JP5154804B2 - Thermosetting resin composition, the cured product, and various articles derived therefrom - Google Patents

Description

  The present invention relates to a thermosetting resin composition, a cured product obtained by thermosetting the composition, and various articles derived therefrom.

  Plastics are used as optical materials such as lenses because they are lighter and easier to process than glass. However, since plastics generally have a low refractive index, the lens becomes thick, and there are problems such as loss of light weight and low heat resistance. As a solution to such a problem, a plastic material having a high refractive index such as a thiourethane resin containing sulfur (for example, see Patent Document 1) is known, but it can be sufficiently satisfied in terms of heat resistance. It is not a thing.

By the way, as a means of further improving the characteristics of the organic material, by combining the organic material and the inorganic material, the so-called high heat resistance, chemical resistance, high surface hardness, etc., which are the characteristics of the inorganic material, are given. In recent years, organic-inorganic hybrid technology has attracted attention. Among the inorganic materials used in the technology, a compound called silsesquioxane represented by RSiO _3/2 can easily form an organic-inorganic hybrid cured product by giving R a reaction site with an organic material. Since it can be provided, practical application studies are underway (see, for example, Patent Documents 2 to 5). However, these organic-inorganic hybrid cured products are excellent in heat resistance, but generally have a problem of low refractive index.

  In order to solve the above problems, the present inventors have developed an organic-inorganic hybrid obtained by reacting silsesquioxane having a thiol group containing sulfur with an organic substance having a carbon-carbon double bond. A cured product was proposed (see, for example, Patent Document 6). Although this hardened | cured material is excellent in heat resistance, and since it contains sulfur, it has the characteristics that it is high refractive index, patent document 6 is related with the thermosetting composition containing this organic-inorganic hybrid, and this thermosetting material. Is not taught.

JP-A-3-236386 Japanese Patent No. 36553976 Japanese Patent No. 3598749 Japanese Patent Laid-Open No. 10-330485 Special Table 2003-533553 Japanese Patent Application No. 2005-219428

  The present invention provides a thermosetting resin composition for realizing a cured product that is easily cured by heating and that can satisfy various properties such as heat resistance, chemical resistance, high surface hardness, and high refractive index. And a cured product obtained from the composition.

  As a result of intensive studies to solve the above problems, the present inventor has found that a composition comprising a hydrolysis condensate of a thiol group-containing alkoxysilane, a compound having an epoxy group and / or a compound having an isocyanate group, and its heat It discovered that the said subject could be solved with hardened | cured material, and came to complete this invention.

That is, the present invention relates to the general formula (1):
R ¹ Si (OR ² ) ₃ (1)
(In the formula, R ¹ represents a hydrocarbon group having 1 to 8 carbon atoms having at least one thiol group, or an aromatic hydrocarbon group having at least one thiol group, and R ² represents a hydrogen atom, having 1 to 1 carbon atoms. 8 represents a hydrocarbon group or an aromatic hydrocarbon group.) A condensate (A) obtained by hydrolysis and condensation of a thiol group-containing alkoxysilane (a1) (hereinafter referred to as component (A)) And a compound (B) having an epoxy group (hereinafter referred to as component (B)) and / or a compound (C) having an isocyanate group (hereinafter referred to as component (C)). The present invention relates to a functional resin composition. The present invention also relates to a cured product obtained by curing the composition with heat. The present invention further relates to various articles derived therefrom.

  ADVANTAGE OF THE INVENTION According to this invention, the thermosetting resin composition which can provide the hardened | cured material in which various characteristics, such as heat resistance, chemical resistance, high surface hardness, and a high refractive index, were improved can be provided. The cured product of the present invention obtained from the thermosetting resin composition is a coating agent (light guide plate, polarizing plate, liquid crystal panel, EL panel, PDP panel, OHP film, optical fiber, color filter, optical disk substrate, lens, liquid crystal Cell plastic substrates or prisms), adhesives (liquid crystal panels, EL panels, PDP panels, color filters, optical disk substrates, etc.), sealing materials (light emitting elements, light receiving elements, photoelectric conversion elements, or optical transmission) This is useful for applications such as related parts).

Component (A) used in the present invention has the general formula (1):
R ¹ Si (OR ² ) ₃ (1)
(In the formula, R ¹ represents a hydrocarbon group having 1 to 8 carbon atoms having at least one thiol group, or an aromatic hydrocarbon group having at least one thiol group, and R ² represents a hydrogen atom, having 1 to 1 carbon atoms. 8 is a compound obtained by hydrolysis and condensation of a thiol group-containing alkoxysilane (a1) represented by 8). Specific examples of the thiol group-containing alkoxysilanes (a1) (hereinafter referred to as component (a1)) include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltripropoxysilane, 3- Mercaptopropyltributoxysilane, 1,4-dimercapto-2- (trimethoxysilyl) butane, 1,4-dimercapto-2- (triethoxysilyl) butane, 1,4-dimercapto-2- (tripropoxysilyl) butane 1,4-dimercapto-2- (tributoxysilyl) butane, 2-mercaptomethyl-3-mercaptopropyltrimethoxysilane, 2-mercaptomethyl-3-mercaptopropyltriethoxysilane, 2-mercaptomethyl-3-mercapto Propyl tripropoxy Silane, 2-mercaptomethyl-3-mercaptopropyltributoxysilane, 1,2-dimercaptoethyltrimethoxysilane, 1,2-dimercaptoethyltriethoxysilane, 1,2-dimercaptoethyltripropoxysilane, 1, Examples include 2-dimercaptoethyltributoxysilane, and the exemplified compounds can be used alone or in appropriate combination. Among the exemplified compounds, 3-mercaptopropyltrimethoxysilane is particularly preferable because of high reactivity of hydrolysis reaction and easy availability.

