HK1176080B - Curable resin composition, cured product thereof, various articles derived from those - Google Patents

Abstract

A curable resin composition which is easily cured by heating or ultraviolet irradiation and capable of forming a thick cured film due to low shrinkage. This curable resin composition enables to obtain a cured product satisfying various characteristics such as heat resistance, chemical resistance, high surface hardness and high refractive index. Also disclosed is a cured product obtained from such a composition. Specifically disclosed is a curable resin composition containing at least one substance selected from the group consisting of condensates (A) obtained by hydrolyzing and condensing a thiol group-containing alkoxysilane (a1) represented by the following general formula (1): R1Si(OR2)3 (1) (wherein, R1 represents a hydrocarbon group having at least one thiol group and 1-8 carbon atoms or an aromatic hydrocarbon group having at least one thiol group, and R2 represents a hydrogen atom, a hydrocarbon group having 1-8 carbon atoms or an aromatic hydrocarbon group), compounds (B) having an epoxy group, compounds (C) having an isocyanate group and compounds (D) having a carbon-carbon double bond.

Description

Curable resin composition, cured product thereof, and various articles derived therefrom

The present application is a divisional application based on the following chinese patent applications:

application date of the original case: 2006, 7 months and 19 days

Original application No.: 200680024100.1(PCT/JP2006/314235)

The original application name: curable resin composition, cured product thereof, and various articles derived therefrom

Technical Field

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

Background

Transparent plastics are lighter and more easily processed than glass, and are used as optical materials such as lenses. However, since plastics generally have a low refractive index, the lens becomes thick, and there are problems such as losing the "lightweight" characteristic and low heat resistance.

As a method for increasing the refractive index of plastics, there is a method of introducing sulfur atoms into the structure of plastics. Compounds having a thiol group are thermally curable with epoxies, isocyanates, and thus can incorporate a sulfur atom derived from the thiol group into the plastic structure. The cured product thus obtained has a high refractive index, and particularly, a thiourethane resin obtained by reaction with isocyanates (see, for example, Japanese unexamined patent publication No. Hei 3-236386) is used for lenses and the like. However, the heat resistance is not yet sufficient.

In addition, a compound having a thiol group may be photocured by reacting an ene-thiol (エン - チオ - ル) with a compound having a carbon-carbon double bond. Compared to the radical polymerization systems commonly used in photocuring systems, the mono-ene-thiol reaction has: the polymerization initiator can be irradiated with ultraviolet rays in the presence or absence of the polymerization initiator, and has advantages of no inhibition of reaction by oxygen, small curing shrinkage, and the like. As a curing method and a cured product using such a reaction, there have been proposed: a resin composition comprising an unsaturated thiol compound having a carbon-carbon double bond and a thiol group in one molecule (see, for example, Japanese patent laid-open publication No. 49-51333), a compound having a plurality of carbon-carbon double bonds in one molecule and a compound having a plurality of thiol groups (see, for example, Japanese patent laid-open publications Nos. 49-54491, 50-27836, 53-134096 and 2003-295431), and the like. Thus, a thick cured product can be produced by the mono-ene-thiol reaction, and thus, a thick article such as a lens can be produced. However, the resulting cured product still does not sufficiently satisfy the requirements in terms of heat resistance.

On the other hand, as a method for further improving the characteristics of organic materials, so-called "organic-inorganic hybrid technology" has recently been attracting attentionThat is, the inorganic material is compounded with an organic material to impart the properties of the inorganic material, such as high heat resistance, chemical resistance, and high surface hardness. In this technique, an organic-inorganic hybrid method using silsesquioxane is used as a method which has excellent transparency and can cure a thick film. One kind of silicon dioxide-RSiO_3/2In the silsesquioxane, R has a substituent reactive with an organic material, and thus an organic-inorganic hybrid cured product can be easily provided, and practical use thereof is being studied (for example, see patent 3653976, 3598749, JP-A-10-330485 and JP-A-2003-533553). However, although these organic-inorganic hybrid cured products have excellent heat resistance, the inorganic component is silica having a low refractive index, and therefore, generally, there is a problem that the refractive index is low.

As organic-inorganic hybrid in which a sulfur atom is introduced to increase the refractive index, there are known: a composition comprising a polysiloxane having a carbon-carbon double bond and a polysiloxane having a thiol group (see, for example, JP-A56-110731, JP-A60-110752, JP-A05-320511 and U.S. Pat. No. 2004/209972). However, in the methods described in these patent documents, since the inorganic component used is silicon (colloidal at room temperature), sufficient heat resistance and surface hardness cannot be obtained.

Disclosure of Invention

The purpose of the present invention is to provide a curable resin composition, which comprises: can be easily cured by heating or ultraviolet rays, can be cured into a thick film due to low shrinkage, and can satisfy various properties such as heat resistance, chemical resistance, high surface hardness, and high refractive index.

The present inventors have made intensive studies to solve the above problems and as a result, have found that a composition containing at least one component selected from the group consisting of: the present inventors have found that the above problems can be solved by a composition comprising a hydrolysis-condensation product of a thiol group-containing alkoxysilane, and one member selected from the group consisting of an epoxy group-containing compound (B), an isocyanate group-containing compound (C), and a compound (D) having a carbon-carbon double bond, and a cured product thereof, and have completed the present invention.

That is, the present invention relates to a curable resin composition comprising at least one monomer selected from the group consisting of: a general formula (1):

R¹Si(OR²)₃ (1)

(in the formula, R¹Represents a C1-8 hydrocarbon group containing at least 1 thiol group, or an aromatic hydrocarbon group containing at least 1 thiol group, R²Represents a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms, or an aromatic hydrocarbon group. ) A condensate (A) obtained by hydrolysis and condensation of the thiol group-containing alkoxysilanes (a1), and one member selected from the group consisting of an epoxy group-containing compound (B), an isocyanate group-containing compound (C), and a compound (D) having a carbon-carbon double bond. The present invention also relates to a cured product obtained by heat curing the composition. In addition, the present invention relates to various articles derived therefrom.

Drawings

FIG. 1 shows the correlation between the temperature and the dynamic storage modulus of cured products obtained from the compositions of example 3 and comparative example 1.

FIG. 2 shows the correlation between the temperature and the dynamic storage modulus of cured products obtained from the compositions of example 12 and comparative example 2.

FIG. 3 shows the correlation between the temperature and the dynamic storage modulus of cured products obtained from the compositions of example 24 and comparative example 6.

Detailed Description

The component (A) used in the present invention contains a compound represented by the general formula (1):

R¹Si(OR²)₃ (1)

(in the formula, R¹Represents a C1-8 hydrocarbon group containing at least 1 thiol group, or an aromatic hydrocarbon group containing at least 1 thiol group, R²Represents a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms, or an aromatic hydrocarbon group. ) The alkoxysilane (a1) containing a thiol group is obtained by hydrolysis and condensation. Specific examples of the alkoxysilane group containing a thiol group (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-mercaptopropyltripropoxysilane, 2-mercaptomethyl-3-mercaptopropyltributoxysilane, and mixtures thereof, 1, 2-dimercaptoethyltrimethoxysilane, 1, 2-dimercaptoethyltriethoxysilane, 1, 2-dimercaptoethyltripropoxysilane, 1, 2-dimercaptoethyltributoxysilane and the like, and these exemplified compounds may be used alone or in an appropriate combination. Among these compounds, 3-mercaptopropyltrimethoxysilane is particularly preferable because it is highly reactive in hydrolysis reaction and easily available.

In addition to the component (a1), trialkyloxysilane such as trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane, triphenylmethoxysilane, triphenylethoxysilane, etc.; dialkyldialkoxysilanes such as dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, and 3-mercaptopropylmethyldimethoxysilane; alkyltrialkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane and phenyltriethoxysilane; tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane; tetraalkoxytitanium compounds such as tetramethoxytitanium, tetraethoxytitanium, tetrapropoxytitanium and tetrabutoxytitanium; metal alkoxides (a2) (hereinafter referred to as component (a2)) such as zirconium tetraalkoxides, e.g., zirconium tetraethoxide, zirconium tetrapropoxide, and zirconium tetrabutoxide. The component (a2) may be used singly or in combination of 2 or more. Among them, the crosslinking density of the component (A) can be adjusted by using trialkylsiloxysilane, dialkyldialkoxysilane, or tetraalkoxysilane. The amount of thiol groups contained in the component (a) can be adjusted by using alkyltrialkoxysilanes. The use of titanium tetraalkoxides and zirconium tetraalkoxides can increase the refractive index of the finally obtained cured product.

When the component (a1) and the component (a2) are used in combination, it is preferable that [ the number of moles of thiol groups contained in the component (a1) ]/[ the total number of moles of the component (a1) and the component (a2) ] (molar ratio: representing the average number of thiol groups contained in 1 molecule) is 0.2 or more. If less than 0.2, the number of thiol groups contained in the component (a) to be obtained is small, so that curability is lowered and the effect of improving physicochemical properties such as hardness of a cured product is insufficient. Further, the [ total mole number of alkoxy groups contained in the component (a1) and the component (a2) ]/[ total mole number of the component (a1) and the component (a2) (molar ratio: representing the average number of alkoxy groups contained per 1 molecule) is preferably 2.5 to 3.5, more preferably 2.7 to 3.2. When the content is less than 2.5, the crosslinking density of the component (A) to be obtained is low, and the heat resistance of the cured product is lowered. When the amount exceeds 3.5, gelation tends to occur during production of the component (a).

The component (A) used in the present invention can be obtained by hydrolyzing and condensing the component (a1) alone or the component (a2) in combination. The alkoxy groups contained in the component (a1) and the component (a2) are converted to hydroxyl groups by hydrolysis reaction, and an alcohol is by-produced. The amount of water necessary for the hydrolysis reaction is 0.4 to 10, preferably 1, [ the number of moles of water used for the hydrolysis reaction ]/[ the total number of moles of alkoxy groups contained in the component (a1) and the component (a 2] (molar ratio). If the content is less than 0.4, the component (A) may contain an unhydrolyzed alkoxy group, which is not preferable. When the amount exceeds 10, the amount of water to be removed in the condensation reaction (dehydration reaction) to be carried out later becomes large, and therefore, the method is not economical.

In addition, when titanium tetraalkoxides, zirconium tetraalkoxides, and the like, particularly metal alkoxides having high hydrolyzability and high condensation reactivity, are used as the component (a2), the hydrolysis and condensation reaction may rapidly proceed, and the reaction system may be gelled. At this time, gelation can be avoided by terminating the hydrolysis reaction of the component (a1) and adding the component (a2) after virtually all the water has been consumed.

The catalyst used for the hydrolysis reaction is not particularly limited, and conventionally known hydrolysis catalysts can be used arbitrarily. Among them, formic acid is preferable because it has high catalytic activity and can be used as a catalyst for the condensation reaction. The amount of formic acid added is preferably 0.1 to 25 weight units, more preferably 1 to 10 weight units, per 100 weight units of the total of the component (a1) and the component (a 2). When the amount exceeds 25 parts by weight, the stability of the obtained curable resin composition tends to be lowered, or even if formic acid can be removed in a subsequent step, the amount of removal tends to be large. On the other hand, if the amount is less than 0.1 parts by weight, the reaction tends to be impractical, or the reaction time tends to be long. The reaction temperature and time can be arbitrarily set depending on the reactivity of the component (a1) and the component (a2), but are usually about 0 to 100 ℃ and preferably about 20 to 60 ℃ for 1 minute to 2 hours. The hydrolysis reaction may be carried out in the presence or absence of a solvent. The type of the solvent is not particularly limited, and 1 or more kinds of solvents can be arbitrarily selected, but it is preferable to use the same solvent as used in the condensation reaction described later. When the reactivity of the component (a1) and the component (a2) is low, it is preferable that no solvent is added.

The hydrolysis reaction is carried out by the above-mentioned method, but the molar ratio of [ the number of moles of hydroxyl groups obtained by hydrolysis ]/[ the total number of moles of alkoxy groups contained in the component (a1) and the component (a2) ], is preferably 0.5 or more, more preferably 0.8 or more. In order to carry out the condensation reaction after the hydrolysis reaction, not only the hydroxyl group generated by the hydrolysis but also the hydroxyl group and the remaining alkoxy group may be hydrolyzed to at least half (a molar ratio of 0.5 or more).

In the condensation reaction, water is formed by the formation of the hydroxyl group, or an alcohol is formed by the formation of the hydroxyl group and the alkoxy group, thereby vitrifying the reaction product. In the condensation reaction, conventionally known dehydration condensation catalysts may be optionally used. As described above, formic acid is preferable because it has high catalytic activity and can be used together with a catalyst for hydrolysis reaction. The reaction temperature and time can be arbitrarily set depending on the reactivity of the component (a1) and the component (a2), but are usually about 40 to 150 ℃ and preferably about 60 to 100 ℃ and 30 minutes to 12 hours.

