Acid generator, curable composition containing that acid generator, and cured product thereof

Abstract

To provide a curable composition that has excellent solubility, rapidly cures upon exposure to photoirradiation treatment or heat treatment, and forms a cured product with excellent adhesiveness, heat resistance, and insulation.SOLUTION: An acid generator of the present invention includes a compound represented by the formula (1) in the figure. In the formula (1): Ct represents a monovalent cation; Ar represents an aromatic hydrocarbon group or an aromatic heterocyclic group; M represents a boron atom, an aluminum atom, or a gallium atom; R1 represents a fluorine atom, an aromatic hydrocarbon group, or an aromatic heterocyclic group; m represents an integer equal to or greater than 1; and n represents an integer from 1 to 4.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a novel acid generator, a curable composition containing the acid generator, and a cured product thereof. [Background technology]

[0002] Benzylanilinium salts, for example, have been known as acid generators for curing cationic curable compounds.

[0003] Patent Document 1 describes a sealant for an organic EL display device that contains a compound represented by the following formula as an acid generator together with a cationic curable compound. [ka] [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2016-51602 A Summary of the Invention [Problem to be solved by the invention]

[0005] Semiconductor devices require electrical reliability, and contamination with ionic substances must be avoided. For this reason, the sealing resin (hardened sealant) of resin-sealed packages of semiconductor elements such as organic electroluminescence (EL) display elements must have electrical insulation properties.

[0006] However, if the acid generator is contained in the sealant without dissolving, the acid generator is likely to remain in the resulting cured product even after light irradiation or heat treatment, and the acid generator remaining in the cured product causes deterioration of electrical properties. Another problem is that the desired curability, adhesiveness, and heat resistance cannot be obtained.

[0007] The acid generator described in Patent Document 1 is difficult to dissolve in resin and tends to leave insoluble residue, but it is extremely difficult to confirm that no insoluble residue of the acid generator remains in the sealant. Therefore, dissolution of the acid generator was ensured by a thorough dissolution process. As a result, the dissolution process took a lot of time, and the work efficiency was poor.

[0008] Therefore, an object of the present invention is to provide a novel acid generator which has excellent solubility, excellent curability through a short dissolution operation, and can produce a curable composition which forms a cured product having excellent adhesive properties, heat resistance, and insulating properties. Another object of the present invention is to provide a curable composition that is rapidly cured by light irradiation treatment or heat treatment to form a cured product having excellent adhesiveness, heat resistance, and insulating properties. Another object of the present invention is to provide a cured product having excellent adhesiveness, heat resistance and insulating properties. Another object of the present invention is to provide novel compounds useful as photo- or thermal acid generators. [Means for solving the problem]

[0009] Means for Solving the Problems The present inventors have conducted intensive research to solve the above problems and have found that a compound represented by the following formula has excellent solubility in cationic curable compounds, and that a curable composition can be efficiently produced by using the compound, and that a curable composition obtained by using the compound has excellent curability and can form a cured product having excellent adhesion, heat resistance, and insulation properties. The present invention was completed based on these findings.

[0010] That is, the present invention provides an acid generator containing a compound represented by the following formula (1). [ka] (In the formula, Ct represents a monovalent cation. Ar represents an aromatic hydrocarbon group or an aromatic heterocyclic group. M represents a boron atom, an aluminum atom, or a gallium atom. R 1represents a fluorine atom, an aromatic hydrocarbon group, or an aromatic heterocyclic group; m represents an integer of 1 or more, and n represents an integer of 1 to 4.

[0011] The present invention also provides the acid generator according to claim 1, wherein the monovalent cation in Ct is a cation selected from a sulfonium ion, an iodonium ion, a selenium ion, an ammonium ion, and a phosphonium ion.

[0012] The present invention also provides a curable composition comprising the acid generator and a cationic curable compound.

[0013] The present invention also provides a cured product of the curable composition.

[0014] The present invention also provides a compound represented by the following formula (1-1): [ka] (In the formula, Ct represents a monovalent cation. Ar represents an aromatic hydrocarbon group or an aromatic heterocyclic group. M' represents a boron atom or a gallium atom. R 1 represents a fluorine atom, an aromatic hydrocarbon group, or an aromatic heterocyclic group. m represents an integer of 1 or more, and n represents an integer of 1 to 4. However, when M' is a boron atom, R 1 is an aromatic hydrocarbon group or an aromatic heterocyclic group. Effect of the Invention

[0015] The acid generator of the present invention has excellent solubility in a cationic curable compound. Therefore, the acid generator can be completely dissolved in the cationic curable compound by simply mixing with the cationic curable compound and stirring for a short time, and can be uniformly dispersed in the cationic curable compound. Therefore, the resulting curable composition has excellent cationic curability, and can be rapidly cured by applying a light irradiation treatment or a heat treatment to form a cured product having excellent adhesiveness, heat resistance, and insulation properties. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] [Acid generator] The acid generator of the present invention contains a compound represented by the following formula (1) (hereinafter, sometimes referred to as "compound (1)"). [ka] (In the formula, Ct represents a monovalent cation. Ar represents an aromatic hydrocarbon group or an aromatic heterocyclic group. M represents a boron atom, an aluminum atom, or a gallium atom. R 1 represents a fluorine atom, an aromatic hydrocarbon group, or an aromatic heterocyclic group; m represents an integer of 1 or more, and n represents an integer of 1 to 4.

[0017] Of these, the above-mentioned M is preferably a boron atom or a gallium atom.

[0018] Therefore, the acid generator is preferably a compound represented by the following formula (1-1). [ka] (In the formula, Ct represents a monovalent cation. Ar represents an aromatic hydrocarbon group or an aromatic heterocyclic group. M' represents a boron atom or a gallium atom. R 1 represents a fluorine atom, an aromatic hydrocarbon group, or an aromatic heterocyclic group; m represents an integer of 1 or more, and n represents an integer of 1 to 4.

[0019] In the above formula, n Ar may be the same or different. In addition, m R 1 may be the same or different.

[0020] The aromatic hydrocarbon group is preferably C 6-14 (Especially C 6-10 ) Aromatic hydrocarbon groups are preferred, such as phenyl and naphthyl groups.

[0021] The aromatic heterocyclic group is a group obtained by removing one hydrogen atom from the structural formula of an aromatic heterocycle. Examples of the aromatic heterocycle include five-membered rings such as pyrrole ring, imidazole ring, pyrazole ring, triazole ring, furan ring, and thiophene ring; six-membered rings such as pyridine ring, pyrazine ring, pyrimidine ring, and pyridazine ring; and condensed rings such as quinoline ring and benzofuran ring.

[0022] Among these, Ar is preferably an aromatic hydrocarbon group, and particularly preferably a phenyl group.

[0023] R 1 Of these, a fluorine atom or an aromatic hydrocarbon group is preferable, a fluorine atom or a phenyl group is particularly preferable, and a fluorine atom is most preferable.

[0024] m SF4R in the above formula (1) (1-1) 1 It is preferred that at least one of the m groups is an SF5 group, and it is particularly preferred that all of the m groups are SF5 groups.