  In addition to component (a1), trialkylalkoxysilanes such as trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane, triphenylmethoxysilane, triphenylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxy Dialkyl dialkoxysilanes such as silane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, 3-mercaptopropylmethyldimethoxysilane, methyltrimethoxysilane Methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, Alkyltrialkoxysilanes such as rutriethoxysilane, tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetramethoxytitanium, tetraethoxytitanium, tetrapropoxytitanium, tetrabutoxytitanium, etc. Metal alkoxides (a2) (hereinafter referred to as component (a2)) such as tetraalkoxyzirconiums such as tetraalkoxytitaniums, tetraethoxyzirconium, tetrapropoxyzirconium, and tetrabutoxyzirconium can be used. The component (a2) can be used either alone or in combination of two or more. Of these, the crosslink density of the component (A) can be adjusted by using trialkylalkoxysilanes, dialkyldialkoxysilanes, and tetraalkoxysilanes. By using alkyltrialkoxysilanes, the amount of thiol groups contained in component (A) can be adjusted. By using tetraalkoxytitaniums or tetraalkoxyzirconiums, the refractive index of the finally obtained thermoset can be increased.

  When component (a1) and component (a2) are used in combination, [number of moles of thiol group contained in component (a1)] / [total number of moles of component (a1) and component (a2)] (molar ratio: 1 The average number of thiol groups contained per molecule is preferably 0.2 or more. When it is less than 0.2, the number of thiol groups contained in the component (A) to be obtained is reduced, so that the thermosetting property is lowered and the effect of improving the physical properties such as hardness of the cured product is insufficient. Tend to be. [Total number of moles of each alkoxy group contained in component (a1) and component (a2)] / [Total number of moles of component (a1) and component (a2)] (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. When it is less than 2.5, the crosslinking density of the obtained component (A) is low, and the heat resistance of the cured product tends to decrease. Moreover, when it exceeds 3.5, when manufacturing a component (A), it exists in the tendency which becomes easy to gelatinize.

  Component (A) used in the present invention can be obtained by condensing component (a1) alone or in combination with component (a2), condensing them after hydrolysis. By the hydrolysis reaction, the alkoxy group contained in component (a1) or component (a2) becomes a hydroxyl group, and alcohol is by-produced. The amount of water required for the hydrolysis reaction is [number of moles of water used in hydrolysis reaction] / [total number of moles of each alkoxy group contained in component (a1) and component (a2)] (molar ratio). 4 or more and 10 or less, preferably 1. When it is less than 0.4, there is an alkoxy group remaining without being hydrolyzed in the component (A), which is not preferable. On the other hand, when it exceeds 10, the amount of water to be removed in the subsequent condensation reaction (dehydration reaction) increases, so that the production time becomes longer, which is economically disadvantageous.

  In addition, when the component (a2) is used in combination with a tetraalkoxytitanium, a tetraalkoxyzirconium or the like, particularly a metal alkoxide having a 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 (a2) after the hydrolysis reaction of the component (a1) has been completed and all 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. Of these, formic acid is preferred because it has high catalytic activity and also functions as a catalyst for the subsequent condensation reaction. The amount of formic acid added is preferably 0.1 to 25 parts by weight, and more preferably 1 to 10 parts by weight with respect to 100 parts by weight as the total of component (a1) and component (a2). When the amount is more than 25 parts by weight, the stability of the resulting thermosetting resin composition tends to decrease, and even if formic acid can be removed in a subsequent step, the removal amount tends to increase. On the other hand, when the amount is less than 0.1 parts by weight, the reaction does not substantially proceed or the reaction time tends to be long. Although reaction temperature and time can be arbitrarily set according to the reactivity of a component (a1) or a component (a2), 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 (a1) or component (a2) is low, it is preferable to carry out without solvent.

  The hydrolysis reaction is carried out by the above method, but the [number of moles of hydroxyl group formed by hydrolysis] / [total number of moles of each alkoxy group contained in component (a1) and component (a2)] (molar ratio) is 0. It is preferable to make it progress so that it may become 0.5 or more, and it is still more preferable to adjust to 0.8 or more. The condensation reaction following the hydrolysis reaction proceeds not only between the hydroxyl groups generated by hydrolysis but also between the hydroxyl groups and the remaining alkoxy groups, so that at least half (molar ratio is 0.5 or more) is hydrolyzed. Just do it.

  In the condensation reaction, water is by-produced between the hydroxyl groups, and alcohol is by-produced between the hydroxyl groups and the alkoxy group to vitrify. 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. The reaction temperature and time can be arbitrarily set according to the reactivity of the component (a1) or component (a2), but are usually about 40 to 150 ° C., preferably 60 to 100 ° C., about 30 minutes to 12 hours. .

  Condensation reaction is carried out by the above method. [Total number of moles of unreacted hydroxyl group and unreacted alkoxy group] / [Total number of moles of alkoxy groups contained in component (a1) and component (a2)] (molar ratio ) Is preferably 0.3 or less, and more preferably 0.2 or less. If it exceeds 0.3, the unreacted hydroxyl group and alkoxy group undergo a condensation reaction during storage of the thermosetting resin composition to gel, or the condensation reaction occurs after curing to generate volatile matter and cracks. This is not preferable because it tends to impair the performance of the cured product.

  The condensation reaction is preferably performed by diluting the solvent so that the concentration of component (a1) (or both when component (a2) is used in combination) is about 2 to 80% by weight. It is more preferable. It is preferable to use a solvent having a boiling point higher than that of water and alcohol generated by the condensation reaction because these can be distilled off from the reaction system. When the concentration is less than 2% by weight, the component (A) contained in the resulting thermosetting composition decreases, which is not preferable. When it exceeds 80% by weight, gelation occurs during the reaction, or the molecular weight of the component (A) to be generated becomes too large, and the storage stability of the resulting thermosetting composition tends to be poor. 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. Component (B) can also be used as part of the solvent.

  It is preferable to remove the used catalyst after completion of the condensation reaction because the stability of the finally obtained thermosetting resin composition 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 by a method such as heating to above the boiling point or depressurization after completion of the condensation reaction, and formic acid is also preferred in this respect.

  The component (B) used in the present invention is not particularly limited, and a conventionally known compound having an epoxy group can be appropriately used. For example, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, stilbene type Epoxy resin, triazine skeleton-containing epoxy resin, fluorene skeleton-containing epoxy resin, linear aliphatic epoxy resin, alicyclic epoxy resin, glycidylamine-type epoxy resin, triphenolphenolmethane-type epoxy resin, alkyl-modified triphenolmethane-type epoxy resin Biphenyl type epoxy resin, dicyclopentadiene skeleton-containing epoxy resin, naphthalene skeleton-containing epoxy resin, arylalkylene type epoxy resin, and the like. These compounds can be used alone or in combination of two or more. Among the exemplified compounds, bisphenol A type epoxy resin (Japan Epoxy Resin Co., Ltd .: trade name “Epicoat 828” and the like), bisphenol F type epoxy resin (Japan Epoxy Resin Co., Ltd .: trade name “Epicoat 807” and the like), Hydrogenated bisphenol A type epoxy resin (Toto Kasei Co., Ltd .: trade name “Santoto ST-3000”, etc.) and alicyclic epoxy resin (Daicel Chemical Industries, Ltd .: trade name “Celoxide 2021”, etc.) The cured product obtained is particularly preferable because it is excellent in colorless transparency, heat resistance and the like and is easily available.

