JP5569703B2 - Epoxy group-containing silsesquioxane-modified epoxy resin, curable resin composition, cured product and coating agent - Google Patents

Description

  The present invention relates to an epoxy group-containing silsesquioxane-modified epoxy resin. The present invention also relates to a curable resin composition, a cured product obtained by curing the curable resin composition, and a coating agent.

  Epoxy resin is generally used as a composition in combination with a curing agent, and the cured product obtained by curing the composition is used for awards in fields such as electrical / electronic materials, paint / adhesives, civil engineering, and architecture. It has been. However, higher adhesion, heat resistance, moisture resistance, and the like are required for the cured epoxy resin composition, particularly in the fields of electrical / electronic materials and paint / adhesives.

  In order to improve the heat resistance of the cured product of the epoxy resin composition, for example, a method of using a composition in which a filler such as glass fiber, glass particles, mica, etc., in addition to the epoxy resin and the curing agent is considered. However, this method cannot provide sufficient heat resistance. Further, the transparency of the cured product obtained by this method is lost, and the adhesiveness at the interface between the filler and the epoxy resin is inferior, so that the mechanical properties such as the elongation rate are insufficient.

  As a method for improving the heat resistance of a cured product of an epoxy resin composition, a method using a composite of an epoxy resin and silica has been proposed (Patent Document 1). In the composite, hydrolyzable alkoxysilane is added to the partially cured epoxy resin solution, the cured product is further cured, the alkoxysilane is hydrolyzed to form a sol, and further polycondensed to gel. Can be obtained. However, the cured product obtained from such a composite has a certain degree of improvement in heat resistance compared to the cured product of the epoxy resin alone, but the cured product is caused by water in the composite, water generated during curing, or alcohol. Voids (bubbles) are generated inside. In addition, when the amount of alkoxysilane is increased for the purpose of further improving heat resistance, the transparency of the cured product obtained by agglomeration of the silica produced by the sol-gel curing reaction is lost and whitened, and a large amount of alkoxysilane is added. A large amount of water is required to form a sol, resulting in warping of the cured product, cracks, and the like.

  Further, a composition (Patent Document 2) in which a silane-modified epoxy resin obtained by reacting an epoxy resin with a silicone compound and a phenol novolac resin as a curing agent, bisphenol A type epoxy resin, tetrabisbromobisphenol A and methoxy are combined. A composition (Patent Documents 3 and 4) in which a silane-modified epoxy resin obtained by reacting a group-containing silicone intermediate and a phenol novolac resin as a curing agent is also proposed. However, the cured products of these epoxy resin compositions are insufficient in heat resistance because the main constituent unit of the silicone compound or methoxy group-containing silicone intermediate is a diorganopolysiloxane unit and cannot produce silica. .

  On the other hand, the present applicants cured the resin by using a methoxy group-containing silane-modified epoxy resin obtained by demethanol reaction of a bisphenol-type epoxy resin and a methoxysilane partial condensate and a curing agent for epoxy resin. It has already been found that the cured product thus obtained loses its glass transition point and has high heat resistance, and exhibits high adhesion to inorganic materials (for example, Patent Documents 5 and 6). In this method, in order to obtain a cured product, the methoxysilyl group in the resin composition is sol-gel cured and the epoxy group is epoxy-cured to obtain an epoxy resin-silica hybrid cured product. However, even in the cured product, adhesion under high temperature and high humidity was insufficient.

  In addition, a cured product obtained by curing an epoxy group-containing silsesquioxane produced by a method of hydrolyzing or condensing an alkoxysilane containing an epoxy group with a curing agent for epoxy resin is also transparent and heat resistant. It is known that it has excellent properties such as chemical resistance, mechanical properties, and electrical properties. The present applicants have already shown that a cured product of a composition comprising an epoxy group-containing silsesquioxane obtained by hydrolyzing and condensing an epoxy group-containing alkoxysilane and an acid anhydride has excellent properties. (Patent Document 7). However, even in the cured product, the adhesion under high temperature and high humidity is often insufficient.

JP-A-8-100107 JP-A-3-2014466 JP-A-61-272243 JP-A-61-272244 Japanese Patent No. 3077695 Japanese Patent No. 3570380 JP 2009-108109 A

  The present invention provides an epoxy group-containing silsesquioxane-modified epoxy resin that is excellent in heat resistance and adhesion to inorganic materials, and can form a cured product that does not lose adhesion to inorganic materials even under high temperature and high humidity. It is an object of the present invention to provide a cured product that is excellent in composition, coating agent, heat resistance, and inorganic material adhesion, and that does not lose adhesion to an inorganic material even under high temperature and high humidity.

  As a result of intensive studies to solve the above problems, the present inventor can solve the above problems with an epoxy group-containing silsesquioxane-modified epoxy resin obtained by modifying a hydroxyl group-containing epoxy resin with a specific silsesquioxane. As a result, the present invention has been completed.

That is, the present invention provides an epoxy group and an alkoxy group obtained by hydrolysis and condensation of a hydroxyl group-containing epoxy resin (A), an epoxy group-containing alkoxysilane (b1), and a metal alkoxide (b2) having no epoxy group. It is obtained by subjecting a silsesquioxane compound (B) containing a dealcoholization condensation reaction, an alkoxy group equivalent is 150 to 3000 g / eq, an epoxy equivalent is 150 to 500 g / eq, The number of moles of the epoxy group derived from the component (A)] / [number of moles of the epoxy group derived from the component (B)] (molar ratio) is from 0.1 to 3, and the components (A) and (B) The component (B) / component (A) = 0.2-8 , and the component (B) is used as a raw material [epoxy contained in epoxy group-containing alkoxysilanes (b1). Number of moles of xyl group] / [total number of moles of epoxy group-containing alkoxysilanes (b1) and metal alkoxides (b2) not containing epoxy group] (molar ratio: average of epoxy groups contained per silicon atom) The present invention relates to an epoxy group-containing silsesquioxane-modified epoxy resin (1), characterized in that the number thereof is 0.10 or more and 0.85 or less . The present invention also relates to a curable resin composition containing the epoxy group-containing silsesquioxane-modified epoxy resin (1) and the epoxy resin curing agent (2) as essential components. Furthermore, this invention relates to the hardened | cured material formed by hardening | curing the said curable resin composition. Furthermore, this invention relates to the coating agent characterized by containing the said curable resin composition.

  According to the present invention, it is possible to provide an epoxy group-containing silsesquioxane-modified epoxy resin that can provide a cured product having improved properties such as heat resistance, inorganic material adhesion, and wet heat adhesion. The cured product of the present invention is particularly useful as a coating agent, an anchor agent and the like.

  In the present invention, a hydroxyl group-containing epoxy resin (A) (hereinafter referred to as component (A)) is essential as a constituent component of the epoxy group-containing silsesquioxane-modified epoxy resin (1). Component (A) used in the present invention is a silicate ester by a demethanol condensation reaction with an alkoxy group of a silsesquioxane compound (B) (hereinafter referred to as component (B)) containing an epoxy group and an alkoxy group. What is necessary is just to have a hydroxyl group for forming.

  Component (A) includes bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol type epoxy resin such as bisphenol S type epoxy resin, hydrogenated bisphenol type epoxy resin obtained by nuclear hydrogenation of the benzene ring of the epoxy resin, phenol Examples include novolac type epoxy resins, cresol novolac type epoxy resins, biphenol type epoxy resins, and naphthalene type epoxy resins.

  Among the above components (A), bisphenol A type epoxy resins and hydrogenated bisphenol A type epoxy resins are easy to obtain because various products are commercially available. This is preferable because the number of hydroxyl groups contained can be adjusted.

  In addition, in the case of the epoxy resin which does not have a hydroxyl group, it can be set as a component (A) by carrying out ring-opening modification | denaturation of a part of epoxy group of the epoxy resin which does not have a hydroxyl group, and producing | generating a hydroxyl group. There is no restriction | limiting in particular about the method of ring-opening modification | denaturation, A well-known and usual method can be applied. Specifically, for example, a ring-opening modification method using an epoxy resin having no hydroxyl group and an active hydrogen compound can be mentioned. Examples of the epoxy resin having no hydroxyl group include polyglycidyl ethers of aliphatic polyhydric alcohols such as 1,6-hexanediol and trimethylolpropane, and alicyclic polycarboxylic acids such as hexahydrophthalic acid and methyltetrahydrophthalic acid. And polyglycidyl esters of acids. Examples of the active hydrogen compound include primary amines such as ethylamine, isopropylamine, 2-ethylhexylamine, 3-methoxypropylamine and allylamine, secondary amines such as diethylamine, diisopropylamine and diisobutylamine, formic acid, acetic acid and propion. Examples thereof include carboxylic acids such as acid, oxalic acid, citric acid, benzoic acid, fumaric acid and maleic acid, and phosphoric acids such as phosphoric acid, methylphosphonic acid and dimethylphosphonic acid.

