 5 minutes, and then cured with ultraviolet light at 500 mJ / cm² using a UV curing belt conveyor device (trade name ECS-4011GX, manufactured by I-Graphics Co., Ltd.) equipped with a metal halide lamp (trade name M04-01L, manufactured by I-Graphics Co., Ltd.). 2 The film was cured by irradiation with light at a specific intensity. Subsequently, the resulting film was post-baked at 100°C for 30 minutes to obtain a film with a silica-containing epoxy resin photocuring coating.

[0104] As a reference example 2, an alicyclic epoxy resin monomer (Celoxide 2021P: Daicel Corporation) and a triarylsulfonium SbF6 salt-based photocationic polymerization initiator (manufactured by Sunapro Co., Ltd., trade name CPI101A, structure is formula (A-2)) were mixed as a photoacid generator to obtain an epoxy resin photocuring composition that does not contain silica sol. Then, coating, photocuring, and post-baking were performed in the same manner to obtain a film with an epoxy resin photocuring film.

[0105] The method for measuring the physical properties of the photocured film is shown below. • Film thickness: Measured using a film thickness measurement system (product name F20-EXR, manufactured by Filmetrix). • Pencil hardness: Measured using a pencil scratch hardness tester (product name 553-S, manufactured by Yasuda Seiki Seisakusho) in accordance with JIS K 5600-5-4. • HAZE value: Measured using a haze meter (product name NDH-5000, manufactured by Nippon Denshoku Industries) in accordance with JIS K 7105. • Flexural resistance test: This flexural resistance test conforms to JIS K5600-5-1. The mandrel was changed to a smaller size until cracking or peeling of the coating occurred. The diameter (mm) of the mandrel at which cracking or peeling first occurred was measured using a cylindrical mandrel bending tester (manufactured by Allgood).

[0106] Table 6 shows the composition and photocuring properties of the epoxy resin compositions using silica sols with organic materials having a carbonyl structure as a dispersion medium, as in Example 3 and Example 5, and the epoxy resin composition without silica sol, as in Reference Example 3.

[0107] [Table 6] F-1: Shows the added mass (g) of silica sol using an organic substance having a carbonyl structure as the dispersion medium in step (D) of Example 3 and Example 5. F-2: Indicates the added mass (g) of alicyclic epoxy resin monomer (Celoxide 2021P: Daicel Corporation). F-3: The added mass (g) of the photoacid generator (manufactured by Sunapro Co., Ltd., trade name CPI101A, structure is formula (A-2)) is shown. F-4: This represents the SiO2 content in the composition, expressed as phr (mass%). F-5: Shows the film thickness (μm) of the photocured film on the substrate. F-6: Indicates the pencil hardness value of the light-cured film. F-7: Indicates the HAZE value of the film. F-8: The results of the bending resistance test are shown. [Industrial applicability]

[0108] This silica sol contains epoxy groups or epoxy-containing organic groups and silica particles containing alkoxy groups as a dispersed phase, and is stably dispersed in an organic solvent. This allows for the creation of a curable composition containing these silica sols and an epoxy cured product.

Claims

1. Epoxy group or epoxy group-containing organic group (R ２ ) and alkoxy group (OR １ A silica sol containing ) and containing silica particles as a dispersed phase having an average primary particle diameter of 5 to 100 nm determined by nitrogen gas adsorption method (BET method), containing organic matter as a dispersion medium, and containing a basic substance, When the average particle diameter of the silica particles determined by dynamic light scattering (DLS) is 5 to 200 nm, the ratio of (average particle diameter by DLS) / (average primary particle diameter by BET) is 1.05 to 2.

00. The silica particles are epoxy groups or epoxy group-containing organic groups (R ２ ) converted to 0.1 to 6.0 particles / nm per unit area of ​​the silica particle surface. ２ Including, Alkoxy group (OR １ ) converted to 0.3 to 4.0 particles / nm per unit area of ​​the silica particle surface. ２ Including, (R ２ ) / ( OR １ ) The molar ratio is between 0.1 and 2.

0. The average particle size of silica particles measured by the dynamic light scattering method after storage at 50°C for 7 days is in the range of 1.0 to 1.2 times compared to the value before storage. The above silica sol.

2. The silica sol according to claim 1, wherein the epoxy group is a glycidyl group or a 3,4-epoxycyclohexyl group.

3. The silica sol according to claim 1, wherein the dispersion medium is an organic substance having a carbonyl structure or an organic substance having an epoxy group.

4. The silica sol according to claim 3, wherein the organic substance having a carbonyl structure in the dispersion medium is methyl ethyl ketone, methyl isobutyl ketone, diisopropyl ketone, diisobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, or propylene glycol monomethyl ether acetate.