[0025] Therefore, the compound represented by the above formula (1) is preferably a compound represented by the following formula (1F), and the compound represented by the above formula (1-1) is preferably a compound represented by the following formula (1-1F), in which Ct, Ar, M, M', m, and n are the same as above. [ka]

[0026] The Ar is a substituent (SFR 1 In addition to the SF5 group, one or more other substituents may be present. Examples of the other substituents include a halogen atom, an oxo group, a hydroxyl group, a substituted oxy group (e.g., C 1-4 Alkoxy group, C 6-10 Aryloxy group, C 7-16 Aralkyloxy group, C 1-4 acyloxy group, etc.), alkyl group (e.g., methyl group, ethyl group, etc. 1-4Alkyl groups, alkenyl groups (e.g., vinyl groups, allyl groups, 1-butenyl groups, etc.) 2-4 alkenyl group), alkynyl group (e.g., ethynyl group, propynyl group, etc. 2-4 Alkynyl groups, etc.), C 3-8 Cycloalkyl groups, aryl groups (e.g., phenyl groups, naphthyl groups, biphenyl groups, etc.) 6-15 aryl group), thio group, substituted thio group (e.g., C 1-6 Alkylthio group, C 6-10 arylthio group, and the like, and the substituents include, for example, a hydroxy group, a cyano group, an alkoxy group, a hydroxyalkoxy group, a sulfo group, a carboxy group, and the like), a carboxyl group, a substituted oxycarbonyl group (for example, C 1-4 Alkoxycarbonyl group, C 6-10 Aryloxycarbonyl group, C 7-16 aralkyloxycarbonyl group, etc.), acyl group (formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, pivaloyl group, etc. 1-6 Aliphatic acyl group, acetoacetyl group, benzoyl group, etc. 7-14 Aromatic acyl groups), substituted or unsubstituted carbamoyl groups (e.g., carbamoyl, methylcarbamoyl, etc. 1-4 C such as alkyl-substituted carbamoyl and phenylcarbamoyl groups 6-10 Aryl-substituted carbamoyl groups, cyano groups, nitro groups, sulfo groups, heterocyclic groups, and the like.

[0027] The m is SF4R shown in the above formula. 1 Number of SF4R groups or SF5 groups (SF4R bound to Ar) 1 In view of excellent solubility, m is preferably an integer of 1 to 5, particularly preferably an integer of 1 to 3, and most preferably 1 or 2.

[0028] The n indicates the number of groups in the parentheses to which n is added in the above formula, and is an integer of 1 to 4. From the viewpoint of excellent solubility, the n is preferably an integer of 2 to 4, particularly preferably 3 or 4, and most preferably 4.

[0029] The anion constituting the compound (1) is preferably an anion represented by the following formulae (A-1) to (A-24). [ka] [ka]

[0030] The Ct represents a monovalent cation. The cation is preferably an organic cation, and more preferably an onium cation.

[0031] The onium cation includes a sulfonium ion, an iodonium ion, a selenium ion, an ammonium ion, a phosphonium ion, and the like.

[0032] The sulfonium ion may, for example, be a sulfonium ion represented by the following formula (s): [ka]

[0033] In the above formula (s), R 11 , R 12 R is the same or different and is selected from the group consisting of a monovalent hydrocarbon group, a monovalent heterocyclic group, and a monovalent group formed by bonding two or more of the above groups via a single bond or a linking group. 11 , R 12 are connected to adjacent S + may form a ring together with

[0034] The monovalent hydrocarbon group includes a monovalent aliphatic hydrocarbon group, a monovalent alicyclic hydrocarbon group, a monovalent aromatic hydrocarbon group, and a monovalent group formed by combining these groups.

[0035] The monovalent aliphatic hydrocarbon group is a group having 1 to 20 carbon atoms (=C 1-20) is preferred, and examples thereof include alkyl groups having about 1 to 20 carbon atoms (preferably 1 to 10, particularly preferably 1 to 3), such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a s-butyl group, a t-butyl group, a pentyl group, a hexyl group, a decyl group, and a dodecyl group; alkenyl groups having about 2 to 20 carbon atoms (preferably 2 to 10, particularly preferably 2 to 3), such as a vinyl group, an allyl group, and a 1-butenyl group; and alkynyl groups having about 2 to 20 carbon atoms (preferably 2 to 10, particularly preferably 2 to 3), such as an ethynyl group, and a propynyl group.

[0036] The monovalent alicyclic hydrocarbon group is, for example, C 3-20 Alicyclic hydrocarbon groups are preferred, and examples thereof include cycloalkyl groups having about 3 to 20 members (preferably 3 to 15 members, particularly preferably 5 to 8 members), such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group; cycloalkenyl groups having about 3 to 20 members (preferably 3 to 15 members, particularly preferably 5 to 8 members), such as a cyclopentenyl group and a cyclohexenyl group; perhydronaphthalene-1-yl group, a norbornyl group, an adamantyl group, a tricyclo[5.2.1.0 2,6 ]decan-8-yl group, tetracyclo[4.4.0.1 2,5 .1 7,10 ]Dodecan-3-yl group and other bridged cyclic hydrocarbon groups.

[0037] The monovalent aromatic hydrocarbon group is C 6-14 (Especially C 6-10 ) Aromatic hydrocarbon groups are preferred, such as phenyl and naphthyl groups.

[0038] Examples of monovalent groups in which an alicyclic hydrocarbon group and an aromatic hydrocarbon group are combined include C groups such as benzyl and phenylethyl groups. 7-18 Examples thereof include aralkyl groups.

[0039] The ring of the alicyclic hydrocarbon group or aromatic hydrocarbon group may be condensed with an aromatic or non-aromatic heterocycle.

[0040] The hydrocarbon group may have a substituent. Examples of the substituent include a halogen atom, an oxo group, a hydroxyl group, a substituted oxy group (e.g., C 1-4 Alkoxy group, C 6-10 Aryloxy group, C 7-16 Aralkyloxy group, C 1-4 acyloxy group, etc.), thio group, substituted thio group (e.g., C 1-6 Alkylthio group, C 6-10 arylthio group, and the like, and the substituents include, for example, a hydroxy group, a cyano group, an alkoxy group, a hydroxyalkoxy group, a sulfo group, a carboxy group, and the like), a carboxyl group, a substituted oxycarbonyl group (for example, C 1-4 Alkoxycarbonyl group, C 6-10 Aryloxycarbonyl group, C 7-16 aralkyloxycarbonyl group, etc.), acyl group (formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, pivaloyl group, etc. 1-6 Aliphatic acyl group, acetoacetyl group, benzoyl group, etc. 7-14 Aromatic acyl groups), substituted or unsubstituted carbamoyl groups (e.g., carbamoyl, methylcarbamoyl, etc. 1-4 C such as alkyl-substituted carbamoyl and phenylcarbamoyl groups 6-10 Examples of the hydrocarbon group include a group containing a perfluoromethyl group or a perfluoromethylene group (for example, C 1-10 Haloalkyl groups may be included.

