JP2015030839A - Method for manufacturing cured product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a cured product, capable of forming the cured product excellent in hardness and transparency using a curable composition including an alicyclic epoxy compound, and a cured product obtained by the method for manufacturing the cured product.SOLUTION: When a cured product is formed using a curable composition including an alicyclic epoxy compound having a specific structure and an acid generator, the cured product is manufactured by performing steps at a temperature of 80°C or less before the step of generating acid from an acid generator in the curable composition molded into a desired shape to cure the curable composition.

Description

  The present invention relates to a method for producing a cured product of a curable composition containing an alicyclic epoxy compound having a specific structure, and a cured product obtained by the production method.

  In recent years, transparent organic materials have attracted attention in terms of light weight and ease of processing, and their use as an alternative material for inorganic transparent materials typified by glass is expanding. Such a transparent resin material can be used as a material for a substrate or a transparent insulating film in, for example, a panel for an image display device typified by a liquid crystal display device.

  As such a transparent organic material, what hardened | cured the composition containing an epoxy compound, an acid anhydride, and a hardening accelerator is known (patent document 1). In Patent Document 1, as a cured product particularly excellent in heat resistance (glass transition temperature) and transparency, a composition (Example 6) containing the following alicyclic epoxy compound is used at 100 ° C. for 2 hours and 200 ° C. A cured product cured by heating for 2 hours is disclosed.

JP 2004-307846 A

  The cured product of the composition containing the alicyclic epoxy compound described in Patent Document 1 has a defect that it is inferior in hardness although it is excellent in transparency and heat resistance.

  The present invention has been made in view of the above problems, and using a curable composition containing an alicyclic epoxy compound, a method for producing a cured product capable of forming a cured product having excellent hardness and transparency, and It aims at providing the hardened | cured material obtained by the manufacturing method of hardened | cured material.

  When the present inventors form a cured product using a curable composition containing an alicyclic epoxy compound having a specific structure and an acid generator, the curable composition molded into a desired shape It was found that the above-mentioned problems can be solved by producing a cured product by performing a step before the step of curing the curable composition by generating an acid from the acid generator at a temperature of 80 ° C. or lower. It came to complete.

（式（１）中、Ｒ^１〜Ｒ^１８は、それぞれ独立に、水素原子、ハロゲン原子、及び有機基からなる群より選択される基である。） 1st aspect of this invention is a manufacturing method of hardened | cured material which hardens the curable composition containing an alicyclic epoxy compound, and manufactures hardened | cured material,
(A) A molding step of molding a curable composition containing an alicyclic epoxy compound represented by the following formula (1) and (B) an acid generator according to a desired shape of the cured product;
And (B) an acid generation step of generating an acid from the acid generator to cure the curable composition in the molded curable composition,
It is a manufacturing method of hardened | cured material which performs the process before an acid generation process at the temperature of 80 degrees C or less.

(In formula (1), R ^{1 to} R ¹⁸ are each independently a group selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group.)

  The second aspect of the present invention is a cured product obtained by the method for producing a cured product according to the first aspect.

  According to the present invention, using a curable composition containing an alicyclic epoxy compound, a method for producing a cured product capable of forming a cured product having excellent hardness and transparency, and a cured product obtained by the method for producing the cured product. And can be provided.

  In the method for producing a cured product according to the present invention, a curable composition containing (A) an alicyclic epoxy compound having a specific structure and (B) an acid generator is cured to produce a cured product. Hereinafter, a curable composition and the manufacturing method of hardened | cured material are demonstrated in order.

≪Curable composition≫
The curable composition contains (A) an alicyclic epoxy compound having a specific structure and (B) an acid generator. The curable composition may contain (S) solvent and various additives as needed. Hereinafter, essential or optional components contained in the curable composition and a method for producing the curable composition will be described in order.

[(A) Alicyclic epoxy compound]
The curable composition used in the manufacturing method of the hardened | cured material of this invention contains the epoxy compound represented by following formula (1) as (A) alicyclic epoxy compound. Since a curable composition contains the epoxy compound represented by following formula (1), it gives the hardened | cured material excellent in transparency and hardness.

（式（１）中、Ｒ^１〜Ｒ^１８は、それぞれ独立に、水素原子、ハロゲン原子、及び有機基からなる群より選択される基である。）

(In formula (1), R ^{1 to} R ¹⁸ are each independently a group selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group.)

When R ^{1 to} R ¹⁸ are organic groups, the organic group is not particularly limited as long as the object of the present invention is not impaired, and may be a hydrocarbon group or a group composed of a carbon atom and a halogen atom. And a group containing a hetero atom such as a halogen atom, an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom together with a carbon atom and a hydrogen atom. Examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom.

  The organic group includes a hydrocarbon group, a group consisting of a carbon atom, a hydrogen atom and an oxygen atom, a halogenated hydrocarbon group, a group consisting of a carbon atom, an oxygen atom and a halogen atom, a carbon atom and a hydrogen atom. And a group consisting of an oxygen atom and a halogen atom. When the organic group is a hydrocarbon group, the hydrocarbon group may be an aromatic hydrocarbon group, an aliphatic hydrocarbon group, or a group including an aromatic skeleton and an aliphatic skeleton. 1-20 are preferable, as for carbon number of an organic group, 1-10 are more preferable, and 1-5 are especially preferable.

  Specific examples of the hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, and n-hexyl group. N-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group Chain alkyl groups such as n-heptadecyl group, n-octadecyl group, n-nonadecyl group and n-icosyl group; vinyl group, 1-propenyl group, 2-n-propenyl group (allyl group), 1-n Chain alkenyl groups such as -butenyl, 2-n-butenyl, and 3-n-butenyl; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl And a cycloalkyl group such as cycloheptyl group; phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, α-naphthyl group, β-naphthyl group, biphenyl-4-yl group, biphenyl-3-yl Group, biphenyl-2-yl group, anthryl group, phenanthryl group and other aryl groups; benzyl group, phenethyl group, α-naphthylmethyl group, β-naphthylmethyl group, α-naphthylethyl group, and β-naphthylethyl group And aralkyl groups such as

  Specific examples of the halogenated hydrocarbon group include chloromethyl group, dichloromethyl group, trichloromethyl group, bromomethyl group, dibromomethyl group, tribromomethyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, 2,2 , 2-trifluoroethyl group, pentafluoroethyl group, heptafluoropropyl group, perfluorobutyl group, and perfluoropentyl group, perfluorohexyl group, perfluoroheptyl group, perfluorooctyl group, perfluorononyl group, and Halogenated chain alkyl group such as perfluorodecyl group; 2-chlorocyclohexyl group, 3-chlorocyclohexyl group, 4-chlorocyclohexyl group, 2,4-dichlorocyclohexyl group, 2-bromocyclohexyl group, 3-bromocyclohexyl group , And 4-bu Halogenated cycloalkyl group such as mocyclohexyl group; 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2,3-dichlorophenyl group, 2,4-dichlorophenyl group, 2,5-dichlorophenyl group, 2,6 -Dichlorophenyl group, 3,4-dichlorophenyl group, 3,5-dichlorophenyl group, 2-bromophenyl group, 3-bromophenyl group, 4-bromophenyl group, 2-fluorophenyl group, 3-fluorophenyl group, 4- Halogenated aryl groups such as fluorophenyl group; 2-chlorophenylmethyl group, 3-chlorophenylmethyl group, 4-chlorophenylmethyl group, 2-bromophenylmethyl group, 3-bromophenylmethyl group, 4-bromophenylmethyl group, 2 -Fluorophenylmethyl group, 3-fluorophenyl Methyl group, a halogenated aralkyl group such as 4-fluorophenyl methyl group.