  Moreover, as a component (B), a thing with a higher molecular weight than the said compound can be used. Thermosetting resin compositions using high molecular weight products tend to improve the flexibility of the resulting cured product. Examples of the high molecular weight substance include bisphenol A type epoxy resin and bisphenol F type epoxy resin having an epoxy equivalent of 2000 g / eq or more (Japan Epoxy Resin Co., Ltd .: trade names “Epicoat 1010”, “Epicoat 4007P”, etc. ), Epoxy-modified silicone (Shin-Etsu Chemical Co., Ltd .: trade name “X-22-163A”, etc.), polyethylene glycol diglycidyl ether, and the like. These compounds can be used alone or in combination of two or more. Among these, polyethylene glycol diglycidyl ether is preferable.

  Moreover, the component (C) used by this invention is not specifically limited, The compound which has a conventionally well-known isocyanate group can be used suitably. As the diisocyanate compound, various known diisocyanates such as aromatic, aliphatic or alicyclic can be used. More specifically, for example, 1,5-naphthylene diisocyanate, 4,4′- Diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, 4,4′-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, butane -1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate Socyanate, 2,4,4-trimethylhexamethylene diisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, lysine diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 1,3 Examples thereof include bis (isocyanatomethyl) cyclohexane, methylcyclohexane diisocyanate, m-tetramethylxylylene diisocyanate, and dimerisocyanate obtained by converting a carboxyl group of dimer acid into an isocyanate group. These compounds can be used alone or in combination of two or more. Among the exemplified compounds, isophorone diisocyanate is particularly preferable because the finally obtained cured product is excellent in colorless transparency, heat resistance and the like and is easily available.

  Moreover, as a component (C), a thing with a higher molecular weight than the said compound can be used. Thermosetting resin compositions using high molecular weight products tend to improve the flexibility of the resulting cured product. Examples of the high molecular weight material include diisocyanate-modified products of polyols such as polycarbonate diol and polyester diol, polymeric MDI (Mitsui Takeda Chemical Co., Ltd .: trade name “Cosmonate M”, etc.) and the like. These compounds can be used alone or in combination of two or more.

  The catalyst that can be used when preparing the thermosetting resin composition of the present invention is not particularly limited, and a conventionally known epoxy curing catalyst can be used when the component (B) is used. For example, tertiary amines such as 1,8-diaza-bicyclo [5.4.0] undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol; 2 -Imidazoles such as methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole; Organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine; Tetraphenylphosphonium / tetraphenylborate, 2-ethyl-4-methylimidazole / tetraphenylborate, N-methylmorpholine / tetraphenylborate, etc. Such as boron salt can be mentioned. The curing catalyst is preferably used at a ratio of 0.01 to 5 parts by weight with respect to 100 parts by weight of the thermosetting resin composition.

  Moreover, when using a component (C), a conventionally well-known urethanation catalyst can be used. For example, organic tin compounds such as dibutyltin dilaurate and tin octylate, 1,8-diaza-bicyclo [5.4.0] undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethyl) And tertiary amines such as (aminomethyl) phenol. The urethanization catalyst is preferably used at a ratio of 0.01 to 5 parts by weight with respect to 100 parts by weight of the thermosetting resin composition.

  The concentration of the active ingredient (A), (B) or (C) of the thermosetting resin composition can be appropriately determined according to the application, and a solvent can be blended as necessary. The solvent only needs to be non-reactive with the component, and various conventionally known solvents can be appropriately selected and used. When the thermosetting resin composition is used as a coating agent, it may be diluted with a solvent to obtain a desired viscosity. Further, when the thermosetting resin composition is cured to a thick film of 1 mm or more or used as an adhesive, the total concentration of the components (A), (B) or (C) is set to 90% by weight or more. It is preferable that the content be 95% by weight or more. The total concentration may be calculated from the concentration of components (A) and (B) or (C) and the amount of solvent added at the time of charging the thermosetting composition, and is included in the thermosetting composition. It can also be obtained by heating for about 2 hours above the boiling point of the solvent to be obtained 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. In addition, since the solvent is indispensably used during the synthesis of component (A), when used in the application, the solvent should be volatilized after the reaction so that the nonvolatile content is 90% by weight or more. Good. Moreover, after preparing a thermosetting resin composition, the used solvent can be volatilized and the total density | concentration of an active ingredient (A), (B) or (C) can also be raised.

  The ratio of components (A) and (B) or (C) used in the preparation of the thermosetting resin composition of the present invention is [number of moles of thiol groups contained in component (A)] / [component (B). It is preferable that the number of moles of epoxy groups contained in or the number of moles of isocyanate groups contained in component (C)] (molar ratio) is 0.9 to 1.1, more preferably 1.0. It is. When it is less than 0.9, epoxy groups and isocyanate groups remain even after thermosetting, and the weather resistance tends to be lowered. Moreover, when it exceeds 1.1, a thiol group may remain | survive and a malodor may be generated by the decomposition | disassembly.

  When using component (B) or (C), [number of moles of epoxy group contained in component (B) or number of moles of isocyanate group contained in component (C)] / [component (B) or component (C ) (Molar ratio: the average number of epoxy groups or isocyanate groups contained per molecule) is preferably 2 or more. When it is less than 2, the curability of the thermosetting composition is lowered, and the crosslink density of the obtained cured product is lowered, so that the physical properties such as heat resistance and surface hardness of the cured product tend to be lowered.