  The average number of hydroxyl groups contained in one molecule of component (A) is preferably 0.3 or more and less than 5.

In addition, if it is a range which does not inhibit the effect of this invention, the epoxy resin which does not have a hydroxyl group can also be used together with a component (A). However, since the epoxy resin which does not have a hydroxyl group does not react with the component (B), it will be present in the curable resin composition unreacted. An epoxy resin having no hydroxyl group can impart flexibility and adhesiveness when forming a semi-cured film after drying the solvent when curing the curable resin composition.

As the component (B) used in the present invention, one general formula ^{(1): R 1 Si (} OR 2) 3 ( wherein, ^{R 1} represents a hydrocarbon having 3 to 8 carbon atoms having at least one epoxy group Represents an epoxy group-containing alkoxysilane (b1) (hereinafter referred to as component (b1)) and an epoxy group represented by R ² represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. metal alkoxides (b2) (hereinafter, component (b2) hereinafter) Ru compounds der obtained by a combined hydrolysis and condensation. Specific examples of the component (b1) include glycidoxypropyltrialkoxysilanes such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltripropoxysilane, (Epoxycyclohexyl) such as 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltripropoxysilane Examples include ethyltrialkoxysilanes, and the exemplified compounds can be used alone or in appropriate combination. Of the exemplified compounds, 3-glycidoxypropyltrimethoxysilane is particularly preferable because of its high reactivity of hydrolysis reaction and easy availability. It is particularly preferable to use 3-glycidoxypropyltrimethoxysilane.

Specific examples of the component (b 2 ) include trialkylalkoxysilanes such as trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane, triphenylmethoxysilane, and triphenylethoxysilane, dimethyldimethoxysilane, Dialkyldialkoxysilanes such as dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, 3-mercaptopropylmethyldimethoxysilane, methyl Trimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane , Alkyltrialkoxysilanes such as phenyltriethoxysilane, tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetramethoxytitanium, tetraethoxytitanium, tetrapropoxytitanium, tetrabutoxy tetraalkoxytitanium such as titanium, to use tetraethoxy zirconium, tetra propoxy zirconium, tetra-alkoxy zirconium such as tetrabutoxyzirconium and the like. Component (b2) can be used either alone or in combination of two or more. By using trialkylalkoxysilanes, dialkyldialkoxysilanes, and tetraalkoxysilanes, crosslinking of component (B) The density can be adjusted. Moreover, the quantity of the epoxy group contained in a component (B) can be adjusted by using alkyl trialkoxysilanes. By using tetraalkoxy titanium and tetraalkoxy zirconium, the refractive index of the finally obtained cured product can be increased. Among the exemplified compounds, methyltrimethoxysilane is particularly preferable because of its high reactivity of hydrolysis reaction and easy availability. As component (b2), it is preferable to use methyltrimethoxysilane.

[Total number of moles of each alkoxy group contained in component (b1) and component (b2)] / [Total number of moles of component (b1) and component (b2)] (molar ratio: alkoxy contained per molecule) The average number of groups) is preferably 2.5 or more and 3.5 or less, and more preferably 2.7 or more and 3.2 or less. By setting it to 2.5 or more and 3.5 or less, moisture resistance adhesion and heat resistance of the cured product can be improved, which is preferable.

Component (B) may be a component (b1) and the component (b2) and have use in specific proportions wherein, after their hydrolysis, obtained by condensation. By the hydrolysis reaction, the alkoxy group contained in component (b1) and component (b2) becomes a silanol group, and alcohol is by-produced. The amount of water required for the hydrolysis reaction is [number of moles of water used for hydrolysis reaction] / [total number of moles of each alkoxy group contained in component (b1) and component (b2)] (molar ratio). .2 or more and 1 or less, preferably 0.3 or more and 0.7 or less. It is preferable to set it to 0.2 or more because the molecular weight of the component (B) obtained can be kept high. Moreover, it is preferable to set it to 1 or less because the wet heat resistance adhesion is improved. The component (B) is a product obtained by hydrolyzing and condensing methyltrimethoxysilane and 3-glycidoxypropyltrimethoxysilane, and has high hydrolyzability as described above. Can be co-condensed at an arbitrary ratio.

  In addition, when a component (b2) is used in combination with a tetraalkoxytitanium, tetraalkoxyzirconium or the like, particularly a metal alkoxide having high hydrolyzability and condensation reactivity, the hydrolysis and condensation reaction proceeds rapidly, and the system May gel. In this case, gelation can be avoided by adding the component (b2) after the hydrolysis reaction of the component (b1) has been completed and all the water has been consumed.

  The catalyst used for the hydrolysis reaction is not particularly limited, and a conventionally known hydrolysis catalyst can be arbitrarily used. Hydrolysis catalysts include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, organic acids such as formic acid and acetic acid, inorganic bases such as ammonia and sodium hydroxide, 1,8-diaza-bicyclo [5.4.0] undecene- 7, organic bases such as 2-ethyl-4-methylimidazole. Further, ion exchange resins, activated clays, carbon-based solid acids and the like, which are solid catalysts having an acidic or basic ionic group and are solid at room temperature, can be mentioned. These exemplified compounds can be used alone or in appropriate combination. Of these, formic acid is preferred because it has high catalytic activity and also functions as a catalyst for the subsequent condensation reaction. A solid catalyst is preferable because it can be easily removed by a method such as filtration after completion of the reaction. Although the addition amount of a hydrolysis catalyst is not specifically limited, It is preferable that it is 0.02-25 weight part with respect to a total of 100 weight part of a component (b1) and a component (b2), and is 1-10 weight part. It is more preferable. Although reaction temperature and reaction time can be arbitrarily set according to the reactivity of a component (b1) or a component (b2), it is about 0-100 degreeC normally, Preferably it is about 20-60 degreeC, 1 minute-about 2 hours. . The hydrolysis reaction can be performed in the presence or absence of a solvent. The type of the solvent is not particularly limited, and one or more arbitrary solvents can be selected and used, but it is preferable to use the same solvent as that used in the condensation reaction described later. When the reactivity of component (b1) or component (b2) is low, it is preferable to carry out without solvent.

  In the condensation reaction, water is by-produced between the silanol groups, and alcohol is by-produced between the silanol group and the alkoxy group to form a siloxane bond (Si—O—Si). A conventionally known dehydration condensation catalyst can be arbitrarily used for the condensation reaction. As described above, formic acid is preferable because it has high catalytic activity and can be used as a catalyst for hydrolysis reaction. A solid catalyst is preferable because it can be easily removed by a method such as filtration after completion of the reaction. The reaction temperature and reaction time can be arbitrarily set according to the reactivity of the component (b1) and component (b2), respectively, but usually about 40 to 150 ° C., preferably 60 to 100 ° C., about 30 minutes to 12 hours. is there.

The condensation reaction is preferably performed by diluting the solvent so that the total concentration of the component (b1) and the component (b2 ) is about 2 to 80% by weight, and more preferably 15 to 60% by weight. As the solvent, one or more arbitrary solvents can be selected and used. It is preferable to use a solvent having a boiling point higher than that of water and alcohol produced by the condensation reaction because these can be distilled off from the reaction system. Examples of such a solvent include toluene, xylene, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, butyl acetate and the like.

  It is preferable to remove the catalyst used after completion of the condensation reaction, since the stability of the finally obtained epoxy group-containing silsesquioxane-modified epoxy resin (1) is improved. The removal method can be appropriately selected from various known methods depending on the catalyst used. For example, when formic acid is used, it can be easily removed after completion of the condensation reaction by heating above the boiling point or by reducing the pressure. For this reason, use of formic acid is preferred. A solid catalyst is preferable because it can be easily removed by a method such as filtration after completion of the reaction.

[Mole number of epoxy groups contained in component (b1)] / [Total number of moles of component (b1) and component (b2)] (molar ratio: average number of epoxy groups contained per silicon atom) Is preferably 0.10 or more and 0.85 or less, and more preferably 0.15 or more and 0.6 or less. As will be described later, the epoxy group-containing silsesquioxane-modified epoxy resin (1) needs to contain an epoxy group in a specific ratio. This is preferable because the wet heat and heat adhesion of the cured product, which is an effect of the present invention, can be maintained high.