[0041] The monovalent heterocyclic group is a group obtained by removing one hydrogen atom from the structural formula of a heterocycle. The heterocycle includes aromatic heterocycles and non-aromatic heterocycles. The heterocycle constituting the heterocyclic group includes aromatic heterocycles and non-aromatic heterocycles. Examples of such heterocycles include 3- to 20-membered rings (preferably 3- to 10-membered rings, particularly preferably 4- to 6-membered rings) having carbon atoms and at least one heteroatom (e.g., oxygen atom, sulfur atom, nitrogen atom, etc.) as atoms constituting the ring, and condensed rings thereof. Specifically, heterocycles containing an oxygen atom as a heteroatom (for example, three-membered rings such as an oxirane ring; four-membered rings such as an oxetane ring; five-membered rings such as a furan ring, a tetrahydrofuran ring, an oxazole ring, an isoxazole ring, and a γ-butyrolactone ring; six-membered rings such as a 4-oxo-4H-pyran ring, a tetrahydropyran ring, and a morpholine ring; condensed rings such as a benzofuran ring, an isobenzofuran ring, a 4-oxo-4H-chromene ring, a chroman ring, and an isochroman ring; 3-oxatricyclo[4.3.1.1 4,8 ]Undecane-2-one ring, 3-oxatricyclo[4.2.1.0 4,8 ]nonan-2-one ring and the like), heterocycles containing a sulfur atom as a heteroatom (for example, 5-membered rings such as a thiophene ring, a thiazole ring, an isothiazole ring, a thiadiazole ring, and the like; 6-membered rings such as a 4-oxo-4H-thiopyran ring, and the like; condensed rings such as a benzothiophene ring, and the like), heterocycles containing a nitrogen atom as a heteroatom (for example, 5-membered rings such as a pyrrole ring, a pyrrolidine ring, a pyrazole ring, an imidazole ring, and a triazole ring, and the like; 6-membered rings such as an isocyanuric ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a piperidine ring, and the like; condensed rings such as an indole ring, an indoline ring, a quinoline ring, an acridine ring, a naphthyridine ring, a quinazoline ring, and a purine ring, and the like).

[0042] The heterocyclic group may have a substituent. The substituent may be an alkyl group (e.g., a C group such as a methyl group or an ethyl group) in addition to the substituent that the hydrocarbon group may have. 1-4 Alkyl groups, alkenyl groups (e.g., vinyl groups, allyl groups, 1-butenyl groups, etc.) 2-4 alkenyl group), alkynyl group (e.g., ethynyl group, propynyl group, etc.2-4 Alkynyl groups, etc.), C 3-8 Cycloalkyl groups, aryl groups (e.g., phenyl groups, naphthyl groups, biphenyl groups, etc.) 6-15 Aryl groups) and the like.

[0043] R 11 , R 12 are connected to each other and adjacent S + The ring that may be formed together with + The heterocycle is a heterocycle containing at least the S + In addition, it may contain a heteroatom (for example, an oxygen atom, a nitrogen atom, a sulfur atom, etc.). The heterocycle is, for example, a 5- or 6-membered heterocycle.

[0044] The benzene ring shown in the above formula (s) may include an alkyl group (e.g., C 1-5 Alkyl groups) and aryl groups (e.g., C 6-15 An aromatic hydrocarbon ring may be condensed to the benzene ring. Furthermore, a substituent may be bonded to the benzene ring, the alkyl group or aryl group bonded to the benzene ring, or the condensed ring of the benzene ring and the aromatic hydrocarbon ring. Examples of the substituent include a hydroxyl group, an SF5 group, a halogen atom, a silyl group, a substituted oxy group (e.g., C 1-4 Alkoxy group, C 6-15 Aryloxy group, C 7-16 Aralkyloxy group, C 1-4 acyloxy groups, etc.), substituted thio groups (e.g., C 1-6 Alkylthio group, C 6-15 Arylthio groups, etc.

[0045] The sulfonium ion may be bonded to a cationic curable compound described later, that is, the sulfonium ion may contain the cationic curable compound described later in its structure.

[0046] As the sulfonium ion represented by the above formula (s), a triarylsulfonium ion represented by the following formula (s-1) or a sulfonium ion represented by the following formula (s-2) is preferable. [ka]

[0047] Specific examples of the sulfonium ion represented by the above formula (s-2) are shown below. The benzene ring shown in the following formula may have the same substituent as above bonded thereto. [ka]

[0048] Examples of the iodonium ion include the iodonium ion represented by the following formula (i). [ka]

[0049] The benzene ring shown in the above formula (i) may have an alkyl group (e.g., C 1-5 Alkyl groups) and aryl groups (e.g., C 6-15 An aromatic hydrocarbon ring may be condensed to the benzene ring. Furthermore, a substituent may be bonded to the benzene ring, the alkyl group or aryl group bonded to the benzene ring, or the condensed ring of the benzene ring and the aromatic hydrocarbon ring. Examples of the substituent include a hydroxyl group, an SF5 group, a halogen atom, a silyl group, a substituted oxy group (e.g., C 1-4 Alkoxy group, C 6-15 Aryloxy group, C 7-16 Aralkyloxy group, C 1-4 acyloxy groups, etc.), substituted thio groups (e.g., C 1-6 Alkylthio group, C 6-15 Arylthio groups, etc.

[0050] Specific examples of the iodonium ion include aryl iodonium ions such as p-cumenyl(p-tolyl)iodonium ion, diphenyliodonium ion, di-p-tolyliodonium ion, bis(4-tert-butylphenyl)iodonium ion, bis(4-dodecylphenyl)iodonium ion, bis(4-methoxyphenyl)iodonium ion, and (4-octyloxyphenyl)phenyliodonium ion.

[0051] Examples of the selenium ion include arylselenium ions such as triphenylselenium ion, tri-p-tolylselenium ion, tri-o-tolylselenium ion, tris(4-methoxyphenyl)selenium ion, 1-naphthyldiphenylselenium ion, tris(4-fluorophenyl)selenium ion, tri-1-naphthylselenium ion, and tri-2-naphthylselenium ion.

[0052] Examples of the ammonium ion include ammonium ions represented by the following formula (n): [ka]

[0053] In the above formula (n), R 13 ~R 16 R may be the same or different and is selected from the group consisting of a monovalent hydrocarbon group, a monovalent heterocyclic group, and a monovalent group formed by bonding two or more of the above groups via a single bond or a linking group. 13 ~R 16 Two or more groups selected from the following are linked to adjacent N + may form a ring together with

[0054] The monovalent hydrocarbon group, the monovalent heterocyclic group, and the monovalent group formed by bonding two or more of the above groups via a single bond or a linking group include R 11 , R 12 Similar examples include:

[0055] Examples of the ammonium ion include quaternary ammonium ions such as tetramethylammonium ion, tetraethylammonium ion, tetrapropylammonium ion, tetrabutylammonium ion, tetrapentylammonium ion, tetrahexylammonium ion, tetraheptylammonium ion, tetraoctylammonium ion, trimethylhexylammonium ion, trimethyloctylammonium ion, benzyltrimethylammonium, dibenzyldimethylammonium, tribenzylmethylammonium, tetrabenzylammonium, phenyltrimethylammonium, diphenyldimethylammonium, triphenylmethylammonium, tetraphenylammonium, and dialkylimidazolium.

