JP2012180464A - Method for producing thiol group-containing silsesquioxane, curable resin composition containing thiol group-containing silsesquioxane, cured product of the resin composition and various goods derived therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a silsesquioxane containing thiol group, essentially free from a residual silanol group, composed mainly of a polyhedral oligomeric silsesquioxane structure, containing multiple thiol groups in a molecule, having high storage stability of the compound itself and a composition containing the compound, and providing a cured material having high heat-resistance.SOLUTION: The method for producing the silsesquioxane (A) containing thiol group and essentially free from residual silanol group comprises hydrolysis of a thiol group-containing alkoxysilane (a1) expressed by general formula (1): RSi(OR)(in the formula, Ris a 1-8C hydrocarbon group having at least one thiol group or aromatic hydrocarbon group having at least one thiol group; and Ris a hydrogen atom, 1-8C hydrocarbon group or aromatic hydrocarbon group) with water and an acidic catalyst, removal of the acidic catalyst and condensation of the reaction product by adding the product to a polar solvent containing a basic catalyst.

Description

  The present invention relates to a method for producing a thiol group-containing silsesquioxane, a curable resin composition containing a thiol group-containing silsesquioxane, the cured product, and various articles derived therefrom.

  Transparent plastics are lighter than glass and have good processability, 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 loss of light weight and low heat resistance.

  As a method of improving the refractive index of plastic, there is a method of introducing sulfur atoms into the structure. A compound having a thiol group can be thermally cured with epoxies and isocyanates, and a sulfur atom derived from a thiol group can be introduced into the structure. The obtained cured product has a high refractive index, and in particular, a thiourethane resin obtained by reacting with isocyanates (see, for example, Patent Document 1) is used for lenses and the like. However, it is not satisfactory in terms of heat resistance.

A compound having a thiol group can be photocured with a compound having a carbon-carbon double bond by an ene-thiol reaction. The ene-thiol reaction is compared with radical polymerization systems commonly used in photocuring systems, proceeds with UV irradiation regardless of the presence or absence of a polymerization initiator, is not subject to reaction inhibition by oxygen, has a small curing shrinkage, etc. There are advantages. Regarding a curing method and a cured product using this reaction, use of an unsaturated thiol compound having a carbon-carbon double bond and a thiol group in one molecule (for example, refer to Patent Document 2), carbon- A resin composition (for example, see Patent Document 3) composed of a compound having a plurality of carbon double bonds and a compound having a plurality of thiol groups has been proposed. As described above, the ene-thiol reaction can produce a cured product having a thick film, and a lens having a thickness such as a lens can also be produced. However, the obtained cured product is still not sufficiently satisfactory in terms of heat resistance.

On the other hand, as a means of further improving the characteristics of the organic material, by combining the organic material and the inorganic material, the so-called high heat resistance, chemical resistance, high surface hardness, etc., which are the characteristics of the inorganic material, have been imparted. There are organic-inorganic hybrid technologies. Among the techniques, a technique that is excellent in transparency and capable of thick film curing is an organic-inorganic hybrid method using silsesquioxane. Silsesquioxane, which is a kind of silica, represented by RSiO _3/2 , can easily provide an organic-inorganic hybrid cured product by giving R a substituent capable of reacting with an organic material. Studies are underway (see, for example, Patent Document 4). However, although these organic-inorganic hybrid cured products are excellent in heat resistance, there is a problem that the refractive index is generally low because the inorganic component is silica having a low refractive index.

  For organic-inorganic hybrids into which sulfur atoms have been introduced for increasing the refractive index, a composition comprising a silicone having a carbon-carbon double bond and a silicone having a thiol group (for example, see Patent Document 5) is known. ing. However, in the methods described in these patent documents, sufficient heat resistance and surface hardness cannot be obtained because the inorganic component used is silicone (a rubber state at room temperature).

  In order to solve the above problems, the present inventors have developed a so-called random-type silsesquioxane having a thiol group containing sulfur (an alkoxy group or a silanol group remaining) and a carbon-carbon double bond. Organic-inorganic hybrid cured product (Patent Document 6) obtained by ene-thiol reaction with an organic material possessed, and an organic-inorganic hybrid cured product thermally cured with an epoxy group compound or isocyanate (Patent Document 7) Proposed. The cured product is excellent in heat resistance and has a high refractive index because it contains sulfur. However, since it is a random silsesquioxane, the silsesquioxane itself and its composition are used for the remaining silanol. There is a problem that some physical properties are insufficient, such as storage stability of the cured product and heat resistance of a cured product particularly in a field where high heat resistance is required.

  As a method for synthesizing a so-called cage-type silsesquioxane, many methods are known including a method of hydrolyzing phenyltrichlorosilane and then carrying out an equilibration reaction using KOH (see Non-Patent Document 1). In general, an acidic or basic catalyst is often used in combination in order to rapidly perform a hydrolysis reaction and a condensation reaction (see Patent Document 8). As an acidic catalyst in the synthesis of this silsesquioxane, organic acids such as formic acid and acetic acid and mineral acids such as hydrochloric acid and sulfuric acid are usually used (see Patent Document 9). As the basic catalyst, alkali salts such as KOH and NaOH, organic amines such as triethylamine and tetramethylammonium hydroxide, and ammonium hydroxides are used. However, the methods described in these documents do not show a method for efficiently synthesizing a thiol group-containing silsesquioxane having a cage silsesquioxane having a plurality of thiol groups as a main component.

JP-A-3-236386 JP 49-51333 A JP-A-49-54491 Japanese Patent No. 36553976 Japanese Patent Laid-Open No. 56-110731 JP 2007-291313 A JP 2007-217673 A JP 2004-143449 A JP 2007-291313 A

John F. Brown Jr. J. Am. Chem. Soc, 82, 6194-6195, 1960, Journal of the American Chemical Society.

  The present invention has substantially no silanol group remaining, has a cage silsesquioxane structure as a main component, has a plurality of thiol groups in the molecule, and itself and a composition containing the same. An object of the present invention is to produce a thiol group-containing silsesquioxane in a high yield, which is capable of providing a cured product having a high heat resistance and high heat resistance. In addition, it can be easily cured by heating or ultraviolet rays, and can be cured with a thick film due to its low shrinkage, realizing a cured product that satisfies various properties such as heat resistance, chemical resistance, high surface hardness, and high refractive index. It aims at providing the curable resin composition for performing, and providing the hardened | cured material obtained from the said composition.

  As a result of intensive studies to solve the above problems, the present inventor has found that the above problems can be solved by using thiol group-containing alkoxysilanes that are substantially free of silanol groups obtained by a specific method. The present invention has been completed.

That is, the present invention relates to the general formula (1): R ¹ Si (OR ² ) ₃ (wherein R ¹ is a hydrocarbon group having 1 to 8 carbon atoms having at least one thiol group, or at least one thiol group). And R ² represents a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms, or an aromatic hydrocarbon group.) And thiol group-containing alkoxysilanes (a1) and water And the silanol group obtained by adding the above reaction product to a polar solvent containing a basic catalyst and condensing it, followed by hydrolysis reaction using an acidic catalyst. The present invention relates to a method for producing a thiol group-containing silsesquioxane (A), characterized by substantially not remaining. In addition, general formula (1): R ¹ Si (OR ² ) ₃ (wherein R ¹ is a hydrocarbon group having 1 to 8 carbon atoms having at least one thiol group, or an aromatic group having at least one thiol group). Represents a hydrocarbon group, and R ² represents a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms, or an aromatic hydrocarbon group.) An acidic catalyst comprising a thiol group-containing alkoxysilane (a1) represented by Then, the silanol group was obtained by the condensation reaction by adding the previous reaction product to a polar solvent containing a basic catalyst, followed by condensation. A thiol group-containing silsesquioxane (A), a compound having a plurality of carbon-carbon double bonds in the molecule (B), a compound having a plurality of epoxy groups in the molecule (C ) And isocyanes The present invention relates to a curable resin composition comprising at least one selected from the group consisting of compounds (D) having a plurality of radical groups in the molecule. The present invention also relates to a cured product obtained by curing the composition with heat. Furthermore, the present invention provides a transparent substrate obtained by impregnating a glass cloth with the curable composition and then curing; a coating layer obtained by curing the curable composition on a substrate An article characterized by comprising: a sealed article obtained by curing using the curable composition as a sealing material.

According to the production method of the present invention, a thiol group-containing silsesquioxane can be produced in a high yield. Moreover, the thiol group containing silsesquioxane obtained by the said method has favorable storage stability, and even when it is set as a curable composition, storage stability becomes favorable. In addition, the curable composition of the present invention can be cured by irradiation with active energy rays such as ultraviolet rays or heating, and the resulting cured product has good heat resistance and can be cured with a thick film due to low shrinkage. It becomes. Moreover, since the said hardened | cured material is excellent in transparency, it can be used as a transparent substrate, a coating agent, and a sealing material. The article provided with the transparent substrate and the coating layer, and the sealed article are suitable for optical member applications.

It is a viscoelasticity measurement result of the transparent sheet obtained in Example 18 and Comparative Example 11.

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

  In addition to component (a1), alkyltrialkoxysilanes (a2) (a) such as methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane Hereinafter, component (a2)) may be used. The component (a2) can be used either alone or in combination of two or more. Since the amount of the thiol group can be adjusted by using these, the refractive index of the finally obtained cured product is adjusted, or the amount of the curing agent to be used is reduced, so the ratio of the inorganic component in the cured product Can be raised.

  When component (a1) and component (a2) are used in combination, [number of moles of component (a2)] / [total number of moles of component (a1) and component (a2)] (molar ratio: included per molecule The average number of thiol groups) is preferably 0.7 or less. When it exceeds 0.7, the number of thiol groups contained in the resulting thiol group-containing silsesquioxane (A) is reduced, so that the curability is lowered and the physical properties such as the hardness of the cured product are improved. Is also insufficient.