Moreover, the alkoxy group contained in the component (B) contributes to the reaction with the hydroxyl group of the component (A), the improvement of adhesion to the inorganic material during curing, and the crosslinking between the inorganic components during curing. For this reason, the alkoxy group contained in the component (B) is 100 to 1000 g / eq in terms of alkoxy equivalent (alkoxy equivalent: represents the weight (gram) of the component (B) including one equivalent of alkoxy group). preferable. As will be described later, the epoxy group-containing silsesquioxane-modified epoxy resin (1) needs to contain an alkoxy group in a specific ratio. This is preferable because the wet heat and heat adhesion of the cured product, which is an effect of the present invention, can be maintained high.

  The epoxy group-containing silsesquioxane-modified epoxy resin (1) of the present invention can be obtained by subjecting component (A) and component (B) to a dealcoholization condensation reaction in the presence or absence of a solvent. The use amount of component (A) and component (B) is not particularly limited, and the use ratio of component (A) and component (B) is not particularly limited, but the weight of component (B) / component (A) The weight (weight ratio) is about 0.2 to 8, preferably 0.5 to 5. If it is less than 0.2, the heat and moisture resistance of the cured product, which is the effect of the present invention, is lowered, and the heat resistance of the cured product and the adhesion to an inorganic material are lowered, which is not preferable. If it exceeds 8, the wet heat and heat adhesion of the cured product, which is the effect of the present invention, is lowered, and the effect of improving the physical properties such as hardness of the cured product is insufficient, which is not preferable.

  In the dealcoholization condensation reaction in the present invention, the reaction temperature is about 50 to 130 ° C, preferably 70 to 110 ° C, and the total reaction time is about 1 to 15 hours. This reaction is preferably carried out under substantially anhydrous conditions in order to prevent hydrolysis and condensation reaction of the alkoxy group of component (B). By the way, the epoxy group-containing silsesquioxane-modified epoxy resin (1) produced in the absence of a solvent can be used as it is as a material such as an adhesive, a molded product, and a sealing agent. There are advantages. In addition, in order to apply to the said solvent-free use, when compatibility with a component (A) and a component (B) is high, it can react without solvent and the epoxy group manufactured in presence of a solvent. The organic solvent solution of the containing silsesquioxane-modified epoxy resin (1) may be depressurized to remove the solvent. As the reaction solvent, a conventionally known solvent can be used as long as it does not react with an epoxy group and has a boiling point equal to or higher than the reaction temperature of the dealcoholization reaction and dissolves the component (A) and the component (B). it can. Examples of such an organic solvent include methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, tetrahydrofuran, dimethyl diglycol, dimethyl triglycol, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone and the like. Among these, organic solvents that have a boiling point of less than 120 ° C. and can be easily dried, such as methyl ethyl ketone, methyl isobutyl ketone, and toluene, are preferable for applications that require processing in a semi-cured state.

  In the above dealcoholization condensation reaction, a conventionally known catalyst that does not open an epoxy ring can be used to promote the reaction. Examples of the catalyst include lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, barium, strontium, zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, arsenic, cerium, boron, cadmium, manganese. And metals such as oxides, organic acid salts, halides, and methoxides of these metals. Among these, organic tin and organic acid tin are particularly preferable, and specifically, dibutyltin dilaurate, dioctyltin dilaurate, tin octylate and the like are effective.

  The epoxy group-containing silsesquioxane-modified epoxy resin (1) has an epoxy group derived from the component (A) and the component (B) in its molecule. Both of these epoxy groups react with the curing agent (2) for epoxy resin to form a crosslinked structure and are used for curing. Since the crosslinked structure by the epoxy group derived from the component (A) is composed of an organic component, it contributes to imparting flexibility, flexibility, moldability and the like to the cured product. On the other hand, the crosslinked structure by the epoxy group derived from the component (B) has a function of strongly incorporating the silsesquioxane skeleton, which is an inorganic component in the component (B), into the organic crosslinked structure by the epoxy group derived from the component (A). And contributes to the formation of a dense organic-inorganic hybrid structure. For this reason, it contributes to imparting heat resistance, adhesion, chemical resistance, hardness and the like to the cured product.

  The total amount of epoxy groups of the epoxy group-containing silsesquioxane-modified epoxy resin (1) is 150 to 500 g as an epoxy equivalent (epoxy equivalent: the weight of the component (1) (in grams) including 1 equivalent of epoxy group). / Eq, the ratio of the number of moles of epoxy groups derived from component (A) to the number of moles of epoxy groups derived from component (B) [number of moles of epoxy groups derived from component (A)] / [component (B ) Derived epoxy group mole number] (molar ratio) may be 0.1 or more and 3 or less. When the epoxy equivalent of the epoxy group-containing silsesquioxane-modified epoxy resin (1) exceeds 500 g / eq, the crosslinking density due to the epoxy group decreases, and the desired moisture and heat resistance, chemical resistance, hardness, etc. of the present application decrease. Tend to. On the other hand, when it is less than 150 g / eq, it becomes brittle due to the influence of water absorption based on the crosslinked structure portion of the epoxy group and the high crosslinking density, and the moisture-and-heat-resistant adhesion tends to decrease. Further, when [number of moles of epoxy group derived from component (A)] / [number of moles of epoxy group derived from component (B)] is less than 0.1, that is, it contains a large amount of epoxy groups derived from component (B). In such a case, the organic cross-linking structure portion is reduced and the portion becomes brittle and the heat-and-moisture resistance tends to be lowered. On the other hand, when the number exceeds 3, that is, when many epoxy groups derived from the component (A) are contained, the silsesquioxane skeleton portion is reduced, and the alkoxy groups derived from the portion are reduced. Chemical resistance and hardness tend to decrease.

  Moreover, the epoxy group-containing silsesquioxane-modified epoxy resin (1) has an alkoxy group derived from the component (B) in its molecule. The alkoxy group contributes to improvement in adhesion with an inorganic material during curing. Moreover, the crosslinked structure by the inorganic component couple | bonded with each other is also formed by sol-gel reaction. The amount of the alkoxy group contained in the epoxy group-containing silsesquioxane-modified epoxy resin (1) is required to be 150 to 3000 g / eq. When it exceeds 3000 g / eq, the adhesiveness to the inorganic material is lowered, and the wet heat resistant adhesiveness which is the effect of the present invention is not expressed. If it is less than 150 g / eq, the crosslinking between inorganic components becomes too large at the time of curing, resulting in brittleness or a high water absorption rate, and also no moisture and heat resistance is exhibited.

  The curable resin composition of the present invention contains the epoxy group-containing silsesquioxane-modified epoxy resin (1) and the epoxy resin curing agent (2).

The epoxy resin curing agent (2) used in the present invention is not particularly limited, and a conventionally known epoxy resin curing agent can be appropriately used. For example, phenol resin curing agents, polyamine curing agents, imidazole curing agents, polymercaptans, acid anhydrides and the like. Examples of the catalyst for ring-opening polymerization of epoxy groups include cation generators and imidazole curing agents. More specifically, examples of phenolic resins include phenol novolac resins, cresol novolac resins, poly p-vinylphenol, and the like, and polyamine curing agents include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dicyandiamide. , Polyamideamine (polyamide resin), ketimine compound, isophoronediamine, m-xylenediamine, m-phenylenediamine, 1,3-bis (aminomethyl) cyclohexane, N-aminoethylpiperazine, 4,4'-diaminodiphenylmethane, 4 4,4'-diamino-3,3'-diethyldiphenylmethane, diaminodiphenylsulfone and the like, and imidazole curing agents include 2-methylimidazole and 2-ethylhexylimidazole. Examples include 2-undecylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2-phenylimidazolium isocyanurate, and polymercaptans include polyoxypropylene poly-2-hydro Ether type polymercaptans such as oxythiol, ethylene glycol type di (poly) hydroxythiol, limonene dihydrooxythiol, bisphenol A type dihydrooxythiol, bisphenol F type dihydroxyoxythiol, and phthalate type dimercaptan , Ester type polymercaptans such as trimethylolpropane polymercaptopropionate, pentaerythritol polymercaptopropionate, and various commercially available products Acid anhydrides include phthalic anhydride, maleic anhydride, tetrahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, pyromellitic anhydride, trimellitic anhydride, biphenyltetracarboxylic acid Dianhydrides, acid anhydrides with unsaturated bonds such as tetrahydrophthalic anhydride, 3-methyl-tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, succinic anhydride, butanetetracarboxylic acid And dianhydride, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic acid anhydride, bicyclo [2.2.1] heptane-2,3-dicarboxylic acid anhydride, and the like. Examples of the cation generator include at least one cation selected from aromatic sulfonium, aromatic iodonium, aromatic diazonium, aromatic ammonium, η5-cyclopentadiel-η6-cumenyl-Fe salt system, BF ₄ ⁻ , Examples include onium salts composed of at least one anion selected from PF ₆ ⁻ and SbF ₆ ^— .