The condensation reaction is carried out by the above-mentioned method, but it is preferable that [ the total mole number of unreacted hydroxyl groups and unreacted alkoxy groups ]/[ the total mole number of alkoxy groups contained in the component (a1) and the component (a 2] (molar ratio) is 0.3 or less, and more preferably 0.2 or less. When the amount exceeds 0.3, the unreacted hydroxyl group and alkoxy group tend to undergo condensation reaction in the curable resin composition to cause gelation, or condensation reaction after curing to cause volatile components, cracks, and the like, thereby impairing the properties of the cured product.

The condensation reaction is preferably carried out by diluting the concentration of the component (a1) (both components in the case of using the component (a2)) with a solvent to about 2 to 80% by weight, more preferably 15 to 60% by weight. It is preferable to use a solvent having a boiling point higher than the boiling points of water and alcohol produced in the condensation reaction because these substances can be distilled off in the reaction system. When the concentration is less than 2% by weight, the amount of the component (A) contained in the obtained curable composition is reduced, which is not preferable. When the amount exceeds 80% by weight, gelation may occur during the reaction, or the molecular weight of the component (a) to be produced becomes too large, so that the storage stability of the curable composition to be obtained tends to be poor. As the solvent, 1 or more kinds of solvents can be arbitrarily selected and used. It is preferable to use a solvent having a boiling point higher than the boiling points of water and alcohol produced in the condensation reaction because these substances can be distilled off in the reaction system. The component (B) may be used as a part of the solvent.

After the completion of the condensation reaction, it is preferable to remove the catalyst used, because the stability of the finally obtained curable resin composition can be improved. The method of removal may be any of various known methods, depending on the catalyst used. For example, when formic acid is used, it can be removed easily by heating to a temperature exceeding the boiling point after completion of the condensation reaction, or by reducing the pressure.

The curable composition of the present invention can be used as a thermosetting resin composition or an ultraviolet-curable resin composition depending on the composition. In the case of a thermosetting resin composition, it is preferable that the thermosetting resin composition contains at least one selected from the group consisting of a condensate (A), an epoxy group-containing compound (B), and an isocyanate group-containing compound (C); in the case of an ultraviolet-curable composition, a composition containing the condensate (A) and the compound (D) having a carbon-carbon double bond is preferable. Further, the following are used in combination: the resin composition contains at least one compound (D) having a carbon-carbon double bond and selected from a compound (B) having an epoxy group and a compound (C) having an isocyanate group, and is curable by both heat and light.

The thermosetting resin composition will be described.

The component (B) used in the present invention is not particularly limited, and conventionally known epoxy group-containing compounds can be suitably used. For example, there are: phenol novolac type epoxy resins, cresol novolac epoxy resins, bisphenol a type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, hydrogenated bisphenol a type epoxy resins, hydrogenated bisphenol F type epoxy resins, 1, 2-diphenylethylene type epoxy resins, triazine skeleton-containing epoxy resins, fluorene skeleton-containing epoxy resins, linear aliphatic epoxy resins, alicyclic epoxy resins, glycidylamine type epoxy resins, triphenylphenolmethane type epoxy resins, alkyl-modified triphenylphenolmethane type epoxy resins, biphenyl type epoxy resins, dicyclopentadiene skeleton-containing epoxy resins, naphthalene skeleton-containing epoxy resins, aralkylene type epoxy resins, and the like. These compounds may be used alone or in combination of 2 or more. Among these exemplified compounds, bisphenol A type epoxy resins (Japanese epoxy resin Co., Ltd.: trade name "エピコ - ト 828" or the like), bisphenol F type epoxy resins (Japanese epoxy resin Co., Ltd.: trade name "エピコ - ト 807" or the like), hydrogenated bisphenol A type epoxy resins (Tokyo chemical Co., Ltd.: trade name "サント - ト ST-3000" or the like), and alicyclic epoxy resins (DAICEL chemical industry Co., Ltd.: trade name "セロキサイド 202" or the like) are particularly preferable because the finally obtained cured products are excellent in colorless transparency, heat resistance and the like, and are easily obtainable.

Further, as the component (B), a higher molecular weight than the above-mentioned compound can be used. The flexibility of a cured product obtained from a thermosetting resin composition containing a high-molecular-weight substance tends to be improved. Examples of the high molecular weight material include: bisphenol A epoxy resins, bisphenol F epoxy resins having an epoxy equivalent of 2000g/eq or more (Japanese epoxy resin Co., Ltd.: trade name "エピコ - ト 1010", "エピコ - ト 4007P", etc.), epoxy-modified silicone resins (shin-Etsu chemical Co., Ltd.: trade name "X-22-163A", etc.), polyethylene glycol diglycidyl ethers, and the like. These compounds may be used alone or in combination of 2 or more. Among them, polyethylene glycol diglycidyl ether is preferable.

The component (C) used in the present invention is not particularly limited, and conventionally known isocyanate group-containing compounds can be suitably used. As the isocyanate compound, for example, various known isocyanates of aromatic, aliphatic or alicyclic type can be used, and more specifically, for example: 1, 5-naphthalene 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, toluene diisocyanate, butane-1, 4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, 2, 4-trimethylhexamethylene diisocyanate, 2, 4, 4-trimethylhexamethylene diisocyanate, cyclohexane-1, 4-diisocyanate, ditolyl diisocyanate, hydrogenated ditolyl diisocyanate, isophorone diisocyanate, 4, 4-dimethylmethane diisocyanate, 4, 4' -dibenzyl diisocyanate, 4, 4-dimethylmethane diisocyanate, tolylene diisocyanate, Lysine diisocyanate, dicyclohexylmethane-4, 4' -diisocyanate, 1, 3-bis (isocyanatomethyl) cyclohexane, methylcyclohexane diisocyanate, m-tetramethylxylylene diisocyanate, or dimer diisocyanate in which the carboxyl group of dimer acid is converted to an isocyanate group. These compounds may be used alone or in combination of 2 or more. Among these exemplified compounds, isophorone diisocyanate is particularly preferable because the cured product obtained as a final product is excellent in colorless transparency, heat resistance, and the like, and is easily available.

Further, as the component (C), a higher molecular weight than the above-mentioned compound can be used. The flexibility of a cured product obtained from a thermosetting resin composition containing a high-molecular-weight substance tends to be improved. Examples of the high molecular weight material include: diisocyanate-modified products of polyols such as polycarbonate diol and polyester diol, and polymeric MDI (Tritsui Kogya chemical Co., Ltd.; trade name: コスモネ - ト oM), etc. These compounds may be used alone or in combination of 2 or more.

The catalyst that can be used in the preparation of the thermosetting resin composition is not particularly limited, and when the component (B) is used, a conventionally known epoxy curing catalyst can be used. For example, there are: tertiary amines such as 1, 8-diaza-bicyclo- [5, 4, 0] -undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol and tris (dimethylaminomethyl) phenol; imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole and 2-heptadecylimidazole; organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, and phenylphosphine; tetraphenyl borates such as tetraphenylphosphonium tetraphenyl borate, 2-ethyl-4-methylimidazolium tetraphenyl borate, and N-methylmorpholine tetraphenyl borate. The curing catalyst is preferably used in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the thermosetting resin composition.

When the component (C) is used, a conventionally known urethanization catalyst can be used. For example, there are: dibutyltin dilaurate, organotin compounds such as tin octylate, tertiary amines such as 1, 8-diaza-bicyclo- [5, 4, 0] -undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol, and the like. The proportion of the urethane-forming catalyst used is preferably 0.01 to 5 parts by weight per 100 parts by weight of the thermosetting resin composition.

The concentration of the active ingredient (a), (B) or (C) in the thermosetting resin composition may be appropriately set according to the application, and a solvent may be added as needed. The solvent may be any solvent that is non-reactive with the component, and various conventionally known solvents can be appropriately selected. When the thermosetting resin composition is used as a coating agent, it may be diluted with a solvent to a desired viscosity. When the thermosetting resin composition is cured to a thick film of 1mm or more or used as a binder, the total concentration of the components (A), (B) and (C) 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 components (a) and (B) or (C) and the amount of the solvent added at the time of charging the thermosetting composition, or may be determined from the weight change before and after heating by heating to exceed the boiling point of the solvent contained in the thermosetting composition for about 2 hours. In the case where the amount is less than 90% by weight in the above-mentioned application, foaming at the time of curing or molding or a solvent remains in a cured product, and the physical properties of the cured product tend to be lowered. In addition, since a solvent is required for the synthesis of the component (a), the solvent may be evaporated after the completion of the reaction until the nonvolatile content exceeds 90% by weight. Furthermore, after the preparation of the thermosetting resin composition, the solvent used can be volatilized to increase the total concentration of the active ingredients (a), (B) or (C).

When preparing the thermosetting resin composition, the components (A) and (B) or (C) are used in such a ratio that [ the number of moles of thiol groups contained in the component (A) ]/[ the number of moles of epoxy groups contained in the component (B) or the number of moles of isocyanate groups contained in the component (C) ] (molar ratio) is preferably 0.9 to 1.1, more preferably 1.0. When the amount is less than 0.9, an epoxy group or an isocyanate group remains after heat curing, and the weather resistance tends to be lowered. When the amount exceeds 1.1, thiol groups remain and decomposition thereof may cause malodor.

When the component (B) or (C) is used, it is preferable that [ the number of moles of epoxy groups contained in the component (B) or the number of moles of isocyanate groups contained in the component (C) ]/[ the number of moles of the component (B) or the component (C) ] (molar ratio: representing the average number of epoxy groups or isocyanate groups contained in 1 molecule) is 2 or more. When the amount is less than 2, curability of the thermosetting composition decreases, and the crosslink density of the obtained cured product decreases, so that physical properties such as heat resistance and surface hardness of the cured product tend to decrease.

The above-mentioned component (a1) and/or a hydrolysate thereof (but not a condensate thereof) (hereinafter collectively referred to as component (E)) may be added to the thermosetting resin composition depending on the application. The component (E) may be used as it is as the component (a1) used in the synthesis of the component (A), or as a hydrolysate thereof, or as a combination thereof. When the thermosetting resin composition containing the component (E) is used as a coating agent for an inorganic substrate such as glass or metal, there is an advantage that the adhesion can be further improved. The amount of the component (E) is preferably about 0.1 to 20 parts by weight per 100 parts by weight of the composition. If the amount is less than 0.1 parts by weight, the adhesion of the thermosetting resin composition to an inorganic substrate tends not to be sufficiently improved. When the amount exceeds 20 parts by weight, the thermosetting resin composition tends to fail to be cured in a thick film form or the resulting cured product tends to be brittle because of an increase in volatile components during hydrolysis and condensation reactions of the component (E). As such component (E), 3-mercaptopropyltrimethoxysilane is particularly preferable in terms of the effect of improving the adhesion.

Further, the metal alkoxides and/or hydrolysates thereof (but not including condensates) (F), which are the component (a2), can be added to the thermosetting resin composition depending on the application (hereinafter collectively referred to as the component (F)). The metal alkoxides used in the synthesis of the component (A) may be used as they are, or a hydrolysate thereof may be used, or a combination thereof may be used as the component (F). The refractive index of the resulting cured product can be adjusted by using the thermosetting resin composition containing the component (F). When the thermosetting resin composition is used as a coating agent having a high refractive index, titanium alkoxides and zirconium alkoxides are suitable as the component (F). The amount of the component (F) is preferably about 0.1 to 20 parts by weight per 100 parts by weight of the thermosetting resin composition. When the amount is less than 0.1 weight unit, the refractive index tends not to be sufficiently increased. When the amount exceeds 20 parts by weight, the amount of volatile matter increases during hydrolysis or condensation of the component (F), and therefore the thermosetting resin composition tends to foam, warp or crack during curing, or the resulting cured product tends to become brittle.

In addition, a plasticizer, a weather resistant agent, an antioxidant, a heat stabilizer, a lubricant, an antistatic agent, a whitening agent, a colorant, a conductive agent, a mold release agent, a surface treatment agent, a viscosity modifier, a filler, and the like may be added to the thermosetting resin composition according to various applications within a range not to impair the effects of the present invention.

For example, a thermosetting composition is used as a cured product. The thermosetting composition was poured into a container coated with teflon (registered trademark), heated, and then solvent-dried and cured to obtain a desired hybrid cured product. The curing temperature and the heating time are appropriately set in consideration of the kind of the component (B) or the component (C) to be used, the kind of the solvent, the thickness of the cured product, and the like. The temperature is usually about 20 to 150 ℃ and about 1 minute to 24 hours. After completion of the curing, the resin composition is heated at about 100 to 300 ℃, preferably 120 ℃ or higher and less than 250 ℃ for 1 minute to 6 hours to completely remove the residual solvent and further progress the curing reaction. The cured film thus obtained has a characteristic of being excellent in heat resistance and chemical resistance due to the effect of compounding silica.

Next, the ultraviolet curable composition will be described.