5. The organic substance having epoxy groups in the above dispersion medium is a bisphenol A liquid epoxy compound, The silica sol according to claim 3, which is a liquid epoxy compound of sphenol F, or 3',4'-epoxycyclohexylmethyl 3',4'-epoxycyclohexanecarboxylate.

6. The silica sol according to claim 1, wherein the basic substance is an amine, ammonia, an inorganic alkali compound, or a quaternary ammonium compound.

7. The silica sol according to claim 6, wherein the above-mentioned amine is a secondary or tertiary amine having a total number of carbon atoms of 5 to 35.

8. The above silica particles are further expressed in formulas (1) to (3): 【Chemistry 1】 In formula (1), R ３ each represents an alkyl group, a halogenated alkyl group, an alkenyl group, an aryl group, or an organic group having a (meth)acryloyl group, a mercapto group, an amino group, a ureido group or a cyano group, and is bonded to the silicon atom via a Si-C bond, and R ４ each represents an alkoxy group, an acyloxy group or a halogen group, a represents an integer of 1 to 3, In equations (2) and (3), R ５ and R ７ Each of these is an alkyl group having 1 to 3 carbon atoms, or an aryl group having 6 to 30 carbon atoms, and is bonded to a silicon atom by a Si-C bond, R ６ and R ８ (wherein 'b' represents an alkoxy group, an acyloxy group, or a halogen group, Y represents an alkylene group, an NH group, or an oxygen atom, b is an integer from 1 to 3, c is an integer of 0 or 1, and d is an integer from 1 to 3.) The silica sol according to claim 1, comprising a hydrolysate of at least one silane compound selected from the group consisting of the following.

9. The silane compound according to claim 8 is of the above formula (1) (wherein R ３ is an organic group having an aryl group and bonded to a silicon atom by a Si-C bond, R ４ The silica sol according to claim 8, wherein each of the following represents an alkoxy group, an acyloxy group, or a halogen group, and a represents an integer from 1 to 3.

10. The above dispersed silica particles contain aluminum atoms. ２ O ３ Converted to 800-10000 ppm / SiO ２ The silica sol according to claim 1, containing in the following proportion.

11. The following steps (A) to (D): (A) Process: Silica particles with an average particle size of 5 to 200 nm are collected by dynamic light scattering (DLS) and then treated with alcohol R １ OH (however R １ This represents an organic group having 1 to 10 carbon atoms, which may have an oxygen atom. The process of obtaining the above silica sol is a silica sol dispersed in ( ), wherein the silica sol contains 5% by mass or less water. (B) Step: A step of adding a basic substance to the silica sol obtained in step (A). (C) Step: Add epoxy groups or epoxy group-containing organic groups (R) to the silica sol obtained in step (B). ２ A step of coating silica particles by adding a silane compound having the following characteristics: (D) Step: Disperse the silica sol obtained in step (C) using alcohol R １ A method for producing silica sol according to any one of claims 1 to 10, comprising the step of substituting the OH group with an organic substance having a carbonyl structure or an organic substance having an epoxy group.

12. The above (C) process is further expressed by formulas (1) to (3): 【Chemistry 2】 (In formula (1), R3 is an alkyl group, a halogenated alkyl group, an alkenyl group, an aryl group, or an organic group having a (meth)acryloyl group, a mercapto group, an amino group, a ureido group, or a cyano group and bonded to a silicon atom by a Si-C bond, R4 is an alkoxy group, an acyloxy group, or a halogen group, and a is an integer from 1 to 3.) In formulas (2) and (3), R5 and R7 are each alkyl groups having 1 to 3 carbon atoms, or aryl groups having 6 to 30 carbon atoms, bonded to a silicon atom by a Si-C bond; R6 and R8 each represent an alkoxy group, an acyloxy group, or a halogen group; Y represents an alkylene group, an NH group, or an oxygen atom; b is an integer from 1 to 3; c is an integer of 0 or 1; and d is an integer from 1 to 3. The manufacturing method according to claim 11, wherein at least one silane compound selected from the group consisting of the above is added to coat the silica particles.

13. The above step (D) involves dispersing the dispersion medium with alcohol R １ The manufacturing method according to claim 11, wherein the OH group is replaced with an organic substance having a carbonyl structure, and then further replaced with an organic substance having an epoxy group.

14. A cured body forming composition comprising a silica sol according to any one of claims 1 to 10, and an amine-based curing agent, an acid anhydride-based curing agent, or an acid-generating agent-based curing agent.

15. The cured body forming composition according to claim 14, further containing an epoxy resin.

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