  The ratio of the epoxy group-containing silsesquioxane-modified epoxy resin (1) and the epoxy resin curing agent (2) used in the preparation of the curable resin composition of the present invention is the same as that used for ring-opening polymerization of epoxy. The [number of moles of epoxy group contained in component (1)] / [number of moles of reactive group contained in component (2)] (molar ratio) is 0.8 to 2.0. Preferably, it is 1.0 to 1.5. By setting it as 0.8-2.0, since a favorable hardened | cured material can be produced and wet heat-resistant adhesiveness improves, it is preferable. About what performs ring-opening polymerization of an epoxy, it is preferable to add in the ratio of 0.01-5 weight part with respect to 100 weight part of component (1).

  A catalyst can be added to the curable resin composition of the present invention as necessary. The catalyst that can be used is not particularly limited, and a conventionally known epoxy curing catalyst suitable for each curing agent can be used. For example, when curing with an acid anhydride, 1,8-diaza-bicyclo [5.4.0] undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol And tertiary amines such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole, and the like. The catalyst is preferably used in a proportion of 0.01 to 5 parts by weight with respect to 100 parts by weight of the curable resin composition. Further, a catalyst for promoting the sol-gel reaction can be blended in the resin composition. Examples of the sol-gel reaction catalyst include conventional catalysts such as acid or basic catalysts and metal catalysts. In particular, tin octylate and dibutyltin dilaurate are highly active and have excellent solubility. preferable. The amount of the catalyst used can be appropriately determined depending on the activity of the catalyst used, the film thickness of the desired cured product, and the like. Usually, about 0.01 to 5 mol% of the catalytic ability of paratoluenesulfonic acid or tin octylate having high catalytic ability in molar ratio with respect to the alkoxy group of the epoxy group-containing silsesquioxane-modified epoxy resin (1). Is used in a low formic acid, acetic acid, etc. in an amount of about 0.1 to 50 mol%.

  The concentration of the epoxy group-containing silsesquioxane-modified epoxy resin (1) and the epoxy resin curing agent (2) can be appropriately determined depending on the application, and a solvent is blended as necessary. can do. Any solvent may be used as long as it does not react with the component, and a conventionally known solvent can be appropriately selected and used. When the curable resin composition is used as a coating agent, it may be diluted with a solvent to obtain a desired viscosity. When the thermosetting resin composition is cured to a thick film of 1 mm or more or used as an adhesive, an epoxy group-containing silsesquioxane-modified epoxy resin (1), an epoxy resin curing agent (2) The total concentration is preferably 90% by weight or more, more preferably 95% by weight or more. The total concentration may be calculated from the concentration of the epoxy group-containing silsesquioxane-modified epoxy resin (1) and the epoxy resin curing agent (2) and the amount of the solvent added when the curable resin composition is charged. It can be obtained by heating for about 2 hours at the boiling point of the solvent contained in the curable resin composition, and by changing the weight before and after heating. In the application, if it is less than 90% by weight, foaming may occur during curing and molding, or a solvent may remain in the cured product, and the physical properties of the cured product tend to decrease. When a solvent is used in the synthesis of the epoxy group-containing silsesquioxane-modified epoxy resin (1), the solvent is volatilized after the reaction so that the nonvolatile content is 90% by weight or more. You can let it go. Moreover, after preparing curable resin composition, the used solvent is volatilized and the total density | concentration of an epoxy-group containing silsesquioxane modified | denatured epoxy resin (1) and the hardening | curing agent for epoxy resins (2) can also be raised. .

  Furthermore, in the curable resin composition, the plasticizer, weathering agent, antioxidant, thermal stabilizer, lubricant, antistatic agent, as long as the effects of the present invention are not impaired, You may mix | blend a whitening agent, a coloring agent, a electrically conductive agent, a mold release agent, a surface treating agent, a viscosity modifier, a filler, etc.

(Application to coating agent)
A coating layer can be obtained by coating a curable resin composition on a desired substrate and curing the composition. As the substrate, inorganic substrates such as glass, iron, aluminum, copper, tin-doped indium oxide (ITO), polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), polyethylene terephthalate (PEN), polymethyl methacrylate Various known materials such as organic base materials such as (PMMA), polystyrene (PSt), polycarbonate (PC), acrylonitrile-butadiene-styrene (ABS) can be appropriately selected and used. Moreover, coating property can also be improved to some extent by diluting a curable composition with a solvent. By coating and curing the curable composition as described above, light guide plate, polarizing plate, liquid crystal panel, EL panel, PDP panel, OHP film, optical fiber, color filter, optical disk substrate, lens, plastic substrate for liquid crystal cell Articles suitable for optical member applications such as prisms can be obtained.

  Moreover, when an acid anhydride or an epoxy polymerization catalyst is used as the component (2), a cured film (coating layer) obtained from the curable composition can be made transparent. When the refractive index is higher than the refractive index of the substrate, an antireflection effect can be imparted. In producing the epoxy group-containing silsesquioxane-modified epoxy resin (1), the refractive index of the cured film obtained from the thermosetting composition is improved by using the component (b2) together with the component (b1). Can be made. Therefore, anti-reflection effect is applied to the coating layer applied to the light guide plate, polarizing plate, liquid crystal panel, EL panel, PDP panel, OHP film, optical fiber, color filter, optical disk substrate, lens, plastic substrate for liquid crystal cell, prism. In the case where it is desired to impart, component (b2) is preferably used in combination with the thermosetting composition.

(Application to adhesive)
A multilayer structure in which various equipments are brought into close contact with each other by applying the curable resin composition to a predetermined substrate (adhered material), pasting the coated surface and another member, and then curing the composition. You can get a body. As the substrate, the same materials as those used when forming the coating layer can be used. In order to prevent foaming of the adhesive layer, it is preferable that the volatile component in the curable composition is less than 10%, preferably less than 5% as described above, or the volatile component is removed before pasting.

(Application to sealing material)
A curable resin composition is applied in a thick film or poured into a predetermined mold, and then cured to obtain a sealed article sealed with a cured product. Such a sealed article is particularly suitable for use in electronic parts such as IC packages, light emitting elements, light receiving elements, photoelectric conversion elements, and optical transmission related parts.

In order to prepare a desired cured product using the curable resin composition of the present invention, the composition is coated on a predetermined substrate or filled in a predetermined mold, and when the solvent is included, the solvent After volatilizing, heat is applied in the case of thermosetting, and ultraviolet light is irradiated in the case of ultraviolet curing. The method for volatilizing the solvent may be appropriately determined according to the type, amount, film thickness, etc. of the solvent, but it is heated to about 40 to 150 ° C., preferably 60 to 100 ° C. The condition is about time. In the case of thermosetting, it is preferable to cure at 100 to 250 ° C. after volatilization of the solvent or including volatilization of the solvent. In the case of ultraviolet curing, the irradiation amount of ultraviolet rays may be appropriately determined according to the type, film thickness, etc. of the ultraviolet curable resin composition, but if the integrated light amount is irradiated so as to be about 50 to 10,000 mJ / cm ^2. Good.

  Moreover, the physical property of hardened | cured material can be improved further by further heating the hardened | cured material obtained by ultraviolet irradiation. The heating method may be appropriately determined, but the heating is performed at about 40 to 300 ° C., preferably 100 to 250 ° C., and the conditions are about 1 minute to 6 hours.

EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated concretely, this invention is not limited to the said Example. In each example, parts and% are based on weight.

Production Example 1 (Production of epoxy group-containing silsesquioxane (B-1))
3-epoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name “KBM-403”) as a component (b1) in a reaction apparatus equipped with a stirrer, a condenser, a water separator, a thermometer, and a nitrogen inlet ) 1000 parts, methyltrimethoxysilane (manufactured by Tama Chemical Co., Ltd .: trade name “methyltrimethoxysilane”) 1729.2 parts ([number of moles of epoxy group contained in component (b1)] as component (b2) / [Total number of moles of component (b1) and component (b2)] = 0.25), 364.27 parts of ion-exchanged water ([number of moles of water used for hydrolysis reaction] / [component (b1) and component ( The total number of moles of each alkoxy group contained in b2) ] (molar ratio) = 0.40), 13.65 parts of 88% formic acid, and 900 parts of toluene were charged and subjected to a hydrolysis reaction at room temperature for 30 minutes. When the reaction was heated and the temperature was raised to 70 ° C., methanol generated by hydrolysis began to distill off. The temperature was raised to 75 ° C. over 30 minutes, and water generated by the condensation reaction was distilled off. After further reacting at 75 ° C. for 30 minutes, the pressure was reduced while gradually reducing the pressure at 50 ° C. for 3 hours, and the remaining methanol, water, formic acid and toluene were distilled off to prepare 851.1 g of dimethyldiethylene glycol, and epoxy was added. 2837 g of a solvent solution of silsesquioxane (B-1) containing a group was obtained. The content of (B-1) was 70%, the methoxy group equivalent was 150 g / eq, and the epoxy equivalent was 470 g / eq.