The component (D) used in the present invention is not particularly limited, and conventionally known compounds having a carbon-carbon double bond can be suitably used. Examples of the functional group related to the carbon-carbon double bond include: vinyl, propenyl, methylpropenyl, allyl, and the like.

The carbon-carbon double bond of the component (D) reacts with the thiol group of the component (A) (ene-thiol reaction), but the reaction mechanism is different depending on the presence or absence of a polymerization initiator.

When no polymerization initiator is used, the reaction proceeds according to the following reaction mechanism [ reaction formula (1) ].

[ solution 1]

(in the formula, R_aRepresents a residue other than a thiol group of the component (A), R_bRepresents a residue other than the carbon-carbon double bond of the component (B). ). Namely, a reaction in which 1 thiol group is added to 1 carbon-carbon double bond.

On the other hand, when a polymerization initiator is used, the reaction proceeds with a side reaction represented by the following chain radical reaction process [ reaction formulae (2) to (5) ] and reaction formula (6) in addition to the addition reaction of the reaction formula (1).

[ solution 2]

(in the formula, I represents a polymerization initiator). Namely, the phases that pass are: reaction formula (2): a step of generating radicals from ultraviolet rays by a polymerization initiator; reaction formula (3): a step of removing hydrogen from a thiol group of the component (A) to form sulfur-containing radicals(s); reaction formula (4): reacting the sulfur-containing radical generated in the component (A) with the carbon-carbon double bond of the component (B) to generate a carbon radical; reaction formula (5): a step in which the carbon radical abstracts hydrogen from the thiol group of the component (A) to regenerate the sulfur-containing radical.

The side reaction is as follows:

[ solution 3]

Reaction formula (6): the carbon radical generated in the reaction formula (4) reacts with the carbon-carbon double bond of the component (D) to regenerate the carbon radical, and the polymerization reaction of the components (D) proceeds simultaneously.

As described above, when the polymerization initiator is not used, the thiol group in the component (A) and the carbon-carbon double bond in the component (D) react at a molar ratio of 1: 1, but when the polymerization initiator is used, the reaction is 1: 1 or more.

From the above-mentioned viewpoints, the use ratio of the components (a) and (D) in the preparation of the ultraviolet-curable resin composition of the present invention is appropriately set depending on the presence or absence of a polymerization initiator. When a polymerization initiator is not used, it is more preferable that [ the number of moles of thiol groups contained in the component (A) ]/[ the number of moles of carbon-carbon double bonds contained in the component (D) ] (molar ratio) is 0.9 to 1.1, and still more preferably 1.0. When the amount is less than 0.9, carbon-carbon double bonds remain even after ultraviolet curing, and the weather resistance tends to be lowered. When the amount exceeds 1.1, thiol groups remain and decomposition thereof may cause malodor.

On the other hand, when a polymerization initiator is used, it is preferable that the molar ratio of [ the number of moles of thiol groups contained in the component (A) ]/[ the number of moles of carbon-carbon double bonds contained in the component (D) ], is 0.01 to 1.1. If the amount is less than 0.01, the amount of the component (a) used is too small, and thus the desired effects of the present invention tend to be difficult to obtain. In addition, carbon-carbon double bonds tend to remain, and the weather resistance of the cured product tends to be lowered. When the amount exceeds 1.1, thiol groups remain and decomposition thereof may cause malodor.

In the component (D), it is preferable that the functional group containing a carbon-carbon double bond is an allyl group so that the disadvantage of mutual polymerization of the functional groups containing a carbon-carbon double bond is not caused preferentially before the functional group containing a carbon-carbon double bond is reacted with a thiol group. As the compound having 1 allyl group, there may be mentioned: cinnamic acid, monoallyl cyanurate, monoallyl isocyanurate, pentaerythritol monoallyl ether, trimethylolpropane monoallyl ether, glycerol monoallyl ether, bisphenol a monoallyl ether, bisphenol F monoallyl ether, ethylene glycol monoallyl ether, diethylene glycol monoallyl ether, triethylene glycol monoallyl ether, propylene glycol monoallyl ether, dipropylene glycol monoallyl ether, tripropylene glycol monoallyl ether, and the like. As compounds containing 2 allyl groups, there may be mentioned: diallyl phthalate, diallyl isophthalate, diallyl cyanurate, diallyl isocyanurate, pentaerythritol diallyl ether, trimethylolpropane diallyl ether, glycerol diallyl ether, bisphenol A diallyl ether, bisphenol F diallyl ether, ethylene glycol diallyl ether, diethylene glycol diallyl ether, triethylene glycol diallyl ether, propylene glycol diallyl ether, dipropylene glycol diallyl ether, tripropylene glycol diallyl ether, and the like. As the compound containing 2 or more allyl groups, there can be mentioned: triallyl isocyanurate, pentaerythritol triallyl ether, pentaerythritol tetraallyl ether, trimethylolpropane triallyl ether and the like. These compounds may be used alone or in combination. Among them, triallyl isocyanurate, diallyl phthalate and pentaerythritol triallyl ether are particularly preferable.

Further, as the component (D), a higher molecular weight than the above-mentioned compound can be used. A cured product obtained from an ultraviolet-curable resin composition containing a high-molecular-weight substance tends to have improved flexibility. Examples of the high molecular weight substance include: a copolymer of methallyl siloxane and dimethyl siloxane, a copolymer of epichlorohydrin and allyl glycidyl ether (DAISO, trade name "エピクロマ one", available from ZEON, Japan, trade name "Gechron", etc.), an allyl-terminated polyisobutylene polymer (KANEKA, trade name "エピオン"), and the like. These compounds may be used alone or in combination of 2 or more.

When the component (D) is used, it is preferable that [ the number of moles of carbon-carbon double bonds contained in the component (D) ]/[ the number of moles of the component (D) ] (molar ratio: representing the average number of carbon-carbon double bonds contained in 1 molecule) is 2 or more. When the amount is less than 2, curability of the ultraviolet-curable resin composition decreases, and the crosslink density of the obtained cured product decreases, so that physical properties such as heat resistance and surface hardness of the cured product tend to decrease.

The polymerization initiator that can be used in the preparation of the ultraviolet-curable resin composition is not particularly limited, and conventionally known cationic photoinitiators, radical photoinitiators, and the like can be arbitrarily selected. Examples of the cationic photoinitiator include sulfonium salts, iodonium salts, metallocene compounds, benzoin tosylate (benzintosylate) and the like which are compounds generating an acid by ultraviolet irradiation, and commercially available products thereof include: CyracareUVI-6970, UVI-6974, UVI-6990 (both trade names available from Union Carbide, USA), Irgacare264 (available from Ciba specialty Chemica), CIT-1682 (available from Nippon Caoda corporation), and the like. The amount of the cationic photopolymerization initiator to be used is usually about 10 weight units or less, preferably 1 to 5 weight units, per 100 weight units of the composition. Examples of the radical photoinitiator include: dalocare1173, Irgacare651, Irgacare184, Irgacare907 (both trade names available from Ciba Specialty Chemicals), benzophenone, and the like, and preferably 1 to 15 weight units based on 100 weight units of the composition. In addition, when the weather resistance of the resulting cured product is likely to be lowered, particularly when the cured product is used for an optical member which is required to have high weather resistance and transparency, it is preferable to use a photoreaction initiator or photosensitizing agent.

In addition, in order to further improve the stability of the ultraviolet curable resin composition, a compound which inhibits the reaction of ene-thiol (エン - チオ - ル) may be added. Examples of such compounds include: phosphorus compounds such as triphenylphosphine and triphenyl phosphite; free radical polymerization inhibitors of p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, t-butylcatechol, cuprous chloride, 2, 6-di-t-butyl-p-cresol, 2 '-methylenebis (4-ethyl-6-t-butylphenol), 2' -methylenebis (4-methyl-6-t-butylphenol), aluminum salt of N-nitrosophenylhydroxylamine, diphenylnitrosamine, and the like; tertiary amines such as benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2, 4, 6-tris (diaminomethyl) phenol, and diazacycloundecene; imidazoles such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-ethylhexyl imidazole, 2-undecylimidazole and 1-cyanoethyl-2-methylimidazole.

Among phosphorus compounds, triphenyl phosphite is preferable because of its high inhibitory effect on ene-thiol (ene-thiol) reaction and its ease of handling at room temperature in a liquid state. The amount of the compound added to the ultraviolet-curable resin composition is: the amount of the composition is preferably about 0.1 to 10 parts by weight per 100 parts by weight of the composition. When the amount is less than 0.1 parts by weight, the effect of suppressing the ene-thiol reaction is insufficient, and when the amount is more than 10 parts by weight, the amount of the residue in the obtained cured product increases, and the physical properties of the cured product tend to be lowered.

Among the radical polymerization inhibitors, a small amount of an aluminum salt of nitrosophenylhydroxylamine is preferable because it has a high effect of inhibiting the ene-thiol reaction and the color tone of the resulting cured product is good. The amount of the compound added to the ultraviolet-curable resin composition is: the amount of the composition is preferably about 0.0001 to 0.1 weight unit per 100 weight units. When the amount is less than 0.0001 weight unit, the effect of inhibiting the ene-thiol reaction is insufficient, and when it exceeds 0.1 weight unit, the ultraviolet curability tends to decrease.

Among tertiary amines, a small amount of benzyldimethylamine is preferable because it has a high effect of inhibiting the ene-thiol reaction and is easy to handle in a liquid state at room temperature. The amount of the compound added to the ultraviolet-curable resin composition is: the amount of the composition is preferably about 0.001 to 5 parts by weight per 100 parts by weight of the composition. When the amount is less than 0.001 parts by weight, the effect of inhibiting the ene-thiol reaction is insufficient, and when the amount is more than 5 parts by weight, the unreacted hydroxyl group and alkoxy group in the component (a) tend to undergo a condensation reaction to form a gel, which is not preferable.

The concentrations of the active ingredients (a) and (D) in the ultraviolet-curable resin composition may be appropriately set according to the application, and a solvent may be added as needed. As the solvent, various conventionally known substances can be arbitrarily used. When the ultraviolet curable resin composition is used as a coating agent, it may be diluted with a solvent to a desired viscosity. When the ultraviolet-curable resin composition is cured to a thick film of 1mm or more, or used as a binder, the total concentration of the components (a) and (D) is preferably 90% by weight or more, more preferably 95% by weight or more. The total concentration may be calculated from the concentrations of the components (a) and (D) and the amount of the solvent added at the time of charging the ultraviolet-curable composition, or may be determined from the change in weight before and after heating by heating to exceed the boiling point of the solvent contained in the ultraviolet-curable composition for about 2 hours. In the case where the amount is less than 90% by weight in the above application, foaming at the time of curing or molding or solvent remains in the cured product, and the physicochemical properties of the cured product tend to be lowered. In addition, since a solvent is required for the synthesis of the component (a), the solvent may be evaporated to a nonvolatile content of more than 90% by weight after the completion of the reaction. After the preparation of the ultraviolet-curable resin composition, the solvent used can be volatilized, and the total concentration of the active ingredients (a) and (D) can be increased.

The essential components of the ultraviolet-curable resin composition are those composed of the component (a) and the component (D) obtained as described above, but as another embodiment of the present invention, there may be mentioned: the component (a1) and the optional component (a2) are obtained by hydrolyzing in the presence of formic acid and then condensing the resultant product in the presence of a solvent and the component (D). The conditions such as the reaction temperature, the reaction time, and the kind of solvent are the same as those in the case of the component (A) described above.

The component (E) may be added to the ultraviolet-curable resin composition according to the use. The component (E) may be used as it is as the component (a1) used in the synthesis of the component (A), or as a hydrolysate thereof, or as a combination thereof. When the ultraviolet-curable resin composition containing the component (E) is used as a coating agent for an inorganic substrate such as glass or metal, the adhesive force can be further improved. The amount of the component (E) is preferably about 0.1 to 20 parts by weight per 100 parts by weight of the composition. When the amount is less than 0.1 parts by weight, the adhesive force of the ultraviolet-curable resin composition to an inorganic substrate tends to be insufficiently improved. When the amount exceeds 20 parts by weight, the ultraviolet-curable resin composition tends to fail to be cured in a thick film form or the obtained cured product tends to be brittle because the amount of volatile components increases during the hydrolysis and condensation reaction of the component (E). As such component (E), 3-mercaptopropyltrimethoxysilane is particularly preferable in terms of the effect of improving the adhesion.