[0056] Examples of the phosphonium ion include tetraarylphosphonium ions such as tetraphenylphosphonium, tetra-p-tolylphosphonium, tetrakis(2-methoxyphenyl)phosphonium, tetrakis(3-methoxyphenyl)phosphonium, and tetrakis(4-methoxyphenyl)phosphonium; triarylphosphonium ions such as triphenylbenzylphosphonium, triphenylphenacylphosphonium, triphenylmethylphosphonium, and triphenylbutylphosphonium; and tetraalkylphosphonium ions such as triethylbenzylphosphonium, tributylbenzylphosphonium, tetraethylphosphonium, tetrabutylphosphonium, tetrahexylphosphonium, triethylphenacylphosphonium, and tributylphenacylphosphonium.

[0057] The organic cation is preferably an ammonium ion, a sulfonium ion, or an iodonium ion, because they have excellent acid generation efficiency.

[0058] The acid generator may contain other components in addition to compound (1), but the proportion of compound (1) in the total amount of compounds contained in the acid generator that generate an acid upon decomposition is, for example, 80% by weight or more, preferably 90% by weight or more, particularly preferably 95% by weight or more, most preferably 99% by weight or more, and particularly preferably 99.9% by weight or more. The upper limit of the proportion is 100% by weight.

[0059] The acid generator has excellent solubility in cationic curable compounds. For example, when 1 part by weight of the acid generator is added to 100 parts by weight of 3',4'-epoxycyclohexylmethyl(3,4-epoxy)cyclohexanecarboxylate (product name "Celloxide 2021P", manufactured by Daicel Corporation) as a cationic curable compound at 25°C and stirred at a stirring speed of 100 rpm with a stirrer tip having a length of 2 cm, the time required for the acid generator to completely dissolve is, for example, 5 minutes or less, preferably 3 minutes or less, and more preferably 2 minutes or less. The lower limit of the time required for the acid generator to completely dissolve is, for example, 0.1 minutes.

[0060] The acid generator has excellent photosensitivity and can be photoirradiated with light (for example, light having a wavelength of 365 nm and an irradiation energy of 10 to 10,000 mJ / cm 2 When it is subjected to irradiation, it quickly decomposes and generates acid.

[0061] Moreover, the acid generator has excellent heat sensitivity, and when subjected to a heat treatment (for example, a heating treatment at a temperature of 70 to 120° C. for 30 to 120 minutes), it is rapidly decomposed to generate an acid.

[0062] Therefore, the acid generator can be suitably used as a photoacid generator or a thermal acid generator.

[0063] [Method of manufacturing the acid generator] The compound (1) has n groups bonded to M, and a compound in which all of the n groups have the same structure can be produced, for example, via the following reactions [1] and [2]. [ka]

[0064] In the above formula, Ct, Ar, M, R 1 , m, and n are the same as above. X represents a halogen atom. R 2 represents an organic group, and is preferably a hydrocarbon group. n' represents an integer of 1 to 3.

[0065] Reaction [1] begins with the Grignard reagent (R 2 -MgX) is reacted with a compound represented by formula (a), then with a compound represented by formula (b), and then with sodium carbonate to obtain a compound represented by formula (ab).

[0066] The reaction [1] can be carried out in the presence of a solvent. The solvent may be any of the solvents commonly used in Grignard reactions (e.g., one or more solvents selected from diethyl ether, tetrahydrofuran, dichloromethane, etc.).

[0067] Reaction [2] is a reaction in which the compound represented by formula (ab) obtained via reaction [1] (hereinafter, may be referred to as "compound (ab)") is reacted with AX to perform salt exchange, thereby obtaining the compound represented by formula (1) (=compound (1)).

[0068] The molar ratio of compound (ab) to AX (compound (ab) / AX) to be subjected to the reaction is, for example, 1 / 3 to 3 / 1, and preferably 1 / 2 to 2 / 1.

[0069] The salt exchange reaction can be carried out in the presence of a solvent. Examples of the solvent include water, ethyl acetate, dichloromethane, etc. These can be used alone or in combination of two or more.

[0070] The reaction temperature is, for example, 15 to 35°C.

[0071] Furthermore, among the compounds (1), a compound in which n is 4 and the four groups bonded to M are two different groups (i.e., a compound represented by the following formula (1')) can be produced, for example, via the following reactions [1-1][1-2][2]. [ka]

[0072] In the above formula, Ct, Ar, M, R 1 , m, and n are the same as above. X represents a halogen atom. R 2 represents an organic group, preferably a hydrocarbon group, and particularly preferably an alkyl group having 1 to 10 carbon atoms. n' represents an integer of 1 to 3. m' represents an integer of 1 or greater, provided that m' represents an integer different from m.

[0073] Reaction [1-1] begins with the Grignard reagent (R 2 -MgX) is reacted with a compound represented by formula (a'), then with a compound represented by formula (b'), and then with sodium carbonate to obtain a compound represented by formula (a'b').

[0074] Reaction [1-2] begins with the Grignard reagent (R 2 -MgX) is reacted with a compound represented by formula (a), the resulting product is reacted with a compound represented by formula (a'b') obtained via reaction [1-1], and then sodium carbonate is reacted to obtain a compound represented by formula (a'b'b).

[0075] The reactions [1-1] and [1-2] can be carried out in the presence of a solvent. The solvent may be any of the solvents commonly used in Grignard reactions (e.g., one or more solvents selected from diethyl ether, tetrahydrofuran, dichloromethane, etc.).

[0076] Reaction [2] is a reaction in which a compound represented by formula (a'b'b), obtained via reactions [1-1] and [1-2], is reacted with AX to perform salt exchange to obtain a compound represented by formula (1'). This reaction can be carried out in the same manner as reaction [2] in which compound (ab) is reacted with AX.

[0077] The atmosphere for the reaction is not particularly limited as long as it does not inhibit the reaction, and may be, for example, any of an air atmosphere, a nitrogen atmosphere, an argon atmosphere, etc. The reaction may be carried out by any method such as a batch method, a semi-batch method, or a continuous method.

[0078] After the reaction is completed, the reaction product obtained may be subjected to a general separation and purification treatment (for example, precipitation, washing, filtration, etc.).

[0079] [Curable composition] The curable composition of the present invention contains the acid generator and the cationic curable compound. The acid generator and the cationic curable compound may each be contained alone or in combination of two or more kinds.

[0080] The content of the acid generator is, for example, 0.05 to 20 parts by weight, and preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the cationic curable compound.

[0081] The cationic curable compound is a compound having one or more cationic curable groups selected from an epoxy group, an oxetanyl group, a vinyl ether group, etc. The epoxy group is a group containing a three-membered cyclic ether skeleton, and the oxetanyl group is a group containing a four-membered cyclic ether skeleton.