Production Example 2 (Production of epoxy group-containing silsesquioxane (B-2))
In a reaction apparatus similar to Production Example 1, 800 parts of 3-epoxypropyltrimethoxysilane as component (b1) and 1383.3 parts of methyltrimethoxysilane as component (b2) (of the epoxy group contained in [component (b1) Number of moles] / [total number of moles of component (b1) and component (b2)] = 0.25), 437.77 parts of ion-exchanged water ([number of moles of water used for hydrolysis reaction] / [component ( b1 )) The total number of moles of each alkoxy group contained in the component (b2) ] (molar ratio) = 0.60), 90.92 parts of 88% formic acid, and 730 parts of toluene were charged, followed by hydrolysis at room temperature for 30 minutes. When the reaction was heated and the temperature was raised to 70 ° C., methanol generated by hydrolysis began to distill off. The temperature was raised to 75 ° C. over 30 minutes, and water generated by the condensation reaction was distilled off. After further reacting at 75 ° C. for 30 minutes, the pressure was reduced while gradually reducing the pressure at 50 ° C. for 3 hours, and the remaining methanol, water, formic acid and toluene were distilled off to prepare 629 g of dimethyldiethylene glycol. 2096 g of a solvent solution of silsesquioxane (B-2) was obtained. The content of (B-2) was 70%, the methoxy group equivalent was 240 g / eq, and the epoxy equivalent was 440 g / eq.

Production Example 3 (Production of epoxy group-containing silsesquioxane (B-3))
In the same reactor as in Production Example 1, 2500 parts of 3-epoxypropyltrimethoxysilane as component (b1) and 288.2 parts of methyltrimethoxysilane as component (b2) (of the epoxy group contained in [component (b1) Number of moles] / [total number of moles of component (b1) and component (b2)] = 0.83), 341.36 parts of ion-exchanged water ([number of moles of water used for hydrolysis reaction] / [component ( b1 )) And the total number of moles of each alkoxy group contained in the component (b2) ] (molar ratio) = 0.50), 13.94 parts of 88% formic acid, and 985 parts of toluene were charged and hydrolyzed at room temperature for 30 minutes. When the reaction was heated and the temperature was raised to 70 ° C., methanol generated by hydrolysis began to distill off. The temperature was raised to 75 ° C. over 30 minutes, and water generated by the condensation reaction was distilled off. After further reacting at 75 ° C. for 30 minutes, the pressure was reduced stepwise at 50 ° C. for 3 hours, and the remaining methanol, water, formic acid and toluene were distilled off to prepare 985 g of dimethyldiethylene glycol, and the epoxy group was removed. 3284 g of a solvent solution of the silsesquioxane (B-3) contained was obtained. The content of (B-3) was 70%, the methoxy group equivalent was 200 g / eq, and the epoxy equivalent was 220 g / eq.

Example 1
To a reactor equipped with a stirrer, a condenser, a thermometer, and a nitrogen blowing port, 400.0 g of bisphenol A type epoxy resin (epoxy equivalent 255 g / eq, manufactured by Mitsubishi Chemical, trade name jER834) and 680.0 g of dimethyldiethylene glycol were added. Dissolved at 70 ° C. Furthermore, 395.46 g of silsesquioxane (B-1) solution containing the epoxy group obtained in Production Example 1 ([number of moles of epoxy group derived from component (A)] / [epoxy group derived from component (B)] Of component (B) / component (A) = 0.69 (weight ratio)) and 10.4 g of dibutyltin dilaurate as a catalyst were added and reacted at 100 ° C. for 20 hours. After the reaction, 112.3 g of methanol was added to obtain 1590 g of a solvent solution of the epoxy group-containing silsesquioxane-modified epoxy resin. The content of the epoxy group-containing silsesquioxane-modified epoxy resin was 40%, the methoxy group equivalent was 450 g / eq, and the epoxy equivalent was 300 g / eq.

Example 2
300.0 g of bisphenol A type epoxy resin (epoxy equivalent 475 g / eq, manufactured by Mitsubishi Chemical Corporation, trade name jER1001) and 60.0 g of dimethyldiethylene glycol were added to the same reactor as in Example 1, and dissolved at 70 ° C. Furthermore, 547.64 g of silsesquioxane (B-3) solution containing epoxy group obtained in Production Example 3 ([number of moles of epoxy group derived from component (A)) / [epoxy group derived from component (B)] Of component (B) / component (A) = 1.3 (weight ratio)) and 4.32 g of dibutyltin dilaurate as a catalyst were added and reacted at 100 ° C. for 20 hours. After the reaction, 99.64 g of methanol was added to obtain 1550 g of a solvent solution of the epoxy group-containing silsesquioxane-modified epoxy resin. The content of the epoxy group-containing silsesquioxane-modified epoxy resin was 40%, the methoxy group equivalent was 390 g / eq, and the epoxy equivalent was 265 g / eq.

Example 3
In the same reactor as in Example 1, 160.0 g of jER1001 and 320.0 g of dimethyldiethylene glycol were added and dissolved at 70 ° C. Further, 915.48 g of silsesquioxane (B-3) containing epoxy group obtained in Production Example 3 ([number of moles of epoxy group derived from component (A)) / [of epoxy group derived from component (B)] Mole number] = 0.12, component (B) / component (A) = 4.0 (weight ratio)) and 0.28 g of dibutyltin dilaurate as a catalyst were added and reacted at 100 ° C. for 20 hours to obtain an epoxy group-containing silyl 1390 g of a solvent solution of sesquioxane-modified epoxy resin was obtained. The content of the epoxy group-containing silsesquioxane-modified epoxy resin was 40%, the methoxy group equivalent was 190 g / eq, and the epoxy equivalent was 175 g / eq.

Example 4
340.0 g of hydrogenated bisphenol A type epoxy resin (epoxy equivalent 305 g / eq, manufactured by Mitsubishi Chemical Corporation, trade name jER YX8034) and 578.0 g of dimethyldiethylene glycol were added to the same reactor as in Example 1 and dissolved at 70 ° C. . Furthermore, 402.23 g of silsesquioxane (B-1) containing the epoxy group obtained in Production Example 1 ([number of moles of epoxy group derived from component (A)) / [of epoxy group derived from component (B)] Mol number] = 1.9, component (B) / component (A) = 0.83 (weight ratio)) and 0.60 g of tin octylate as a catalyst are added and reacted at 100 ° C. for 2 hours to contain an epoxy group 1315 g of a solvent solution of silsesquioxane-modified epoxy resin was obtained. The content of the epoxy group-containing silsesquioxane-modified epoxy resin was 40%, the methoxy group equivalent was 360 g / eq, and the epoxy equivalent was 310 g / eq.

Example 5
To the same reactor as in Example 1, 300.0 g of jER1001 and 60.0 g of dimethyldiethylene glycol were added and dissolved at 70 ° C. Further, 523.26 g of silsesquioxane (B-2) containing epoxy group obtained in Production Example 2 ([number of moles of epoxy group derived from component (A)) / [of epoxy group derived from component (B)] Mole number] = 0.76, component (B) / component (A) = 1.2 (weight ratio)) and 0.27 g of tin octylate as a catalyst were added and reacted at 100 ° C. for 2 hours to contain an epoxy group 1415 g of a solvent solution of silsesquioxane-modified epoxy resin was obtained. The content of the epoxy group-containing silsesquioxane-modified epoxy resin was 40%, the methoxy group equivalent was 650 g / eq, and the epoxy equivalent was 390 g / eq.

Example 6
In the same reactor as in Example 1, 160.0 g of jER1001 and 60.0 g of dimethyldiethylene glycol were added and dissolved at 70 ° C. Further, 915.48 g of silsesquioxane (B-3) containing epoxy group obtained in Production Example 3 ([number of moles of epoxy group derived from component (A)) / [of epoxy group derived from component (B)] Mole number] = 0.12, component (B) / component (A) = 4.0 (weight ratio)) and 0.14 g of tin octylate as a catalyst were added and reacted at 100 ° C. for 2 hours to contain an epoxy group 1415 g of a solvent solution of silsesquioxane-modified epoxy resin was obtained. The content of the epoxy group-containing silsesquioxane-modified epoxy resin was 40%, the methoxy group equivalent was 195 g / eq, and the epoxy equivalent was 175 g / eq.