  The thiol group-containing silsesquioxane (A) used in the present invention can be obtained by condensing component (a1) alone or in combination with component (a2), hydrolyzing them, and condensing them. By the hydrolysis reaction, the alkoxy group contained in component (a1) or component (a2) becomes a silanol group, and alcohol is by-produced. The amount of water required for the hydrolysis reaction is [number of moles of water used in hydrolysis reaction] / [total number of moles of each alkoxy group contained in component (a1) and component (a2)] (molar ratio). 4-10. In the case of 0.4 or more and less than 0.5, some alkoxy groups remain in the resulting thiol group-containing silsesquioxane (A), but the adhesion to inorganic materials is improved. Moreover, in the case of 0.5-10, an alkoxy group does not remain substantially in the thiol group containing silsesquioxane (A) obtained, and it is easy to produce thick film hardened | cured material. If it is less than 0.4, the alkoxy group remaining without being hydrolyzed in the thiol group-containing silsesquioxane (A) is too much, so that a large amount of volatile matter is generated during curing and a thick film cured product cannot be produced. It is not preferable. On the other hand, if it exceeds 10, the amount of water to be removed in the subsequent condensation reaction (dehydration reaction) increases, which is economically disadvantageous.

  As the catalyst used in the hydrolysis reaction, an acidic catalyst that can function as a conventionally known hydrolysis catalyst can be arbitrarily used. However, since it is necessary to substantially remove the acid catalyst after the hydrolysis reaction, it is preferable that the removal is easy. As such, thiol group-containing alkoxysilanes (a1) that can be easily removed by a method such as filtration, formic acid that can be removed by reduced pressure because of low boiling point, do not have a thiol group Examples thereof include alkyltrialkoxysilanes (a2), hydrolysates thereof, solvents used during hydrolysis, and solid acid catalysts that are insoluble in water. Examples of the solid acid catalyst include a cation exchange resin, activated clay, and a carbon-based solid acid. Among these, cation exchange resins are preferable because they have high catalytic activity and are easily available. As the cation exchange resin, a strong acid cation exchange resin or a weak acid cation exchange resin can be used. As strong acid type ion exchange resins, Diaion SK series, UBK series, PK series, HPK25 / PCP series (all are trade names of Mitsubishi Chemical Corporation), Amberlite IR120B, IR124, 200CT, 252, Amberjet 1020, 1024, 1060, 1220, Amberlist 15DRY, 15JWET, 16WET, 31WET, 35WET (all trade names of Organo Co., Ltd.) , Diaion WK series, WK40 (all are trade names manufactured by Mitsubishi Chemical Corporation), Amberlite FPC3500, IRC76 (all are trade names manufactured by Organo Corporation), and the like. Although the type of ion exchange resin to be used can be arbitrarily selected depending on the reaction rate, side reaction suppression, and the like, strong acidic ion exchange resins are particularly preferable in terms of reactivity.

  The addition amount of the acid catalyst is preferably 0.1 to 25 parts by weight, and more preferably 1 to 10 parts by weight with respect to 100 parts by weight as the total of the component (a1) and the component (a2). When the amount is more than 25 parts by weight, it tends to be difficult to remove in a later step or economically disadvantageous. On the other hand, when the amount is less than 0.1 parts by weight, the reaction does not substantially proceed or the reaction time tends to be long.

  Although reaction temperature and time can be arbitrarily set according to the reactivity of a component (a1) or a component (a2), it is about 0-100 degreeC normally, Preferably it is about 20-60 degreeC, 1 minute-about 2 hours. The hydrolysis reaction can be performed in the presence or absence of a solvent, but it is preferable not to use a solvent. When the solvent is used, the type of the solvent is not particularly limited, and one or more arbitrary solvents can be selected and used, but it is preferable to use the same solvent as that used in the condensation reaction described later.

  After completion of the hydrolysis reaction, it is necessary to substantially remove the acid catalyst from the system. Otherwise, the reaction will not proceed in the condensation reaction described below, the silanol groups will not be consumed completely, or the system will gel due to abnormally high molecular weight. Oxan (A) cannot be obtained. The removal method can be appropriately selected from various known methods depending on the catalyst used. For example, as described above, when formic acid is used, it can be easily removed by a reduced pressure, and when a solid acid catalyst is used, it can be easily removed by a method such as filtration after completion of the condensation reaction.

  Further, after the hydrolysis reaction is completed and the acid catalyst is removed from the system, or at the same time as the removal of the acid catalyst, by-product alcohol or excess water may be removed by a method such as decompression. Moreover, by diluting with a solvent used for the condensation reaction after the removal, the hydrolysis reaction product can be easily added in the subsequent condensation reaction.

In the condensation reaction, water is by-produced between the silanol groups, and alcohol is by-produced between the silanol group and the alkoxy group to form a siloxane bond. In the condensation reaction, a basic catalyst that can function as a conventionally known dehydration condensation catalyst can be arbitrarily used. Among them, those having high basicity are preferable, and specific examples thereof include alkali salts such as sodium hydroxide (NaOH), potassium hydroxide (KOH), calcium hydroxide (Ca (OH) ₂ ), 1,8-diazabicyclo [5 4.0] undec-7-ene, organic amines such as 1,5-diazabicyclo [4.3.0] non-5-ene, ammonium hydroxy such as tetramethylammonium hydroxide, tetrabutylammonium hydroxide, etc. Dosage and the like. These exemplified compounds can be used alone or in appropriate combination. Of the exemplified compounds, tetramethylammonium hydroxide is particularly preferable because of its high catalytic activity and easy availability. In addition, when these basic catalysts are used as aqueous solutions, the hydrolysis reaction proceeds in the condensation reaction step, so the amount of water used during hydrolysis is reduced in advance by the amount of water contained in the basic catalyst. It is necessary to adjust appropriately.

  The addition amount of the basic catalyst is preferably 0.01 to 5 parts by weight and preferably 0.1 to 2 parts by weight with respect to 100 parts by weight as a total of the component (a1) and the component (a2). More preferred. If the amount is more than 5 parts by weight, the cured product produced using the resulting thiol group-containing silsesquioxane (A) is likely to be colored, or when the catalyst is removed, it cannot be removed or removed. The process tends to be long. On the other hand, when the amount is less than 0.1 parts by weight, the reaction does not substantially proceed or the reaction time tends to be long.

  Although reaction temperature can be arbitrarily set according to the reactivity of a component (a1) or a component (a2), respectively, it is about 40-150 degreeC normally, Preferably it is about 60-100 degreeC. The condensation reaction is performed in the presence of a polar solvent. When the reaction is carried out in a nonpolar solvent, the silanol groups are not completely consumed, or the system becomes gelled due to abnormal high molecular weight, which is not preferable. As the polar solvent, polar solvents that are compatible with water are preferable, and glycol ethers are particularly preferable. Of the glycol ethers, dialkyl glycol ether solvents are particularly preferred because the above-described abnormal high molecular weight is unlikely to occur. Examples of dialkyl glycol ether solvents that are compatible with water include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and diethylene glycol diethyl ether.

  The condensation reaction is carried out by a method in which the reaction temperature is set and a solution containing the hydrolyzate obtained by the hydrolysis reaction is sequentially added to the polar solvent to which the dehydration condensation catalyst is added. The method of addition can be appropriately selected from various known methods. The time required for the addition can be arbitrarily set according to the reactivity of the component (a1) or component (a2), but is usually about 30 minutes to 12 hours.

  When performing the condensation reaction by the above method, it is preferable to carry out the reaction until there is substantially no unreacted silanol group. When unreacted silanol groups remain, the storage stability of the resulting composition containing the thiol group-containing silsesquioxane (A) or the thiol group-containing silsesquioxane (A) is reduced, or silsesquioxane Since this structure is a random type, the heat resistance is lowered, which is not preferable. Moreover, it is made to advance so that [total number of moles of unreacted alkoxy group] / [total number of moles of each alkoxy group contained in component (a1) or component (a2)] (molar ratio) is 0.2 or less. It is preferable that the value is substantially 0. If it exceeds 0.2, the amount of random silsesquioxane increases and the heat resistance of the resulting cured product decreases, or the unreacted alkoxy group undergoes a condensation reaction after curing to generate volatile matter and cracks. It is not preferable because it impairs the performance of the cured product. On the other hand, when it is greater than 0 and less than or equal to 0.2, a part of the alkoxy group remains in the resulting thiol group-containing silsesquioxane (A), but the adhesion to inorganic materials is improved. preferable. By setting it to 0, the alkoxy group does not substantially remain, and a thick film cured product can be easily produced, and the cage structure contained in the resulting thiol group-containing silsesquioxane (A) is maximized. Particularly preferred from the viewpoint of improving the heat resistance of the cured product. When it is not 0, the amount of random silsesquioxane contained in the resulting thiol group-containing silsesquioxane (A) tends to increase and the molecular weight (Mw) tends to increase.

  The condensation reaction is preferably performed by diluting the solvent so that the concentration of component (a1) (or both when component (a2) is used in combination) is about 2 to 80% by weight. It is more preferable. It is preferable to use a solvent having a boiling point higher than that of water and alcohol generated by the condensation reaction because these can be distilled off from the reaction system. When the concentration is less than 2% by weight, the thiol group-containing silsesquioxane (A) contained in the resulting curable composition is decreased, which is not preferable. If it exceeds 80% by weight, it tends to gel during the reaction, or the molecular weight of the thiol group-containing silsesquioxane (A) to be generated tends to be too large.

  When the used catalyst is removed after completion of the condensation reaction, the stability of the thiol group-containing silsesquioxane (A) and the curable resin composition containing the thiol group-containing silsesquioxane (A) is improved. Therefore, it is preferable. The removal method can be appropriately selected from various known methods depending on the catalyst used. For example, when tetramethylammonium hydroxide is used, it can be removed by a method such as adsorption and removal with a cation exchange resin after completion of the condensation reaction.

  The thiol group-containing silsesquioxane (A) of the present invention can be made into a thermosetting resin composition or an ultraviolet curable resin composition by blending various curing agents. When making it into an ultraviolet curable composition, it is preferable to set it as the composition containing the compound (B) which has a thiol group containing silsesquioxane (A) and a carbon-carbon double bond, and is a thermosetting resin composition. In the case of a product, a composition containing at least one selected from a thiol group-containing silsesquioxane (A), a compound having an epoxy group (C), and a compound having an isocyanate group (D) may be used. preferable. Moreover, at least 1 type selected from a compound (C) and a compound (D) and a compound (B) can be used together, and it can be set as the resin composition hardened | cured by both a heat | fever and light.

  The ultraviolet curable composition will be described.

  The component (B) used in the present invention is not particularly limited, and a compound having a plurality of conventionally known carbon-carbon double bonds in the molecule can be appropriately used. Since there are a plurality of carbon-carbon double bonds in the molecule, a cured product can be produced by forming a crosslinked structure with the thiol group-containing silsesquioxane (A) having a plurality of thiol groups in the molecule. Examples of the functional group related to the carbon-carbon double bond include a vinyl group, an acrylic group, a methacryl group, and an allyl group.