  Specific examples of the group consisting of a carbon atom, a hydrogen atom, and an oxygen atom include hydroxy chain groups such as a hydroxymethyl group, a 2-hydroxyethyl group, a 3-hydroxy-n-propyl group, and a 4-hydroxy-n-butyl group. Alkyl groups; halogenated cycloalkyl groups such as 2-hydroxycyclohexyl, 3-hydroxycyclohexyl, and 4-hydroxycyclohexyl groups; 2-hydroxyphenyl, 3-hydroxyphenyl, 4-hydroxyphenyl, 2,3 -Hydroxyaryl groups such as dihydroxyphenyl group, 2,4-dihydroxyphenyl group, 2,5-dihydroxyphenyl group, 2,6-dihydroxyphenyl group, 3,4-dihydroxyphenyl group, and 3,5-dihydroxyphenyl group ; 2-hydroxyphenylmethyl group, 3-hydroxy Hydroxy aralkyl groups such as enylmethyl group and 4-hydroxyphenylmethyl group; methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group N-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n- Tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, n-octadecyloxy group, n-nonadecyloxy group, n-icosyloxy group, etc. A chain alkoxy group; vinyloxy group, 1-pro Chain alkenyloxy groups such as nyloxy group, 2-n-propenyloxy group (allyloxy group), 1-n-butenyloxy group, 2-n-butenyloxy group, and 3-n-butenyloxy group; phenoxy group, o-tolyloxy Group, m-tolyloxy group, p-tolyloxy group, α-naphthyloxy group, β-naphthyloxy group, biphenyl-4-yloxy group, biphenyl-3-yloxy group, biphenyl-2-yloxy group, anthryloxy group, And aryloxy groups such as phenanthryloxy group; benzyloxy group, phenethyloxy group, α-naphthylmethyloxy group, β-naphthylmethyloxy group, α-naphthylethyloxy group, β-naphthylethyloxy group, etc. Aralkyloxy group; methoxymethyl group, ethoxymethyl group, n-propylo group Xymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-n-propyloxyethyl group, 3-methoxy-n-propyl group, 3-ethoxy-n-propyl group, 3-n-propyloxy-n Alkoxy groups such as -propyl, 4-methoxy-n-butyl, 4-ethoxy-n-butyl, and 4-n-propyloxy-n-butyl; methoxymethoxy, ethoxymethoxy, n- Propyloxymethoxy group, 2-methoxyethoxy group, 2-ethoxyethoxy group, 2-n-propyloxyethoxy group, 3-methoxy-n-propyloxy group, 3-ethoxy-n-propyloxy group, 3-n- Propyloxy-n-propyloxy group, 4-methoxy-n-butyloxy group, 4-ethoxy-n-butyloxy group, and 4-n-pro Alkoxyalkoxy groups such as ruoxy-n-butyloxy group; alkoxyaryl groups such as 2-methoxyphenyl group, 3-methoxyphenyl group, and 4-methoxyphenyl group; 2-methoxyphenoxy group, 3-methoxyphenoxy group, and 4 -Alkoxyaryloxy groups such as methoxyphenoxy group; aliphatic acyl groups such as formyl group, acetyl group, propionyl group, butanoyl group, pentanoyl group, hexanoyl group, heptanoyl group, octanoyl group, nonanoyl group and decanoyl group; benzoyl group , Α-naphthoyl group, β-naphthoyl group and other aromatic acyl groups; methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, n-butyloxycarbonyl group, n-pentyloxycarbonyl group, n-hexyl Carboni A chain alkyloxycarbonyl group such as a group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, n-nonyloxycarbonyl group, and n-decyloxycarbonyl group; phenoxycarbonyl group, α-naphthoxycarbonyl group, And aryloxycarbonyl groups such as β-naphthoxycarbonyl group; formyloxy group, acetyloxy group, propionyloxy group, butanoyloxy group, pentanoyloxy group, hexanoyloxy group, heptanoyloxy group, octanoyloxy group An aliphatic acyloxy group such as a nonanoyloxy group and a decanoyloxy group; an aromatic acyloxy group such as a benzoyloxy group, an α-naphthoyloxy group, and a β-naphthoyloxy group.

R ^{1 to} R ¹⁸ are each preferably a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms, and particularly a curable composition. From the viewpoint of the hardness of the cured product obtained using the product, it is more preferable that R ^{1 to} R ¹⁸ are all hydrogen atoms.

  The curable composition may contain an epoxy compound other than the epoxy compound represented by the formula (1) together with the epoxy compound represented by the formula (1) as long as the object of the present invention is not impaired. Examples of epoxy compounds that can be used with the epoxy compound represented by formula (1) are bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, naphthalene type epoxy resin, and biphenyl. Bifunctional epoxy resins such as phenolic epoxy resins; novolak epoxy resins such as phenol novolac epoxy resins, brominated phenol novolac epoxy resins, orthocresol novolac epoxy resins, bisphenol A novolac epoxy resins, and bisphenol AD novolac epoxy resins An epoxy resin having a tricyclodecene oxide group; a cycloaliphatic epoxy resin such as an epoxidized product of a dicyclopentadiene type phenol resin; a naphthalene type phenol resin Epoxy resins such as dimer acid glycidyl ester and glycidyl ester type epoxy resin such as triglycidyl ester; tetraglycidylaminodiphenylmethane, triglycidyl-p-aminophenol, tetraglycidylmetaxylylenediamine, and tetraglycidyl Glycidylamine type epoxy resins such as bisaminomethylcyclohexane; heterocyclic epoxy resins such as triglycidyl isocyanurate; phloroglicinol triglycidyl ether, trihydroxybiphenyl triglycidyl ether, trihydroxyphenylmethane triglycidyl ether, glycerin triglycidyl ether 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4- (2,3-epoxy) Cypropoxy) phenyl] ethyl] phenyl] propane and 1,3-bis [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1- [4- [1- [4- (2, Trifunctional epoxy resins such as 3-epoxypropoxy) phenyl] -1-methylethyl] phenyl] ethyl] phenoxy] -2-propanol; tetrahydroxyphenylethane tetraglycidyl ether, tetraglycidyl benzophenone, bisresorcinol tetraglycidyl ether, and Tetrafunctional epoxy resin such as tetraglycidoxybiphenyl; 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenylcarboxylate, limonene diepoxide, ε-caprolactone modified 3,4-epoxycyclohexenylmethyl -3 ', 4'-D Xycyclohexenylcarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, epoxidized 3-cyclohexene-1,2-dicarboxylic acid bis-3-cyclohexenyl methyl ester, epoxidized 3-cyclohexene-1,2-dicarboxylic acid Ε-caprolactone adduct of bis 3-cyclohexenyl methyl ester, epoxidized butanetetracarboxylic acid tetrakis-3-cyclohexenyl methyl ester, and epoxidized butanetetracarboxylic acid tetrakis-3-cyclohexenyl methyl ester And alicyclic epoxy resins.