The component (B) may be added to the ultraviolet-curable resin composition according to the use. As the component (B), conventionally known compounds having an epoxy group can be used. When the ultraviolet-curable resin composition containing the component (B) is used as a coating agent for an organic substrate such as a plastic, the adhesive force can be further improved. The component (B) reacts with the thiol group of the component (a) and enters the cured product through a chemical bond, and there is an advantage that deterioration of physicochemical properties such as heat resistance of the cured product is suppressed. In the case of a compound containing 1 or more epoxy groups, the crosslinking density with the component (a) is increased, and the decrease in physicochemical properties is minimized, which is preferable. The amount of the component (B) to be added is preferably about 0.1 to 20 weight units per 100 weight units of the ultraviolet-curable resin composition, and the molar ratio of [ the number of moles of thiol groups contained in the component (a) ]/[ the total number of moles of carbon-carbon double bonds contained in the component (D) and the number of moles of epoxy groups contained in the component (B) ] (molar ratio) is preferably about 0.9 to 1.1, more preferably 1.0. When the amount is less than 0.1 weight unit, the adhesion to the organic base material tends not to be sufficiently improved. When the amount exceeds 20 parts by weight, the storage stability of the ultraviolet-curable resin composition tends to be lowered, or the ultraviolet curability tends to be lowered. The bisphenol A epoxy resin in the component (B) is particularly preferable because it contains 2 epoxy groups and is easily available.

The component (F) may be added to the ultraviolet-curable resin composition according to the use. The metal alkoxides used in the synthesis of the component (A) may be used as they are, or a hydrolysate thereof may be used, or a combination thereof may be used as the component (F). The refractive index of the obtained cured product can be adjusted by using the ultraviolet-curable resin composition containing the component (F). When the ultraviolet curable resin composition is used as a coating agent having a high refractive index, titanium alkoxides and zirconium alkoxides are suitable as the component (F). The amount of the component (F) added is preferably about 0.1 to 20 parts by weight per 100 parts by weight of the ultraviolet-curable resin composition. When the amount is less than 0.1 weight unit, the refractive index tends not to be sufficiently increased. When the amount exceeds 20 parts by weight, the ultraviolet-curable resin composition tends to form bubbles, warp, or cracks during curing, or the obtained cured product tends to become brittle, because the amount of volatile components increases during hydrolysis or condensation reaction of the component (F).

In addition, the ultraviolet-curable resin composition may contain, in accordance with various applications, plasticizers, weather-resistant agents, antioxidants, heat stabilizers, lubricants, antistatic agents, whitening agents, colorants, conductive agents, mold release agents, surface treatment agents, viscosity modifiers, fillers, and the like, as long as the effects of the present invention are not impaired.

In order to produce a desired cured product using the thus obtained ultraviolet-curable resin composition, the composition may be applied to a predetermined substrate or filled into a predetermined mold, and the solvent may be volatilized when the solvent is contained and then irradiated with ultraviolet rays. The solvent is volatilized by a method appropriately set depending on the kind, amount, film thickness and the like of the solvent, but the conditions are such that the solvent is heated to about 40 to 150 ℃, preferably 60 to 100 ℃, and the solvent is heated under normal pressure or reduced pressure for about 5 seconds to 2 hours. The dose of ultraviolet ray irradiation may be appropriately set according to the kind, film thickness, etc. of the ultraviolet ray-curable resin composition, but the cumulative luminous flux of irradiation is 50 to 10000mJ/cm²The method is suitable for the left and the right. In addition, when the coating or filling is carried out as a thick film, it is preferable to add a photoreaction initiator or a photosensitizer to the composition as described above to improve the photocurability.

Further, the physical properties of the cured product can be further improved by further heating the cured product obtained after the ultraviolet irradiation. The heating method may be appropriately set, but the conditions are such that the heating is about 40 to 300 ℃, preferably about 100 ℃ to 250 ℃, for about 1 minute to 6 hours.

(for application of coating agent)

The curable resin composition is applied to a desired substrate, and the resultant is cured by heat or ultraviolet light to obtain a coating layer. As the substrate, various known ones can be appropriately selected and used: inorganic substrates such as glass, iron, aluminum, copper, and ITO; and organic substrates such as PE, PP, PET, PEN, PMMA, PSt, PC, and ABS. When the adhesive force is insufficient when the composition is applied to an inorganic substrate, it is preferable to use the component (C) in combination as described above. When the adhesive force is insufficient when the composition is applied to an organic substrate, it is preferable to use the component (D) in combination as described above. Further, the coating property can be improved to some extent by diluting the curable composition with a solvent. The thermosetting composition can be applied to 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, a prism, or the like by heat curing or ultraviolet curing.

When the refractive index of the cured film obtained from the curable resin composition is higher than that of the substrate, an antireflection effect can be imparted thereto. When the component (a) is produced, the refractive index of the cured film obtained from the curable resin composition can be increased by using the component (a2) in combination with the component (a1) or by using the metal alkoxide as the component (E) as described above. Therefore, when it is desired to impart an antireflection effect to a coating layer applied to 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, it is preferable to add an appropriate amount of the above component to the curable composition.

(for adhesive)

The objective adhesive layer can be obtained by adding a curable resin composition between predetermined substrates and thermally curing or ultraviolet-curing the composition. As the substrate, the same one as that used in the formation of the coating layer described above can be used. However, in order to thermally cure or ultraviolet-cure the adhesive layer, at least one surface must be thermally and ultraviolet-transmissive. In order to prevent the adhesive layer from foaming, it is preferable to set the volatile content in the curable resin composition to 10% or less, preferably 5% or less, as described above, or to remove the volatile content before the application. The adhesive layer can be bonded with the curable resin composition to obtain a transparent adhesive, and thus is suitable for producing liquid crystal panels, EL panels, PDP panels, color filters, optical disk substrates, and the like.

(for sealing materials)

The sealing molding material can be obtained by applying a curable resin composition to a thick film, or by pouring the composition into a predetermined mold and then thermally curing or ultraviolet-curing the composition. The material is particularly suitable for optical components such as light-emitting devices, photodetecting devices, photoelectric conversion devices, and light transmission-related components. When the molded cured product is produced, as described above, it is preferable to add an appropriate amount of a photo-curing catalyst or a photo-sensitizer to the composition or to make the volatile content in the composition less than 10%, preferably less than 5%.

(for transparent substrate)

The curable resin composition is impregnated into a glass cloth (base material) and cured by heat or ultraviolet rays to obtain a transparent substrate. As the glass cloth, various known materials can be appropriately selected and used. As the glass cloth, various kinds of cloth obtained from various known glass fibers (strands, yarns, roving, etc. composed of E-glass, C-glass, ECR-glass, etc.) can be used, but glass cloth made of E-glass is particularly preferable because it is inexpensive and easy to obtain. The method for impregnating the curable resin composition into the glass cloth is not particularly limited, and various known methods may be employed, or a coating method may be employed. In order to make the obtained transparent substrate colorless and transparent, the difference in refractive index between the cured product obtained from the curable resin composition and the glass cloth is preferably 0.05 or less, more preferably 0.01 or less, and the same is more preferable. In addition, the impregnation property into the glass cloth can be further improved by diluting the curable resin composition with a solvent. The applicable ratio of the thermosetting resin composition to the glass cloth can be appropriately set according to the application of the obtained transparent substrate, and is usually 20 to 500 weight units per 100 weight units of the glass cloth. The thickness of the transparent substrate obtained may be set appropriately according to the application, and is usually 20 μm to 1 mm. Transparent substrates obtained by impregnating the thermosetting composition into glass cloth and thermally curing the composition are excellent in transparency and heat resistance, and therefore, are suitable for producing coatings on light guide plates, polarizing plates, liquid crystal panels, EL panels, PDP panels, color filters, optical disk substrates, plastic substrates for liquid crystal cells, and the like.

Examples

The present invention will be specifically described below with reference to examples and comparative examples. In each example, "weight unit" and% are based on weight unless otherwise specified.

Production example 1 (production of condensate (A-1))

190 parts by weight of 3-mercaptopropyltrimethoxysilane (trade name: SH-6062, manufactured by Toray Dow Corning Co., Ltd.), 52.3 parts by weight of deionized water ([ mole of water used for hydrolysis ]/[ mole of alkoxy group contained in the component (a 1] (molar ratio): 1.0)) and 9.5 parts by weight of 95% formic acid were charged into a reaction apparatus equipped with a stirrer, a cooling tube, a water separator, a thermometer, and a nitrogen gas inlet, and the hydrolysis was carried out at room temperature for 30 minutes. During the reaction, the temperature was raised to 22 ℃ at the maximum with heat generation. After the reaction, 287.36 parts by weight of propylene glycol monomethyl ether acetate (product name: MFG-AC, manufactured by Nippon emulsifier Co., Ltd.) was added and heated. When the temperature was raised to 82 ℃, methanol produced accompanying the hydrolysis began to be distilled off. The temperature was raised to 105 ℃ over 30 minutes and the water produced by the condensation reaction was distilled off. After further reaction at 105 ℃ for 1 hour and 30 minutes, the residual methanol, water, formic acid and a part of propylene glycol monomethyl ether acetate were distilled off under reduced pressure of 70 to 150mmHg to obtain 385.2g of the condensate (A-1). [ the number of moles of unreacted hydroxyl groups and alkoxy groups ]/[ the number of moles of alkoxy groups contained in the component (a 1] (molar ratio) was 0.15, and the concentration was 32.0%. The condensate (A-1) had a mercaptan equivalent of 398 g/eq.

Production example 2 (production of condensate (A-2))

In a reaction apparatus similar to that of production example 1, 180 parts by weight of 3-mercaptopropyltrimethoxysilane and 49.55 parts by weight of deionized water ([ number of moles of water used for hydrolysis ]/[ number of moles of alkoxy groups contained in the component (a 1] (molar ratio): 1.0) and 9.00 parts by weight of 95% formic acid were charged, and the mixture was subjected to hydrolysis reaction at room temperature for 30 minutes. During the reaction, the temperature was raised to 22 ℃ at the maximum with heat generation. After the reaction, 272.23 parts by weight of toluene were added and heated. When the temperature was raised to 72 ℃, a part of methanol and toluene generated accompanying the hydrolysis began to be distilled off. The temperature was raised to 75 ℃ over 20 minutes and the water produced by the condensation reaction was distilled off. Further, the reaction was carried out for 1 hour at 75 ℃ under reduced pressure of 70 to 150mmHg to distill off residual methanol, water and formic acid, and further under reduced pressure of 70 to 150mmHg to distill off toluene, whereby 124.49 parts by weight of a condensate (A-2) was obtained. [ the number of moles of unreacted hydroxyl groups and alkoxy groups ]/[ the number of moles of alkoxy groups contained in the component (a 1] (molar ratio) was 0.16, and the concentration was 93.7%. The mercaptan equivalent of the condensate (A-2) was 136 g/eq.

Production example 3 (production of condensate (A-3))

In a reaction apparatus similar to that of production example 1, 15.0 weight units of 3-mercaptopropyltrimethoxysilane, 5.05 weight units of phenyltrimethoxysilane ([ the number of moles of thiol groups contained in the component (a1) ]/[ the total number of moles of the component (a1) and the component (a2) ] -0.75, [ the total number of moles of alkoxy groups contained in the component (a1) and the component (a2) ]/[ the total number of moles of alkoxy groups contained in the component (a1) and the component (a2) ] -3), 5.51 weight units of deionized water ([ the number of moles of water used for hydrolysis ]/[ the total number of moles of alkoxy groups contained in the component (a1) and the component (a2) ], and 1.00 weight units of 95% formic acid were charged, and the hydrolysis reaction was carried out at room temperature for 30 minutes. During the reaction, the temperature increased to 20 ℃ at the maximum with heat generation. After the reaction, 19.52 parts by weight of toluene was added and heated. When the temperature was raised to 72 ℃, a part of methanol and toluene generated accompanying the hydrolysis began to be distilled off. The temperature was raised to 75 ℃ over 20 minutes and the water produced by the condensation reaction was distilled off. Further, the reaction was carried out for 1 hour at 75 ℃ under reduced pressure of 70 to 150mmHg to distill off residual methanol, water and formic acid, and further under reduced pressure of 70 to 150mmHg to distill off toluene, whereby a condensate (A-3) having 13.84 weight units was obtained. [ the number of moles of unreacted hydroxyl groups and alkoxy groups ]/[ the total number of moles of alkoxy groups contained in component (a1) and component (a2) ] (molar ratio) was 0.16, and the concentration was 94.0%. The condensate (A-3) had a mercaptan equivalent of 181 g/eq.

Production example 4 (production of condensate (A-4))

In the same reaction apparatus as in production example 1, 18.0 weight units of 3-mercaptopropyltrimethoxysilane, 2.24 weight units of diphenyldimethoxysilane ([ the number of moles of thiol groups contained in the component (a1) ]/[ the total number of moles of the component (a1) and the component (a2) ] -0.91, [ the total number of moles of alkoxy groups contained in the component (a1) and the component (a2) ]/[ the total number of moles of alkoxy groups contained in the component (a1) and the component (a2) ] -2.9), 5.29 weight units of deionized water ([ the number of moles of water used for hydrolysis ]/[ the total number of moles of alkoxy groups contained in the component (a1) and the component (a2) ], and 0.90 weight units of 95% formic acid were charged and hydrolyzed at room temperature for 30 minutes. During the reaction, the temperature increased to 20 ℃ at the maximum with heat generation. After the reaction, 20.23 parts by weight of toluene was added and heated. When the temperature was raised to 72 ℃, a part of methanol and toluene generated accompanying the hydrolysis began to be distilled off. The temperature was raised to 75 ℃ over 20 minutes and the water produced by the condensation reaction was distilled off. Further, the reaction was carried out for 1 hour at 75 ℃ under reduced pressure of 70 to 150mmHg to distill off residual methanol, water and formic acid, and further under reduced pressure of 70 to 150mmHg to distill off toluene, whereby a condensate (A-4) having 13.84 weight units was obtained. [ the number of moles of unreacted hydroxyl groups and alkoxy groups ]/[ the total number of moles of alkoxy groups contained in the component (a1) and the component (a2) ] (molar ratio) was 0.16, and the concentration was 93.60%. The condensate (A-4) had a mercaptan equivalent of 181 g/eq.