  The carbon-carbon double bond of the component (B) reacts with the thiol group of the thiol group-containing silsesquioxane (A) (ene-thiol reaction), but the reaction involves the type of carbon-carbon double bond, The reaction mechanism varies depending on the presence or absence of a radical polymerization initiator. That is, when a compound having a vinyl group or an allyl group having low radical polymerizability is used as the component (B), only the ene-thiol reaction proceeds, and the thiol group in the thiol group-containing silsesquioxane (A). And the carbon-carbon double bond in the component (B) react at about 1: 1 (molar ratio). On the other hand, when a compound having a highly radically polymerizable acrylic group or methacrylic group is used as the component (B), a carbon-carbon double bond in the component (B) is used particularly when a radical polymerization initiator is used in combination. The polymerization reaction proceeds in parallel, and the thiol group in the thiol group-containing silsesquioxane (A) and the carbon-carbon double bond in the component (B) react at about 1: 1 to 100 (molar ratio). To do.

  From the above viewpoint, the use ratio of the thiol group-containing silsesquioxane (A) and the component (B) in the preparation of the ultraviolet curable resin composition of the present invention depends on the type of carbon-carbon double bond and the radical. It is determined appropriately depending on the presence or absence of a polymerization initiator. When the component (B) having a vinyl group and an allyl group having low radical polymerizability is used, [the number of moles of thiol groups contained in the thiol group-containing silsesquioxane (A)] / [component (B) The number of moles of carbon-carbon double bonds contained] (molar ratio) is preferably 0.9 to 2.5, and more preferably 1.0. If it is less than 0.9, carbon-carbon double bonds remain even after UV curing, and the weather resistance tends to be lowered. Moreover, when exceeding 2.5, the crosslinking density of hardened | cured material falls and heat resistance may be reduced.

  On the other hand, when a component (B) having a highly radical polymerizable acryl group or methacryl group is used, particularly when a radical polymerization initiator is used in combination, it is included in [thiol group-containing silsesquioxane (A). It is preferable that the number of moles of thiol group] / [number of moles of carbon-carbon double bonds contained in component (B)] (molar ratio) is 0.01 to 1.1. When it is less than 0.01, the amount of the component (A) to be used is too small, so that it is difficult to obtain the desired effects of the present invention such as improvement of the refractive index. Furthermore, the carbon-carbon double bond tends to remain, and the weather resistance of the cured product tends to be lowered. Moreover, when it exceeds 1.1, since a thiol group remains, the crosslinking density of hardened | cured material may fall and heat resistance may be reduced.

Examples of the component (B) having a vinyl group and an allyl group having low radical polymerizability include diallyl phthalate, diallyl isophthalate, diallyl cyanurate, diallyl isocyanurate, pentaerythritol diallyl ether, trimethylolpropane diallyl ether, glyceryl 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, triallyl isocyanurate, pentaerythritol triallyl Ether, pentaerythritol tetraallyl ether Ether, trimethylolpropane triallyl ether, divinyl benzene, divinyl adipate and the like. These compounds can be used either alone or in combination. Among these, an allyl group-containing compound is preferable because the storage stability of the resulting composition is high, and triallyl isocyanurate, diallyl phthalate, and pentaerythritol triallyl ether are particularly preferable because they are easily available.

  Examples of the component (B) having an acrylic group and a methacryl group having high radical polymerization include 2-hydroxy-3-acryloyloxypropyl methacrylate, tricyclodecane dimethanol diacrylate, 1,10-decanediol diacrylate, 1, 6-hexanediol diacrylate, 1,9-nonanediol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, tris (2-acryloyloxyethyl) isocyanurate, trimethylolpropane triacrylate, pentaerythritol triacrylate, 1,4-butanediol dimethacrylate, neopentyl glycol dimethacrylate and the like. These compounds can be used either alone or in combination.

  Moreover, as a component (B), a thing with a higher molecular weight than the said compound can be used. The ultraviolet curable resin composition using a high molecular weight product tends to improve the flexibility of the resulting cured product. Examples of the high molecular weight compound include a copolymer composed of methylallylsiloxane and dimethylsiloxane, a copolymer composed of epichlorohydrin and allylglycidyl ether (Daiso Co., Ltd .: trade name “Epichromer”, Nippon Zeon Co., Ltd .: Commodity Name “Gechron”, etc.), allyl group-terminated polyisobutylene polymer (Kaneka Co., Ltd .: trade name “Epion”), urethane acrylate (manufactured by Arakawa Chemical Industries, Ltd .: trade name “Beamset 550B”), and the like. These compounds can be used alone or in combination of two or more.

  When using component (B), [number of moles of carbon-carbon double bonds contained in component (B)] / [number of moles of component (B)] (molar ratio: carbon-carbon contained per molecule) The average number of double bonds is preferably 2 or more. When it is less than 2, since the curability of the ultraviolet curable resin composition is lowered and the cross-linking density of the obtained cured product is lowered, physical properties such as heat resistance and surface hardness of the cured product tend to be lowered.

  It does not specifically limit as a polymerization initiator which can be used when preparing an ultraviolet curable resin composition, A conventionally well-known photocationic initiator, a photoradical initiator, etc. can be selected arbitrarily. Examples of the photocation initiator include sulfonium salts, iodonium salts, metallocene compounds, benzoin tosylate, and the like, which are compounds that generate an acid upon irradiation with ultraviolet rays. Examples of such commercially available products include Cyracure UVI-6970 and UVI. -6974, UVI-6990 (all trade names of Union Carbide, USA), Irgacure 264 (BASF), CIT-1682 (Nippon Soda Co., Ltd.) and the like. The usage-amount of a photocationic polymerization initiator is normally about 10 weight part or less with respect to 100 weight part of this composition, Preferably it is 1-5 weight part. Examples of the photoradical initiator include Darocur 1173, Irgacure 651, Irgacure 184, Irgacure 907 (all trade names manufactured by BASF), benzophenone, and the like. Is 0.1 to 2 parts by weight. When there is a concern about a decrease in the weather resistance of the resulting cured product, it is better not to use a photoinitiator or a photosensitizer, especially when used for an optical member that requires high weather resistance and transparency. .

  Moreover, in order to improve the stability of an ultraviolet curable resin composition more, the compound which suppresses ene-thiol reaction can be mix | blended. Examples of such compounds include phosphorus compounds such as triphenylphosphine and triphenyl phosphite; p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2, 6-di-tert-butyl-p-cresol, 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol) Radical), N-nitrosophenylhydroxylamine aluminum salt, diphenylnitrosamine and other radical polymerization inhibitors; benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (diaminomethyl) phenol, diaza Tertiary amines such as bicycloundecene; 2-methylimidazole, 2- Examples include imidazoles such as ethyl-4-methylimidazole, 2-ethylhexylimidazole, 2-undecylimidazole, and 1-cyanoethyl-2-methylimidazole.

  Among the phosphorus compounds, triphenyl phosphite is preferable because it has a high inhibitory effect on the ene-thiol reaction, is liquid at room temperature, and is easy to handle. The amount of the compound to be blended in the ultraviolet curable resin composition is preferably about 0.1 to 10 parts by weight with respect to 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 exceeds 10 parts by weight, the remaining amount in the obtained cured product is increased and the physical properties of the cured product are deteriorated. Tend.

  Of the radical polymerization inhibitors, nitrosophenylhydroxylamine aluminum salt is preferable because it has a high inhibitory effect on the ene-thiol reaction even in a small amount and is excellent in the color tone of the resulting cured product. The amount of the compound to be blended in the ultraviolet curable resin composition is preferably about 0.0001 to 0.1 parts by weight with respect to 100 parts by weight of the composition. When the amount is less than 0.0001 part by weight, the effect of suppressing the ene-thiol reaction is insufficient, and when it exceeds 0.1 part by weight, the ultraviolet curability tends to be lowered.

  Of the tertiary amines, benzyldimethylamine is preferable because it has a high inhibitory effect on the ene-thiol reaction even in a small amount and is liquid at room temperature and easy to handle. The amount of the compound to be blended in the ultraviolet curable resin composition is preferably about 0.001 to 5 parts by weight with respect to 100 parts by weight of the composition. When the amount is less than 0.001 part by weight, the effect of suppressing the ene-thiol reaction is insufficient. When the amount exceeds 5 parts by weight, an unreacted hydroxyl group and alkoxy group in the component (A) undergo a condensation reaction. This is not preferable because it tends to gel.

  The concentrations of the active ingredients (A) and (B) of the ultraviolet curable resin composition can be appropriately determined according to the application, and a solvent can be blended as necessary. A conventionally well-known thing can be arbitrarily used as a solvent. When the ultraviolet curable resin composition is used as a coating agent, it may be diluted with a solvent to obtain a desired viscosity. When the UV curable resin composition is cured to a thick film of 1 mm or more or used as an adhesive, the total concentration of thiol group-containing silsesquioxane (A) and component (B) is 90% by weight. It is preferable to make it above, and it is more preferable to make it 95% by weight or more. The total concentration may be calculated from the concentration of the thiol group-containing silsesquioxane (A) and the component (B) and the amount of the solvent added during the preparation of the ultraviolet curable resin composition. It can also be determined by heating for about 2 hours above the boiling point of the solvent contained in the resin composition, and by changing the weight before and after heating. In the application, if it is less than 90% by weight, the physical properties of the cured product tend to be lowered due to foaming during curing and molding, or solvent remaining in the cured product. In addition, since the solvent is indispensably used in the synthesis of the thiol group-containing silsesquioxane (A), the solvent is used so that the nonvolatile content becomes 90% by weight or more after completion of the reaction when used in this application. Should be volatilized. Moreover, after preparing an ultraviolet curable resin composition, the used solvent can be volatilized and the total density | concentration of an active ingredient (A) and (B) can also be raised.

  Furthermore, the ultraviolet curable resin composition has a plasticizer, a weather resistance agent, an antioxidant, a heat stabilizer, a lubricant, and an antistatic agent within the range that does not impair the effects of the present invention. , Whitening agents, colorants, conductive agents, mold release agents, surface treatment agents, viscosity modifiers, fillers, and the like may be blended.