[0082] The number of cationically curable groups in one molecule of the cationically curable compound is 1 or more, preferably 1 to 4, more preferably 2 to 4, and particularly preferably 2 to 3.

[0083] The molecular weight per cationic curable group of the cationic curable compound (for example, cationic curable group equivalent such as epoxy equivalent or oxetane equivalent) is, for example, 50 to 500 g / eq, preferably 100 to 400 g / eq, and more preferably 100 to 300 g / eq.

[0084] Examples of the cationic curable compound include a compound having an epoxy group as a cationic curable group (=epoxy compound), a compound having an oxetanyl group as a cationic curable group (=oxetane compound), a compound having a vinyl ether group as a cationic curable group (=vinyl ether compound), a compound having an epoxy group and an oxetanyl group as cationic curable groups, a compound having an epoxy group and a vinyl ether group as cationic curable groups, a compound having an oxetanyl group and a vinyl ether group as cationic curable groups, and the like.

[0085] (Epoxy compounds) Examples of epoxy compounds include epoxy-modified siloxane compounds, alicyclic epoxy compounds (alicyclic epoxy resins), aromatic epoxy compounds (aromatic epoxy resins), and aliphatic epoxy compounds (aliphatic epoxy resins).

[0086] <Epoxy modified siloxane compound> Examples of the epoxy-modified siloxane compound include epoxy-modified silicone and epoxy-modified polyorganosilsesquioxane.

[0087] <Alicyclic epoxy compounds> Examples of the alicyclic epoxy compound include known or commonly used compounds having one or more alicyclic rings and one or more epoxy groups in the molecule, and are not particularly limited. Examples of the alicyclic epoxy compound include the following compounds: (1) Compounds with alicyclic epoxy groups (= epoxy groups consisting of two adjacent carbon atoms and an oxygen atom that form an alicyclic ring within the molecule) (2) Compounds having an alicyclic ring and a glycidyl ether group

[0088] Examples of the compound (1) having an alicyclic epoxy group include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexylmethyl-3,4-epoxy-1-methylcyclohexanecarboxylate, ... Examples of such bis(3,4-epoxycyclohexylmethyl)-5-methylcyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane metadioxane, bis(3,4-epoxycyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexylcarboxylate, methylene bis(3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene bis(3,4-epoxycyclohexanecarboxylate), and the like.

[0089] Examples of the compound (2) having an alicyclic ring and a glycidyl ether group include glycidyl ethers of alicyclic alcohols (particularly, alicyclic polyhydric alcohols). More specifically, for example, compounds obtained by hydrogenating bisphenol A type epoxy compounds such as 2,2-bis[4-(2,3-epoxypropoxy)cyclohexyl]propane and 2,2-bis[3,5-dimethyl-4-(2,3-epoxypropoxy)cyclohexyl]propane (hydrogenated bisphenol A type epoxy compounds); bis[o,o-(2,3-epoxypropoxy)cyclohexyl]methane, bis[o,p-(2,3-epoxypropoxy)cyclohexyl]methane, bis[p,p-(2,3-epoxypropoxy)cyclohexyl]methane, Examples of such epoxy compounds include hydrogenated compounds of bisphenol F type epoxy compounds such as bis[3,5-dimethyl-4-(2,3-epoxypropoxy)cyclohexyl]methane and bis[3,5-dimethyl-4-(2,3-epoxypropoxy)cyclohexyl]methane (hydrogenated bisphenol F type epoxy compounds); hydrogenated biphenol type epoxy compounds; hydrogenated phenol novolac type epoxy compounds; hydrogenated cresol novolac type epoxy compounds; hydrogenated cresol novolac type epoxy compounds of bisphenol A; hydrogenated naphthalene type epoxy compounds; and hydrogenated products of trisphenolmethane type epoxy compounds.

[0090] <Aromatic epoxy compounds> Examples of the aromatic epoxy compound include epi-bis-type glycidyl ether type epoxy resins obtained by a condensation reaction between bisphenols [e.g., bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, etc.] and epihalohydrin; high molecular weight epi-bis-type glycidyl ether type epoxy resins obtained by further addition reaction of these epi-bis-type glycidyl ether type epoxy resins with the above-mentioned bisphenols; phenols [e.g., phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol Novolak alkyl type glycidyl ether epoxy resins obtained by condensing polyhydric alcohols obtained by the condensation reaction of polyphenols (e.g., phenolic acid, phenol F, bisphenol S, etc.) with aldehydes (e.g., formaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, salicylaldehyde, etc.) with epihalohydrin; epoxy compounds in which two phenol skeletons are bonded to the 9-position of the fluorene ring and a glycidyl group is bonded to each of the oxygen atoms obtained by removing the hydrogen atom from the hydroxyl group of the phenol skeletons, either directly or via an alkyleneoxy group.

[0091] <Aliphatic epoxy compounds> Examples of the aliphatic epoxy compound include glycidyl ethers of q-valent alcohols (where q is a natural number) that do not have a cyclic structure; glycidyl esters of monovalent or polyvalent carboxylic acids (e.g., acetic acid, propionic acid, butyric acid, stearic acid, adipic acid, sebacic acid, maleic acid, itaconic acid, etc.); epoxidized products of oils and fats having double bonds, such as epoxidized linseed oil, epoxidized soybean oil, and epoxidized castor oil; and epoxidized products of polyolefins (including polyalkadienes), such as epoxidized polybutadiene. Examples of the q-valent alcohols not having a cyclic structure include monohydric alcohols such as methanol, ethanol, 1-propyl alcohol, isopropyl alcohol, and 1-butanol; dihydric alcohols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol, and polypropylene glycol; and trihydric or higher polyhydric alcohols such as glycerin, diglycerin, erythritol, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, and sorbitol. The q-valent alcohol may be polyether polyol, polyester polyol, polycarbonate polyol, polyolefin polyol, and the like.

[0092] (Oxetane Compounds) Examples of the oxetane compound include 3,3-bis(vinyloxymethyl)oxetane, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(hydroxymethyl)oxetane, 3-ethyl-3-[(phenoxy)methyl]oxetane, 3-ethyl-3-(hexyloxymethyl)oxetane, 3-ethyl-3-(chloromethyl)oxetane, 3,3-bis(chloromethyl)oxetane, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, and bis(vinyloxymethyl)oxetane. Examples of the bis([1-ethyl(3-oxetanyl)]methyl)ether include 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]bicyclohexyl, 4,4'-bis[3-ethyl-(3-oxetanyl)methoxymethyl]biphenyl, 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]cyclohexane, 1,4-bis([(3-ethyl-3-oxetanyl)methoxy]methyl)benzene, 3-ethyl-3([(3-ethyloxetan-3-yl)methoxy]methyl)oxetane, and xylylene bisoxetane.

[0093] (Vinyl ether compounds) Examples of the vinyl ether compound include aryl vinyl ethers such as phenyl vinyl ether; alkyl vinyl ethers such as n-butyl vinyl ether and n-octyl vinyl ether; cycloalkyl vinyl ethers such as cyclohexyl vinyl ether; vinyl ethers having a hydroxyl group such as 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether and 2-hydroxybutyl vinyl ether; and polyfunctional vinyl ethers such as hydroquinone divinyl ether, 1,4-butanediol divinyl ether, cyclohexane divinyl ether, cyclohexane dimethanol divinyl ether, ethylene glycol divinyl ether, diethylene glycol divinyl ether and triethylene glycol divinyl ether.