Production example 5 (production of condensate (A-5))

In the same reaction apparatus as in production example 1, 20.0 parts by weight of 3-mercaptopropyltrimethoxysilane, 3.06 parts by weight of deionized water ([ the number of moles of water used for the hydrolysis ]/[ the total number of moles of alkoxy groups contained in the component (a1) ] (molar ratio): 0.56) and 1.17 parts by weight of 95% formic acid were charged and subjected to hydrolysis reaction at room temperature for 30 minutes. During the reaction, the temperature increased to 20 ℃ at the maximum with heat generation. After the reaction, 3.30 parts by weight of zirconium tetrabutoxide (product of Songbuck Co., Ltd.; trade name: オルガチツクス ZA-60) dissolved in 11.34 parts by weight of n-butanol was added, and hydrolysis reaction was further carried out at room temperature for 15 minutes. [ the number of moles of thiol groups contained in the component (a1) ]/[ the total number of moles of the component (a1) and the component (a2) ] -0.92, and [ the total number of moles of alkoxy groups contained in the component (a1) and the component (a2) ]/[ the total number of moles of the component (a1) and the component (a2) ] -3.1. In the reaction, the temperature rise due to heat generation was 5 ℃ at the maximum. 45.36 parts by weight of toluene was added, and the mixture was heated to 80 ℃ to conduct condensation reaction for 30 minutes. Further, the reaction mixture was distilled off under reduced pressure of 70 to 150mmHg for 2 hours to remove the remaining methanol, n-butanol, water and formic acid, thereby obtaining a condensate (A-5) having a weight of 16.82 units. [ the number of moles of unreacted hydroxyl groups and alkoxy groups ]/[ the number of moles of alkoxy groups contained in the component (a 1] (molar ratio) was 0.12, and the concentration was 83.4%. The condensate (A-5) had a mercaptan equivalent of 165 g/eq.

Production example 6 (production of component (C-1))

120 parts by weight of a polycarbonate diol (manufactured by Nippon polyurethane industries, Ltd.: trade name: ニツポラン 951; average molecular weight: 1000) and 58.7 parts by weight of isophorone diisocyanate (the number of moles of an isocyanate group contained in isophorone diisocyanate)/[ the number of moles of a hydroxyl group contained in a polycarbonate diol ] (molar ratio): 2.2) were charged into a reaction apparatus equipped with a stirrer, a cooling tube, a thermometer and a nitrogen gas blowing port, and reacted at 90 ℃ for 4 hours to obtain 203g of a condensate of the component (C-1). The isocyanate equivalent weight of the component (C-1) was 620 g/eq.

Production example 7 (production of condensate (A-6))

In a reaction apparatus similar to that of production example 1, 190 parts by weight of 3-mercaptopropyltrimethoxysilane, 52.3 parts by weight of deionized water ([ the number of moles of water used for the hydrolysis ]/[ the number of moles of alkoxy groups contained in the component (a1) ] (molar ratio) ═ 1.0) and 9.5 parts by weight of 95% formic acid were charged, and the mixture was subjected to hydrolysis reaction at room temperature for 30 minutes. During the reaction, the temperature was raised to 22 ℃ at the maximum with heat generation. After the reaction, 287.36 parts by weight of toluene were added and heated. When the temperature was raised to 72 ℃, a part of methanol and toluene generated accompanying the hydrolysis began to be distilled off. The temperature was raised to 75 ℃ over 20 minutes and the water produced by the condensation reaction was distilled off. Further, the reaction was carried out at 75 ℃ for 1 hour, and the reaction was carried out under reduced pressure of 70 to 150mmHg to distill off the remaining methanol, water and formic acid, which was then diluted with 200.99 parts by weight of methanol to obtain 525.11 parts by weight of a condensate (A-6). [ the number of moles of unreacted hydroxyl groups and alkoxy groups ]/[ the number of moles of alkoxy groups contained in the component (a 1] (molar ratio) was 0.14, and the concentration was 23.5%. The condensate (A-6) had a mercaptan equivalent of 398 g/eq.

Production example 8 (production of condensate (A-7))

190 parts by weight of 3-mercaptopropyltrimethoxysilane, 52.30 parts by weight of deionized water ([ mole of water used for hydrolysis ]/[ mole of alkoxy groups contained in the component (a 1] (molar ratio): 1.0), and 9.50 parts by weight of 95% formic acid were charged into the same reaction apparatus as in production example 1, and subjected to hydrolysis reaction at room temperature for 30 minutes. During the reaction, the temperature was raised to 22 ℃ at the maximum with heat generation. After the reaction, 287.36 parts by weight of diglyme was added and heated. When the temperature was raised to 75 ℃, methanol produced accompanying the hydrolysis began to be distilled off. Further, the reaction was carried out at 75 ℃ for 30 minutes under reduced pressure of 70 to 150mmHg, and the remaining methanol, water and formic acid were distilled off to obtain 389.44 parts by weight of a condensate (A-7). [ the number of moles of unreacted hydroxyl groups and alkoxy groups ]/[ the number of moles of alkoxy groups contained in the component (a 1] (molar ratio) was 0.14, and the concentration was 31.6%. The mercaptan equivalent of the condensate (A-7) was 402 g/eq.

Production example 9 (production of condensate (A-8))

In a reaction apparatus similar to that of production example 1, 15.0 weight units of 3-mercaptopropyltrimethoxysilane, 5.05 weight units of phenyltrimethoxysilane (manufactured by tokyo chemical industries, ltd.) ([ the number of moles of thiol groups contained in the component (a1) ]/[ the total number of moles of the component (a1) and the component (a2) ] -0.75, [ the total number of moles of alkoxy groups contained in the component (a1) and the component (a2) ]/[ the total number of moles of alkoxy groups contained in the component (a1) and the component (a2) ] -3), 5.51 weight units of deionized water ([ the number of moles of water used for hydrolysis ]/[ the total number of alkoxy groups contained in the component (a1) and the component (a2) ] (molar ratio): 1.0), and 1.00 weight units of 95% formic acid were added, and subjected to hydrolysis reaction at room temperature for 30 minutes. During the reaction, the temperature increased to 20 ℃ at the maximum with heat generation. After the reaction, 19.52 parts by weight of propylene glycol monomethyl ether acetate was added and heated. When the temperature was raised to 82 ℃, methanol produced accompanying the hydrolysis began to be distilled off. The temperature was raised to 105 ℃ over 30 minutes and the water produced by the condensation reaction was distilled off. Further, the reaction was carried out at 105 ℃ for 1 hour and 30 minutes, and the residual methanol, water and formic acid were distilled off under reduced pressure of 70 to 150mmHg to obtain a condensate (A-8) having 25.13 parts by weight. [ the number of moles of unreacted hydroxyl groups and alkoxy groups ]/[ the total number of moles of alkoxy groups contained in component (a1) and component (a2) ] (molar ratio) was 0.12, and the concentration was 51.8%. The mercaptan equivalent of the condensate (A-8) was 329 g/eq.

Production example 10 (production of condensate (A-9))

In a reaction apparatus similar to that of production example 1, 18.0 weight units of 3-mercaptopropyltrimethoxysilane and 2.24 weight units of diphenyldimethoxysilane (manufactured by tokyo chemical industries, ltd.) ([ the number of moles of thiol groups contained in the component (a1) ]/[ the total number of moles of the component (a1) and the component (a2) ] -0.91, [ the total number of moles of alkoxy groups contained in the component (a1) and the component (a2) ]/[ the total number of moles of alkoxy groups contained in the component (a1) and the component (a2) ] -2.9), 5.29 weight units of deionized water ([ the number of moles of water used for hydrolysis ]/[ the total number of alkoxy groups contained in the component (a1) and the component (a2) ] (molar ratio): 1.0), 0.90 weight units of 95% formic acid were added and subjected to hydrolysis reaction at room temperature for 30 minutes. During the reaction, the temperature increased to 20 ℃ at the maximum with heat generation. After the reaction, 20.23 parts by weight of propylene glycol monomethyl ether acetate was added and heated. When the temperature was raised to 82 ℃, methanol produced accompanying the hydrolysis began to be distilled off. The temperature was raised to 105 ℃ over 30 minutes and the water produced by the condensation reaction was distilled off. Further, the reaction was carried out at 105 ℃ for 1 hour and 30 minutes, and the residual methanol, water and formic acid were distilled off under reduced pressure of 70 to 150mmHg to obtain a condensate (A-9) having a weight of 29.0 units. [ the number of moles of unreacted hydroxyl groups and alkoxy groups ]/[ the total number of moles of alkoxy groups contained in component (a1) and component (a2) ] (molar ratio) was 0.10 and the concentration was 46.5%. The mercaptan equivalent of the condensate (A-9) was 316 g/eq.

Production example 11 (production of condensate (A-10))

In a reaction apparatus similar to that of production example 1, 12.0 parts by weight of 3-mercaptopropyltrimethoxysilane, 3.06 parts by weight of deionized water ([ the number of moles of water used for the hydrolysis ]/[ the number of moles of alkoxy groups contained in the component (a1) ] (molar ratio): 1.0), and 0.67 parts by weight of 95% formic acid were charged, and the hydrolysis reaction was carried out at room temperature for 30 minutes. During the reaction, the temperature increased to 20 ℃ at the maximum with heat generation. After the reaction, 1.39 parts by weight of tetrabutyltitanate (manufactured by Tokyo chemical Co., Ltd.) and 20.25 parts by weight of diglyme were added thereto and heated. The temperature was raised to 75 ℃ to carry out a condensation reaction for 30 minutes. [ the number of moles of thiol groups contained in the component (a1) ]/[ the total number of moles of the component (a1) and the component (a2) ] -0.94, and [ the total number of moles of alkoxy groups contained in the component (a1) and the component (a2) ]/[ the total number of moles of the component (a1) and the component (a2) ] -3.1. After further carrying out the distillation under reduced pressure of 70 to 150mmHg for 1 hour, the remaining methanol, water and formic acid were removed to obtain 29.39 parts by weight of a condensate (A-10). [ the number of moles of unreacted hydroxyl groups and alkoxy groups ]/[ the number of moles of alkoxy groups contained in the component (a 1] (molar ratio) was 0.17, and the concentration was 27.8%. The thiol equivalent of the condensate (A-10) was 481 g/eq.

Production example 12 (production of condensate (A-11))

In the same reaction apparatus as in production example 1, 18.0 weight units of 3-mercaptopropyltrimethoxysilane, 2.24 weight units of diphenyldimethoxysilane ([ the number of moles of thiol groups contained in the component (a1) ]/[ the total number of moles of the component (a1) and the component (a2) ] -0.91, [ the total number of moles of alkoxy groups contained in the component (a1) and the component (a2) ]/[ the total number of moles of alkoxy groups contained in the component (a1) and the component (a2) ] -2.9), 5.29 weight units of deionized water ([ the number of moles of water used for hydrolysis ]/[ the total number of moles of alkoxy groups contained in the component (a1) and the component (a2) ], and 0.90 weight units of 95% formic acid were charged and hydrolyzed at room temperature for 30 minutes. During the reaction, the temperature increased to 20 ℃ at the maximum with heat generation. After the reaction, 20.23 parts by weight of toluene was added and heated. When the temperature was raised to 72 ℃, a part of methanol and toluene generated accompanying the hydrolysis began to be distilled off. Further, the reaction is carried out for 1 hour at 75 ℃ under reduced pressure of 70 to 150mmHg, and the remaining methanol, water and formic acid are distilled off. The residual toluene was distilled off under reduced pressure of 70 to 150mmHg to obtain a condensate (A-11) of 14.41 parts by weight. [ the number of moles of unreacted hydroxyl groups and alkoxy groups ]/[ the total number of moles of alkoxy groups contained in component (a1) and component (a 2] (molar ratio) was 0.16, and the concentration was 93.6%. The mercaptan equivalent of the condensate (A-11) was 157 g/eq.