In order to prepare a desired cured product using the ultraviolet curable resin composition thus obtained, when the composition is coated on a predetermined substrate or filled in a predetermined mold and contains a solvent, What is necessary is just to irradiate an ultraviolet-ray after volatilizing this solvent. The method for volatilizing the solvent may be appropriately determined according to the type, amount, film thickness, etc. of the solvent, but it is heated to about 40 to 150 ° C., preferably 60 to 100 ° C., for 5 seconds to 2 at normal pressure or reduced pressure. The condition is about time. The irradiation amount of ultraviolet rays may be appropriately determined according to the type and film thickness of the ultraviolet curable resin composition, but when a high pressure mercury lamp is used, the integrated light amount at 365 nm is about 50 to 10,000 mJ / cm ^2. Irradiation is sufficient. Moreover, when coating or filling with a thick film, it is preferable to improve photocurability by adding a photoreaction initiator or a photosensitizer to the composition as described above.

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

  Next, the thermosetting resin composition will be described.

  The component (C) used in the present invention is not particularly limited, and a conventionally known compound having an epoxy group can be appropriately used. For example, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, stilbene type Epoxy resin, triazine skeleton-containing epoxy resin, fluorene skeleton-containing epoxy resin, linear aliphatic epoxy resin, alicyclic epoxy resin, glycidylamine-type epoxy resin, triphenolphenolmethane-type epoxy resin, alkyl-modified triphenolmethane-type epoxy resin Biphenyl type epoxy resin, dicyclopentadiene skeleton-containing epoxy resin, naphthalene skeleton-containing epoxy resin, arylalkylene type epoxy resin, and the like. These compounds can be used alone or in combination of two or more. Among the exemplified compounds, bisphenol A type epoxy resins (for example, Mitsubishi Chemical Corporation: trade name “JER828”) and bisphenol F type epoxy resins (for example, Mitsubishi Chemical Corporation) ): Trade name “JER807”, etc., hydrogenated bisphenol A type epoxy resin (commercially available products such as Nippon Steel Chemical Co., Ltd .: trade name “ST-3000”, etc.), alicyclic epoxy resin (commercially available) As the product, for example, Daicel Chemical Industries, Ltd .: trade name “Celoxide 2021P” and the like are particularly preferable because the finally obtained cured product is excellent in colorless transparency, heat resistance and the like and is easily available. .

  Moreover, as a component (C), a thing with a higher molecular weight than the said compound can be used. Thermosetting resin compositions using high molecular weight products tend to improve the flexibility of the resulting cured product. Examples of the high molecular weight substance include bisphenol A type epoxy resin and bisphenol F type epoxy resin having an epoxy equivalent of 2000 g / eq or more (Mitsubishi Chemical Corporation: trade names “JER1010”, “JER4007P”, etc.), epoxy Examples thereof include modified silicone (Shin-Etsu Chemical Co., Ltd .: trade name “X-22-163A”, etc.), polyethylene glycol diglycidyl ether, and the like. These compounds can be used alone or in combination of two or more. Among these, polyethylene glycol diglycidyl ether is preferable.

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

  Moreover, as a component (D), the thing of higher molecular weight than the said compound can be used. Thermosetting resin compositions using high molecular weight products tend to improve the flexibility of the resulting cured product. Examples of the high molecular weight products include modified diisocyanates of polyols such as polycarbonate diol and polyester diol, polymeric MDI (Mitsui Takeda Chemical Co., Ltd .: trade name “Cosmonate M”, etc.), isocyanurate of hexamethylene diisocyanate (Japan) Polyurethane Industry Co., Ltd. product name: “Coronate HX”). These compounds can be used alone or in combination of two or more. Among these exemplified compounds, hexamethylene diisocyanate isocyanurate is particularly preferred because the finally obtained cured product is excellent in colorless transparency, heat resistance and the like and is easily available.

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

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

  The concentration of the active ingredient (A), (C) or (D) of the thermosetting resin composition can be appropriately determined according to the application, and a solvent can be blended as necessary. The solvent only needs to be non-reactive with the component, and various conventionally known solvents can be appropriately selected and used. When the thermosetting resin composition is used as a coating agent, it may be diluted with a solvent to obtain a desired viscosity. Further, when the thermosetting resin composition is cured to a thick film of 1 mm or more or used as an adhesive, the total concentration of the thiol group-containing silsesquioxane (A), component (C) or (D) Is preferably 90% by weight or more, and more preferably 95% by weight or more. The total concentration may be calculated from the concentration of the thiol group-containing silsesquioxane (A) and the component (C) or (D) and the amount of the solvent added at the time of charging the thermosetting composition, It can also be determined by heating for about 2 hours above the boiling point of the solvent contained in the thermosetting composition, and by changing the weight before and after heating. In the application, if it is less than 90% by weight, foaming may occur during curing and molding, or a solvent may remain in the cured product, and the physical properties of the cured product tend to decrease. In addition, since the solvent is indispensably used in the synthesis of the thiol group-containing silsesquioxane (A), the solvent is used so that the nonvolatile content becomes 90% by weight or more after completion of the reaction when used in this application. Should be volatilized. Moreover, after preparing a thermosetting resin composition, the used solvent can be volatilized and the total density | concentration of an active ingredient (A), (C) or (D) can also be raised.

  The use ratio of the thiol group-containing silsesquioxane (A) and the component (C) or (D) in preparing the thermosetting resin composition is [the thiol group contained in the thiol group-containing silsesquioxane (A). The number of moles of the epoxy group contained in the component (C) or the number of moles of the isocyanate group contained in the component (D) (molar ratio) is 0.9 to 2.5. Is more preferable, and 1.0 is more preferable. When it is less than 0.9, epoxy groups and isocyanate groups remain even after thermosetting, and the weather resistance tends to be lowered. Moreover, when exceeding 2.5, the crosslinking density of hardened | cured material falls and heat resistance may be reduced.

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

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

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

  Further, the heat and ultraviolet curable resin composition will be described.

  The composition comprising thiol group-containing silsesquioxane (A) and component (B) as essential components and either or both of component (C) and component (D) is cured in two stages with ultraviolet and heat. Composition. Each component has [{number of thiol groups in thiol group-containing silsesquioxane (A)} / {number of double bonds contained in component (B)}] of 0.1 to 0.8, [ {Number of thiol groups in component (A)} / {number of epoxy groups in component (C) + number of isocyanate groups in component (D)}] is 0.1 to 0.8, [{component ( Number of thiol groups in A) / {number of double bonds contained in component (B) + number of epoxy groups in component (C) + number of isocyanate groups in component (D)} is 0 .9 to 1.1. [{Number of thiol groups in component (A)) / {number of double bonds contained in component (B) + number of epoxy groups in component (C) + number of isocyanate groups in component (D) }] Is 1.1 or more, the thiol group remains and may cause malodor due to its decomposition. If it is less than 0.9, carbon-carbon double bonds, epoxy groups, and isocyanate groups remain after curing, and the weather resistance tends to decrease. When [{the number of thiol groups in the thiol group-containing silsesquioxane (A)} / {the number of double bonds contained in the component (B)}] is less than 0.1, UV curing is the first When the stage is set, curing proceeds too much, and when the thermosetting is set as the first stage, too much unreacted component (B) in the semi-cured product, both of which lose the moldability There is. Moreover, when it exceeds 0.8, the component (C) and the component (D) are inevitably [{number of thiol groups in the component (A)} / {number of epoxy groups in the component (C) + component]. The number of isocyanate groups in (D)}] exceeds 0.8, and when UV curing is the first stage, the amount of unreacted (C) component is excessive in the semi-cured product. When the thermosetting is the first stage, the curing proceeds too much, and in any case, the molding processability may be lost.

When [{number of thiol groups in component (A)} / {number of epoxy groups in component (C) + number of isocyanate groups in component (D)}] is less than 0.1, UV curing is performed. In the case of the first stage, since there are too many unreacted components (C) and components (D) in the semi-cured product, if the thermal curing is set to the first stage, the curing proceeds too much. Moldability may be lost. Moreover, when it exceeds 0.8, the component (B) is inevitably [{the number of thiol groups in the thiol group-containing silsesquioxane (A)} / {the double bond contained in the component (B). Number}] exceeds 0.8, and when UV curing is the first step, curing proceeds too much, and when heat curing is the first step, unreacted in the semi-cured product. Since the component (B) is too much, molding processability may be lost in any case.

  As the components (B), (C), and (D), those described above can be arbitrarily used. In addition, as components (B) and (D), methacryloyloxyethyl isocyanate (manufactured by Showa Denko KK: trade name “Karenz MOI”), acryloyloxyethyl isocyanate (manufactured by Showa Denko KK: trade name “ It is also possible to use a compound in which a double bond and an isocyanate group are simultaneously present in one molecule, such as Karenz AOI ”). When such a compound is used, it can be considered that the components (B) and (D) are simultaneously contained, and is used in consideration of the number of double bonds and the number of isocyanate groups contained in the molecule. The amount needs to be determined.

  Furthermore, in the heat and ultraviolet curable resin composition, plasticizers, weathering agents, antioxidants, heat stabilizers, lubricants, electrifications are required as long as the effects of the present invention are not impaired. You may mix | blend an inhibitor, a whitening agent, a coloring agent, a electrically conductive agent, a mold release agent, a surface treating agent, a viscosity modifier, a filler, etc. In addition, the curing catalyst and stabilizer used in preparing the curable composition comprising the thiol group-containing silsesquioxane (A) and the component (B), (C) or (D) should be used in the same manner. Can do.

The heat and ultraviolet curable resin composition of the present invention is poured into a container or a flat plate, preferably a container that has been subjected to a release treatment such as Teflon (registered trademark) coating, heated to dry the solvent, and then heated and irradiated with ultraviolet light. It can be cured by stepwise curing. As a method of performing the two-stage curing, there is a method in which the thermosetting is performed in the first stage and then the UV curing is performed in the second stage, the UV curing is performed in the first stage, and the thermosetting is performed in the second stage. It is done.