[0094] The cationic curable compound preferably contains at least an alicyclic epoxy compound having one or more (preferably 1 to 4) alicyclic epoxy groups (particularly, a polyfunctional alicyclic epoxy compound having two or more (preferably 2 to 4) alicyclic epoxy groups).

[0095] The cationic curable compound may be a combination of the alicyclic epoxy compound and a glycidyl ether type epoxy compound having one or more (preferably 1 to 4) glycidyl ether groups and / or an oxetane compound having one or more (preferably 1 to 4) oxetanyl groups. When used in combination, the mixing ratio [alicyclic epoxy compound / (glycidyl ether type epoxy compound and oxetane compound); weight ratio] is, for example, 95 / 5 to 5 / 95, preferably 95 / 5 to 30 / 70, more preferably 95 / 5 to 40 / 60, even more preferably 95 / 5 to 60 / 40, particularly preferably 90 / 10 to 65 / 35, and most preferably 85 / 15 to 65 / 35.

[0096] The curable composition may contain one or more other components as necessary in addition to the above components. Examples of other components include sensitizers, sensitization assistants, antioxidants, stabilizers, surfactants, solvents, rheology control agents, leveling agents, silane coupling agents, fillers, conductive particles, polymerization inhibitors, light stabilizers, plasticizers, defoamers, foaming agents, UV absorbers, tackifiers, curing retarders, ion adsorbents, pigments, dyes, fluorescent materials, release agents, antistatic agents, flame retardants, radical curing compounds, polyimide resins, polyamide resins, phenoxy resins, poly(meth)acrylate resins, polyurethane resins, polyurea resins, polyester resins, polyvinyl butyral resins, SBS, and SEBS. The content of these (the total amount when two or more types are contained) is, for example, 50% by weight or less, preferably 10% by weight or less, and particularly preferably 5% by weight or less of the total amount (100% by weight) of the curable composition. The content of these is, for example, 0.05% by weight or more, and preferably 0.1% by weight or more, based on the total amount (100% by weight) of the curable composition.

[0097] The curable composition can be produced by uniformly mixing the acid generator, the cationic curable compound, and other components added as necessary, using a commonly known mixing device such as a self-revolving stirring defoamer, a homogenizer, a planetary mixer, a three-roll mill, a bead mill, etc. The components may be mixed simultaneously or sequentially.

[0098] The uses of the curable composition are not particularly limited, and examples thereof include paints, coating agents, various coating materials (hard coats, stain-resistant coating materials, anti-fogging coating materials, contact-resistant coating materials, optical fibers, etc.), back treatment agents for adhesive tapes, release coating materials for release sheets for adhesive labels (release paper, release plastic film, release metal foil, etc.), printing plates, dental materials (dental compounds, dental composites), inks, inkjet inks, positive resists (connection terminals and wiring pattern formation in the manufacture of electronic components such as circuit boards, CSPs, and MEMS elements), resist films, liquid resists, and negative resists (permanent film materials such as surface protective films for semiconductor elements, interlayer insulating films, and planarizing films, etc.). , resists for MEMS, positive-type photosensitive materials, negative-type photosensitive materials, various adhesives (temporary fixing agents for various electronic components, adhesives for HDDs, adhesives for pickup lenses, adhesives for functional films for FPDs (deflectors, anti-reflection films, etc.)), resins for holographs, FPD materials (color filters, black matrices, partition materials, photospacers, ribs, alignment films for liquid crystals, sealants for FPDs, etc.), optical components, molding materials (for building materials, optical components, lenses), casting materials, putties, glass fiber impregnating agents, filling materials, sealing materials, encapsulants, optical semiconductor (LED) encapsulants, optical waveguide materials, nanoimprint materials, materials for photolithography, and materials for microphotolithography.

[0099] The acid generator contained in the curable composition has excellent solubility in the cationic curable compound and can be reliably dissolved in a short dissolving operation. In addition, precipitation over time can be suppressed. Therefore, the curable composition can be efficiently prepared, and after preparation, there is a time leeway until use, and the curable composition has excellent handleability.

[0100] The curable composition has excellent curability because it contains the acid generator in a completely dissolved state, and the resulting cured product has excellent electrical insulation properties and does not exhibit electrostatic charge caused by the insoluble portion of the acid generator.

[0101] [Cured product] The cured product of the present invention is a cured product of the above-mentioned curable composition.

[0102] The cured product can be obtained by curing the curable composition.

[0103] The curable composition can be cured, for example, by subjecting it to a light irradiation treatment. Examples of light rays used in the light irradiation treatment include ultraviolet rays, electron beams, X-rays, and radiation. Among these, ultraviolet rays are most economically preferable. Examples of light sources for ultraviolet rays include ultraviolet lasers, mercury lamps, xenon lasers, and metal halide lamps. The amount of irradiation energy of the light rays is, for example, 10 to 10,000 mJ / cm. 2 It is.

[0104] The curable composition can also be cured by subjecting it to a heat treatment. The heating temperature is, for example, 70 to 120° C. The heating time is, for example, 0.5 to 2 hours.

[0105] The cured product does not contain any acid generator that remains without being decomposed even when exposed to light or heat, or the content of acid generator that remains without being decomposed even when exposed to light or heat is extremely low, and the extracted water obtained by extracting the ionic components contained in the cured product with water (more specifically, the extracted water obtained by the method described in the Examples) has an electrical conductivity of, for example, less than 50 μS / cm, preferably 40 μS / cm or less, particularly preferably 30 μS / cm or less, and most preferably less than 25 μS / cm.

[0106] The cured product does not contain any residual acid generator or contains only a very small amount of the acid generator, and therefore has excellent insulating properties. Therefore, when the cured product is used for sealing purposes, a semiconductor device having excellent short-circuit prevention properties and high reliability can be obtained.