  The thermosetting resin composition may contain the component (a1) and / or a hydrolyzate thereof (excluding the condensate) [hereinafter also referred to as component (D)] depending on the application. . As the component (D), the component (a1) used in the synthesis of the component (A) can be used as it is, or a hydrolyzate thereof can be used in combination. When the thermosetting resin composition containing the component (D) is used as a coating agent for inorganic substrates such as glass and metal, there is an advantage that the adhesion can be further improved. It is preferable that the compounding quantity of a component (D) is about 0.1-20 weight part with respect to 100 weight part of this composition. When the amount is less than 0.1 part by weight, the effect of improving the adhesion of the thermosetting resin composition to the inorganic substrate tends to be insufficient. On the other hand, when the amount exceeds 20 parts by weight, since the volatile component when the component (D) undergoes hydrolysis and condensation reaction increases, the thermosetting resin composition cannot be cured thickly or the resulting cured product is brittle. Tend to be. As such a component (D), 3-mercaptopropyltrimethoxysilane is particularly preferable in terms of the effect of improving the adhesion.

  In addition, the thermosetting resin composition includes a metal alkoxide as the component (a2) and / or a hydrolyzate thereof (excluding a condensate) (E) [hereinafter also referred to as a component, depending on the application. (E)] can be blended. As the component (E), the metal alkoxides used in the synthesis of the component (A) can be used as they are, their hydrolysates can be used, or these can be used in combination. By using the thermosetting resin composition containing the component (E), the refractive index of the obtained cured product can be adjusted. When the thermosetting resin composition is used as a coating agent having a high refractive index, alkoxytitaniums and alkoxyzirconiums are suitable as the component (E). It is preferable that the compounding quantity of a component (E) is about 0.1-20 weight part with respect to 100 weight part of thermosetting resin compositions. If it is less than 0.1 part by weight, the refractive index improving effect tends to be insufficient. Moreover, when it exceeds 20 weight part, since a volatile matter at the time of a component (E) hydrolyzing and a condensation reaction increases, a thermosetting resin composition will foam at the time of hardening, a curvature and a crack may generate | occur | produce. The resulting cured product tends to be brittle.

  Furthermore, in the thermosetting resin composition, a plasticizer, a weathering agent, an antioxidant, a heat stabilizer, a lubricant, and an antistatic agent are used as long as they do not impair the effects of the present invention. , Whitening agents, colorants, conductive agents, mold release agents, surface treatment agents, viscosity modifiers, fillers, and the like may be blended.

  An example of using the thermosetting composition of the present invention as a cured product is illustrated. The thermosetting composition is poured into a container coated with Teflon (registered trademark), heated to dry the solvent, and cured to obtain a desired hybrid cured product. The curing temperature and heating time are appropriately determined in consideration of the type of component (B) or component (C) used, the type of solvent, the thickness of the cured product, and the like. Usually, it is preferable to set the conditions at about 20 to 150 ° C. for about 1 minute to 24 hours. Moreover, after completion | finish of hardening, about 100 degreeC-300 degreeC, Preferably it is 120 degreeC or more and less than 250 degreeC, It heats for about 1 minute-about 6 hours, and removes a residual solvent completely and also advances hardening reaction. The cured film thus obtained is characterized by excellent heat resistance and chemical resistance due to the effect of silica complexation.

(Application to coating agent)
A coating layer can be obtained by coating a thermosetting resin composition on a desired substrate and thermosetting the composition. As the substrate, various known materials such as inorganic substrates such as glass, iron, aluminum, copper, and ITO, and organic substrates such as PE, PP, PET, PEN, PMMA, PSt, PC, and ABS are appropriately selected. Can be used. When coating on an inorganic base material, when the adhesion is insufficient, it is preferable to use the component (C) in combination as described above. Moreover, when coating to an organic base material, when adhesiveness is insufficient, it is preferable to use a component (D) together as mentioned above. Also, the coating property can be improved to some extent by diluting the thermosetting composition with a solvent. For light guide plate, polarizing plate, liquid crystal panel, EL panel, PDP panel, OHP film, optical fiber, color filter, optical disk substrate, lens, liquid crystal cell by coating and thermosetting the above thermosetting composition A coating layer can be formed on a plastic substrate, a prism, or the like.

  Moreover, when the refractive index of the cured film obtained from a thermosetting composition is higher than a base material, an antireflection effect can be provided. Curing obtained from the thermosetting composition by using the component (a2) together with the component (a1) or using the metal alkoxide as the component (E) as described above in the production of the component (A) The refractive index of the film can be improved. 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 of imparting, it is preferable to add an appropriate amount of the component to the thermosetting composition.

(Application to sealing material)
A molding material sealed with a transparent cured product can be obtained by applying a thick film of the thermosetting resin composition or pouring the thermosetting resin composition into a predetermined mold, followed by thermosetting. Such a material is particularly suitable for use in optical parts such as a light emitting element, a light receiving element, a photoelectric conversion element, and an optical transmission related part.

(Application to transparent substrate)
A transparent substrate can be obtained by impregnating a glass cloth (base material) with a thermosetting resin composition and thermosetting the composition. Various known glass cloths can be appropriately selected and used. As the glass cloth, various kinds of fabrics obtained from various known glass fibers (strands composed of E glass, C glass, T glass, ECR glass, etc., yarn, roving, etc.) can be used. Glass cloth is particularly preferred because it is inexpensive and has excellent availability. The method of impregnating the glass cloth with the thermosetting resin composition is not particularly limited, and various known methods can be employed, and a coating method may be employed. Moreover, in order to make the transparent substrate obtained colorless and transparent, the difference in refractive index between the cured product obtained from the thermosetting composition and the glass cloth is preferably within 0.05, and within 0.01 More preferably, it is more preferable to make the same. Moreover, the impregnation property to a glass cloth can also be improved by diluting a thermosetting composition with a solvent. In addition, the usage-amount of the thermosetting resin composition with respect to a glass cloth can be suitably determined according to the use of the transparent substrate obtained, and is normally 20-500 weight part per 100 weight part of glass cloth. Moreover, the thickness of the transparent substrate obtained can also be suitably determined according to this use, and is normally set to 20 μm to 1 mm. A transparent substrate obtained by impregnating a glass cloth with the thermosetting composition as described above and thermosetting it is excellent in transparency and heat resistance. Therefore, a light guide plate, a polarizing plate, a liquid crystal panel, an EL panel, and a PDP panel. It is suitable for producing a coating layer on a color filter, an optical disk substrate, a plastic substrate for a liquid crystal cell, and the like.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. In each example, parts and% are based on weight unless otherwise specified.