  When the curable composition contains other epoxy compounds of the epoxy compound represented by the formula (1), the amount of the epoxy compound represented by the formula (1) with respect to the total mass in the epoxy compound in the curable composition is 70 mass% or more is preferable, 80 mass% or more is more preferable, and 90 mass% or more is particularly preferable.

  The content of the (A) alicyclic epoxy compound in the curable composition is preferably 50 to 99.9% by mass with respect to the total mass of components other than the (S) solvent in the curable composition, 80-99.9 mass% is more preferable.

[(B) Acid generator]
(B) As an acid generator, if it can generate an acid at the temperature of 80 degrees C or less, it will not be specifically limited, It can use. Typically, a photoacid generator that generates an acid upon irradiation with actinic rays or radiation, or a thermal acid generator that generates an acid upon heating is preferably used.

  As a photo-acid generator, the acid generator of the 1st-5th aspect demonstrated below is preferable. Hereinafter, suitable ones among the photoacid generators will be described as first to fifth embodiments.

  As a 1st aspect in a photo-acid generator, the compound represented by a following formula (b1) is mentioned.

In the formula (b1), X ^1b represents a sulfur atom or an iodine atom having a valence g, and g is 1 or 2. h represents the number of repeating units in the structure in parentheses. R ^1b is an organic group bonded to X ^1b , an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 4 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, and an alkyl group having 2 to 30 carbon atoms. Represents an alkenyl group or an alkynyl group having 2 to 30 carbon atoms, and R ^1b is alkyl, hydroxy, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthiocarbonyl, acyloxy, arylthio, alkylthio, aryl, It may be substituted with at least one selected from the group consisting of heterocycle, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, alkyleneoxy, amino, cyano, nitro, and halogen. The number of R ^1b is g + h (g−1) +1, and R ^1b may be the same as or different from each other. In addition, two or more R ^1b may be directly selected from each other, or —O—, —S—, —SO—, —SO ₂ —, —NH—, —NR ^2b —, —CO—, —COO—, —CONH—. May be bonded via an alkylene group having 1 to 3 carbon atoms or a phenylene group to form a ring structure containing X ^1b . R ^2b is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms.

X ^2b is a structure represented by the following formula (b2).

In the formula (b2), X ^4b represents a divalent group of an alkylene group having 1 to 8 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a heterocyclic compound having 8 to 20 carbon atoms, and X ^4b represents carbon. It may be substituted with at least one selected from the group consisting of alkyl having 1 to 8 carbons, alkoxy having 1 to 8 carbons, aryl having 6 to 10 carbons, hydroxy, cyano, nitro, and halogen. . X ^5b is —O—, —S—, —SO—, —SO ₂ —, —NH—, —NR ^2b —, —CO—, —COO—, —CONH—, an alkylene group having 1 to 3 carbon atoms, Or represents a phenylene group. h represents the number of repeating units in the structure in parentheses. The h + 1 X ^4b and the h X ^5b may be the same or different. R ^2b is the same as defined above.

X ^3b- is an onium counter ion, and examples thereof include an alkylfluorophosphate anion represented by the following formula (b17) or a borate anion represented by the following formula (b18).

In the above formula (b17), R ^3b represents an alkyl group which may be substituted with a fluorine atom. When R ^3b is an alkyl group substituted with a fluorine atom, 80% or more of the hydrogen atoms in the alkyl group are preferably substituted with a fluorine atom. j shows the number and is an integer of 1-5. j R ^3b may be the same or different.

In the formula (b18), R ^{4b to} R ^7b each independently represent a fluorine atom or a phenyl group, and part or all of the hydrogen atoms of the phenyl group are selected from the group consisting of a fluorine atom and a trifluoromethyl group. It may be substituted with at least one selected from the above.

  Examples of the onium ion in the compound represented by the formula (b1) include triphenylsulfonium, tri-p-tolylsulfonium, 4- (phenylthio) phenyldiphenylsulfonium, bis [4- (diphenylsulfonio) phenyl] sulfide, Bis [4- {bis [4- (2-hydroxyethoxy) phenyl] sulfonio} phenyl] sulfide, bis {4- [bis (4-fluorophenyl) sulfonio] phenyl} sulfide, 4- (4-benzoyl-2- Chlorophenylthio) phenylbis (4-fluorophenyl) sulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yldi-p-tolylsulfonium, 7-isopropyl-9-oxo-10 -Thia-9,10-dihydroanthracene 2-yldiphenylsulfonium, 2-[(diphenyl) sulfonio] thioxanthone, 4- [4- (4-tert-butylbenzoyl) phenylthio] phenyldi-p-tolylsulfonium, 4- (4-benzoylphenylthio) phenyldiphenylsulfonium Diphenylphenacylsulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 2-naphthylmethyl (1-ethoxycarbonyl) ethylsulfonium, 4-hydroxyphenylmethylphenacylsulfonium, phenyl [4- (4-biphenylthio) phenyl] 4- Biphenyllsulfonium, phenyl [4- (4-biphenylthio) phenyl] 3-biphenylsulfonium, [4- (4-acetophenylthio) phenyl] diphenylsulfonium, octade Rumethylphenacylsulfonium, diphenyliodonium, di-p-tolyliodonium, bis (4-dodecylphenyl) iodonium, bis (4-methoxyphenyl) iodonium, (4-octyloxyphenyl) phenyliodonium, bis (4-decyloxy) Examples thereof include phenyliodonium, 4- (2-hydroxytetradecyloxy) phenylphenyliodonium, 4-isopropylphenyl (p-tolyl) iodonium, and 4-isobutylphenyl (p-tolyl) iodonium.

  Of the onium ions in the compound represented by the above formula (b1), a preferable onium ion includes a sulfonium ion represented by the following formula (b19).