[0107] The above-mentioned configurations of the present invention and combinations thereof are merely examples, and additions, omissions, substitutions, and modifications of the configurations are possible as appropriate without departing from the spirit of the present invention. EXAMPLES

[0108] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0109] Preparation Example 1 Preparation of sodium tetrakis[3,5-bis(pentafluorosulfanyl)phenyl]borate (A-3) 8.0 g of 1-bromo-3,5-bis(pentafluorosulfanyl)benzene and 80 mL of anhydrous diethyl ether were added to a 200 mL four-neck flask thoroughly dried under a nitrogen atmosphere. The solution in the flask was cooled to -78°C, and 19.6 mL of an isopropyl magnesium chloride diethyl ether solution (1 mol / L) was added dropwise. The mixture in the flask was stirred at -78°C for 5 minutes, then at 0°C for 25 minutes, and then allowed to warm to room temperature over 60 minutes. Thereafter, the mixture was cooled to 0° C., 3.2 mL of a boron trichloride heptane solution (1 mol / L) was added, and the mixture was stirred at 0° C. for 15 minutes and further stirred at room temperature for 19 hours. The resulting reaction solution was added to 800 mL of 2% aqueous sodium carbonate solution with stirring, and the mixture was further stirred vigorously for 1 hour. The aqueous layer was extracted four times with 200 mL of diethyl ether. The organic layers were combined, washed with saturated saline, and filtered through Celite, and the solvent was removed under reduced pressure. The residue was dissolved in 50 mL of acetone, and hexane was slowly added to precipitate a white solid. The liquid phase was removed by decantation, and the remaining solid was washed with hexane and dried under reduced pressure. The resulting solid was dispersed in 300 mL of toluene and dried by azeotropic distillation for 1 hour. The solid was removed by filtration and dried under reduced pressure overnight to obtain 2.7 g of a white solid. 1 H-NMR, 19F-NMR confirmed that this white solid was the anion precursor (A-3) shown in Table 1 below (yield 61%).

[0110] Preparation Example 2 Preparation of sodium tetrakis(4-pentafluorosulfanylphenyl)borate (A-1) A white solid was obtained (2.0 g) in the same manner as in Preparation Example 1, except that 8.0 g of 1-bromo-3,5-bis(pentafluorosulfanyl)benzene was changed to 5.5 g of 1-bromo-4-pentafluorosulfanylbenzene. 1 H-NMR, 19 F-NMR confirmed that this white solid was the anion precursor (A-1) shown in Table 1 below (yield 74%).

[0111] Preparation Example 3 Preparation of sodium tetrakis[3,4-bis(pentafluorosulfanyl)phenyl]borate (A-2) A white solid was obtained (2.9 g) in the same manner as in Preparation Example 1, except that 8.0 g of 1-bromo-3,5-bis(pentafluorosulfanyl)benzene was used instead of 8.0 g of 1-bromo-3,4-bis(pentafluorosulfanyl)benzene. 1 H-NMR, 19 F-NMR confirmed that this white solid was the anion precursor (A-2) shown in Table 1 below (yield 67%).

[0112] Preparation Example 4 Preparation of sodium tetrakis(3-pentafluorosulfanylphenyl)borate (A-4) A white solid was obtained (1.9 g) in the same manner as in Preparation Example 1, except that 8.0 g of 1-bromo-3,5-bis(pentafluorosulfanyl)benzene was changed to 5.5 g of 1-bromo-3-pentafluorosulfanylbenzene. 1 H-NMR, 19 F-NMR confirmed that this white solid was the anion precursor (A-4) shown in Table 1 below (yield 70%).

[0113] Preparation Example 5 Preparation of sodium tetrakis[2,5-bis(pentafluorosulfanyl)phenyl]borate (A-5) A white solid was obtained (1.5 g) in the same manner as in Preparation Example 1, except that 8.0 g of 1-bromo-3,5-bis(pentafluorosulfanyl)benzene was used instead of 8.0 g of 1-bromo-2,5-bis(pentafluorosulfanyl)benzene. 1 H-NMR, 19 F-NMR confirmed that this white solid was the anion precursor (A-5) shown in Table 1 below (yield 35%).

[0114] Preparation Example 6 Preparation of sodium tetrakis[3,4,5-tris(pentafluorosulfanyl)phenyl]borate (A-6) A white solid was obtained (1.6 g) in the same manner as in Preparation Example 1, except that 8.0 g of 1-bromo-3,5-bis(pentafluorosulfanyl)benzene was changed to 10.5 g of 1-bromo-3,4,5-tris(pentafluorosulfanyl)benzene. 1 H-NMR, 19 F-NMR confirmed that this white solid was the anion precursor (A-6) shown in Table 1 below (yield 27%).

[0115] Preparation Example 7 Preparation of sodium tris(3,5-bis(pentafluorosulfanyl)phenyl)phenylborate (A-9) A white solid was obtained (3.2 g) in the same manner as in Preparation Example 1, except that 3.2 mL of the boron trichloride heptane solution (1 mol / L) was changed to 0.78 g of dichlorophenylborane. 1 H-NMR, 19 F-NMR confirmed that this white solid was the anion precursor (A-9) shown in Table 2 below (yield 60%).

[0116] Preparation Example 8 Preparation of sodium tris(3,5-bis(pentafluorosulfanyl)phenyl)(4-pentafluorosulfanylphenyl)borate (A-12) (4-Pentafluorosulfanylphenyl)trifluoroborate potassium salt was prepared by the method described in Organic Letters, 2013, 15, 20, p. 5147. A white solid was obtained (3.7 g) in the same manner as in Preparation Example 1, except that 3.2 mL of the boron trichloride heptane solution (1 mol / L) was changed to 1.5 g of (4-pentafluorosulfanylphenyl)trifluoroborate potassium salt. 1 H-NMR, 19 F-NMR confirmed that this white solid was the anion precursor (A-12) shown in Table 2 below (yield 62%).

[0117] Preparation Example 9 Preparation of lithium tetrakis(4-pentafluorosulfanylphenyl)gallate (A-13) 11.3 g of 4-bromopentafluorosulfanylbenzene and 100 mL of anhydrous diethyl ether were added to a 300 mL four-neck flask that had been thoroughly dried under a nitrogen atmosphere. The solution in the flask was cooled to -78°C, and 25 mL of tert-butyllithium pentane solution (1.6 mol / L) was added dropwise while stirring, and the mixture was stirred for 15 minutes. Then, 1.2 g of gallium chloride (III) was added and the mixture was stirred for 30 minutes. The reaction solution in the flask was warmed to room temperature and stirred for 19 hours. The reaction solution was cooled in an ice bath and quenched by adding water. The reaction solution was then added to 300 mL of water and stirred for 1 hour. After separation, the organic layer was removed, the aqueous layer was extracted three times with 100 mL of ethyl acetate, the organic layers were combined, and washed three times with 100 mL of water. The organic layer was desolvated, and the resulting oily matter was recrystallized with hexane to obtain 3.4 g of a pale yellow solid. 1 H-NMR, 19 F-NMR confirmed that this white solid was the anion precursor (A-13) shown in Table 2 below (yield 56%).

[0118] Preparation Example 10 Preparation of lithium tetrakis[3,5-bis(pentafluorosulfanyl)phenyl]gallate (A-15) A slightly yellow solid was obtained (6.3 g) in the same manner as in Preparation Example 9, except that 11.3 g of 4-bromopentafluorosulfanylbenzene was changed to 16.3 g of 1-bromo-3,5-bis(pentafluorosulfanyl)benzene. 1 H-NMR, 19F-NMR confirmed that this white solid was the anion precursor (A-15) shown in Table 2 below (yield 67%).

[0119] Preparation Example 11 Preparation of sodium tris(3-pentafluorosulfanylphenyl)phenyl gallate (A-20) A white solid was obtained (2.2 g) in the same manner as in Preparation Example 1, except that 3.2 mL of boron trichloride heptane solution (1 mol / L) was replaced with 1.07 g of dichlorophenylgallium and 8.0 g of 1-bromo-3,5-bis(pentafluorosulfanyl)benzene was replaced with 5.5 g of 1-bromo-3-pentafluorosulfanylbenzene. 1 H-NMR, 19 F-NMR confirmed that this white solid was the anion precursor (A-20) shown in Table 2 below (yield 58%).