The two-stage curing is preferably one in which the heat and ultraviolet curable resin composition are thermally cured to a semi-cured state, molded, and then ultraviolet cured. The semi-cured state means a state in which only the component (A) and the component (C) or the component (D) are reacted with heat and the ultraviolet curable resin composition by heat. It means a state in which the elastic modulus at the temperature to be performed is 10 ⁵ to 10 ⁷ Pa. Since such a semi-cured state during curing is not sufficiently cured, various molding processes are possible. As a method of molding processing, for example, a flat plate is coated with a heat and ultraviolet curable resin composition, and then a semi-cured state is obtained by thermosetting, and the flat plate is made to prevent the heat and ultraviolet curable resin composition from flowing from the flat plate. Bending, completely curing with ultraviolet rays in the bent state, a method of producing a transparent sheet adhered to the curved surface, and after coating a flat plate with heat and ultraviolet curable resin composition, it is in a semi-cured state by heat curing, After the mold is pressed and cured with ultraviolet light, the so-called imprint method, or after coating the flat plate with heat and ultraviolet curable resin composition, the resin is semi-cured by heat curing and exposed with the photomask attached. So-called photolithography method, etc. that removes unexposed parts after UV irradiation so that the part has the desired shape And the like. The first stage curing temperature and heating time by heat are appropriately determined in consideration of the type of component (A), component (C) and component (D) used, the type of solvent, the thickness of the transparent sheet, and the like. However, it is usually preferable to set the temperature at about 20 to 150 ° C. for about 1 minute to 24 hours. In addition, in the curing by ultraviolet rays in the second stage after the molding process, the irradiation amount of the ultraviolet rays may be appropriately determined according to the type of ultraviolet curable resin composition, the film thickness, etc. What is necessary is just to irradiate so that the integrated light quantity in 365 nm may be about 50-10000 mJ / cm < ² >. Moreover, when coating or filling with a thick film, it is preferable to improve photocurability by adding a photoreaction initiator or a photosensitizer to the composition as described above. In this way, the component (A) and the component (B) are reacted to cause the curing to proceed completely.

The two-stage curing is preferably one in which the heat and ultraviolet curable resin composition is ultraviolet cured to be in a semi-cured state, molded and then thermally cured. The semi-cured state means a state in which only the component (A) and the component (B) are reacted with heat and the ultraviolet curable resin composition by ultraviolet rays, and specifically, at a temperature at which molding processing is performed. It means a state where the elastic modulus is 10 ⁵ to 10 ⁷ Pa. Since such a semi-cured state during curing is not sufficiently cured, various molding processes are possible. As a method of molding processing, for example, a flat plate is coated with a heat and ultraviolet curable resin composition, and then is made into a semi-cured state by ultraviolet curing so that the heat and ultraviolet curable resin composition do not flow from the flat plate. Bending, by completely curing with heat in the bent state, a method for producing a transparent sheet adhered to the curved surface, and after coating the heat and ultraviolet curable resin composition on a flat plate, it is in a semi-cured state by ultraviolet curing, Examples include a so-called imprint method in which a mold is pressed and cured by heat. When a solvent is used in the heat and ultraviolet curable resin composition, it is preferable to dry the solvent before ultraviolet irradiation and use it as a substantially solvent-free. The irradiation amount of the first stage ultraviolet ray by the ultraviolet ray is appropriately determined in consideration of the used component (A), the type of component (B), the type of solvent, the thickness of the transparent sheet, etc., but a high pressure mercury lamp is used. In this case, irradiation may be performed so that the integrated light amount at 365 nm is about 50 to 10,000 mJ / cm ² . Moreover, when coating or filling with a thick film, it is preferable to improve photocurability by adding a photoreaction initiator or a photosensitizer to the composition as described above. In addition, in the second stage heat curing after the molding process, the curing temperature and the heating time are determined based on the types of components (A), (C) and (D) used, the types of solvents, and the transparent sheet. The thickness is appropriately determined in consideration of the thickness and the like, but usually at about 20 to 150 ° C. for 1 minute to 24 hours, the residual solvent is completely removed and the curing reaction is further advanced.

  The concentrations of the active ingredients (A), (B), (C) and (D) of the heat and ultraviolet curable resin composition can be determined as appropriate according to the application, and a solvent can be blended as necessary. . The solvent only needs to be non-reactive with the component, and various conventionally known solvents can be appropriately selected and used. When the heat and ultraviolet curable resin composition is used as a coating agent, it may be diluted with a solvent to obtain a desired viscosity. When the heat and ultraviolet curable resin composition is cured into a thick film of 1 mm or more, or when used as an adhesive, the total concentration of the components (A), (C) or (D) is 90% by weight or more. It is preferable to make it 95% by weight or more. The total concentration may be calculated from the concentration of the components (A) and (C) or (D) and the amount of the solvent added at the time of charging the heat and ultraviolet curable composition. It can also be determined by heating for about 2 hours above the boiling point of the solvent contained in the composition, and by changing the weight before and after heating. In the application, if it is less than 90% by weight, foaming may occur during curing and molding, or a solvent may remain in the cured product, and the physical properties of the cured product tend to decrease. In addition, since the solvent is indispensably used during the synthesis of component (A), when used in the application, the solvent should be volatilized after the reaction so that the nonvolatile content is 90% by weight or more. Good. Moreover, after preparing a thermosetting resin composition, the used solvent is volatilized and the total density | concentration of an active ingredient (A), (B), (C), (D) can also be raised.

  According to each curable resin composition obtained by the above-described method, a cured product having excellent transparency can be obtained, and can be put to practical use by the following method.

(Application to coating agent)
A coating layer can be obtained by coating a curable resin composition on a desired substrate and then heat-curing and / or UV-curing. As the substrate, inorganic substrates such as glass, iron, aluminum, copper, tin-doped indium oxide (ITO), polyethylene (PE), polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), polyethylene terephthalate (PEN) ), Polymethyl methacrylate (PMMA), polystyrene (PSt), polycarbonate (PC), organic base materials such as acrylonitrile-butadiene-styrene (ABS), and the like can be appropriately selected and used. Moreover, coating property can also be improved to some extent by diluting a curable composition with a solvent. 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, by coating the thermosetting composition as described above, and thermosetting and / or ultraviolet curing. A coating layer can be formed on a lens, a plastic substrate for a liquid crystal cell, a prism, or the like. Moreover, when the refractive index of the coating layer obtained from a curable resin composition is higher than the refractive index of a base material, an antireflection effect can be provided. Moreover, in the case of an ultraviolet curable composition, a pattern can also be provided by removing an unexposed part after irradiating an ultraviolet-ray so that an exposed part may become a target shape.

(Application to adhesive)
A desired adhesive layer can be obtained by interposing a curable resin composition between predetermined substrates, and then thermally curing and / or ultraviolet-curing the composition. As the substrate, the same materials as those used when forming the coating layer can be used. However, in order to cure the adhesive layer with ultraviolet rays, at least one surface needs to transmit heat or ultraviolet rays. In order to prevent foaming of the adhesive layer, it is preferable that the volatile component in the curable resin composition is less than 10%, preferably less than 5%, as described above, or the volatile component is removed before pasting. . Adhesion with a curable resin composition as described above provides an adhesive with a transparent adhesive layer, which is suitable for producing liquid crystal panels, EL panels, PDP panels, color filters, optical disk substrates, and the like. .

(Application to sealing material)
After the curable resin composition is applied in a thick film or poured into a predetermined mold, it is cured by heat and / or ultraviolet rays, whereby a sealed article sealed with a transparent cured product can be obtained. Such a material is particularly suitable for use in optical parts such as a light emitting element, a light receiving element, a photoelectric conversion element, and an optical transmission related part. When preparing the molded cured product, as described above, a suitable amount of a photocuring catalyst or a photosensitizer is blended in the composition, or the volatile content in the composition is less than 10%, Preferably it is less than 5%.

(Application to transparent substrate)
A transparent substrate can be obtained by impregnating a glass cloth (base material) with a curable resin composition, followed by heat curing and / or ultraviolet curing. Various known glass cloths can be appropriately selected and used. As the glass cloth, various fabrics obtained from various known glass fibers (strands composed of E glass, C glass, ECR glass, etc., yarn, roving, etc.) can be used. It is particularly preferable because it is inexpensive and has excellent availability. The method for impregnating the glass cloth with the curable resin composition is not particularly limited, and various known methods can be employed, and a coating method may be employed. Moreover, in order to make the transparent substrate obtained colorless and transparent, it is preferable that the difference in refractive index between the cured product obtained from the curable resin composition and the glass cloth is within 0.010, and within 0.005. More preferably, it is more preferable that they are substantially the same. Moreover, the impregnation property to a glass cloth can also be improved more by carrying out solvent dilution of the curable resin composition. In addition, the usage-amount of the thermosetting resin composition with respect to a glass cloth can be suitably determined according to the use of the transparent substrate obtained, and is normally 20-500 weight part per 100 weight part of glass cloth. Moreover, the thickness of the transparent substrate obtained can also be suitably determined according to this use, and is normally set to 20 μm to 1 mm. A transparent substrate obtained by impregnating a glass cloth with the thermosetting composition as described above and thermosetting it is excellent in transparency and heat resistance. Therefore, a light guide plate, a polarizing plate, a liquid crystal panel, an EL panel, and a PDP panel. It is suitable for producing a coating layer on a color filter, an optical disk substrate, a plastic substrate for a liquid crystal cell, and the like.

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

Example 1 (Production of thiol group-containing silsesquioxane solution (A-1))
To a reaction apparatus equipped with a stirrer, a condenser, a water separator, a thermometer, a dropping funnel, and a nitrogen blowing port, 300 g of 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name “KBM-803”) , 162.8 g of ion-exchanged water ([number of moles of water used for hydrolysis reaction] / [number of moles of alkoxy group contained in component (a1)] (molar ratio) = 2.0), cation exchange resin 0 g (manufactured by Mitsubishi Chemical Corporation: trade name “Diaion PK228LH”, H-type strongly acidic cation exchange resin) was charged and subjected to a hydrolysis reaction at room temperature for 30 minutes. During the reaction, the temperature rose up to 28 ° C due to exotherm. After the reaction, the cation exchange resin was filtered off, and then the pressure was reduced at 70 ° C. and 20 kPa for 3 hours to obtain 228 g of a hydrolyzate. This was diluted with 82 g of ethylene glycol dimethyl ether to obtain 310 g of a hydrolyzate solution.
Subsequently, 325.9 g of ethylene glycol dimethyl ether and 1.25 g of a 25% aqueous solution of tetramethylammonium hydroxide were charged into another reaction vessel and heated to 80 ° C. Tetramethylammonium hydroxide does not dissolve in ethylene glycol dimethyl ether and is somewhat turbid. 300 g of the previous hydrolyzate solution was added dropwise over 2 hours and 30 minutes. During the dropwise addition, tetramethylammonium hydroxide was dissolved and the reaction solution became clear. After the dropwise addition, the mixture was further reacted at 80 ° C. for 15 minutes, and then cooled to 25 ° C. At 25 ° C., tetramethylammonium hydroxide was not dissolved, and the reaction solution became slightly turbid. Here, 6.4 g of cation exchange resin was charged and stirred at room temperature for 4 hours. During the stirring, tetramethylammonium hydroxide was adsorbed and the reaction solution became clear. After filtering off the cation exchange resin, 196 g of a thiol group-containing silsesquioxane solution (A-1) was obtained by reducing the pressure at 70 ° C. and 20 kPa for 2 hours and further at 70 ° C. and 0.7 kPa for 1 hour. . As a result of analysis by infrared spectroscopy, there was no absorption of silanol groups observed in the vicinity of 3500 cm ⁻¹ . Further, even by analysis by nuclear magnetic resonance, no silanol group was found, and [number of moles of alkoxy group] / [number of moles of alkoxy group contained in component (a1)] (molar ratio) was 0. The concentration was 94.7%, and the thiol equivalent was 133 g / eq.