Production Example 1 (Production of condensate (A-1))
In a reactor equipped with a stirrer, a condenser, a water separator, a thermometer, and a nitrogen inlet, 190 parts of 3-mercaptopropyltrimethoxysilane (manufactured by Toray Dow Corning Co., Ltd .: trade name “SH-6062”), 52.3 parts of ion-exchanged water ([number of moles of water used for hydrolysis reaction] / [number of moles of alkoxy groups contained in component (a1)] (molar ratio) = 1.0), 95% formic acid 9.5 The portion was charged and hydrolyzed at room temperature for 30 minutes. During the reaction, the temperature rose by a maximum of 22 ° C. due to exotherm. After the reaction, 287.36 parts of propylene glycol monomethyl ether acetate (manufactured by Nippon Emulsifier Co., Ltd .: trade name “MFG-AC”) was charged and heated. When the temperature was raised to 82 ° C., methanol generated by hydrolysis began to be distilled off. The temperature was raised to 105 ° C. over 30 minutes, and water generated by the condensation reaction was distilled off. The reaction was further carried out at 105 ° C. for 1 hour and 30 minutes, and then the pressure was reduced at 70 ° C. to 150 mmHg, and a part of the remaining methanol, water, formic acid, and propylene glycol monomethyl ether acetate was distilled off to obtain a condensate (A -1) 385.2g was obtained. [Mole number of unreacted hydroxyl group and alkoxy group] / [Mole number of alkoxy group contained in component (a1)] (molar ratio) was 0.15, and the concentration was 32.0%. Moreover, the thiol equivalent of the condensate (A-1) was 398 g / eq.

Production Example 2 (Production of condensate (A-2))
In the same reactor as in Production Example 1, 180 parts of 3-mercaptopropyltrimethoxysilane and 49.55 parts of ion-exchanged water ([number of moles of water used for hydrolysis reaction] / [alkoxy group contained in component (a1)) Number of moles] (molar ratio) = 1.0), and 9.00 parts of 95% formic acid were charged and subjected to a hydrolysis reaction at room temperature for 30 minutes. During the reaction, the temperature rose by a maximum of 22 ° C. due to exotherm. After the reaction, 272.23 parts of toluene was charged and heated. When the temperature was raised to 72 ° C., part of methanol and toluene generated by hydrolysis began to be distilled off. The temperature was raised to 75 ° C. over 20 minutes, and water was distilled off by condensation reaction. After further reacting at 75 ° C. for 1 hour, the pressure was reduced at 70 ° C. to 150 mmHg to distill off the remaining methanol, water and formic acid. Furthermore, it reduced pressure at 70 degreeC-5mmHg, and distilled toluene, and obtained 124.49 parts of condensates (A-2). [Mole number of unreacted hydroxyl group and alkoxy group] / [Mole number of alkoxy group contained in component (a1)] (molar ratio) was 0.16, and the concentration was 93.7%. Moreover, the thiol equivalent of the condensate (A-2) was 136 g / eq.

Production Example 3 (Production of condensate (A-3))
In the same reactor as in Production Example 1, 15.0 parts of 3-mercaptopropyltrimethoxysilane, 5.05 parts of phenyltrimethoxysilane ([number of moles of thiol group contained in component (a1)] / [component (a1 ) And the total number of moles of component (a2)] = 0.75, [total number of moles of each alkoxy group contained in component (a1) and component (a2)] / [total of component (a1) and component (a2) Number of moles] = 3), 5.51 parts of ion-exchanged water ([number of moles of water used for hydrolysis reaction] / [total number of moles of each alkoxy group contained in component (a1) and component (a2)]) Ratio) = 1.0), and 1.00 part of 95% formic acid was charged and hydrolyzed at room temperature for 30 minutes. During the reaction, the temperature rose by a maximum of 20 ° C. due to exotherm. After the reaction, 19.52 parts of toluene was charged and heated. When the temperature was raised to 72 ° C., part of methanol and toluene generated by hydrolysis began to be distilled off. The temperature was raised to 75 ° C. over 20 minutes, and water was distilled off by condensation reaction. After further reacting at 75 ° C. for 1 hour, the pressure was reduced at 70 ° C. to 150 mmHg to distill off the remaining methanol, water and formic acid. Further, the pressure was reduced at 70 ° C. to 5 mmHg, and toluene was distilled off to obtain 13.84 parts of condensate (A-3). [Number of moles of unreacted hydroxyl group and alkoxy group] / [total number of moles of each alkoxy group contained in component (a1) and component (a2)] (molar ratio) is 0.16, and the concentration is 94.0%. there were. Moreover, the thiol equivalent of the condensate (A-3) was 181 g / eq.

Production Example 4 (Production of condensate (A-4))
In the same reactor as in Production Example 1, 18.0 parts of 3-mercaptopropyltrimethoxysilane, 2.24 parts of diphenyldimethoxysilane ([number of moles of thiol group contained in component (a1)] / [component (a1)) And the total number of moles of component (a2)] = 0.91, [total number of moles of each alkoxy group contained in component (a1) and component (a2)] / [total number of moles of component (a1) and component (a2) Number] = 2.9), 5.29 parts of ion-exchanged water ([number of moles of water used for hydrolysis reaction] / [total number of moles of each alkoxy group contained in component (a1) and component (a2)]) (Molar ratio) = 1.0), 0.90 part of 95% formic acid was charged, followed by hydrolysis at room temperature for 30 minutes. During the reaction, the temperature rose by a maximum of 20 ° C. due to exotherm. After the reaction, 20.23 parts of toluene was charged and heated. When the temperature was raised to 72 ° C., part of methanol and toluene generated by hydrolysis began to be distilled off. The temperature was raised to 75 ° C. over 20 minutes, and water was distilled off by condensation reaction. After further reacting at 75 ° C. for 1 hour, the pressure was reduced at 70 ° C. to 150 mmHg to distill off the remaining methanol, water and formic acid. Furthermore, pressure-reduced at 70 degreeC-5mmHg, and 13.84 parts of condensates (A-4) were obtained by distilling toluene off. [Mole number of unreacted hydroxyl group and alkoxy group] / [total mole number of each alkoxy group contained in component (a1) and component (a2)] (molar ratio) is 0.16, and the concentration is 93.6%. there were. Moreover, the thiol equivalent of the condensate (A-4) was 181 g / eq.