In the above formula (b19), R ^8b is independently a hydrogen atom, alkyl, hydroxy, alkoxy, alkylcarbonyl, alkylcarbonyloxy, alkyloxycarbonyl, halogen atom, aryl optionally having substituent (s), arylcarbonyl, Represents a group selected from the group consisting of X ^2b represents the same meaning as X ^2b in the formula (b1).

  Specific examples of the sulfonium ion represented by the formula (b19) include 4- (phenylthio) phenyldiphenylsulfonium, 4- (4-benzoyl-2-chlorophenylthio) phenylbis (4-fluorophenyl) sulfonium, 4- (4-benzoylphenylthio) phenyldiphenylsulfonium, phenyl [4- (4-biphenylthio) phenyl] 4-biphenylsulfonium, phenyl [4- (4-biphenylthio) phenyl] 3-biphenylsulfonium, [4- (4 -Acetophenylthio) phenyl] diphenylsulfonium, diphenyl [4- (p-terphenylthio) phenyl] diphenylsulfonium.

The alkylfluorophosphate anion represented by the above formula (b17) represents an alkyl group which may be substituted with an R ^3b fluorine atom, preferably having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms. . Specific examples of the alkyl group include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl and octyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl and tert-butyl; and cyclopropyl, cyclobutyl and cyclopentyl. The ratio of the hydrogen atom of the alkyl group substituted by a fluorine atom is usually 80% or more, preferably 90% or more, and more preferably 100%. When the substitution rate of fluorine atoms is less than 80%, the acid strength of the onium alkylfluorophosphate represented by the above formula (b1) is lowered.

Particularly preferred R ^3b is a linear or branched perfluoroalkyl group having 1 to 4 carbon atoms and a fluorine atom substitution rate of 100%. Specific examples include CF ₃ , CF ₃ CF ₂ , (CF ₃ ) ₂ CF, CF ₃ CF ₂ CF ₂ , CF ₃ CF ₂ CF ₂ CF ₂ , (CF ₃ ) ₂ CFCF ₂ , CF ₃ CF ₂ (CF ₃ ) CF, (CF ₃ ) ₃ C may be mentioned. . The number j of R ^3b is an integer of 1 to 5, preferably 2 to 4, particularly preferably 2 or 3.

Specific examples of preferred alkyl fluorophosphate anions include [(CH ₃ CH ₂ ) ₂ PF ₄ ] ⁻ , [(CH ₃ CH ₂ ) ₃ PF ₃ ] ⁻ , [((CH ₃ ) ₂ CH) ₂ PF _{4. ^{] -, [((CH 3}} ) 2 CH) 3 PF 3] -, [(CH 3 CH 2 CH 2) 2 PF 4] -, [(CH 3 CH 2 CH 2) 3 PF 3] -, [( (CH ₃ ) ₂ CHCH ₂ ) ₂ PF ₄ ] ⁻ , [((CH ₃ ) ₂ CHCH ₂ ) ₃ PF ₃ ] ⁻ , [(CH ₃ CH ₂ CH ₂ CH ₂ ) ₂ PF ₄ ] ⁻ , or [( CH ₃ CH ₂ CH ₂ ) ₃ PF ₃ ] ⁻ , [(CF ₃ CF ₂ ) ₂ PF ₄ ] ⁻ , [(CF ₃ CF ₂ ) ₃ PF ₃ ] ⁻ , [((CF ₃ ) ₂ CF) ₂ PF ₄ ] ⁻ , [((CF ₃ ) ₂ CF) ₃ PF ₃ ] ⁻ , [(CF ₃ CF ₂ CF ₂ ) ₂ PF ₄ ] ⁻ , [(CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ] ⁻ , [(CF ₃ ) ₂ CFCF ₂ ) ₂ PF ₄ ] ⁻ , [((CF ₃ ) ₂ CFCF ₂ ) ₃ PF ₃ ] ⁻ , [(CF ₃ CF ₂ CF ₂ CF ₂ ) ₂ PF ₄ ] ⁻ , or [(CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ] ⁻ Of these, [(CH ₃ CH ₂ ) ₃ PF ₃ ] ⁻ , [(CH ₃ CH ₂ CH ₂ ) ₃ PF ₃ ] ⁻ , [((CH ₃ ) ₂ CH) ₃ PF ₃ ] ⁻ , [ ((CH ₃ ) ₂ CH) ₂ PF ₄ ] ⁻ , [((CH ₃ ) ₂ CHCH ₂ ) ₃ PF ₃ ] ⁻ , or [((CH ₃ ) ₂ CHCH ₂ ) ₂ PF ₄ ] ⁻ , [(CF _{3 CF 2) 3 PF 3]} -, [(CF 3 CF 2 CF 2 ) ₃ PF ₃ ] ⁻ , [((CF ₃ ) ₂ CF) ₃ PF ₃ ] ⁻ , [((CF ₃ ) ₂ CF) ₂ PF ₄ ] ⁻ , [((CF ₃ ) ₂ CFCF ₂ ) ₃ PF ₃ ] ^-, or _{[((CF 3) 2 CFCF} 2) 2 PF 4] - it is particularly preferred.

Preferred specific examples of the borate anion represented by the above formula (b18) include tetrakis (pentafluorophenyl) borate ([B (C ₆ F ₅ ) ₄ ] ⁻ ), tetrakis [(trifluoromethyl) phenyl] borate ( [B (C ₆ H ₄ CF ₃ ) ₄ ] ⁻ ), difluorobis (pentafluorophenyl) borate ([(C ₆ F ₅ ) ₂ BF ₂ ] ⁻ ), trifluoro (pentafluorophenyl) borate ([(C ^{_{6 F 5) BF 3] -}} ), tetrakis (difluorophenyl) borate _{([B (C 6 H 3} F 2) 4] -) , and the like. Among these, tetrakis (pentafluorophenyl) borate ([B (C ₆ F ₅ ) ₄ ] ⁻ ) is particularly preferable.

  As a second aspect of the photoacid generator, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- ( 2-furyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methyl-2-furyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) ) -6- [2- (5-Ethyl-2-furyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-propyl-2-furyl) ethenyl]- s-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,5-dimethoxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- ( 3,5-diethoxypheny ) Ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,5-dipropoxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6 -[2- (3-methoxy-5-ethoxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (3-methoxy-5-propoxyphenyl) ethenyl] -s -Triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-methylenedioxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- (3 4-methylenedioxyphenyl) -s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-triazine Loromethyl-6- (2-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) styrylphenyl-s-triazine, 2,4- Bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-Methoxynaphthyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (2-furyl) ethenyl] -4,6-bis (trichloromethyl)- 1,3,5-triazine, 2- [2- (5-methyl-2-furyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3 , 5-Zime Toxiphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl)- 1,3,5-triazine, 2- (3,4-methylenedioxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, tris (1,3-dibromopropyl) -1 , 3,5-triazine, halogen-containing triazine compounds such as tris (2,3-dibromopropyl) -1,3,5-triazine, and the following formula (b3) such as tris (2,3-dibromopropyl) isocyanurate The halogen-containing triazine compound represented by these is mentioned.