Examples 1 to 15 (production of thermosetting composition)

To 10 weight units of the condensate (a-1) obtained in production example 1, 4.40 weight units of bisphenol a epoxy resin was added as component (B) (product name: エピコ - ト 828 ", epoxy equivalent 370g/eq, manufactured by japan epoxy resin corporation) ([ number of moles of thiol groups contained in component (a) ]/[ number of moles of epoxy groups contained in component (B) ] (molar ratio): 1.0) to form a thermosetting composition (F-1). To 10 weight units of the condensate (a-1) obtained in accordance with preparation of claim 1, 2.79 weight units of isophorone diisocyanate was added as component (C) (manufactured by tokyo chemical industries, ltd.: isocyanate equivalent 111g/eq, hereinafter IPDI) ([ number of moles of thiol groups contained in component (a) ]/[ number of moles of isocyanate groups contained in component (C) ] (molar ratio): 1.0), and 0.013g of dibutyltin dilaurate (product name: ネオスタン U-100, manufactured by rito chemical industries, ltd.) to form a thermosetting composition (F-2). Similarly, using (A-1-5) obtained in production examples 1-5, thermosetting compositions (F-3-F-15) were prepared according to the following table.

In table, セロキサイド 2021: alicyclic epoxy resin (available from DAICEL chemical Co., Ltd.: trade name: セロキサイド 2021, epoxy equivalent 126g/eq), SR-8 EG: polyethylene glycol diglycidyl ether (trade name, epoxy equivalent 285g/eq, manufactured by Saba Takayaku Co., Ltd.).

Comparative example 1 (production of thermosetting composition)

A thermosetting composition was prepared by adding 16.2 weight units of エピコ - ト 828 to 10 weight units of pentaerythritol tetrakis (3-mercaptopropionate) (made by Sakai chemical industry Co., Ltd.: trade name: PEMP).

Comparative example 2 (production of thermosetting composition)

10.3 parts by weight of isophorone diisocyanate and 0.020 part by weight of dibutyltin dilaurate were added to 10 parts by weight of pentaerythritol tetrakis (3-mercaptopropionate) to prepare a thermosetting composition.

Comparative example 3 (production of thermosetting composition)

A comparative thermosetting composition was synthesized in accordance with example 3 of JP-A-2005-290286. Specifically, 8 parts by weight of bisphenol A type glycidyl ether (product name: エピコ - ト 828 ", epoxy equivalent 190g/eq, manufactured by Nippon epoxy resin Co., Ltd.) was dissolved in 8g of tetrahydrofuran to prepare a resin solution. A thermosetting composition was prepared by refluxing 18 parts by weight of phenyltrimethoxysilane, 8 parts by weight of 3-glycidoxypropyltriethoxysilane, 8 parts by weight of a 10% aqueous solution of formic acid and 49 parts by weight of tetrahydrofuran at 60 ℃ for 3 hours while stirring, and adding 1 part by weight of a thermosetting agent (product of Asahi Denka Kogyo Co., Ltd., trade name: アデカオプトン CP-66) and 16 parts by weight of the above resin solution.

(curability and surface hardness of thermosetting composition)

The thermosetting compositions obtained in examples 1 to 15 and comparative examples 1 and 2 were applied to a glass plate to give a cured film having a thickness of about 15 μm, and solvent drying and curing reaction were carried out at 80 ℃ for 2 hours. The curability of the resulting cured product was confirmed to have a significantly reduced peak value or almost no peak value of thiol around 2600cm-1 by Raman spectrophotometry (trade name "NRS-3100", manufactured by Nippon spectral Co., Ltd.). Further, the surface hardness of the cured product obtained was evaluated by a pencil hardness test according to a general test method of JIS K-5401.

TABLE 2

	Surface hardness
		Example 1	4H
Example 2	2H
		Example 3	4H
Example 4	3H
		Example 5	HB
Example 6	2H
		Example 7	3B
Example 8	4H
		Example 9	2H

Example 10	4H
		Example 11	3H
Example 12	H
		Example 13	3B
Example 14	3H
		Example 15	4H
Comparative example 1	2H
		Comparative example 2	HB

As is clear from table 2, comparing comparative example 1 and examples 1, 3, 8, 10, 11, 14, and 15 cured with the same component (B) and comparative example 2 and examples 2, 6, 9, and 12 cured with the same component (C), the cured products of the examples had higher surface hardness than the cured products of the comparative examples. This proves that the curable composition of the present invention is more suitable as a hard coating agent.

(weather resistance of cured film)

The thermosetting compositions obtained in examples 3, 4 and 6 and comparative examples 1 and 2 were applied to a glass plate to give a cured film having a thickness of about 15 μm, and solvent drying and curing reaction were carried out at 80 ℃ for 2 hours. The cured product thus obtained was cured by irradiating with ultraviolet light using an ultraviolet irradiation apparatus (trade name "UV-152" manufactured by USHIO Motor Co., Ltd.) so that the integrated luminous flux of a 365nm ultraviolet detector was 20000mJ/cm²The degree of coloration after irradiation was visually evaluated. Further, the resultant was heated at 200 ℃ for 30 minutes, and the degree of coloring after heating was visually evaluated. The evaluation criteria are as follows.

O … … was scarcely colored

Delta … … is slightly colored (slightly yellow)

X … … deep color (dark brown)

TABLE 3

As is clear from Table 2, the cured product of comparative example 1 was colored brown, and the cured product of example 3 was inhibited from coloring. Furthermore, the cured products of examples 4 and 6 were hardly colored by both ultraviolet irradiation and heating, and it was found that the cured products of the present invention were more excellent in weather resistance.

(adhesion to inorganic Material)

The thermosetting compositions obtained in examples 3, 6, 8 and 9 were applied to various inorganic substrates to give a cured film thickness of about 15 μm, and solvent drying and curing reaction were carried out at 80 ℃ for 2 hours. The resulting cured product was evaluated by a checkered cellophane tape peeling test in accordance with the general test method of JIS K-5400.

As shown in tables 2 and 4, the cured products of examples 8 and 9 to which the component (E) was added had the same curability and surface hardness as those of the cured products of examples 3 and 6, but had greatly improved adhesion to inorganic substrates. This shows that the thermosetting compositions of examples 8 and 9 are suitable as coating agents for light guide plates, polarizing plates, liquid crystal panels, EL panels, PDP panels, optical fibers, color filters, optical disk substrates, lenses, prisms, and the like, which are made of inorganic substrates.

TABLE 4

	Example 3	Example 6	Example 8	Example 9
					Steel plate	0/100	0/100	100/100	100/100
Glass plate	0/100	100/100	100/100	100/100
					Copper plate	100/100	100/100	100/100	100/100

(refractive index)

The thermosetting compositions obtained in examples 3 to 6, 10, 11 and 15 were diluted with propylene glycol monomethyl ether acetate to a nonvolatile content of 30 wt%, applied onto a silicon substrate to a cured film thickness of about 50nm, and subjected to solvent drying and curing reaction at 80 ℃ for 30 minutes. The thermosetting composition obtained in comparative example 3 was diluted with propylene glycol monomethyl ether acetate to a nonvolatile content of 30 wt%, applied to a silicon substrate, cured to a film thickness of about 50nm, and solvent-dried at 60 ℃ for 10 minutes. Then, the resultant was thermally cured at 120 ℃ for 30 minutes. The refractive index of the resulting cured product was measured using an ellipsometer (product name: ESM-1, manufactured by Nippon vacuum technologies Co., Ltd.).

Table 5:

as shown in Table 5, the refractive index of the cured products of example 15 containing zirconium as component (a2) and the refractive index of the cured products of example 10 containing titanate as component (F) were improved as compared with the cured products of examples 3, 4, 5, 6 and 11. This shows that the thermosetting compositions of examples 10 and 15 are suitable as coating agents for antireflection films for light guide plates, polarizing plates, liquid crystal panels, EL panels, PDP panels, OHP films, optical fibers, color filters, optical disk substrates, lenses, plastic substrates for liquid crystal cells, prisms, and the like.

(preparation of transparent substrate)

The compositions obtained in examples 4 and 6 were dipped in a commercially available glass cloth (glass cloth cut microB, film thickness 28 μm, refractive index 1.54) and (weight of glass cloth)/(weight of composition) after curing was 100/200, and solvent drying and curing reaction were carried out at 80 ℃ for 2 hours to obtain a transparent substrate having a thickness of 80 μm. Further, the composition obtained in comparative example 3 was dipped in a glass cloth, the solvent was evaporated by a dryer at 60 ℃, and then the resultant was heated at 120 ℃ for 3 hours and molded by a press at 150 ℃ for 1 hour to obtain a transparent substrate having a thickness of 80 μm. The appearance of the obtained transparent substrate was visually evaluated. The evaluation criteria are as follows.

O … … almost transparent

Δ … … translucency

X … … opaque

The flexibility of the transparent substrate was evaluated from the radius of curvature of cracks generated when the substrate was bent.

Table 6:

	example 4	Example 6	Comparative example 3
				Transparency of	○	○	○
Flexibility	＜1cm	1cm	5cm
				Refractive index difference between cured product and glass cloth	0.01	0.02	0.01

As shown in table 6, the obtained substrates were all almost transparent. In addition, the transparent substrate of example 6 was cracked when the radius of curvature was 1cm or less, while the transparent substrate of example 4 was not cracked when it was further bent, compared to the transparent substrate of comparative example 3, when the radius of curvature was 5cm or less. Therefore, it is more suitable as a substrate for flexible liquid crystal panels, EL panels, PDP panels, color filters, and the like.

(Heat resistance)

The thermosetting compositions obtained in examples 3 and 12 and comparative examples 1 and 2 were poured into an aluminum cup, and the cured film thickness was about 1mm, and solvent drying and curing reaction were carried out at 80 ℃ for 2 hours. The obtained cured product was further heated in a 200 ℃ dryer for 30 minutes. The cured product was cut into a size of 5mm × 25mm, and the dynamic storage modulus of elasticity was measured with a viscoelasticity measuring apparatus (manufactured by セイコ - インすツルメント, trade name "DMS 6100", measurement conditions: frequency 1Hz, inclination 3 ℃/min) to evaluate the heat resistance. The measurement results are shown in FIGS. 1 and 2. As is clear from fig. 1 and 2, example 3 has an improved Tg and a smaller decrease in elastic modulus at high temperatures than comparative examples 1 and 12 and is excellent in heat resistance than comparative example 2. In addition, in comparative example 1, the measurement limit (10) was lowered⁶) The following.

(coefficient of linear expansion)

The thermosetting compositions obtained in examples 3 and 12 and comparative examples 1 and 2 were poured into an aluminum cup, and the cured film thickness was about 1mm, and solvent drying and curing reaction were carried out at 80 ℃ for 2 hours. The obtained cured product was further heated in a 200 ℃ dryer for 30 minutes. The resulting cured product was used to measure the linear expansion coefficient at 120 to 150 ℃ using a thermal stress deformation measuring apparatus (セイコ - インすツルメント, product name "TMA 120C"). The results are shown in Table 7.

Table 7:

	example 3	Example 12	Comparative example 1	Comparative example 2
					Coefficient of linear expansion (× 10)6/℃)	170	105	210	140

Comparing comparative example 1 and example 3 cured with the same component (B) and comparative example 2 and example 12 cured with the same component (C), the cured products of the examples had lower linear expansion coefficients than the cured products of the comparative examples. This proves that the curable composition of the present invention is useful 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, which require thermal stability.

(Water absorption)

The thermosetting compositions obtained in examples 3 and 12 and comparative examples 1 and 2 were poured into an aluminum cup, and the cured film thickness was about 1mm, and solvent drying and curing reaction were carried out at 80 ℃ for 2 hours. The obtained cured product was further heated in a 200 ℃ dryer for 30 minutes. The water absorption of the resulting cured product was calculated from the difference between the measured weight of the cured product after being left in a thermostatic bath at 50 ℃ for 24 hours and the measured weight of the cured product after being immersed in a thermostatic bath at 23 ℃ for 24 hours. The results are shown in Table 8.

Table 8:

	example 3	Example 12	Comparative example 1	Comparative example 2
					Water absorption 24h (%)	0.6	0.9	0.5	0.8

As is clear from table 8, examples 3 and 12 showed water absorption rates of the same degree as comparative examples 1 and 2.

(drug resistance)

The thermosetting compositions obtained in examples 3 and 12 and comparative examples 1 and 2 were poured into an aluminum cup, and the cured film thickness was about 1mm, and solvent drying and curing reaction were carried out at 80 ℃ for 2 hours. The obtained cured product was further heated in a 200 ℃ dryer for 30 minutes. The resulting cured product was immersed in a solvent (methanol, toluene, THF, DMF) for 3 hours, and the appearance was visually observed. The swelling degree was calculated from the difference between the measured weights before and after immersion (calculation method (weight after immersion-weight before immersion)/weight before immersion × 100, 0% in the case of no absorption). The results are shown in Table 9.

Table 9:

as shown in Table 9, the cured products obtained from the thermosetting compositions of examples 3 and 12 were superior in solvent resistance to the cured products obtained from the thermosetting compositions of comparative examples 1 and 2.