Production Example 5 (Production of condensate (A-5))
In the same reaction apparatus as in Production Example 1, 20.0 parts of 3-mercaptopropyltrimethoxysilane and 3.06 parts of ion-exchanged water ([number of moles of water used for hydrolysis reaction] / [component (a1)) Mole number of alkoxy group] (molar ratio) = 0.56), 1.17 parts of 95% formic acid were charged, and the mixture was subjected to a hydrolysis reaction at room temperature for 30 minutes. During the reaction, the temperature rose by a maximum of 20 ° C. due to exotherm. After the reaction, a solution prepared by dissolving 3.30 parts of tetrabutoxyzirconium (manufactured by Matsumoto Kosho Co., Ltd .: trade name “Orgachix ZA-60”) in 11.34 parts of n-butanol was further added at room temperature for 15 minutes. Hydrolysis reaction was performed. In addition, [number of moles of thiol group contained in component (a1)] / [total number of moles of component (a1) and component (a2)] = 0.92, included in [component (a1) and component (a2) The total number of moles of each alkoxy group] / [total number of moles of component (a1) and component (a2)] = 3.1. During the reaction, the temperature rose by a maximum of 5 ° C due to exotherm. 45.36 parts of toluene was charged, heated to 80 ° C., and a condensation reaction was performed for 30 minutes. The pressure was further reduced at 70 ° C. to 150 mmHg for 2 hours, and the remaining methanol, n-butanol, water and formic acid were distilled off to obtain 16.82 parts of the condensate (A-5). [Mole number of unreacted hydroxyl group and alkoxy group] / [Mole number of alkoxy group contained in component (a1)] (molar ratio) was 0.12, and the concentration was 83.4%. Moreover, the thiol equivalent of the condensate (A-5) was 165 g / eq.

Production Example 6 (Production of component (C-1))
In a reactor equipped with a stirrer, a condenser, a thermometer, and a nitrogen inlet, 120 parts of polycarbonate diol (manufactured by Nippon Polyurethane Industry Co., Ltd .: trade name “Nipporan 951”, average molecular weight: 1000), 58.7 parts of isophorone diisocyanate (Mole number of isocyanate group contained in isophorone diisocyanate) / [Mole number of hydroxyl group contained in polycarbonate diol] (molar ratio) = 2.2) and reacted at 90 ° C. for 4 hours, whereby component (C— 1) 203 g of condensate was obtained. The isocyanate equivalent of component (C-1) was 620 g / eq.

Examples 1 to 19 (Production of thermosetting composition)
For 10 parts of the condensate (A-1) obtained in Production Example 1, bisphenol A type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd .: trade name “Epicoat 828”, epoxy equivalent 370 g / eq) as component (B) ) 4.40 parts ([number of moles of thiol group contained in component (A)] / [number of moles of epoxy group contained in component (B)] (molar ratio) = 1.0) and thermosetting Composition (F-1). Further, isophorone diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd .: isocyanate equivalent 111 g / eq, hereinafter referred to as IPDI) 2.79 with respect to 10 parts of the condensate (A-1) obtained in Production Example 1 Parts ([number of moles of thiol group contained in component (A)) / [number of moles of isocyanate group contained in component (C)] (molar ratio) = 1.0), dibutyltin dilaurate (Nitto Kasei Co., Ltd.): 0.013 g of a trade name “Neostan U-100”) was provided to obtain a thermosetting composition (F-2). Similarly, it was set as the thermosetting composition (F-3 to F-19) according to the following table using the condensate (A-1-5) obtained by manufacture example 1-5.

  In the table, Celoxide 2021: Alicyclic epoxy resin (manufactured by Daicel Chemical Industries, Ltd .: trade name “Celoxide 2021”, epoxy equivalent 126 g / eq), SR-8EG: Polyethylene glycol diglycidyl ether (Sakamoto Pharmaceutical Co., Ltd.) Product name: Epoxy equivalent 285 g / eq), MDI: 4,4′-diphenylmethane diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd .: Product name “Millionate MT”, isocyanate equivalent 125 g / eq), HMDI: Hexamethylene diisocyanate ( Shown by Nippon Polyurethane Industry Co., Ltd .: trade name “HDI”, isocyanate equivalent 84.1 g / eq).

Comparative Example 1 (Production of thermosetting composition)
Epicoat 828 16.2 parts was blended with 10 parts of pentaerythritol tetrakis (3-mercaptopropionate) (manufactured by Sakai Chemical Industry Co., Ltd .: trade name “PEMP”) to give a thermosetting composition.

Comparative Example 2 (Production of thermosetting composition)
Isophorone diisocyanate 10.3 parts and dibutyltin dilaurate 0.020 parts were blended with 10 parts of pentaerythritol tetrakis (3-mercaptopropionate) to obtain a thermosetting composition.

Comparative Example 3 (Production of thermosetting composition)
A comparative thermosetting composition was synthesized according to Example 3 of JP-A-2005-290286. Specifically, 8 parts of bisphenol A glycidyl ether (manufactured by Japan Epoxy Resin Co., Ltd., trade name “Epicoat 828”, epoxy equivalent 190 g / eq) was dissolved in 8 g of tetrahydrofuran to obtain a resin solution. Next, 18 parts of phenyltrimethoxysilane, 8 parts of 3-glycidoxypropyltriethoxysilane, 8 parts of a 10% by weight aqueous solution of formic acid, and 49 parts of tetrahydrofuran were refluxed at 60 ° C. for 3 hours with stirring, and a thermosetting agent (Asahi) 1 part of Denka Kogyo Co., Ltd., trade name “ADEKA OPTON CP-66”) and 16 parts of the resin solution were added to obtain a thermosetting composition.

(Curability of the thermosetting composition, surface hardness)
The thermosetting compositions obtained in Examples 1 to 19 and Comparative Examples 1 and 2 were coated on a glass plate so that the film thickness after curing was about 15 μm, followed by solvent drying and curing reaction at 80 ° C. for 2 hours. went. The curability of the obtained cured product is that the peak of thiol near 2600 cm ⁻¹ is greatly reduced or almost disappeared by Raman spectroscopic analysis (JASCO Corporation: trade name “NRS-3100”). Each confirmed. Moreover, the surface hardness of the obtained hardened | cured material was evaluated by the pencil hardness test by the general test method of JISK-5401.