In the above formula (b3), R ^9b , R ^10b and R ^11b each independently represent a halogenated alkyl group.

  In addition, as a third aspect of the photoacid generator, α- (p-toluenesulfonyloxyimino) -phenylacetonitrile, α- (benzenesulfonyloxyimino) -2,4-dichlorophenylacetonitrile, α- (benzenesulfonyloxy) Imino) -2,6-dichlorophenylacetonitrile, α- (2-chlorobenzenesulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (ethylsulfonyloxyimino) -1-cyclopentenylacetonitrile, and the following containing oxime sulfonate groups Examples thereof include compounds represented by formula (b4).

In the formula (b4), R ^12b represents a monovalent, divalent, or trivalent organic group, and R ^13b represents a substituted or unsubstituted saturated hydrocarbon group, unsaturated hydrocarbon group, or aromaticity. A compound group is represented, and n represents the number of repeating units having a structure in parentheses.

In the above formula (b4), the aromatic compound group refers to a group of a compound exhibiting physical and chemical properties peculiar to an aromatic compound, for example, an aryl group such as a phenyl group or a naphthyl group, or a furyl group. And a heteroaryl group such as a thienyl group. These may have one or more suitable substituents such as a halogen atom, an alkyl group, an alkoxy group, and a nitro group on the ring. R ^13b is particularly preferably an alkyl group having 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group and a butyl group. In particular, a compound in which R ^12b is an aromatic compound group and R ^13b is an alkyl group having 1 to 4 carbon atoms is preferable.

As the acid generator represented by the above formula (b4), when n = 1, R ^12b is any one of a phenyl group, a methylphenyl group, and a methoxyphenyl group, and R ^13b is a compound having a methyl group. Specifically, α- (methylsulfonyloxyimino) -1-phenylacetonitrile, α- (methylsulfonyloxyimino) -1- (p-methylphenyl) acetonitrile, α- (methylsulfonyloxyimino) -1- (p- Methoxyphenyl) acetonitrile, [2- (propylsulfonyloxyimino) -2,3-dihydroxythiophene-3-ylidene] (o-tolyl) acetonitrile, and the like. When n = 2, the photoacid generator represented by the above formula (b4) is specifically a photoacid generator represented by the following formula.

  Moreover, as a 4th aspect in a photo-acid generator, the onium salt which has a naphthalene ring in a cation part is mentioned. This “having a naphthalene ring” means having a structure derived from naphthalene, and means that at least two ring structures and their aromaticity are maintained. The naphthalene ring may have a substituent such as a linear or branched alkyl group having 1 to 6 carbon atoms, a hydroxyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms. The structure derived from the naphthalene ring may be a monovalent group (one free valence) or a divalent group (two free valences) or more, but may be a monovalent group. Desirable (however, at this time, the free valence is counted excluding the portion bonded to the substituent). The number of naphthalene rings is preferably 1 to 3.

As the cation part of the onium salt having a naphthalene ring in such a cation part, a structure represented by the following formula (b5) is preferable.

In the above formula (b5), at least one of R ^14b , R ^15b and R ^16b represents a group represented by the following formula (b6), and the rest is a linear or branched alkyl having 1 to 6 carbon atoms. Represents a group, a phenyl group which may have a substituent, a hydroxyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms. Alternatively, one of R ^14b , R ^15b , and R ^16b is a group represented by the following formula (b6), and the remaining two are each independently a linear or branched alkylene having 1 to 6 carbon atoms. It is a group, and these ends may be bonded to form a ring.

In the above formula (b6), R ^17b and R ^18b each independently represent a hydroxyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, or a linear or branched alkyl group having 1 to 6 carbon atoms. R ^19b represents a single bond or a linear or branched alkylene group having 1 to 6 carbon atoms which may have a substituent. l and m each independently represent an integer of 0 to 2, and l + m is 3 or less. However, when a plurality of R ^17b are present, they may be the same as or different from each other. When a plurality of R ^18b are present, they may be the same as or different from each other.

Of the R ^14b , R ^15b , and R ^16b , the number of groups represented by the formula (b6) is preferably one from the viewpoint of the stability of the compound, and the rest is a straight chain having 1 to 6 carbon atoms. Or it is a branched alkylene group, The terminal may couple | bond together and it may become cyclic | annular. In this case, the two alkylene groups constitute a 3- to 9-membered ring including a sulfur atom. The number of atoms (including sulfur atoms) constituting the ring is preferably 5-6.

  Examples of the substituent that the alkylene group may have include an oxygen atom (in this case, a carbonyl group is formed together with a carbon atom constituting the alkylene group), a hydroxyl group, and the like.

  Examples of the substituent that the phenyl group may have include a hydroxyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, and a linear or branched alkyl group having 1 to 6 carbon atoms. Is mentioned.

Suitable examples of these cationic moieties include those represented by the following formulas (b7) and (b8), and the structure represented by the following formula (b8) is particularly preferred.

  Such a cation moiety may be an iodonium salt or a sulfonium salt, but a sulfonium salt is desirable from the viewpoint of acid generation efficiency and the like.

  Therefore, an anion capable of forming a sulfonium salt is desirable as a suitable anion portion for an onium salt having a naphthalene ring in the cation portion.

  The anion portion of such an acid generator is a fluoroalkyl sulfonate ion or an aryl sulfonate ion in which a part or all of hydrogen atoms are fluorinated.

  The alkyl group in the fluoroalkylsulfonic acid ion may be linear, branched or cyclic having 1 to 20 carbon atoms, and preferably has 1 to 10 carbon atoms from the bulk of the acid generated and its diffusion distance. In particular, a branched or annular shape is preferable because of its short diffusion distance. Moreover, since it can synthesize | combine cheaply, a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group etc. can be mentioned as a preferable thing.

  The aryl group in the aryl sulfonate ion is an aryl group having 6 to 20 carbon atoms, and examples thereof include an alkyl group, a phenyl group which may or may not be substituted with a halogen atom, and a naphthyl group. In particular, an aryl group having 6 to 10 carbon atoms is preferable because it can be synthesized at low cost. Specific examples of preferable ones include a phenyl group, a toluenesulfonyl group, an ethylphenyl group, a naphthyl group, and a methylnaphthyl group.

  In the fluoroalkyl sulfonate ion or aryl sulfonate ion, the fluorination rate when part or all of the hydrogen atoms are fluorinated is preferably 10 to 100%, more preferably 50 to 100%, In particular, those in which all hydrogen atoms are substituted with fluorine atoms are preferred because the strength of the acid is increased. Specific examples thereof include trifluoromethane sulfonate, perfluorobutane sulfonate, perfluorooctane sulfonate, and perfluorobenzene sulfonate.