Examples 16 to 35 (production of ultraviolet curable composition)

To 10 weight units of the condensate (a-1) obtained in production example 1, 2.09 weight units of triallylisocyanurate (manufactured by japan chemical industry co., ltd.: trade name "タイク", [ the number of moles of carbon-carbon double bonds contained in the component (D) ]/[ the number of moles of the component (D) ], which is 3) [ the number of moles of thiol groups contained in the component (a) ]/[ the number of moles of carbon-carbon double bonds contained in the component (D) ] (molar ratio): 1.0), and 0.20 weight units of triphenyl phosphite (manufactured by tokyo chemical industry co., ltd.) were added to prepare an ultraviolet-curable resin composition (G-1). Similarly, by using the condensates (A-1 to 3, 6 to 11) obtained in production examples 1 to 3, 7 to 12, ultraviolet-curable resin compositions (G-2 to G-20) were prepared according to the following table.

In the table, DAP: diallyl phthalate (manufactured by daiiso corporation: trade name "ダイソ - ダツプモノマ -one ], [ the number of moles of carbon-carbon double bonds contained in the component (D) ]/[ the number of moles of the component (D) ], P-30M: pentaerythritol triallyl ether (manufactured by daiiso corporation: trade name "ネオアリル P-30M", [ number of moles of carbon-carbon double bonds contained in the component (D) ]/[ number of moles of the component (D) ], SH-6062: 3-mercaptopropyltrimethoxysilane (manufactured by Dow Corning corporation, Tooli), SR-8 EG: polyethylene glycol diglycidyl ether (product name, epoxy equivalent 285g/eq, manufactured by Sabourauba pharmaceutical industries Co., Ltd.), エピコ - ト 828: bisphenol A type liquid epoxy resin (trade name, epoxy equivalent 89g/eq, manufactured by Nippon epoxy resin Co., Ltd.), Q-1301: n-nitrosophenylhydroxylamine salt (trade name of Wako pure chemical industries, Ltd.).

Example 36 (production of ultraviolet curable composition)

In a reaction apparatus similar to that of production example 1, 25.0 parts by weight of 3-mercaptopropyltrimethoxysilane, 8.42 parts by weight of phenyltrimethoxysilane, 9.18 parts by weight of deionized water ([ mole number of water used for hydrolysis ]/[ total mole number of alkoxy groups contained in the component (a1) and the component (a 2] (molar ratio): 1.0) and 1.67 parts by weight of 95% formic acid were charged, and the hydrolysis reaction was carried out at room temperature for 30 minutes. During the reaction, the temperature increased to 26 ℃ at the maximum with heat generation. After the reaction, 50.54 parts by weight of toluene was added and heated. When the temperature was raised to 72 ℃, part of methanol and toluene produced accompanying the hydrolysis began to be distilled off. The temperature was raised to 75 ℃ over 1 hour and the water produced by the condensation reaction was distilled off. 10.58g of triallyl isocyanurate was added thereto, and the mixture was subjected to vacuum distillation at 70 to 150mmHg to remove toluene, water and formic acid. Then, toluene was distilled off under reduced pressure of 70 to 150mmHg to obtain 33.97 parts by weight of an ultraviolet-curable resin composition (G-21). [ the number of moles of unreacted hydroxyl groups and alkoxy groups ]/[ the total number of moles of alkoxy groups contained in component (a1) and component (a2) ] (molar ratio) was 0.14, and the concentration was 95.0%.

Example 37 (production of ultraviolet curable composition)

In a reaction apparatus similar to that of production example 1, 25.0g of 3-mercaptopropyltrimethoxysilane, 8.42 weight units of phenyltrimethoxysilane, 9.18 weight units of deionized water ([ mole number of water used for hydrolysis ]/[ total mole number of alkoxy groups contained in the component (a1) and the component (a 2] (molar ratio): 1.0) and 1.67 weight units of 95% formic acid were charged, and the hydrolysis reaction was carried out at room temperature for 30 minutes. During the reaction, the temperature increased to 26 ℃ at the maximum with heat generation. After the reaction, 50.54 parts by weight of toluene was added and heated. When the temperature was raised to 72 ℃, part of methanol and toluene produced accompanying the hydrolysis began to be distilled off. The temperature was raised to 75 ℃ over 1 hour and the water produced by the condensation reaction was distilled off. Then, 15.68 parts by weight of diallyl phthalate was added thereto, and the mixture was subjected to vacuum distillation under 70 to 150mmHg to remove the remaining methanol, water and formic acid. Then, toluene was distilled off under reduced pressure of 70 to 150mmHg to obtain 39.65 parts by weight of an ultraviolet-curable resin composition (G-22). [ the number of moles of unreacted hydroxyl groups and alkoxy groups ]/[ the total number of moles of alkoxy groups contained in component (a1) and component (a2) ] (molar ratio) was 0.14, and the concentration was 94.2%.

Example 38 (production of ultraviolet curable composition)

In a reaction apparatus similar to that of production example 1, 25.0 parts by weight of 3-mercaptopropyltrimethoxysilane, 8.42 parts by weight of phenyltrimethoxysilane, 9.18 parts by weight of deionized water ([ mole number of water used for hydrolysis ]/[ total mole number of alkoxy groups contained in the component (a1) and the component (a 2] (molar ratio): 1.0) and 1.67 parts by weight of 95% formic acid were charged, and the hydrolysis reaction was carried out at room temperature for 30 minutes. During the reaction, the temperature increased to 26 ℃ at the maximum with heat generation. After the reaction, 50.54 parts by weight of toluene was added and heated. When the temperature was raised to 72 ℃, a part of methanol and toluene generated accompanying the hydrolysis began to be distilled off. The temperature was raised to 75 ℃ over 1 hour and the water produced by the condensation reaction was distilled off. Then 10.88 parts by weight of pentaerythritol triallyl ether was added, and the mixture was subjected to a reduced pressure of 70 to 150mmHg to distill off the remaining methanol, water and formic acid. Then, toluene was distilled off under reduced pressure of 70 to 150mmHg to obtain 34.69 parts by weight of an ultraviolet-curable resin composition (G-23). [ the number of moles of unreacted hydroxyl groups and alkoxy groups ]/[ the total number of moles of alkoxy groups contained in component (a1) and component (a 2] (molar ratio) was 0.14, and the concentration was 93.9%.

Comparative example 4 (production of ultraviolet curable composition)

Dipentaerythritol hexaacrylate (manufactured by Mitsukawa chemical Co., Ltd.; trade name: ビ - ムセツト -700) was used as it was.

Comparative example 5 (production of ultraviolet curable composition)

A UV-curable resin composition was prepared by adding 0.5 parts by weight of a free-radical photoinitiator (product name: イルガキユア Irg-184, manufactured by Ciba Specialty Chemicals) to 10 parts by weight of dipentaerythritol hexaacrylate.

Comparative example 6 (production of ultraviolet curable composition)

An ultraviolet-curable resin composition was prepared by adding 6.20 parts by weight of triallyl isocyanurate and 0.20 parts by weight of triphenyl phosphite to 10 parts by weight of pentaerythritol tetrakis (3-mercaptopropionate) (made by Sakai chemical industry Co., Ltd.: trade name "PEMP").

Comparative example 7 (production of ultraviolet curable composition)

10.08 parts by weight of diallyl phthalate and 0.20 part by weight of triphenyl phosphite were added to 10 parts by weight of pentaerythritol tetrakis (3-mercaptopropionate) to prepare an ultraviolet-curable resin composition.

Comparative example 8 (production of ultraviolet curable composition)

An ultraviolet-curable resin composition was prepared by adding 6.99 parts by weight of pentaerythritol triacrylate and 0.20 parts by weight of triphenyl phosphite to 10 parts by weight of pentaerythritol tetrakis (3-mercaptopropionate).

(curing Property of composition)

The ultraviolet-curable resin compositions obtained in examples 16 to 23 and 29 to 33 were applied to a steel plate, and the thickness after curing was about 15 μm, followed by solvent drying at 120 ℃ for 30 minutes. After drying, the resultant was irradiated with ultraviolet rays using an ultraviolet irradiation apparatus (product name: UV-152, manufactured by USHIO Motor Co., Ltd.) so that the integrated luminous flux of a 365nm ultraviolet detector was 200mJ/cm²). In the same way as above, the first and second,the UV-curable compositions obtained in examples 24 to 28, 34 to 38 and comparative examples 4 to 8 were applied to give a cured film thickness of about 15 μm, and then irradiated with UV light using a UV irradiation apparatus (manufactured by USHIO Motor Co., Ltd.; trade name: UV-152) so that the cumulative luminous flux of a 365nm UV detector was 200mJ/cm²). The thermosetting composition obtained in comparative example 3 was applied, and the cured film thickness was about 15 μm, and solvent drying was performed at 60 ℃ for 30 minutes. Then, the resultant was thermally cured at 120 ℃ for 3 hours and 150 ℃ for 1 hour. The curability of the resulting cured product was evaluated by a pencil hardness test according to a general test method of JIS K5401.

TABLE 11

	Surface hardness
		Example 16	7H
Example 17	6H
		Example 18	4H
Example 19	7H
		Example 20	7H
Example 21	6H
		Example 22	6H
Example 23	7H
		Example 24	7H
Example 25	6H
		Example 26	4H
Example 27	6H
		Example 28	6H
Example 29	7H
		Example 30	7H
Example 31	6H
		Example 32	6H
Example 33	5H
		Example 34	7H
Example 35	7H
		Example 36	7H
Example 37	7H
		Example 38	4H
Comparative example 4	Not cured
		Comparative example 5	Semi-curing
Comparative example 6	4H
		Comparative example 7	3H
Comparative example 8	2H

As shown in table 11, the ultraviolet-curable resin composition of comparative example 4 was not cured at all, and the ultraviolet-curable resin composition of comparative example 5 was not sufficiently cured. That is, in curing by general radical polymerization, curing cannot be performed without an initiator, or curing cannot be performed in a thick film even if a curing agent is added. On the other hand, the ultraviolet-curable resin compositions of examples 16 to 38 and comparative examples 6 to 8 were cured without any problem, and the curing system using the ene-thiol (ene-thiol) reaction was capable of ultraviolet curing without an initiator, and even the curing system of the present invention had the same curability as the conventional organic-organic system. Furthermore, the cured products of examples 16 to 36 cured with the same component (D) had higher surface hardness than the cured products of comparative examples 6 to 8, and it was confirmed that the curable resin composition of the present invention was suitable as a hard coating agent.

(stability of ultraviolet-curable resin composition)

The ultraviolet-curable resin compositions obtained in examples 24, 34 and 35 were taken out and put in brown bottles, and left at room temperature, and the stability of the ultraviolet-curable resin compositions was evaluated based on the number of days of gelation.

TABLE 12

	Days to gelation (days)
		Example 24	3 days
Example 34	7 days
		Example 35	For more than 1 month

As shown in tables 11 and 12, the ultraviolet-curable resin compositions of examples 34 and 35 have curability equivalent to that of the ultraviolet-curable resin composition of example 24, and stability is greatly improved. Therefore, in the use where stability is particularly required when it is used in the single-liquid polymerization, the addition of a radical polymerization inhibitor such as a tertiary amine such as benzyldimethylamine or an aluminum salt of N-nitrosophenylhydroxylamine improves the stability.

(weather resistance of cured film)

The ultraviolet-curable resin compositions obtained in examples 23 to 25 and comparative examples 5 to 8 were applied to a glass plate, the cured film thickness was about 5 μm, and ultraviolet rays were irradiated using the above-mentioned ultraviolet irradiation apparatus so that the integrated luminous flux of a 365nm ultraviolet detector was 200mJ/cm²The obtained cured product was further irradiated with ultraviolet rays so that the cumulative luminous flux was 20000mJ/cm²The degree of coloration after irradiation was visually evaluated. The evaluation criteria are as follows.

O: almost uncolored Δ: slightly colored (slightly yellow) ×: deep color (dark brown)

Watch 13

	Weatherability (ultraviolet resistance)
		Example 23	○
Example 24	○
		Example 25	○
Comparative example 5	×
		Comparative example 6	△
Comparative example 7	△
		Comparative example 8	△

As shown in Table 13, the cured product of comparative example 5 was brown in color, and the cured products of comparative examples 6 to 8 were slightly yellowish in color. On the other hand, the cured products of examples 23 to 25 were almost uncolored, indicating that the cured products of the present invention are more excellent in weather resistance than conventional organic-organic systems.

(adhesion to inorganic Material)

The ultraviolet-curable resin compositions obtained in examples 24 and 29 were applied to various inorganic substrates to give cured films having a thickness of about 15 μm, and irradiated with ultraviolet rays using the above-mentioned ultraviolet irradiation apparatus so that the integrated luminous flux of a 365nm ultraviolet detector was 500mJ/cm². The resulting cured product was evaluated by a checkered cellophane tape peeling test in accordance with the general test method of JIS K-5400.