  As is apparent from Table 2, Comparative Example 1 cured using the same component (B) and Comparative Examples cured using Examples 1, 3, 8, 10, 11, 14, 15 and the same component (C). 2 and Examples 2, 6, 9, and 12 are compared, it can be seen that the cured product of the example has higher surface hardness than the cured product of the comparative example. From this, it is recognized that the thermosetting composition of the present invention is more suitable as a hard coat agent.

(Weather resistance of cured film)
The thermosetting compositions obtained in Examples 3, 4, 6 and Comparative Examples 1 and 2 were coated on a glass plate so that the film thickness after curing was about 15 μm, and the solvent was dried and cured at 80 ° C. for 2 hours. Reaction was performed. The obtained cured product was irradiated with ultraviolet rays using an ultraviolet irradiation device (USHIO INC .: trade name “UV-152”) so that the integrated light amount was 20000 mJ / cm ² with a 365 nm ultraviolet detector. The degree of coloring after irradiation was visually evaluated. Moreover, it heated at 200 degreeC for 30 minute (s), and also evaluated the degree of coloring after a heating visually. The evaluation criteria are as follows.
○ ・ ・ ・ No coloration △ ・ ・ ・ Slight coloration (slightly yellow)
× ・ ・ ・ Deep coloring (brown)

  As is clear from Table 3, the cured product of Comparative Example 1 was colored brown, while the cured product of Example 3 was suppressed from being colored. In addition, it can be seen that the cured products of Examples 4 and 6 are hardly colored with respect to both ultraviolet irradiation and heating, and the cured product of the present invention is more excellent in weather resistance.

(Adhesion to inorganic materials)
The thermosetting compositions obtained in Examples 3, 6, 8, and 9 were coated on various inorganic substrates so that the film thickness after curing was about 15 μm, and solvent drying and curing reaction were performed at 80 ° C. for 2 hours. . About the obtained hardened | cured material, it evaluated by the gobang eyes cellophane tape peeling test by the general test method of JISK-5400.

  As is clear from Tables 2 and 4, the cured products of Examples 8 and 9 in which component (D) is arranged have the same curability and surface hardness as the cured products of Examples 3 and 6. It can be seen that the adhesion to the inorganic base material is greatly improved. From this, the thermosetting compositions of Examples 8 and 9 can be applied to a light guide plate, a polarizing plate, a liquid crystal panel, an EL panel, a PDP panel, an optical fiber, a color filter, an optical disk substrate, a lens, a prism and the like made of an inorganic base material. It is recognized that it is suitable as a coating agent.

(Refractive index)
The thermosetting compositions obtained in Examples 3 to 6, 10 to 12, and 15 to 19 were poured into an aluminum cup so that the film thickness after curing was about 300 μm, and solvent drying and curing reaction were performed at 80 ° C. for 2 hours. went. The obtained cured product was further heated with a dryer at 200 ° C. for 30 minutes. About the obtained hardened | cured material, the refractive index was measured using the Abbe refractometer (Shimadzu Corporation make: brand name "Abbe 3L").

  As is clear from Table 5, the cured product of Example 15 in which zirconium was arranged as the component (a2) and the cured product of Example 10 in which titanate was arranged as the component (E) were obtained in Examples 3 to 6, 11, It turns out that the refractive index is improving compared with the cured | curing material of 12 and 16-19. Thus, the thermosetting compositions of Examples 10 and 15 are light guide plates, polarizing plates, liquid crystal panels, EL panels, PDP panels, OHP films, optical fibers, color filters, optical disk substrates, lenses, and plastic substrates for liquid crystal cells. It is recognized that it is suitable as a coating agent for an antireflection film such as a prism.

(Production of transparent substrate)
Commercially available glass cloth (clipper glass cloth micro-B, film thickness 28 μm, so that the composition obtained in Examples 4 and 6 is 100/200 after curing (weight of glass cloth) / (weight of composition), A transparent substrate having a thickness of 80 μm was obtained by impregnating with a refractive index of 1.54) and performing a solvent drying and curing reaction at 80 ° C. for 2 hours. Further, the glass cloth was impregnated with the composition obtained in Comparative Example 3, and after the solvent was volatilized with a dryer at 60 ° C., it was heated at 120 ° C. for 3 hours, and then press molded at 150 ° C. for 1 hour. A transparent substrate having a thickness of 80 μm was obtained. The appearance of the obtained transparent substrate was visually evaluated. The evaluation criteria are as follows.
○ ・ ・ ・ Almost transparent △ ・ ・ ・ Translucent × ・ ・ ・ Opaque

  Further, the flexibility of the transparent substrate was evaluated by the radius of curvature at which cracks occur when the substrate is bent.

  As is clear from Table 6, all of the obtained substrates were almost transparent. The transparent substrate of Comparative Example 3 cracks when the radius of curvature is 5 cm or less, whereas the transparent substrate of Example 6 cracks when the radius of curvature is 1 cm or less, and the transparent substrate of Example 4 exceeds that. No cracks occurred when bent. For this reason, it is recognized that it is more suitable to use as base materials, such as a flexible liquid crystal panel, EL panel, PDP panel, and a color filter.

(Heat-resistant)
The thermosetting compositions obtained in Examples 3 and 12 and Comparative Examples 1 and 2 were poured into an aluminum cup so that the film thickness after curing was about 1 mm, followed by solvent drying and curing reaction at 80 ° C. for 2 hours. . The obtained cured product was further heated with a dryer at 200 ° C. for 30 minutes. The cured product is cut into 5 mm × 25 mm, and dynamically stored using a viscoelasticity measuring instrument (trade name “DMS6100” manufactured by Seiko Instruments Inc., measurement condition: frequency 1 Hz, slope 3 ° C./min). The elastic modulus was measured to evaluate the heat resistance. The measurement results are shown in FIGS. As is apparent from FIGS. 1 and 2, Example 3 has improved Tg compared to Comparative Example 1 and Example 12 has improved Tg compared to Comparative Example 2, and has a small decrease in elastic modulus even at high temperatures, and has heat resistance. It is recognized that Moreover, in the comparative example 1, it fell to the measurement limit (106) or less.