Among these, a preferable anion moiety includes those represented by the following formula (b9).

In the formula (b9), R ^20b is a group represented by the following formulas (b10) and (b11) or a group represented by the following formula (b12).

In said formula (b10), x represents the integer of 1-4. In the formula (b11), R ^21b represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 6 carbon atoms, or a linear or branched alkoxy group having 1 to 6 carbon atoms. Y represents an integer of 1 to 3. Among these, trifluoromethanesulfonate and perfluorobutanesulfonate are preferable from the viewpoint of safety.

  Moreover, as an anion part, what contains the nitrogen represented by following formula (b13), (b14) can also be used.

In the formulas (b13) and (b14), ^Xb represents a linear or branched alkylene group in which at least one hydrogen atom is substituted with a fluorine atom, and the alkylene group has 2 to 6 carbon atoms. Yes, preferably 3-5, most preferably 3 carbon atoms. Y ^b and Z ^b each independently represent a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and the alkyl group has 1 to 10 carbon atoms, Is 1-7, more preferably 1-3.

The number of carbon atoms of the alkylene group X ^b, or Y ^b, solubility in more organic solvents number of carbon atoms in the alkyl group of Z ^b is less preferred because it is excellent.

Further, an alkylene group or Y ^b of X ^b, the alkyl group for Z ^b, the larger the number of hydrogen atoms substituted with fluorine atoms is large, preferred because the acid strength increases. The proportion of fluorine atoms in the alkylene group or alkyl group, that is, the fluorination rate is preferably 70 to 100%, more preferably 90 to 100%, and most preferably all hydrogen atoms are substituted with fluorine atoms. A perfluoroalkylene group or a perfluoroalkyl group.

  Preferable examples of the onium salt having a naphthalene ring in such a cation moiety include compounds represented by the following formulas (b15) and (b16).

  Further, as a fifth aspect of the photoacid generator, bis (p-toluenesulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (2,4-dimethylphenyl) Bissulfonyldiazomethanes such as sulfonyl) diazomethane; 2-nitrobenzyl p-toluenesulfonate, 2,6-dinitrobenzyl p-toluenesulfonate, nitrobenzyl tosylate, dinitrobenzyl tosylate, nitrobenzyl sulfonate, nitrobenzyl carbo Nitrobenzyl derivatives such as narate and dinitrobenzyl carbonate; pyrogallol trimesylate, pyrogallol tritosylate, benzyl tosylate, benzyl sulfonate, N-methylsulfonyloxysuccinimate Sulfonic acid esters such as N-trichloromethylsulfonyloxysuccinimide, N-phenylsulfonyloxymaleimide and N-methylsulfonyloxyphthalimide; trifluoromethanesulfonic acid esters such as N-hydroxyphthalimide and N-hydroxynaphthalimide; diphenyliodonium Hexafluorophosphate, (4-methoxyphenyl) phenyliodonium trifluoromethanesulfonate, bis (p-tert-butylphenyl) iodonium trifluoromethanesulfonate, triphenylsulfonium hexafluorophosphate, (4-methoxyphenyl) diphenylsulfonium trifluoro Lomethanesulfonate, (p-tert-butylphenyl) diphenylsulfonium trifluorometa Onium salts sulfonate and the like; benzoin tosylate, benzoin tosylate such as α- methyl benzoin tosylate; other diphenyliodonium salts, triphenylsulfonium salts, phenyldiazonium salts, benzyl carbonate and the like.

  Preferred examples of the thermal acid generator include oxime ester compounds of organic sulfonic acids, 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, and other organic sulfonic acids. Examples include alkyl esters. Further, sulfonium salts, iodonium salts, benzothiazonium salts, ammonium salts, onium salts such as phosphonium salts, and the like can be appropriately used as the thermal acid generator.

  In addition, as mentioned later, in the manufacturing method of the hardened | cured material which concerns on this invention, the process before the acid generation process which is a process of hardening a curable composition is performed at the temperature of 80 degrees C or less. For this reason, the thermal acid generator used in the present invention needs to start acid generation at a temperature of 80 ° C. or lower. For this reason, in this invention, the thermal acid generator whose acid generation start temperature measured by the method shown below is 80 degrees C or less is used.

  The acid generation start temperature of the thermal acid generator can be measured by a differential heat / thermogravimetry apparatus (for example, TG / DTA-6200, manufactured by Hitachi High-Tech Science Co., Ltd.). Specifically, the starting point of weight reduction in the TG curve of the thermal acid generator obtained by measurement using a differential heat / thermogravimetry apparatus is defined as the acid generation start temperature of the thermal acid generator.

  The content of the acid generator (B) in the curable composition is not particularly limited as long as the object of the present invention is not impaired. The content of the acid generator (B) in the curable composition is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the alicyclic epoxy compound represented by the formula (1). 0.1-15 mass parts is more preferable, and 0.1-13 mass parts is especially preferable.

[(S) solvent]
The curable composition may contain a (S) solvent for improving the coating property and adjusting the viscosity.

  Specific examples of the (S) solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono- n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n -Butyl ether, dipropylene glycol monomethyl ether (Poly) alkylene glycol monoalkyl ethers such as dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether; (Poly) alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate Kind; Other ethers such as glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; methyl 2-hydroxypropionate and 2-hydroxypropionic acid Lactic acid alkyl esters such as ethyl; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate , Ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3- Methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, n-butyl propionate, butyric acid Other esters such as ethyl, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate Aromatic hydrocarbons such as toluene and xylene; amides such as N-methylpyrrolidone, N, N-dimethylformamide and N, N-dimethylacetamide; Among these, alkylene glycol monoalkyl ethers, alkylene glycol monoalkyl ether acetates, other ethers described above, alkyl lactate esters, and other esters described above are preferable, alkylene glycol monoalkyl ether acetates described above. Other ethers and other esters described above are more preferred.

  Among the solvents described above, as described later, the (S) solvent in the curable composition quickly volatilizes in the step before the acid generation step performed at 80 ° C. or lower when producing a cured product. A solvent having a boiling point of 80 ° C. or lower is also preferably used. Among the specific examples of the (S) solvent, tetrahydrofuran, acetone, methyl ethyl ketone, and ethyl acetate have a boiling point of 80 ° C. or lower. These (S) solvents can be used alone or in combination of two or more.

  The content of the (S) solvent in the curable composition is not particularly limited. The content of the (S) solvent in the curable composition is appropriately adjusted in consideration of the handleability of the curable composition such as applicability. For example, when a curable composition is applied to a substrate to form a coating film, the concentration of components other than the solvent of the curable composition is typically preferably 1 to 50% by mass, and 5 to 30% by mass. % Is more preferable, and 5 to 15% by mass is more preferable.