TABLE 14

	Example 24	Example 29
			Steel plate	80/100	100/100
Glass plate	0/100	100/100
			Copper plate	80/100	100/100

As shown in tables 11 and 14, the cured product of example 29 to which the component (E) was added had the same curability and much improved adhesion to the inorganic base material as compared with the cured product of example 24. This shows that the ultraviolet-curable resin composition of example 29 is suitable as a coating agent for 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, or the like, which is made of an inorganic base material, and an adhesive for a liquid crystal panel, an EL panel, a PDP panel, a color filter, and an optical disk substrate, which are made of an inorganic base material.

(adhesion to organic Material)

Obtained in examples 24, 31 and 32The ultraviolet-curable resin composition was applied to various inorganic substrates, the cured film thickness was about 15 μm, and ultraviolet rays were irradiated using the above-mentioned ultraviolet irradiation apparatus so that the integrated luminous flux of a 365nm ultraviolet detector was 500mJ/cm². The resulting cured product was subjected to heat treatment at 100 ℃ for 1 hour. The cured product thus obtained was evaluated by a checkered cellophane tape peeling test in accordance with the general test method of JIS K-5400.

Watch 15

	Example 24	Example 31	Example 32
				PC	95/100	100/100	100/100
PMMA	0/100	100/100	100/100
				PET	20/100	100/100	100/100
TAC	0/100	100/100	100/100

As shown in tables 11 and 15, the cured products of examples 31 and 32 to which the component (B) was added had a slightly lower surface hardness than the cured product of example 24, but the adhesion to the organic substrate was greatly improved. This shows that the ultraviolet-curable resin compositions of examples 31 and 32 are suitable as coating agents for light guide plates, polarizing plates, liquid crystal panels, EL panels, PDP panels, OHP films, optical fibers, color filters, optical disk substrates, lenses, plastic substrates for liquid crystal cells, prisms, etc., which are made of organic substrates, and adhesives for liquid crystal panels, EL panels, PDP panels, color filters, optical disk substrates, which are made of organic substrates.

(refractive index)

The ultraviolet-curable resin compositions obtained in examples 23, 24, 30, 33 and comparative example 6 were diluted with propylene glycol monomethyl ether acetate to a nonvolatile content of 30 wt%, then applied to a silicon substrate to give a cured film having a thickness of about 50nm, and solvent-dried at 120 ℃ for 15 minutes. After drying, the resultant was irradiated with ultraviolet rays using the above-mentioned ultraviolet irradiation apparatus so that the integrated luminous flux of the 365nm ultraviolet detector became 200mJ/cm². The thermosetting composition obtained in comparative example 3 was diluted with propylene glycol monomethyl ether acetate to a nonvolatile content of 30 wt%, applied to a silicon substrate, cured to a film thickness of about 50nm, and solvent-dried at 60 ℃ for 10 minutes. Then, the resultant was thermally cured at 120 ℃ for 30 minutes. The refractive index of the resulting cured product was measured using an ellipsometer (product name: ESM-1, manufactured by Nippon vacuum technologies Co., Ltd.).

TABLE 16

	Example 23	Example 24	Example 30	Example 33	Comparative example 6	Comparative example 3
							Refractive index	1.60	1.56	1.60	1.54	1.56	1.53

As is clear from Table 16, the refractive index of the cured product of example 23 to which the titanate ester as the component (a2) was added and the refractive index of the cured product of example 30 to which the titanate ester as the component (F) was added were improved as compared with the refractive index of the cured product of example 24. This shows that the ultraviolet-curable resin compositions of examples 23 and 30 are suitable as coating agents for antireflection films of light guide plates, polarizing plates, liquid crystal panels, EL panels, PDP panels, OHP films, optical fibers, color filters, optical disk substrates, lenses, plastic substrates for liquid crystal cells, prisms, and the like.

(preparation of transparent substrate)

The compositions obtained in example 33 and comparative example 6 were dipped in a commercially available glass cloth (cut glass cloth microB, film thickness 28 μm, refractive index 1.54), and the cured (weight of glass cloth)/(weight of composition) was 100/200, and the resultant was irradiated with ultraviolet light using the above-mentioned ultraviolet irradiation apparatus so that the integrated luminous flux of a 365nm ultraviolet detector was 2000mJ/cm². A transparent substrate having a thickness of 80 μm was obtained. Further, the composition obtained in comparative example 3 was dipped in a glass cloth, the solvent was evaporated by a dryer at 60 ℃, and then the resultant was heated at 120 ℃ for 3 hours and molded by a press at 150 ℃ for 1 hour to obtain a transparent substrate having a thickness of 80 μm. The appearance of the obtained transparent substrate was visually evaluated. The evaluation criteria are as follows.

O … … almost transparent

Δ … … translucency

X … … opaque

The flexibility of the transparent substrate was evaluated from the radius of curvature of cracks generated when the substrate was bent.

TABLE 17

Example 33

Comparative example 6

Comparative example 3

Transparency of	○	△	○
				Flexibility	＜1cm	＜1cm	5cm
Difference in refractive index from glass cloth	0	0.02	0.01

As shown in table 17, the substrates obtained in example 33 and comparative example 3 were almost transparent, while the substrate obtained in comparative example 6 was translucent. Further, cracks were generated even when the substrate of comparative example 3 had a radius of curvature of 5cm or less, and cracks were not generated even when the substrates of example 33 and comparative example 6 had a radius of curvature of 1em or less. According to the above experimental results, the physicochemical properties of example 33 were excellent as compared with those of the substrates of comparative examples 6 and 3, which indicates that the substrate is more suitable as a substrate for flexible liquid crystal panels, EL panels, PDP panels, color filters, and the like.

(adhesive force)

The ultraviolet-curable resin compositions obtained in example 24 and comparative examples 5 and 6 were applied to a steel plate, the cured film thickness was about 5 μm, and a polycarbonate plate having a thickness of 2mm or a glass plate having a thickness of 2mm was covered, and then ultraviolet rays were irradiated using the above-mentioned ultraviolet irradiation apparatus, so that the cumulative luminous flux of a 365nm ultraviolet detector was 1000mJ/cm in the uncovered state². The obtained cured product was evaluated by a pencil hardness test according to a general test method of JIS K5401.

Table 18:

as shown in table 18, the ultraviolet-curable resin compositions of comparative examples 6 and 24 were completely cured, compared to the ultraviolet-curable resin composition of comparative example 5, which was not cured at all. From the above-mentioned various experimental results, compared with the cured product of comparative example 6, the cured product of example 24 has excellent physical and chemical properties, and is suitable for the liquid crystal panel, EL panel, PDP panel, color filter, CD substrate adhesive.

(Heat resistance)

The ultraviolet-curable resin compositions obtained in example 24 and comparative example 6 were poured into an aluminum cup, and the cured film thickness was about 1mm, and ultraviolet rays were irradiated using the above-mentioned ultraviolet irradiation apparatus so that the integrated luminous flux of a 365nm ultraviolet detector was 5000mJ/cm². The obtained cured product was further heated in a 200 ℃ dryer for 30 minutes. The cured product was cut into a size of 5mm × 25mm, and the dynamic storage modulus of elasticity was measured with a viscoelasticity measuring apparatus (manufactured by セイコ - インすツルメント, trade name "DMS 6100", measurement conditions: frequency 1Hz, inclination 3 ℃/min) to evaluate the heat resistance. The measurement results are shown in FIG. 3. As shown in fig. 3, example 24 has an improved Tg and a smaller decrease in elastic modulus at high temperatures than comparative example 6, and is excellent in heat resistance.

Industrial applicability

The present invention provides a curable resin composition which can provide a cured product having improved properties such as heat resistance, chemical resistance, high surface hardness, and high refractive index. Furthermore, the cured product of the present invention obtained from the thermosetting resin composition can be used for: coating agents (applications such as light guide plates, polarizing plates, liquid crystal panels, EL panels, PDP panels, OHP films, optical fibers, color filters, optical disk substrates, lenses, plastic substrates for liquid crystal cells, prisms, and the like), adhesives (applications such as liquid crystal panels, EL panels, PDP panels, color filters, optical disk substrates, and the like), sealing materials (applications such as light-emitting devices, light-receiving devices, photoelectric conversion devices, and light transmission-related members), and the like. Further, according to the present invention, ultraviolet curability by an ene-thiol (ene-thiol) reaction can be utilized.

Claims (24)

1. A curable resin composition characterized by:

it contains a compound selected from: a general formula (1):

R¹Si(OR²)₃（1）

a condensate A obtained by hydrolysis and condensation of a thiol group-containing alkoxysilane a1, and at least one member selected from the group consisting of an epoxy group-containing compound B, an isocyanate group-containing compound C and a compound D having a carbon-carbon double bond, wherein R in the formula (1)¹Means containing at least 1 thiol groupA hydrocarbon group having 1 to 8 carbon atoms or an aromatic hydrocarbon group containing at least 1 thiol group, R²Represents a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms, or an aromatic hydrocarbon group, wherein

[ total molar amount of unreacted hydroxyl groups and unreacted alkoxy groups ]/[ molar number of alkoxy groups in the thiol group-containing alkoxysilanes a 1] is 0.12 to 0.17.

2. The curable resin composition according to claim 1, wherein the condensate A is obtained by hydrolyzing an alkoxysilane a1 in the presence of formic acid and then performing a condensation reaction in the presence of a solvent.

3. A curable resin composition characterized by:

the curable resin composition is prepared by mixing a compound represented by the general formula (1):

R¹Si(OR²)₃（1）

the alkoxysilane a1 containing a thiol group represented by the formula (1) wherein R is R, is obtained by hydrolyzing in the presence of formic acid, and then condensing in the presence of a solvent and a compound D having a carbon-carbon double bond¹Represents a C1-8 hydrocarbon group containing at least 1 thiol group, or an aromatic hydrocarbon group containing at least 1 thiol group, R²Represents a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms, or an aromatic hydrocarbon group, wherein

[ total molar amount of unreacted hydroxyl groups and unreacted alkoxy groups ]/[ molar number of alkoxy groups in the thiol group-containing alkoxysilanes a 1] is 0.12 to 0.17.

4. The curable resin composition according to claim 1, 2 or 3, wherein the alkoxysilane a1 is 3-mercaptopropyltrimethoxysilane.

5. The curable resin composition according to any one of claims 1, 2 or 3, wherein the compound B is at least 1 compound selected from the group consisting of bisphenol A epoxy resins, bisphenol F epoxy resins, hydrogenated bisphenol A epoxy resins and alicyclic epoxy resins.

6. The curable resin composition according to any one of claims 1, 2 or 3, wherein the compound B has 2 or more epoxy groups per 1 molecule.

7. The curable resin composition according to any one of claims 1, 2 or 3, wherein the compound C is isophorone diisocyanate.

8. The curable resin composition according to any one of claims 1, 2 or 3, wherein the compound D is an allyl group-containing compound.

9. The curable resin composition according to claim 1, 2 or 3, further comprising E which is an alkoxysilane a1 and/or a hydrolysate thereof, but does not contain a condensate.

10. The curable resin composition according to claim 9, wherein component E is 3-mercaptopropyltrimethoxysilane and/or a hydrolysate thereof, and does not contain a condensate.

11. The curable resin composition according to any one of claims 1, 2, 3 or 10, further comprising F which is a metal alkoxide a2 and/or a hydrolysate thereof, but does not contain a condensate.

12. The curable resin composition according to claim 11, wherein the component F is at least 1 selected from the group consisting of alkoxysilanes, alkoxytitanium compounds and alkoxyzirconium compounds.

13. The curable resin composition according to any one of claims 1, 2, 3, 10 or 12, wherein the nonvolatile content is 90% by weight or more.

14. The curable resin composition according to any one of claims 1, 2, 3, 10 or 12, further comprising a compound which inhibits an ene-thiol reaction.

15. A cured product obtained by curing the curable composition according to any one of claims 1, 2, 3, 10 or 12.

16. A coated article comprising a substrate and a coating layer formed on the substrate by curing the curable resin composition according to any one of claims 1, 2, 3, 10 or 12.

17. The coated article of claim 16, wherein the coating layer has a higher refractive index than the substrate.

18. The coated article according to claim 17, which is suitable for use in 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.

19. A sealed article obtained by curing the curable resin composition according to any one of claims 1, 2, 3, 10 or 12 as a sealing material.

20. The sealed article according to claim 19, which is suitable for use in a light-emitting element, a light-receiving element, a photoelectric conversion element, or a member related to optical transmission.

21. A transparent substrate obtained by impregnating a glass cloth with the curable resin composition according to any one of claims 1, 2, 3, 10 or 12 and then curing the composition.

22. The transparent substrate according to claim 21, which is suitable for use in 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.

23. A multilayer structure which is obtained by applying the curable resin composition according to any one of claims 1, 2, 3, 10 or 12 to a substrate, bonding the composition to another member, and curing the composition.

24. The multilayer structure according to claim 23, which is suitable for use in a liquid crystal panel, an EL panel, a PDP panel, a color filter, or an optical disk substrate.