Example 7
In a reactor similar to that in Example 1, 560.0 g of jER1001 and 850.0 g of dimethyldiethylene glycol were added and dissolved at 70 ° C. Furthermore, 230.3 g of silsesquioxane (B-3) containing an epoxy group obtained in Production Example 3 ([number of moles of epoxy group derived from component (A)) / [of epoxy group derived from component (B)] Mol number] = 1.6, component (B) / component (A) = 0.29 (weight ratio)) and 0.25 g of tin octylate as a catalyst were added and reacted at 100 ° C. for 2 hours to contain an epoxy group 1630 g of a solvent solution of silsesquioxane-modified epoxy resin was obtained. The content of the epoxy group-containing silsesquioxane-modified epoxy resin was 40%, the methoxy group equivalent was 2500 g / eq, and the epoxy equivalent was 345 g / eq.

Example 8
To the same reactor as in Example 1, 287.0 g of jER1001 and 560.0 g of dimethyldiethylene glycol were added and dissolved at 70 ° C. Furthermore, 647.03 g of silsesquioxane (B-1) containing the epoxy group obtained in Production Example 1 ([number of moles of epoxy group derived from component (A)) / [of epoxy group derived from component (B)] Mole number] = 0.61, component (B) / component (A) = 1.6 (weight ratio)) and 8.00 g of dibutyltin dilaurate as a catalyst were added and reacted at 100 ° C. for 2 hours. After the reaction, 56.00 g of methanol was added to obtain 1550 g of a solvent solution of the epoxy group-containing silsesquioxane-modified epoxy resin. The content of the epoxy group-containing silsesquioxane-modified epoxy resin was 40%, the methoxy group equivalent was 260 g / eq, and the epoxy equivalent was 400 g / eq.

Example 9
With respect to 75.0 parts of the epoxy group-containing silsesquioxane-modified epoxy resin solution obtained in Example 1, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride and bicyclo [2.2 .1] Mixture with heptane-2,3-dicarboxylic acid anhydride (Shin Nippon Rika Co., Ltd .: trade name “Licacid HNA-100”) 18.4 parts ([epoxy group-containing silsesquioxane modified epoxy resin Number of moles of epoxy group contained] / [Methylbicyclo [2.2.1] heptane-2,3-dicarboxylic acid anhydride and bicyclo [2.2.1] heptane-2,3-dicarboxylic acid anhydride The number of moles of reactive groups contained in the mixture with the mixture] (molar ratio) = 1.0) and 17.6 parts of methyl isobutyl ketone were blended to obtain a thermosetting resin composition.

Example 1 0
With respect to 66.3 parts of the epoxy group-containing silsesquioxane-modified epoxy resin solution obtained in Example 2, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride and bicyclo [2.2 .1] 18.4 parts of a mixture with heptane-2,3-dicarboxylic anhydride ([number of moles of epoxy group contained in epoxy group-containing silsesquioxane-modified epoxy resin] / [methyl bicyclo [2.2. 1] Number of moles of reactive groups contained in a mixture of heptane-2,3-dicarboxylic anhydride and a mixture of bicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride] (molar ratio) ) = 1.0) and 17.6 parts of methyl isobutyl ketone were blended to prepare a thermosetting resin composition.

Example 1 1
With respect to 43.8 parts of the epoxy group-containing silsesquioxane-modified epoxy resin solution obtained in Example 3, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride and bicyclo [2.2 .1] 18.4 parts of a mixture with heptane-2,3-dicarboxylic anhydride ([number of moles of epoxy group contained in epoxy group-containing silsesquioxane-modified epoxy resin] / [methyl bicyclo [2.2. 1] Number of moles of reactive groups contained in a mixture of heptane-2,3-dicarboxylic anhydride and a mixture of bicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride] (molar ratio) ) = 1.0) and 18.4 parts of methyl isobutyl ketone were blended to prepare a thermosetting resin composition.

Example 1 2
With respect to 77.5 parts of the epoxy group-containing silsesquioxane-modified epoxy resin solution obtained in Example 4, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride and bicyclo [2.2 .1] 18.4 parts of a mixture with heptane-2,3-dicarboxylic anhydride ([number of moles of epoxy group contained in epoxy group-containing silsesquioxane-modified epoxy resin] / [methyl bicyclo [2.2. 1] Number of moles of reactive groups contained in a mixture of heptane-2,3-dicarboxylic anhydride and a mixture of bicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride] (molar ratio) ) = 1.0) and 25.2 parts of methyl isobutyl ketone were blended to prepare a thermosetting resin composition.

Example 1 3
With respect to 97.5 parts of the epoxy group-containing silsesquioxane-modified epoxy resin solution obtained in Example 5, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride and bicyclo [2.2 .1] 18.4 parts of a mixture with heptane-2,3-dicarboxylic anhydride ([number of moles of epoxy group contained in epoxy group-containing silsesquioxane-modified epoxy resin] / [methyl bicyclo [2.2. 1] Number of moles of reactive groups contained in a mixture of heptane-2,3-dicarboxylic anhydride and a mixture of bicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride] (molar ratio) ) = 1.0) and 25.2 parts of methyl isobutyl ketone were blended to prepare a thermosetting resin composition.

Example 1 4
For 43.8 parts of the epoxy group-containing silsesquioxane-modified epoxy resin solution obtained in Example 6, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride and bicyclo [2.2 .1] 18.4 parts of a mixture with heptane-2,3-dicarboxylic anhydride ([number of moles of epoxy group contained in epoxy group-containing silsesquioxane-modified epoxy resin] / [methyl bicyclo [2.2. 1] Number of moles of reactive groups contained in a mixture of heptane-2,3-dicarboxylic anhydride and a mixture of bicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride] (molar ratio) ) = 1.0) and 25.2 parts of methyl isobutyl ketone were blended to prepare a thermosetting resin composition.

Example 1 5
With respect to 86.3 parts of the epoxy group-containing silsesquioxane-modified epoxy resin solution obtained in Example 7, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride and bicyclo [2.2 .1] 18.4 parts of a mixture with heptane-2,3-dicarboxylic anhydride ([number of moles of epoxy group contained in epoxy group-containing silsesquioxane-modified epoxy resin] / [methyl bicyclo [2.2. 1] Number of moles of reactive groups contained in a mixture of heptane-2,3-dicarboxylic anhydride and a mixture of bicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride] (molar ratio) ) = 1.0) and 25.2 parts of methyl isobutyl ketone were blended to prepare a thermosetting resin composition.

Example 1 6
For 100 parts of the epoxy group-containing silsesquioxane-modified epoxy resin solution obtained in Example 8, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride and bicyclo [2.2.1]. 18.4 parts of a mixture with heptane-2,3-dicarboxylic acid anhydride ([number of moles of epoxy groups contained in epoxy group-containing silsesquioxane-modified epoxy resin] / [methylbicyclo [2.2.1] Number of moles of reactive groups contained in a mixture of heptane-2,3-dicarboxylic anhydride and a mixture of bicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride] (molar ratio) = 1.0) and 25.2 parts of methyl isobutyl ketone were blended to prepare a thermosetting resin composition.

Example 1 7
50% methyl ethyl ketone solution of phenol novolak resin (Arakawa Chemical Industries, Ltd .: trade name “Tamanor 759”) with respect to 110.1 parts of the epoxy group-containing silsesquioxane-modified epoxy resin solution obtained in Example 1. 4 parts ([number of moles of epoxy group contained in epoxy group-containing silsesquioxane-modified epoxy resin] / [number of moles of reactive group contained in phenol novolac resin] (molar ratio) = 1.0), 2- Ethyl-4-methylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd .: trade name “Cureazole 2E4MZ”) 0.1 part was blended to prepare a thermosetting resin composition.

Example 1 8
124.6 parts of the epoxy group-containing silsesquioxane-modified epoxy resin solution obtained in Example 2 is 24.6 parts of 50% methyl ethyl ketone solution of tamanor 759 ([included in epoxy group-containing silsesquioxane-modified epoxy resin The number of moles of epoxy groups] / [number of moles of reactive groups contained in the phenol novolac resin] (molar ratio) = 1.0) and 0.1 part of Curazole 2E4MZ were blended to obtain a thermosetting resin composition.

Example 19
For 10 parts of the epoxy group-containing silsesquioxane-modified epoxy resin solution obtained in Example 1, 0.20 g of a thermal cation generation catalyst (manufactured by Sanshin Chemical Industry Co., Ltd., trade name “Sun-Aid SI-60L”) It mix | blended and it was set as the thermosetting resin composition.

Example 2 0
Except that the epoxy group-containing silsesquioxane-modified epoxy resin solution obtained in Example 1 was changed to the epoxy group-containing silsesquioxane-modified epoxy resin solution obtained in Example 3, the same procedure as in Example 19 was performed. A thermosetting resin composition was obtained.