[Other ingredients]
The curable composition can contain additives such as a surfactant, an adhesion improver, a thermal polymerization inhibitor, and an antifoaming agent as necessary. Any additive can be used as the additive. Examples of the surfactant include anionic, cationic, and nonionic compounds, examples of the adhesion improver include conventionally known silane coupling agents, and examples of the thermal polymerization inhibitor include hydroquinone and hydroquinone mono Examples of the antifoaming agent include silicone-based and fluorine-based compounds.

[Method for producing curable composition]
The manufacturing method of a curable composition is not specifically limited. A curable composition can be manufactured by mixing each component demonstrated above uniformly with a well-known mixing apparatus. When the curable composition is a solid or a highly viscous gel at room temperature, the components are mixed using a kneader, a melt-kneader such as a two-roll, or a three-roll. May be.

≪Method for producing cured product≫
The method for producing a cured product according to the present invention includes:
Forming the curable composition described above according to the desired shape of the cured product; and
In the molded curable composition, the acid generation process of generating an acid from the above-mentioned (B) acid generator contained in a curable composition and hardening a curable composition is included.
And the process before an acid generation process is performed at the temperature of 80 degrees C or less.

  When a curable composition containing an alicyclic epoxy compound is cured to form a cured product, there is a problem that it is difficult to form a cured product having both high transparency and high hardness. In particular, when a cured product is formed using a curable composition containing the alicyclic epoxy compound represented by the above formula (1), a cured product having a high hardness even if a highly transparent cured product can be formed. There is a problem that it is difficult to form.

  However, according to the manufacturing method of the hardened | cured material which concerns on this invention, the highly transparent hardened | cured material of the alicyclic epoxy compound represented by Formula (1) by hardening a curable composition at said predetermined process. It is possible to form a cured product having high hardness while taking advantage of the property of imparting.

[Molding process]
The method for molding the curable composition according to the desired shape is not particularly limited, and various conventionally known methods can be used. For example, when the curable composition is formed into a film, a method of applying a liquid curable composition on a substrate or a solid or high-viscosity gel-like curable composition may be used as necessary. A method of pressing while heating to a temperature of 0 ° C. or lower can be used. When the curable composition is applied onto a substrate, for example, a contact transfer type coating device such as a roll coater, reverse coater, bar coater, slit coater, or non-contact such as a spinner (rotary coating device) or curtain flow coater. A mold applicator can be used.

  When the cured product has a three-dimensional shape other than a film shape, the curable composition can be formed into a desired shape by injecting or filling the curable composition into a mold having a recess having a desired shape. .

  When a curable composition contains the (S) solvent, you may remove a solvent from a curable composition as needed, after shape | molding a curable composition. The solvent is removed by heating the curable composition or placing the curable composition in a reduced-pressure atmosphere. When the curable composition is heated to remove the solvent, the heating temperature is 80 ° C. or lower. When the curable composition contains a thermal acid generator, the temperature at which the curable composition is heated to remove the solvent is preferably lower than the acid generation start temperature of the thermal acid generator.

[Acid generation step]
When the curable composition is a composition containing a photoacid generator, the curable composition molded into a desired shape is subjected to an active energy ray such as an ultraviolet ray or an electron beam at a temperature of 80 ° C. or lower. By exposing, an acid can be generated in the curable composition and the curable composition can be cured. As a light source for curing the curable composition, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, or the like is used. Although the exposure amount at the time of hardening a curable composition by exposure can be adjusted arbitrarily, it is preferable to carry out in the range of 1-100 mJ / cm < ² >, for example.

  When the curable composition is a composition containing a thermal acid generator, the curable composition molded into a desired shape is heated to a temperature not higher than 80 ° C. and not lower than the acid generation start temperature of the thermal acid generator. Thus, an acid can be generated in the curable composition to cure the curable composition. The heating time is appropriately adjusted according to the size of the molded curable composition.

In the manufacturing method of the hardened | cured material which concerns on this invention, highly hardened | cured material can be obtained, without impairing transparency of hardened | cured material by performing the process before an acid generation process at 80 degrees C or less. On the other hand, when a cured product is produced by performing at least one of the steps before the acid generation step on the curable composition described above at a temperature of 80 ° C. or higher, it is difficult to obtain a cured product with high hardness. This tendency is remarkable when a compound represented by the above formula (1) and all of R ^{1 to} R ¹⁸ are hydrogen atoms is used as the (A) alicyclic epoxy compound.

  This seems to be due to the following reasons. According to the results of the study by the present inventors, the cause is unknown, but when the cured product is produced by treating the curable composition at a temperature of 80 ° C. or higher, (A) alicyclic in the cured product. It was confirmed that the content of the unit derived from the epoxy compound tends to be lower than the theoretical value obtained from the composition of the curable composition. It is thought that the hardness of hardened | cured material falls by the reduction | decrease of content of the unit derived from the (A) alicyclic epoxy compound in hardened | cured material. For this reason, in the method for producing a cured product according to the present invention, the step before the acid generation step is more preferably performed at 75 ° C. or less, and more preferably at 60 ° C. or less.

  The cured product thus produced is excellent in hardness and transparency. Specifically, according to the method for producing a cured product according to the present invention, a cured product having a pencil hardness of 9H or more and a light transmittance of a wavelength of 400 nm when the thickness is 10 μm is 95% or more. Can do. In a transparent cured product, the absorption tends to increase as the wavelength of light is shorter. For this reason, when the light transmittance of the cured product is 90 μm or more at a wavelength of 400 nm when the thickness is 10 μm, the cured product has sufficiently high transparency in the wavelength range of visible light. For these reasons, the light transmittance at a wavelength of 400 nm is used as an index of the transparency of the cured product.

  As explained above, according to the manufacturing method of the hardened | cured material which concerns on this invention, the hardened | cured material excellent in hardness and transparency can be formed. The cured product formed in this manner is excellent in hardness and transparency, and thus is suitably used for applications such as transparent insulating films and protective films used in various display devices and the like, sealing materials for light emitting elements, and the like.

  Examples of the present invention will be described below, but the scope of the present invention is not limited to these examples.

  In Examples 1 to 6, Comparative Example 3, and Comparative Example 4, the following compound 1 which is an alicyclic epoxy compound represented by the above formula (1) was used as an epoxy compound. In Comparative Examples 1 and 2, the following compounds 2 and 3 which are epoxy compounds not included in the above formula (1) were used as the epoxy compounds.

  In Examples 1-3 and Comparative Examples 1-3, PAG1 of the following formula which is a photo-acid generator was used as an acid generator. In Examples 4 to 6 and Comparative Example 4, TAG1 (Sunade (registered trademark) SI-60L, aromatic sulfonium salt, manufactured by Sanshin Chemical Industry Co., Ltd., acid generation start temperature 60 ° C.) was used as the thermal acid generator. TAG2 (Sunade (registered trademark) SI-80L, aromatic sulfonium salt, manufactured by Sanshin Chemical Industry Co., Ltd., acid generation start temperature 75 ° C.).