(Linear expansion coefficient)
The thermosetting compositions obtained in Examples 3 and 12 and Comparative Examples 1 and 2 were poured into an aluminum cup so that the film thickness after curing was about 1 mm, followed by solvent drying and curing reaction at 80 ° C. for 2 hours. . The obtained cured product was further heated with a dryer at 200 ° C. for 30 minutes. Using the obtained cured product, the linear expansion coefficient at 120 to 150 ° C. was measured with a thermal stress strain measuring device (Seiko Instruments Inc., trade name TMA120C). The results are shown in Table 7.

  Comparing Comparative Example 1 and Example 3 cured using the same component (B) and Comparative Example 2 and Example 12 cured using the same component (C), compared to the cured product of the comparative example, It can be seen that the cured product has a low linear expansion coefficient. From this, the thermosetting composition of the present invention is suitable as a light guide plate, a polarizing plate, a liquid crystal panel, an EL panel, a PDP panel, a color filter, an optical disk substrate, or a plastic substrate for a liquid crystal cell, for which thermal stability is required. Is recognized.

(Water absorption rate)
The thermosetting compositions obtained in Examples 3 and 12 and Comparative Examples 1 and 2 were poured into an aluminum cup so that the film thickness after curing was about 1 mm, followed by solvent drying and curing reaction at 80 ° C. for 2 hours. . The obtained cured product was further heated with a dryer at 200 ° C. for 30 minutes. From the difference between the measured weight after leaving for 24 hours in a constant temperature bath maintained at 50 ° C. and the measured weight after being immersed in a constant temperature water bath maintained at 23 ° C. for 24 hours using the obtained cured product The water absorption was calculated. The results are shown in Table 8.

  As is apparent from Table 8, Examples 3 and 12 have the same water absorption rate as Comparative Examples 1 and 2.

(chemical resistance)
The thermosetting compositions obtained in Examples 3 and 12 and Comparative Examples 1 and 2 were poured into an aluminum cup so that the film thickness after curing was about 1 mm, followed by solvent drying and curing reaction at 80 ° C. for 2 hours. . The obtained cured product was further heated with a dryer at 200 ° C. for 30 minutes. The obtained cured product was immersed in a solvent (methanol, toluene, THF, DMF) for 3 hours, and the appearance was visually observed. The degree of swelling was calculated from the difference in measured weight before and after immersion (calculation method: (weight after immersion−weight before immersion) / weight before immersion × 100, and 0% when there was no absorption). The results are shown in Table 9.

  As is clear from Table 9, the cured products obtained from the thermosetting compositions of Examples 3 and 12 are superior in solvent resistance compared to the cured products obtained from the thermosetting compositions of Comparative Examples 1 and 2. I understand that.

The correlation of the temperature and the dynamic storage elastic modulus about the hardened | cured material obtained from the composition of Example 3 and Comparative Example 1 is illustrated. The correlation of the temperature and dynamic storage elastic modulus about the hardened | cured material obtained from the composition of Example 12 and Comparative Example 2 is illustrated.

Claims (17)

General formula (1):
R ¹ Si (OR ² ) ₃ (1)
(In the formula, R ¹ represents a hydrocarbon group having 1 to 8 carbon atoms having at least one thiol group, or an aromatic hydrocarbon group having at least one thiol group, and R ² represents a hydrogen atom, having 1 to 1 carbon atoms. And the thiol group-containing alkoxysilanes (a1) or the thiol group-containing alkoxysilanes (a1) and the metal alkoxide (a2). condensed condensate obtained (a), it contains at least one selected from compounds having a b isocyanate group (C) as well,
The amount of water used for hydrolysis is [number of moles of water used for hydrolysis reaction] / [total number of moles of each alkoxy group contained in component (a1) and component (a2)] (molar ratio). 10 or less, [total number of moles of each alkoxy group contained in component (a1) and component (a2)] / [total number of moles of component (a1) and component (a2)] (molar ratio: 1 molecule The thermosetting resin composition is characterized in that the average number of alkoxy groups contained per unit is 2.5 or more and 3.5 or less . Condensate (A) is, alkoxyalkyl after silanes with (a1) was hydrolyzed in the presence of formic acid, according to claim 1 Symbol placement of the thermosetting resin composition is obtained by a condensation reaction in the presence of a solvent object. The thermosetting resin composition according to claim 1 or 2 , wherein the alkoxysilane (a1) is 3-mercaptopropyltrimethoxysilane. The thermosetting resin composition according to any one of claims 1 to 3 , wherein the compound (C) is isophorone diisocyanate. Furthermore, the thermosetting resin composition in any one of Claims 1-4 containing alkoxysilane (a1) and / or its hydrolyzate (however, a condensate is not included) (D). 6. The thermosetting resin composition according to claim 5 , wherein the component (D) is 3-mercaptopropyltrimethoxysilane and / or a hydrolyzate thereof (however, a condensate is not included). Furthermore, metal alkoxy de (a2) and / or a hydrolyzate thereof (however, condensate is free) (E) the thermosetting resin composition according to any one of claims 1 to 6 containing a. Component (E) is alkoxysilane down, Arukokishichita emissions Contact and alkoxy zirconates Niu nothing Ranaru least one kind of claim 7 thermosetting resin composition according selected from the group. The thermosetting composition according to any one of claims 1 to 8 , which has a nonvolatile content of 90% or more. A cured product obtained by thermosetting the thermosetting composition according to any one of claims 1 to 9 . A transparent substrate obtained by impregnating a glass cloth with the thermosetting composition according to any one of claims 1 to 10 , followed by thermosetting. The transparent substrate according to claim 11 for a light guide plate, a polarizing plate, a liquid crystal panel, an EL panel, a PDP panel, a color filter, an optical disk substrate or a plastic substrate for a liquid crystal cell. A coated article comprising a coating layer obtained by thermosetting the thermosetting composition according to any one of claims 1 to 9 on a substrate. The coated article according to claim 13, wherein the coating layer is formed to have a refractive index higher than that of the substrate. The coated article according to claim 14 for a light guide plate, a polarizing plate, a liquid crystal panel, an EL panel, a PDP panel, an OHP film, an optical fiber, a color filter, an optical disk substrate, a lens, a plastic substrate for a liquid crystal cell, or a prism. Using the thermosetting composition according to any one of claims 1 to 9 as a sealing material, sealing articles, characterized in that it is obtained by thermally curing. The sealing article according to claim 16 for a light emitting element, a light receiving element, a photoelectric conversion element, or an optical transmission related part.

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