Example 2 (Production of thiol group-containing silsesquioxane solution (A-2))
In the same reactor as in Example 1, 180 g of 3-mercaptopropyltrimethoxysilane, 25.0 g of methyltrimethoxysilane (manufactured by Tama Chemical Co., Ltd .: trade name “methyltrimethoxysilane”) ([component (a2) Number of moles] / [total number of moles of component (a1) and component (a2)] = 0.17), 118.8 parts of ion-exchanged water ([number of moles of water used for hydrolysis reaction] / [component (a1) , (Total number of moles of alkoxy groups contained in (a2)] (molar ratio) = 2.0), and 1.0 part of 95% formic acid was charged and subjected to a hydrolysis reaction at room temperature for 30 minutes. During the reaction, the temperature rose by a maximum of 22 ° C. due to exotherm. After the reaction, 138 g of a hydrolyzate was obtained by reducing the pressure at 70 ° C. and 20 kPa for 3 hours. This was diluted with 74 g of ethylene glycol dimethyl ether to obtain 212 g of a hydrolyzate solution.
Subsequently, 206 g of ethylene glycol dimethyl ether and 0.82 g of a 25% aqueous solution of tetramethylammonium hydroxide were charged into another reaction vessel and heated to 80 ° C. Tetramethylammonium hydroxide does not dissolve in ethylene glycol dimethyl ether and is somewhat turbid. The previous hydrolyzate solution 201g was dripped here over 2 hours and 30 minutes. During the dropwise addition, tetramethylammonium hydroxide was dissolved and the reaction solution became clear. After the dropwise addition, the mixture was further reacted at 80 ° C. for 15 minutes, and then cooled to 25 ° C. At 25 ° C., tetramethylammonium hydroxide was not dissolved, and the reaction solution became slightly turbid. The cation exchange resin 4.0g was prepared here, and it stirred at room temperature for 4 hours. During the stirring, tetramethylammonium hydroxide was adsorbed and the reaction solution became clear. After filtering off the cation exchange resin, 132 g of a thiol group-containing silsesquioxane solution (A-2) was obtained by reducing the pressure at 70 ° C. and 20 kPa for 2 hours and further at 70 ° C. and 0.7 kPa for 1 hour. . As a result of analysis by infrared spectroscopy, there was no absorption of silanol groups observed in the vicinity of 3500 cm ⁻¹ . Further, even in the analysis by nuclear magnetic resonance, no silanol group was observed, and [number of moles of alkoxy group] / [total number of moles of alkoxy groups contained in components (a1) and (a2)] (molar ratio) was 0. The concentration was 90.1%, and the thiol equivalent was 156 g / eq.

Example 3 (Production of thiol group-containing silsesquioxane solution (A-3))
In the same reactor as in Example 1, 100 g of 3-mercaptopropyltrimethoxysilane, 48.5 g of methyltrimethoxysilane ([number of moles of component (a2)] / [total moles of component (a1) and component (a2)) Number] = 0.41), 19.9 parts of ion-exchanged water ([number of moles of water used for hydrolysis reaction] / [total number of moles of alkoxy groups contained in components (a1) and (a2)]) Ratio) = 0.45), and 3.0 g of a cation exchange resin was charged, followed by hydrolysis at room temperature for 30 minutes. During the reaction, the temperature rose by a maximum of 12 ° C due to exotherm. This was diluted with 74 g of ethylene glycol dimethyl ether to obtain 201 g of a hydrolyzate solution.
Subsequently, 89 g of ethylene glycol dimethyl ether and 0.56 g of a 25% aqueous solution of tetramethylammonium hydroxide were charged into another reaction vessel and heated to 80 ° C. Tetramethylammonium hydroxide does not dissolve in ethylene glycol dimethyl ether and is somewhat turbid. 191 g of the previous hydrolyzate solution was added dropwise thereto over 2 hours and 30 minutes. During the dropwise addition, tetramethylammonium hydroxide was dissolved and the reaction solution became clear. After the dropwise addition, the mixture was further reacted at 80 ° C. for 15 minutes, and then cooled to 25 ° C. At 25 ° C., tetramethylammonium hydroxide was not dissolved, and the reaction solution became slightly turbid. The cation exchange resin 2.9g was prepared here, and it stirred at room temperature for 4 hours. During the stirring, tetramethylammonium hydroxide was adsorbed and the reaction solution became clear. By filtering the cation exchange resin, 280 g of a thiol group-containing silsesquioxane solution (A-3) was obtained. As a result of analysis by infrared spectroscopy, there was no absorption of silanol groups observed in the vicinity of 3500 cm ⁻¹ . Further, even in the analysis by nuclear magnetic resonance, no silanol group was observed, and [number of moles of alkoxy group] / [total number of moles of alkoxy groups contained in components (a1) and (a2)] (molar ratio) was 0.1. The concentration was 30.2% and the thiol equivalent was 579 g / eq.

Example 4 (Production of thiol group-containing silsesquioxane solution (A-4))
In the same reactor as in Example 1, 100 g of 3-mercaptopropyltrimethoxysilane, 50.5 g of phenyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name “KBM-103”) ([component (a2) Number of moles] / [total number of moles of component (a1) and component (a2)] = 0.33), 81.4 parts of ion-exchanged water ([number of moles of water used for hydrolysis reaction] / [component (a1) , (Total number of moles of alkoxy groups contained in (a2)] (molar ratio) = 0.45), and 3.1 g of a cation exchange resin were charged and subjected to a hydrolysis reaction at room temperature for 30 minutes. During the reaction, the temperature rose by a maximum of 24 ° C. due to exotherm. After the reaction, 115 g of a hydrolyzate was obtained by reducing the pressure at 70 ° C. and 20 kPa for 3 hours. This was diluted with 150 g of ethylene glycol dimethyl ether to obtain 265 g of a hydrolyzate solution.
Subsequently, 62 g of ethylene glycol dimethyl ether and 0.62 g of a 25% aqueous solution of tetramethylammonium hydroxide were charged into another reaction vessel and heated to 80 ° C. Tetramethylammonium hydroxide does not dissolve in ethylene glycol dimethyl ether and is somewhat turbid. The previous hydrolyzate solution 247g was dripped here over 2 hours and 30 minutes. During the dropwise addition, tetramethylammonium hydroxide was dissolved and the reaction solution became clear. After the dropwise addition, the mixture was further reacted at 80 ° C. for 15 minutes, and then cooled to 25 ° C. At 25 ° C., tetramethylammonium hydroxide was not dissolved, and the reaction solution became slightly turbid. The cation exchange resin 2.9g was prepared here, and it stirred at room temperature for 4 hours. During the stirring, tetramethylammonium hydroxide was adsorbed and the reaction solution became clear. By filtering off the cation exchange resin, 306 g of a thiol group-containing silsesquioxane solution (A-4) was obtained. As a result of analysis by infrared spectroscopy, there was no absorption of silanol groups observed in the vicinity of 3500 cm ⁻¹ . Further, even in the analysis by nuclear magnetic resonance, no silanol group was observed, and [number of moles of alkoxy group] / [total number of moles of alkoxy groups contained in components (a1) and (a2)] (molar ratio) was 0. The concentration was 30.7%, and the thiol equivalent was 632 g / eq.

Comparative Example 1 (Production of condensate (a-1): hydrolysis using an acid catalyst and condensation reaction using an acid catalyst in a nonpolar solvent)
In the same reactor as in Example 1, 180 g of 3-mercaptopropyltrimethoxysilane and 49.55 g of ion-exchanged water ([number of moles of water used for hydrolysis reaction] / [mol of alkoxy group contained in component (a1)] Number] (molar ratio) = 1.0), and 9.00 g of 95% formic acid were charged and hydrolyzed at room temperature for 30 minutes. During the reaction, the temperature rose by a maximum of 22 ° C. due to exotherm. After the reaction, 272.23 g of toluene was charged and heated. When the temperature was raised to 72 ° C., part of methanol and toluene generated by hydrolysis began to be distilled off. The temperature was raised to 75 ° C. over 20 minutes, and water was distilled off by condensation reaction. After further reacting at 75 ° C. for 1 hour, the pressure was reduced at 70 ° C. and 20 kPa to distill off the remaining methanol, water and formic acid. Further, the pressure was reduced at 70 ° C. and 0.7 kPa, and toluene was distilled off to obtain 124.5 g of random silsesquioxane (a-1). As a result of analysis by infrared spectroscopy, the absorption of silanol groups was weakly observed in the vicinity of 3500 cm ⁻¹ . Further, in the analysis by the nuclear magnetic resonance method, [number of moles of silanol group] / [number of moles of alkoxy group contained in component (a1)] (molar ratio) was 0.08, [number of moles of alkoxy group] / [ The number of moles of alkoxy groups contained in the component (a1)] (molar ratio) was 0.08. The concentration was 93.7%, and the thiol equivalent was 136 g / eq.

Comparative Example 2 (basic catalyst, hydrolysis without solvent)
In the same reactor as in Example 1, 18 g of 3-mercaptopropyltrimethoxysilane and 4.79 g of ion-exchanged water ([number of moles of water used for hydrolysis reaction] / [mol of alkoxy group contained in component (a1)] Number] (molar ratio) = 1.0), 0.22 g of 25% tetramethylammonium hydroxide was charged and reacted at room temperature. During the reaction, an exotherm occurred and gradually became cloudy and thickened. Since gelation occurred after 30 minutes, no thiol group-containing silsesquioxane was obtained.