[Example 1]
100 parts by mass of the epoxy compound (Compound 1) and 13 parts by mass of the acid generator (PAG1) were uniformly mixed to obtain a curable composition. The obtained curable composition was applied onto a glass substrate using a spin coater to form a coating film. The formed coating film was heated at 80 ° C. for 120 seconds. Thereafter, the coating film was exposed with broadband light to form a cured film having a thickness of 10 μm. About the formed cured film, pencil hardness and transparency were evaluated in accordance with the following method.
The evaluation results are shown in Table 1.

<Pencil hardness>
The formed cured film was subjected to a hardness test 5 times with a load of 1 kg ± 50 g using a pencil, and the presence or absence of scratches after applying the load was observed. Of the pencil hardnesses in which the cured film was not damaged in five tests, the hardest pencil hardness was taken as the test result.

<Transparency>
Using a spectrophotometer (MCPD-3000, manufactured by Otsuka Electronics Co., Ltd.), the transmittance of the obtained cured film was measured in a measurement wavelength range of 400 nm.
Regarding transparency, a transmittance of 95% or more was judged as ◎, 90% or more and less than 95% was judged as ○, and less than 90% was judged as ×.
Table 1 shows the determination results of transparency.

[Example 2]
A curable composition was prepared in the same manner as in Example 1. A cured film having a thickness of 10 μm was formed in the same manner as in Example 1 except that the coating film was not heated using the obtained curable composition. The pencil hardness and transparency of the formed cured film were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 3
A curable composition was prepared in the same manner as in Example 1. Using the obtained curable composition, a cured film having a thickness of 10 μm was formed in the same manner as in Example 1 except that the coated film was exposed and then heated at 150 ° C. for 10 minutes. The pencil hardness and transparency of the formed cured film were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 4
A curable composition was prepared in the same manner as in Example 1 except that 13 parts by mass of the acid generator (PAG1) was changed to 10 parts by mass of the acid generator (TAG1). Using the obtained curable composition, a cured film having a thickness of 10 μm was formed in the same manner as in Example 1 except that the exposure of the coating film was changed to heating at 80 ° C. for 2 minutes. The pencil hardness and transparency of the formed cured film were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 5
A curable composition was prepared in the same manner as in Example 1 except that 13 parts by mass of the acid generator (PAG1) was changed to 10 parts by mass of the acid generator (TAG2). Using the obtained curable composition, a cured film having a thickness of 10 μm was formed in the same manner as in Example 1 except that the exposure of the coating film was changed to heating at 80 ° C. for 5 minutes. The pencil hardness and transparency of the formed cured film were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 6
A curable composition was prepared by uniformly mixing 100 parts by mass of an epoxy compound (Compound 1), 10 parts by mass of an acid generator (TAG2), and 990 parts by mass of acetone. The obtained curable composition was applied onto a glass substrate using a spin coater to form a coating film. The formed coating film was heated at 65 ° C. for 5 minutes and further heated at 80 ° C. for 5 minutes to form a cured film having a thickness of 10 μm. About the formed cured film, pencil hardness and transparency were evaluated in accordance with the following method. The evaluation results are shown in Table 1.

[Comparative Example 1]
A curable composition was prepared in the same manner as in Example 1 except that the epoxy compound (Compound 1) was changed to the epoxy compound (Compound 2). A cured film having a thickness of 10 μm was formed in the same manner as in Example 1 using the obtained curable composition. The pencil hardness and transparency of the formed cured film were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

[Comparative Example 2]
A curable composition was prepared in the same manner as in Example 1 except that the epoxy compound (Compound 1) was changed to the epoxy compound (Compound 3). A cured film having a thickness of 10 μm was formed in the same manner as in Example 1 using the obtained curable composition. The pencil hardness and transparency of the formed cured film were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

[Comparative Example 3]
A curable composition was prepared in the same manner as in Example 1. A cured film having a thickness of 10 μm was formed in the same manner as in Example 1 except that the heating temperature of the coating film was changed from 80 ° C. to 120 ° C. using the obtained curable composition. The pencil hardness and transparency of the formed cured film were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

[Comparative Example 4]
A curable composition was prepared in the same manner as in Example 4. A cured film having a thickness of 10 μm was formed in the same manner as in Example 4 except that the heating temperature during curing was changed from 80 ° C. to 120 ° C. The pencil hardness and transparency of the formed cured film were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

  According to Examples 1-6, when performing all the processes before generating an acid in a curable composition at 80 degrees C or less and hardening a curable composition, the hardened | cured material excellent in hardness and transparency is formed. I understand that I can do it. In addition, when all steps from Example 3 to generation of acid in the curable composition are performed at 80 ° C. or lower to cure the curable composition, the cured product is treated at a temperature of 80 ° C. or higher after curing. However, it turns out that the hardness of hardened | cured material does not fall.

  From Comparative Examples 1 and 2, the epoxy compound contained in the curable composition, even if the curable composition is cured by performing all the steps before generating the acid in the curable composition at 80 ° C. or lower, It turns out that it is hard to form the hardened | cured material which is excellent in hardness when it is a compound not contained in said Formula (1).

  From Comparative Examples 3 and 4, it can be seen that it is difficult to form a cured product having excellent hardness when a process performed at a temperature higher than 80 ° C. is included in the process before generating the acid in the curable composition.

Claims (5)

A method for producing a cured product, comprising producing a cured product by curing a curable composition containing an alicyclic epoxy compound,
(A) A molding step of molding a curable composition containing an alicyclic epoxy compound represented by the following formula (1) and (B) an acid generator according to a desired shape of the cured product;
An acid generation step of generating an acid from the acid generator (B) to cure the curable composition in the molded curable composition,
The manufacturing method of hardened | cured material which performs the process before the said acid generation process at the temperature of 80 degrees C or less.

(In formula (1), R ^{1 to} R ¹⁸ are each independently a group selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group.)   The content of the acid generator (B) in the curable composition is 0.1 to 20 parts by mass with respect to 100 parts by mass of the alicyclic epoxy compound represented by the formula (1). The manufacturing method of the hardened | cured material of Claim 1 which is.   The method for producing a cured product according to claim 1 or 2, wherein the (B) acid generator is at least one selected from a photoacid generator and a thermal acid generator.   Hardened | cured material obtained by the manufacturing method of hardened | cured material of any one of Claims 1-3.   The hardened | cured material of Claim 4 whose transmittance | permeability of light with a wavelength of 400 nm in case pencil thickness is 9H or more and thickness is 10 micrometers is 95% or more.