Example 2 1
Except that the epoxy group-containing silsesquioxane-modified epoxy resin solution obtained in Example 1 was changed to the epoxy group-containing silsesquioxane-modified epoxy resin solution obtained in Example 4, the same procedure as in Example 19 was performed. A thermosetting resin composition was obtained.

Example 2 2
The thermosetting resin composition obtained in Example 9 was applied on glass at a film thickness of 100 μm, and subjected to a curing reaction at 100 ° C. for 1 hour and at 200 ° C. for 1 hour to obtain a thermoset.

Example 2 3
The exception that the heat-curable resin composition obtained in Example 9 in the thermosetting resin composition obtained in Example 1 0 was heat cured in the same manner as in Example 2 2.

Example 2 4
The exception that the heat-curable resin composition obtained in Example 9 in the thermosetting resin composition obtained in Example 1 1, was thermally cured in the same manner as in Example 2 2.

Example 2 5
The exception that the heat-curable resin composition obtained in Example 9 in the thermosetting resin composition obtained in Example 1 2 was heat cured in the same manner as in Example 2 2.

Example 2 6
The exception that the heat-curable resin composition obtained in Example 9 in the thermosetting resin composition obtained in Example 1 3 was heat cured in the same manner as in Example 2 2.

Example 27
The exception that the heat-curable resin composition obtained in Example 9 in the thermosetting resin composition obtained in Example 1 4 was heat cured in the same manner as in Example 2 2.

Example 28
The exception that the heat-curable resin composition obtained in Example 9 in the thermosetting resin composition obtained in Example 1 5 was heat cured in the same manner as in Example 2 2.

Example 29
The exception that the heat-curable resin composition obtained in Example 9 in the thermosetting resin composition obtained in Example 1 6 was heat cured in the same manner as in Example 2 2.

Example 3 0
Example 17 The thermosetting resin composition obtained in 7 was poured into an aluminum cup so that the film thickness after curing was about 0.5 mm, and a curing reaction was performed at 120 ° C. for 1 hour and at 180 ° C. for 1 hour. It was.

Example 3 1
The exception that the heat-curable resin composition obtained a thermosetting resin composition obtained in Example 1 7 Example 1 8, was heat-cured in the same manner as in Example 3 0.

Example 3 2
The thermosetting resin composition obtained in Example 19 was applied on glass at a film thickness of 100 μm and subjected to a curing reaction at 120 ° C. for 1 hour and at 180 ° C. for 1 hour to obtain a thermoset.

Example 3 3
The exception that the heat-curable resin composition obtained in Example 19 in the thermosetting resin composition obtained in Example 2 0 was heat cured in the same manner as in Example 3 2.

Example 3 4
The exception that the heat-curable resin composition obtained in Example 19 in the thermosetting resin composition obtained in Example 2 1, was thermally cured in the same manner as in Example 3 2.

Comparative Example 1
A reactor similar to Example 1 was charged with 480 g of jER1001 and 401.76 g of dimethyldipropylene glycol, heated to 90 ° C. with stirring under a nitrogen stream, and then a tetramethoxysilane partial condensate (Tama Chemical Co., Ltd.). ), Trade name “MS-51”) 923.91 g ([number of moles of epoxy group derived from component (A)) / [number of moles of epoxy group derived from tetramethoxysilane partial condensate] = infinity, tetramethoxy Silane partial condensate / component (A) = 1.9 (weight ratio)) was charged, and the temperature was raised to 90 ° C. Thereafter, 0.42 g of dibutyltin dilaurate was added as a catalyst and reacted for 4 hours. The reaction system was cooled to room temperature to obtain 1800 g of a solvent solution of an alkoxysilane-modified epoxy resin. The content of the obtained alkoxysilane-modified epoxy resin was 52%, the methoxy group equivalent was 55 g / eq, and the epoxy equivalent was 930 g / eq.

Comparative Example 2
In a reactor similar to that in Example 1, 700 g of jER1001 and 840 g of dimethyldiethylene glycol were charged, and the temperature was raised to 70 ° C. while stirring under a nitrogen stream. Product name “MTMS-A”) 529 g ([number of moles of epoxy group derived from component (A)) / [number of moles of epoxy group derived from methyltrimethoxysilane partial condensate] = infinity, partial condensation of methyltrimethoxysilane Product / component (A) = 0.76 (weight ratio)) and heated to 90 ° C. Thereafter, 2.0 g of dibutyltin dilaurate was added as a catalyst and reacted for 7 hours. The reaction system was cooled to room temperature to obtain 2071 g of a solvent solution of an alkoxysilane-modified epoxy resin. The content of the resulting alkoxysilane-modified epoxy resin solution was 50%, the methoxy group equivalent was 155 g / eq, and the epoxy equivalent was 700 g / eq.

Comparative Example 3
To the same reactor as in Example 1, 1050 g of jER1001, 1758.3 g of jER828 and 503.47 g of glycidol were added and melt-mixed at 90 ° C. Further, 2252.8 g of MS-51 ([number of moles of epoxy group derived from component (A)) / [number of moles of epoxy group derived from glycidol] = 1.7, tetramethoxysilane partial condensate / component (A) = 0.80 (weight ratio)) and 1.13 g of dibutyltin dilaurate as a catalyst were added, and demethanol reaction was performed at 90 ° C. for 15 hours under a nitrogen stream to obtain 5285 g of an alkoxysilane-modified epoxy resin. . The content of the resulting alkoxysilane-modified epoxy resin solution was 100%, the methoxy group equivalent was 124 g / eq, and the epoxy equivalent was 285 g / eq.

Comparative Example 4
The solvent solution of the epoxy group-containing silsesquioxane (B-1) obtained in Production Example 1 was used as it was. ([Mole number of epoxy group derived from component (A)] / [Mole number of epoxy group derived from component (B)] = 0, component (B) / component (A) = infinity (weight ratio)), ( The content of B-1) was 70%, the methoxy group equivalent was 150 g / eq, and the epoxy equivalent was 470 g / eq.

Comparative Example 5
jER828 was used as it was. ([Number of moles of epoxy group derived from component (A)] / [number of moles of epoxy group derived from component (B)] = infinity, component (B) / component (A) = 0 (weight ratio)) methoxy group The equivalent was infinite and the epoxy equivalent was 185 g / eq.

Comparative Example 6
With respect to 179 parts of the alkoxysilane-modified epoxy resin solution obtained in Comparative Example 1, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride and bicyclo [2.2.1] heptane-2, 18.4 parts of mixture with 3-dicarboxylic anhydride ([number of moles of epoxy group contained in alkoxysilane-modified epoxy resin] / [methylbicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride) And the number of moles of reactive groups contained in a mixture of bismuth and bicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride] (molar ratio) = 1.0), methyl isobutyl ketone 28. 0 part was mix | blended and it was set as the thermosetting resin composition.

Comparative Example 7
For 140 parts of the alkoxysilane-modified epoxy resin solution obtained in Comparative Example 2, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride and bicyclo [2.2.1] heptane-2, 18.4 parts of mixture with 3-dicarboxylic anhydride ([number of moles of epoxy group contained in alkoxysilane-modified epoxy resin] / [methylbicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride) And the number of moles of reactive groups contained in a mixture of bismuth and bicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride] (molar ratio) = 1.0), methyl isobutyl ketone 28. Three parts were blended to obtain a thermosetting resin composition.

Comparative Example 8
With respect to 28.5 parts of the alkoxysilane-modified epoxy resin solution obtained in Comparative Example 3, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride and bicyclo [2.2.1] heptane- Mixture with 2,3-dicarboxylic anhydride 18.4 parts ([number of moles of epoxy group contained in alkoxysilane-modified epoxy resin] / [methylbicyclo [2.2.1] heptane-2,3-dicarboxylic acid Mole number of reactive groups contained in a mixture of an anhydride and a mixture of bicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride] (molar ratio) = 1.0), methyl isobutyl ketone 28.3 parts was blended to obtain a thermosetting resin composition.

Comparative Example 9
With respect to 67.1 parts of the epoxy group-containing silsesquioxane (B-1) solution of Comparative Example 4, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride and bicyclo [2.2. 1] 18.4 parts of a mixture with heptane-2,3-dicarboxylic anhydride ([number of moles of epoxy group contained in alkoxysilane-modified epoxy resin] / [methylbicyclo [2.2.1] heptane-2, Number of moles of reactive groups contained in a mixture of 3-dicarboxylic anhydride and a mixture of bicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride] (molar ratio) = 1.0) Then, 28.3 parts of methyl isobutyl ketone was blended to prepare a thermosetting resin composition.