Comparative Example 3 (hydrolysis with basic catalyst in polar solvent and condensation reaction with basic catalyst in polar solvent)
In the same reactor as in Example 1, 18 g of 3-mercaptopropyltrimethoxysilane and 4.79 g of ion-exchanged water ([number of moles of water used for hydrolysis reaction] / [mol of alkoxy group contained in component (a1)] Number] (molar ratio) = 1.0), 0.22 g of 25% tetramethylammonium hydroxide and 30 g of ethylene glycol dimethyl ether were charged and reacted at room temperature. During the reaction, an exotherm occurred and the viscosity gradually increased. After 30 minutes, 1.1 g of cation exchange resin was charged and stirred at room temperature for 4 hours to remove tetramethylammonium hydroxide.
Subsequently, 32.6 g of ethylene glycol dimethyl ether and 0.13 g of a 25% aqueous solution of tetramethylammonium hydroxide were charged into another reaction vessel and heated to 80 ° C. Tetramethylammonium hydroxide does not dissolve in ethylene glycol dimethyl ether and is somewhat turbid. When the previous hydrolyzate solution was added dropwise thereto, the viscosity gradually increased and gelled before completion of the addition, so that a thiol group-containing silsesquioxane was not obtained.

Comparative Example 4 (hydrolysis with basic catalyst in polar solvent and condensation reaction with basic catalyst in nonpolar solvent)
In the same reactor as in Example 1, 18 g of 3-mercaptopropyltrimethoxysilane and 4.79 g of ion-exchanged water ([number of moles of water used for hydrolysis reaction] / [mol of alkoxy group contained in component (a1)] Number] (molar ratio) = 1.0), 0.22 g of 25% tetramethylammonium hydroxide and 30 g of ethylene glycol dimethyl ether were charged and reacted at room temperature. During the reaction, an exotherm occurred and the viscosity gradually increased. After 30 minutes, 1.1 g of cation exchange resin was charged and stirred at room temperature for 4 hours to remove tetramethylammonium hydroxide.
Subsequently, 32.6 g of toluene and 0.13 g of a 25% aqueous solution of tetramethylammonium hydroxide were charged in another reaction vessel and heated to 80 ° C. Tetramethylammonium hydroxide does not dissolve in toluene but appears to stick to the reaction vessel. When the previous hydrolyzate solution was added dropwise thereto, the solution became cloudy and a solid was formed, so that a thiol group-containing silsesquioxane was not obtained.

Comparative Example 5 (hydrolysis with basic catalyst in polar solvent and condensation reaction with basic catalyst in nonpolar solvent)
In the same reactor as in Example 1, 18 g of 3-mercaptopropyltrimethoxysilane and 4.79 g of ion-exchanged water ([number of moles of water used for hydrolysis reaction] / [mol of alkoxy group contained in component (a1)] Number] (molar ratio) = 1.0), 0.22 g of 25% tetramethylammonium hydroxide and 30 g of ethylene glycol dimethyl ether were charged and reacted at room temperature. During the reaction, an exotherm occurred and the viscosity gradually increased. After 30 minutes, 1.1 g of cation exchange resin was charged and stirred at room temperature for 4 hours to remove tetramethylammonium hydroxide.
Subsequently, 32.6 g of toluene and 0.10 g of triethylamine were charged into another reaction vessel and heated to 80 ° C. The previous hydrolyzate solution was added dropwise over 2 hours and 30 minutes, and the mixture was further reacted at 80 ° C. for 15 minutes. As a result of analysis by infrared spectroscopy, strong absorption of silanol groups was observed in the vicinity of 3500 cm ⁻¹ , and the reaction was further carried out at 110 ° C. for 4 hours. When the obtained product was analyzed by infrared spectroscopy, the absorption of silanol groups was weakly observed in the vicinity of 3500 cm ⁻¹ . In the analysis by the nuclear magnetic resonance method, [number of moles of silanol group] / [number of moles of alkoxy group contained in component (a1)] (molar ratio) was 0.03, [number of moles of alkoxy group] / [ The number of moles (molar ratio) of alkoxy groups contained in component (a1) was 0. When GPC was measured, the molecular weight was significantly increased compared to (A-1), and a cage-type silsesquioxane was not obtained because a high molecular weight random type or ladder type silsesquioxane was produced. I understood.

(Stability of thiol group-containing silsesquioxane)
Stability was evaluated based on the rate of change in viscosity before and after storage after storing the thiol group-containing silsesquioxane obtained in Examples 1 to 4 and Comparative Example 1 in a mayonnaise bottle and heating to 50 ° C. did. The results are shown in Table 1.

  As is apparent from Table 1, comparing the stability of Examples 1 and 2 and Comparative Example 1 in which the solvent was removed at the final stage of production, it can be seen that Examples 1 and 2 have improved stability.

Examples 5 to 15 and Comparative Examples 6 to 10 (Production of Curable Resin Composition)
To 10 g of the thiol group-containing silsesquioxane (A-1) obtained in Example 1, triallyl isocyanurate (manufactured by Nippon Kasei Co., Ltd .: trade name “Tyke”, [carbon contained in component (B) -Number of moles of carbon double bond] / [number of moles of component (B)] = 3, hereinafter referred to as TAIC) 2.09 g (number of moles of thiol group contained in [thiol group-containing silsesquioxane (A)) ] / [Number of moles of carbon-carbon double bond contained in component (B)] (molar ratio) = 1.0) to give an ultraviolet curable resin composition (E-1). Similarly, using the thiol group-containing silsesquioxane (A-1 to 4) obtained in Examples 1 to 4, curable resin compositions (E-2 to E-11) were prepared according to the following table. Similarly, the random silsesquioxane (a-1) obtained in Comparative Example 1 was used to obtain curable resin compositions (e-1 to 5) according to the table below.

  In the table, DAP: diallyl phthalate (manufactured by Daiso Co., Ltd .: trade name “Daiso Dup Monomer”, [number of moles of carbon-carbon double bonds contained in component (B)] / [number of moles of component (B)] = 2), JER828: Bisphenol A type epoxy resin (Mitsubishi Chemical Corporation: trade name “JER828”, epoxy equivalent 370 g / eq, [number of moles of epoxy group contained in component (C)] / [component (C ))] = 2), cello 2021P: alicyclic epoxy resin (manufactured by Daicel Chemical Industries, Ltd .: trade name “Celoxide 2021”, epoxy equivalent 126 g / eq, [epoxy group contained in component (C)] [Number of moles] / [number of moles of component (C)] = 2), IPDI: isophorone diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd .: isocyanate equivalent 111 g / eq, included in [component (D) Mole number of socyanate group] / [Mole number of component (D)] = 2), Koro HX: polyisocyanurate type HDI (manufactured by Nippon Polyurethane Industry Co., Ltd .: trade name “Coronate HX”, isocyanate equivalent 200 g / eq [Mole number of isocyanate group contained in component (D)] / [Mole number of component (D)] = 2), Irg184: Hydroxycyclohexyl phenyl ketone (manufactured by BASF: trade name “Irgacure 184”), U- 600: Bismuth tris (2-ethylhexanoate) (Nitto Kasei Co., Ltd., trade name “Neostan U-600”), DMG: Ethylene glycol dimethyl ether (trade name “DMG” manufactured by Nippon Emulsifier Co., Ltd.) NV represents the nonvolatile content. Moreover, the unit of the usage-amount of each component is g.

(Stability of curable resin composition)
The curable resin compositions obtained in Examples 5, 10, 13, 14 and Comparative Examples 6, 7, 8, and 9 are placed in brown bottles and allowed to stand at room temperature. The curable resin composition is determined depending on the time until gelation. The stability of the product was evaluated. The results are shown in Table 3.

  As is clear from Table 3, the curable resin compositions of Examples 5, 10, 13, and 14 have comparative stability to the curable resin compositions of Comparative Examples 6, 7, 8, and 9 using the same curing agent. It can be seen that it has improved.

(Curability of composition)
The ultraviolet curable resin compositions obtained in Examples 5 to 9 and Comparative Example 6 were coated on a glass plate so that the film thickness after curing was about 15 μm, and the solvent was dried at 90 ° C. for 5 minutes. After drying, ultraviolet rays were irradiated using an ultraviolet ray irradiation device (USHIO INC., Trade name: “UV-152”) with a 365 nm ultraviolet ray detector so that the integrated light amount was 250 mJ / cm ² . Similarly, the ultraviolet curable resin composition obtained in Comparative Example 6 was also coated so that the film thickness after curing was about 15 μm, and an integrated light amount was 250 mJ / cm with a 365 nm ultraviolet detector using an ultraviolet irradiation device. Ultraviolet rays were irradiated so as to be ² . The thermosetting compositions obtained in Examples 10 to 13 and Comparative Examples 7 and 8 were coated so that the film thickness after curing was about 15 μm, and the solvent was dried at 90 ° C. for 5 minutes. Subsequently, thermosetting was performed at 120 ° C. for 3 hours and at 150 ° C. for 1 hour. The ultraviolet and thermosetting compositions obtained in Examples 14 and 15 and Comparative Examples 9 and 10 were coated so that the film thickness after curing was about 15 μm, and the solvent was dried at 90 ° C. for 5 minutes. Subsequently, ultraviolet rays were irradiated using an ultraviolet irradiation device so that the integrated light amount was 250 mJ / cm ² with a 365 nm ultraviolet detector. Furthermore, it was heat-cured at 120 ° C. for 30 minutes. Similarly, the ultraviolet ray and thermosetting composition obtained in Comparative Example 8 was coated so that the film thickness after curing was about 15 μm, and the solvent was dried at 90 ° C. for 5 minutes. Subsequently, ultraviolet rays were irradiated using an ultraviolet irradiation device so that the integrated light amount was 250 mJ / cm ² with a 365 nm ultraviolet detector. Furthermore, it was heat-cured at 120 ° C. for 30 minutes. The curability of the obtained cured product was evaluated by a pencil hardness test according to a general test method of JIS K-5401. The results are shown in Table 4.