Comparative Example 10
With respect to 18.5 parts of the epoxy resin of Comparative Example 5, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride and bicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride 18.4 parts ([number of moles of epoxy group contained in alkoxysilane-modified epoxy resin] / [methylbicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride and bicyclo [2. 2.1] moles of reactive groups contained in a mixture with a mixture with heptane-2,3-dicarboxylic anhydride] (molar ratio) = 1.0), 28.3 parts of methyl isobutyl ketone A thermosetting resin composition was obtained.

Comparative Example 11
To 10 parts of the alkoxysilane-modified epoxy resin solution obtained in Comparative Example 1, 0.20 g of a thermal cation generating catalyst (manufactured by Sanshin Chemical Industry Co., Ltd., trade name “Sun-Aid SI-60L”) is arranged and thermoset. The resin composition was obtained.

Comparative Example 12
A thermosetting resin composition was prepared in the same manner as in Comparative Example 11, except that the alkoxysilane-modified epoxy resin solution obtained in Comparative Example 1 was replaced with the alkoxysilane-modified epoxy resin solution obtained in Comparative Example 2.

Comparative Example 13
A thermosetting resin composition was prepared in the same manner as in Comparative Example 11, except that the alkoxysilane-modified epoxy resin solution obtained in Comparative Example 1 was replaced with the alkoxysilane-modified epoxy resin solution obtained in Comparative Example 3.

Comparative Example 14
To 57.0 parts of the epoxy group-containing silsesquioxane-modified epoxy resin solution obtained in Comparative Example 3, 43.2 parts of 50% methyl ethyl ketone solution of tamanor 759 ([mol of epoxy group contained in alkoxysilane-modified epoxy resin) Number] / [number of moles of reactive groups contained in phenol novolac resin] (molar ratio) = 1.0), 0.1 part of 2-ethyl-4-methylimidazole, 40.0 parts of dimethyldiethylene glycol, A thermosetting resin composition was obtained.

Comparative Example 15
In Comparative Example 14, a thermosetting resin composition was prepared in the same manner except that the alkoxysilane-modified epoxy resin solution obtained in Comparative Example 3 was replaced with the epoxy resin of Comparative Example 5.

Comparative Example 16 (Production of thermoset)
The thermosetting resin composition obtained in Comparative Example 6 was applied on glass at a film thickness of 100 μm, and subjected to a curing reaction at 100 ° C. for 1 hour and at 200 ° C. for 1 hour to obtain a thermoset.

Comparative Example 17 (Production of thermoset)
A thermoset was obtained in the same manner as in Comparative Example 16 except that the thermosetting resin composition obtained in Comparative Example 6 was changed to the thermosetting composition obtained in Comparative Example 7.

Comparative Example 18 (Production of thermoset)
A thermoset was obtained in the same manner as in Comparative Example 16 except that the thermosetting resin composition obtained in Comparative Example 6 was changed to the thermosetting composition obtained in Comparative Example 8.

Comparative Example 19 (Production of thermoset)
A thermoset was obtained in the same manner as in Comparative Example 16 except that the thermosetting resin composition obtained in Comparative Example 6 was changed to the thermosetting composition obtained in Comparative Example 9.

Comparative Example 20 (Production of thermoset)
A thermoset was obtained in the same manner as in Comparative Example 16, except that the thermosetting resin composition obtained in Comparative Example 6 was changed to the thermosetting composition obtained in Comparative Example 10.

Comparative Example 21 (Production of thermoset)
The thermosetting resin composition obtained in Comparative Example 11 was poured into an aluminum cup so that the film thickness after curing was about 0.5 mm, and a curing reaction was performed at 120 ° C. for 1 hour and at 180 ° C. for 1 hour. did.

Comparative Example 22 (Production of thermoset)
A thermoset was obtained in the same manner as in Comparative Example 21, except that the thermosetting resin composition obtained in Comparative Example 11 was changed to the thermosetting resin composition obtained in Comparative Example 12.

Comparative Example 23 (Production of thermoset)
A thermosetting product was obtained in the same manner as in Comparative Example 21, except that the thermosetting resin composition obtained in Comparative Example 11 was changed to the thermosetting resin composition obtained in Comparative Example 13.

Comparative Example 24 (Production of thermoset)
The thermosetting resin composition obtained in Comparative Example 14 was coated on glass at a film thickness of 100 μm, and subjected to a curing reaction at 120 ° C. for 1 hour and at 180 ° C. for 1 hour to obtain a thermoset.

Comparative Example 25 (Production of thermoset)
A thermosetting product was obtained in the same manner as in Comparative Example 12, except that the thermosetting resin composition obtained in Comparative Example 14 was changed to the thermosetting resin composition obtained in Comparative Example 15.

The wet heat adhesiveness Example 2 2-3 4 and Comparative Example thermoset product obtained at 16 to 25 121 ° C., 100% humidity, General Tests JIS K-5400 and those 1 hour under 2 atm It was evaluated by a cross cellophane tape peeling test. The results are shown in Table 1. From Table 1, it can be seen that in Examples 2 2 to 3 4 , the moisture and heat resistant adhesion is greatly improved as compared with Comparative Examples 16 to 25.

Scratch resistance Example 3 2, applying a load of 500 g 3 4 and heat cured products obtained in Comparative Examples 21 to 23 steel wool # 0000, 5 is reciprocated by observing the surface visually following A Table 2 shows the results of the evaluation with ~ C.
A: scratches 0-5 present B: scratches 6-14 present C: from scratch 15 or more Table 2, in Examples 3 2 and 3 4, as compared with Comparative Example 21 to 23, greater scratch resistance It can be seen that it has improved.

The pencil hardness Example 3 2-3 4 and Comparative Example thermoset product obtained in 21-23 was evaluated by a pencil hardness test according to the general test method of JIS K-5400. The results are shown in Table 3. From Table 3, in Example 3 2-3 4, as compared with Comparative Example 21 to 23, it can be seen that pencil altitude is significantly improved.

After water absorption Example 3 0, 3 1 and heat cured products obtained in Comparative Examples 24 and 25 were dried at 50 ° C. for 24 hours, weighed, then immersed in distilled water 100 ml, and allowed to stand at room temperature for 24 hours. The water content of each thermoset was wiped off and lightened to measure the water absorption. The results are shown in Table 4. From Table 4, in Example 3 0, 3 1, compared with Comparative Examples 24 and 25, it can be seen that water absorption is improved.

Claims (9)

Silsesquioxy containing an epoxy group and an alkoxy group, which are hydrolyzed and condensed hydroxyl group-containing epoxy resin (A), epoxy group-containing alkoxysilanes (b1) and metal alkoxides (b2) having no epoxy group It is obtained by subjecting a sun compound (B) to a dealcoholization condensation reaction, having an alkoxy group equivalent of 150 to 3000 g / eq, an epoxy equivalent of 150 to 500 g / eq, [derived from component (A) The number of moles of epoxy group] / [number of moles of epoxy group derived from component (B)] (molar ratio) is 0.1 or more and 3 or less, and the weight ratio of component (A) to component (B) is: Component (B) / Component (A) = 0.2 to 8 , and the component (B) is [Mole number of epoxy group contained in epoxy group-containing alkoxysilane (b1)] / [ The total number of moles of epoxy group-containing alkoxysilanes (b1) and metal alkoxides (b2) not containing epoxy groups] (molar ratio: the average number of epoxy groups contained per silicon atom) is 0.10. The epoxy group-containing silsesquioxane-modified epoxy resin (1), which is at least 0.85 .   The epoxy group-containing silsesquik according to claim 1, wherein the hydroxyl group-containing epoxy resin (A) is at least one selected from the group consisting of a bisphenol A type epoxy resin and a hydrogenated bisphenol A type epoxy resin. Oxan-modified epoxy resin (1).   The silsesquioxane compound (B) containing an epoxy group and an alkoxy group is obtained by hydrolyzing and condensing methyltrimethoxysilane and 3-glycidoxypropyltrimethoxysilane. Or the epoxy group-containing silsesquioxane-modified epoxy resin (1) according to 2; Silsesquioxane compound (B) containing an epoxy group and an alkoxy group is 100 to 1000 g / eq in terms of alkoxy equivalent (alkoxy equivalent: represents the weight (gram) of component (B) including an equivalent of alkoxy group). The epoxy group-containing silsesquioxane-modified epoxy resin (1) according to any one of claims 1 to 3 , wherein A curable resin composition comprising the epoxy group-containing silsesquioxane-modified epoxy resin (1) and the epoxy resin curing agent (2) according to any one of claims 1 to 4 as essential components. The curable resin composition according to claim 5, wherein the epoxy resin curing agent (2) is at least one selected from the group consisting of an acid anhydride and a cation generator. Cured product obtained by curing the curable resin composition according to claim 5 or 6. A coating agent comprising the curable resin composition according to claim 5 or 6 . A coating obtained by applying the coating agent according to claim 8 to a substrate and then curing the coating.