  As is apparent from Table 4, cured products could be obtained from all Examples and Comparative Examples. Further, in Example 5 and Comparative Example 6 using the same curing agent, Example 5 is used. In Example 10 and Comparative Example 7, Example 10 is used. In Example 13 and Comparative Example 8, Example 13 is used. In Example 14 and Comparative Example 9, Example 14 has high surface hardness, and it is recognized that the curable resin composition of the present invention is more suitable as a hard coat agent.

(Refractive index)
Using the Abbe refractometer (manufactured by Atago Co., Ltd .: trade name “multi-wavelength Abbe refractometer DR-M2”), the curable resin compositions obtained in Examples 5 to 15 and Comparative Examples 6 to 10 were used. The refractive index at 589 nm was measured. The results are shown in Table 5.

  As is clear from Table 5, Example 5 and Comparative Example 6 using the same curing agent were Example 5, and Example 10 and Comparative Example 7 were Example 10, and Example 13 and Comparative Example 8 were Then, in Example 13 and in Example 14 and Comparative Example 9, Example 14 has a high refractive index, and by using the thiol group-containing silsesquioxane (A) of the present invention, curing with a higher refractive index is performed. It is possible to make an object. For this reason, the curable resin composition of the present invention includes 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, and the like. It is recognized that it is suitable as a coating agent for an antireflection film.

Example 16 (Formation of pattern)
The ultraviolet curable resin composition (E-1) was coated on a glass substrate so as to have a film thickness of 5 μm, dried at 80 ° C. for 2 minutes, and the solvent was volatilized. At this stage, since there was tack and contact exposure could not be performed, ultraviolet rays were irradiated with a 365 nm detector using an ultraviolet irradiation device so that the integrated light amount was 500 mJ / cm ² with the mask floating. A substrate with a pattern was obtained by developing using a 2.38% tetramethylammonium hydroxide aqueous solution (manufactured by Tama Chemical Co., Ltd .: trade name “TMAH 2.38%”). Further, even when a 1.0% sodium hydroxide aqueous solution was used as a developer instead of the 2.38% tetramethylammonium hydroxide aqueous solution, it was possible to develop well. Thus, the curable resin composition of the present invention can be suitably used as a photoengraving resist, solder resist, etching resist, color filter resist, hologram, stereolithography, and UV ink.

Example 17 (Production of a laminate having a pattern formed on the surface)
The ultraviolet curable resin composition (E-1) was coated on a glass substrate so as to have a film thickness of 5 μm, dried at 80 ° C. for 2 minutes, and the solvent was volatilized. Subsequently, a glass mold (line width: 144 nm, depth: 200 nm) subjected to a release treatment was placed thereon, heated to 60 ° C., and pressed. A laminate with a pattern formed on the surface could be obtained by irradiating ultraviolet rays through a mold using an ultraviolet irradiation device so that the integrated light amount was 500 mJ / cm ² with a 365 nm detector, and then removing the mold. From this, the laminated body in which the pattern was formed on the surface obtained in Examples 1 to 3, the substrate for flat panel display, the prism sheet, the color filter, the optical circuit board, the diffraction type condensing film, the polarizing film, In addition to optical devices such as optical waveguides, it is suitable for reflectors, recording media, semiconductors, electronic devices, biochips, chemical chips, and the like.

Example 18 (Preparation of transparent sheet by glass cloth impregnation)
The heat and ultraviolet curable composition (E-11) obtained in Example 15 was impregnated into a glass cloth having a thickness of 90 μm (manufactured by Nitto Boseki Co., Ltd .: refractive index 1.558), and at 110 ° C. for 5 minutes, 110 Solvent drying and thermosetting were carried out at 12 ° C. for 12 minutes to produce a transparent sheet. Furthermore, 20 μm of the heat and ultraviolet curable composition (E-11) was coated on both surfaces of the sheet, and solvent drying and heat curing were performed at 80 ° C. for 5 minutes and at 110 ° C. for 12 minutes to obtain a semi-cured product. The obtained semi-cured product was wound around a paper tube having a diameter of 15 cm and stored at room temperature in a dark place for 24 hours. Subsequently, after press forming at 120 ° C. for 30 seconds, a transparent sheet having a film thickness of 105 μm is obtained by irradiating ultraviolet rays with a 365 nm detector so that the integrated light quantity becomes 2000 mJ / cm ² using an ultraviolet irradiation device. It was.

Comparative Example 11 (Production of transparent sheet by glass cloth impregnation)
The heat and ultraviolet curable composition (e-5) obtained in Comparative Example 10 was impregnated into a 90 μm-thick glass cloth (manufactured by Nitto Boseki Co., Ltd .: refractive index: 1.558), 5 minutes at 80 ° C., 110 Solvent drying and thermosetting were carried out at 12 ° C. for 12 minutes to produce a transparent sheet. Furthermore, 20 μm of the heat and ultraviolet curable composition (e-5) was coated on both surfaces of the sheet, and solvent drying and heat curing were performed at 80 ° C. for 5 minutes and at 110 ° C. for 12 minutes to obtain a semi-cured product. The obtained semi-cured product was wound around a paper tube having a diameter of 15 cm and stored at room temperature in a dark place for 24 hours. Subsequently, after press forming at 120 ° C. for 30 seconds, a transparent sheet having a film thickness of 105 μm is obtained by irradiating ultraviolet rays with a 365 nm detector so that the integrated light quantity becomes 2000 mJ / cm ² using an ultraviolet irradiation device. It was.

  Table 6 shows the results of measuring the total light transmittance, haze, and dynamic viscoelasticity of the transparent sheets obtained in Example 18 and Comparative Example 11, and the storage stability in the semi-cured state. The evaluation criteria are as follows.

(Storage property in semi-cured state)
○: The semi-cured state is maintained for 24 hours or more.
Δ: A semi-cured state is maintained for 24 hours or more, but cannot be wound and stored because of tackiness.
X: The semi-cured state is lost by 24 hours and cannot be molded.

  As a result, the transparent sheets obtained in Example 18 and Comparative Example 11 had high total light transmittance because the refractive index of the resin used matched the refractive index of the glass cloth. In addition, both had processability in a semi-cured state and were flattened, so there was no light scattering due to fine irregularities on the surface, and haze was low.

(Heat-resistant)
The transparent sheet obtained in Example 18 and Comparative Example 11 was cut into 5 mm × 30 mm, and viscoelasticity measuring instrument (manufactured by Seiko Instruments Inc., trade name “DMS6100”, measurement conditions: frequency 10 Hz, slope 3 ° C. / Min) was used to measure the dynamic storage modulus to evaluate the heat resistance. The measurement results are shown in FIG. As is clear from FIG. 1, the transparent sheet of Comparative Example 10 has Tg near 120 ° C., and a decrease in elastic modulus after Tg is observed. On the other hand, it is recognized that the transparent sheet obtained in Example 15 has a substantially constant elastic modulus regardless of temperature and is extremely excellent in heat resistance.

Claims (18)

General formula (1): R ¹ Si (OR ² ) ₃ (wherein R ¹ is a hydrocarbon group having 1 to 8 carbon atoms having at least one thiol group, or an aromatic hydrocarbon having at least one thiol group) R ² represents a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms, or an aromatic hydrocarbon group.) Using an acidic catalyst, thiol group-containing alkoxysilanes (a1) represented by After the hydrolysis reaction, the acidic catalyst is removed, and then the silanol group obtained by adding and condensing the previous reaction product in a polar solvent containing a basic catalyst substantially remains. The manufacturing method of the thiol group containing silsesquioxane (A) characterized by not having. The thiol group-containing silsesquioxane is an alkyltrialkoxysilane (a2) having no thiol group as a constituent component, [number of moles of (a2)] / [number of moles of (a1) and moles of (a2). The method for producing a thiol group-containing silsesquioxane (A) according to claim 1, characterized in that the total content of the thiol group-containing silsesquioxane (A) is 0.7% or less. The method for producing a thiol group-containing silsesquioxane (A) according to claim 1 or 2, wherein the acidic catalyst is a solid acid catalyst. The method for producing a thiol group-containing silsesquioxane (A) according to any one of claims 1 to 3, wherein the polar solvent is a glycol ether. The method for producing a thiol group-containing silsesquioxane (A) according to any one of claims 1 to 4, wherein the basic catalyst is tetramethylammonium hydroxide. General formula (1): R ¹ Si (OR ² ) ₃ (wherein R ¹ is a hydrocarbon group having 1 to 8 carbon atoms having at least one thiol group, or an aromatic hydrocarbon having at least one thiol group) R ² represents a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms, or an aromatic hydrocarbon group.) Using an acidic catalyst, thiol group-containing alkoxysilanes (a1) represented by After the hydrolysis reaction, the acidic catalyst is removed, and then the silanol group obtained by adding and condensing the previous reaction product in a polar solvent containing a basic catalyst substantially remains. A thiol group-containing silsesquioxane (A), a compound (B) having a plurality of carbon-carbon double bonds in the molecule, a compound (C) having a plurality of epoxy groups in the molecule, and Isocyanate group A curable resin composition comprising at least one selected from the group consisting of a compound (D) having a plurality in a molecule. Thiol group-containing silsesquioxane (A) and compound (B) having a plurality of carbon-carbon double bonds in the molecule, and compound (C) having a plurality of epoxy groups in the molecule and an isocyanate group in the molecule The curable resin composition according to claim 6, comprising at least one selected from the group consisting of a plurality of compounds (D). The curable resin composition according to claim 6 or 7, wherein the compound (B) is an allyl group-containing compound. The compound (C) is at least one compound selected from the group consisting of a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a hydrogenated bisphenol A type epoxy resin, and an alicyclic epoxy resin. The curable resin composition according to any one of the above. The curable resin composition according to any one of claims 6 to 9, wherein the compound (D) is an isocyanurate of isophorone diisocyanate or hexamethylene diisocyanate. A cured product obtained by curing the curable composition according to claim 6. A transparent substrate obtained by impregnating a glass cloth with the curable composition according to claim 6 and then curing the glass cloth. The transparent substrate according to claim 12 suitable for an optical member application. An article having a coating layer obtained by curing the curable composition according to any one of claims 6 to 10 on a substrate. The article according to claim 14, wherein the refractive index of the coating layer is higher than the refractive index of the substrate. The article of claim 15 suitable for optical member applications. 11. A sealed article obtained by curing using the curable composition according to claim 6 as a sealing material. The sealed article according to claim 17, which is suitable for use as an optical member.

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