[0120] Preparation Example 12 Preparation of sodium tris(4-pentafluorosulfanylphenyl)(4-fluorophenyl)gallate (A-22) A white solid was obtained (2.5 g) in the same manner as in Preparation Example 1, except that 3.2 mL of boron trichloride heptane solution (1 mol / L) was replaced with 1.16 g of dichloro-4-fluorophenylgallium and 8.0 g of 1-bromo-3,5-bis(pentafluorosulfanyl)benzene was replaced with 5.5 g of 1-bromo-4-pentafluorosulfanylbenzene. 1 H-NMR, 19 F-NMR confirmed that this white solid was the anion precursor (A-22) shown in Table 2 below (yield 64%).

[0121] The anion precursors obtained in the above Preparation Examples and sodium tetrakis(pentafluorophenyl)borate (H-1) are shown in Tables 1 and 2 below.

[0122] [Table 1]

[0123] [Table 2]

[0124] <Preparation of Photoacid Generator> Example 1 Preparation of [4-(phenylthio)phenyl]sulfonium tetrakis[3,5-bis(pentafluorosulfanyl)phenyl]borate (PAG-1) 0.8 g of [4-(phenylthio)phenyl]sulfonium chloride was dissolved in 30 mL of dichloromethane, and 30 g of an aqueous solution containing 2.7 g of the anion precursor (A-3) obtained in Preparation Example 1 was added and mixed at room temperature, followed by stirring for 5 hours. The aqueous layer was removed by a separation operation, and the dichloromethane layer was washed five times with water, then transferred to a rotary evaporator to distill off the solvent. This resulted in an oily product. The resulting oily product was recrystallized with a dichloromethane-cyclohexane mixture to obtain 2.4 g of a pale yellow solid. 1 H-NMR, 19 F-NMR confirmed that this pale yellow solid was the above-mentioned PAG-1 (yield 71%).

[0125] Example 2 Preparation of [4-(phenylthio)phenyl]sulfonium tris(3,5-bis(pentafluorosulfanyl)phenyl)phenylborate (PAG-2) The same procedure as in Example 1 was repeated except that 2.7 g of the anion precursor (A-3) obtained in Preparation Example 1 was changed to 2.1 g of the anion precursor (A-9) obtained in Preparation Example 7, to obtain 2.1 g of a pale yellow solid. 1 H-NMR, 19 F-NMR confirmed that this pale yellow solid was the above-mentioned PAG-2 (yield 73%).

[0126] Example 3 Preparation of [4-(phenylthio)phenyl]sulfonium tetrakis[3,5-bis(pentafluorosulfanyl)phenyl]gallate (PAG-3) The same procedure as in Example 1 was repeated, except that 2.7 g of the anion precursor (A-3) obtained in Preparation Example 1 was changed to 2.8 g of the anion precursor (A-15) obtained in Preparation Example 10, to obtain 2.8 g of a pale yellow solid. 1 H-NMR, 19F-NMR confirmed that this pale yellow solid was the above-mentioned PAG-3 (yield 80%).

[0127] Example 4 Preparation of [4-(phenylthio)phenyl]sulfonium (4-fluorophenyl)tris(4-pentafluorosulfanylphenyl)gallate (PAG-4) The same procedure as in Example 1 was repeated except that 2.7 g of the anion precursor (A-3) obtained in Preparation Example 1 was changed to 1.6 g of the anion precursor (A-22) obtained in Preparation Example 12, to obtain 2.1 g of a pale yellow solid. 1 H-NMR, 19 F-NMR confirmed that this pale yellow solid was the above-mentioned PAG-4 (yield 73%).

[0128] Example 5 Preparation of [4-(4-biphenylthio)phenyl]-4-biphenylphenylsulfonium tetrakis(3-pentafluorosulfanylphenyl)borate (PAG-5) 11 g of 4-[(phenyl)sulfinyl]biphenyl, 12 g of 4-(phenylthio)biphenyl, 22 g of acetic anhydride, and 16 g of methanesulfonic acid were added to a reaction vessel, mixed uniformly, and reacted at 65°C for 3 hours. The reaction solution was cooled to room temperature, poured into 100 mL of ion-exchanged water, extracted with 100 g of dichloromethane, and washed with water until the pH of the aqueous layer became neutral. The dichloromethane layer was transferred to a rotary evaporator and the solvent was distilled off to obtain a brown solid. This was washed with ethyl acetate / hexane, and the organic solvent was concentrated to obtain (Intermediate-1). 1.2 g of the obtained (intermediate-1) was dissolved in 30 mL of dichloromethane, and 30 g of an aqueous solution containing 1.7 g of the anion precursor (A-4) obtained in Preparation Example 4 was added and mixed at room temperature, followed by stirring for 5 hours. The aqueous layer was removed by a separation operation, and the dichloromethane layer was washed five times with water, then transferred to a rotary evaporator to distill off the solvent. This resulted in a light brown solid. Recrystallization was performed with dichloromethane-hexane to obtain 2.2 g of a pale yellow solid. 1 H-NMR, 19 F-NMR confirmed that this pale yellow solid was the above-mentioned PAG-5 (yield 82%).

[0129] Example 6 Preparation of [4-(4-biphenylthio)phenyl]-4-biphenylphenylsulfonium tris(3,5-bis(pentafluorosulfanyl)phenyl)(4-pentafluorosulfanylphenyl)borate (PAG-6) In Example 5, 1.7 g of the anion precursor (A-4) obtained in Preparation Example 4 was changed to 1.6 g of the anion precursor (A-12) obtained in Preparation Example 8, and the same procedure as in Example 5 was repeated to obtain 2.5 g of a slightly yellow solid. 1 H-NMR, 19 F-NMR confirmed that this pale yellow solid was the above-mentioned PAG-6 (yield 80%).

[0130] Example 7 Preparation of [4-(4-biphenylthio)phenyl]-4-biphenylphenylsulfonium tetrakis(4-pentafluorosulfanylphenyl)gallate (PAG-7) The same procedure as in Example 5 was repeated, except that 1.7 g of the anion precursor (A-4) obtained in Preparation Example 4 was replaced with 1.8 g of the anion precursor (A-13) obtained in Preparation Example 9, to obtain 1.9 g of a pale yellow solid. 1 H-NMR, 19 F-NMR confirmed that this pale yellow solid was the above-mentioned PAG-7 (yield 76%).

[0131] Example 8 Preparation of [4-(4-biphenylthio)phenyl]-4-biphenylphenylsulfonium tris(3-pentafluorosulfanylphenyl)phenyl gallate (PAG-8) The same procedure as in Example 5 was repeated, except that 1.7 g of the anion precursor (A-4) obtained in Preparation Example 4 was replaced with 1.6 g of the anion precursor (A-20) obtained in Preparation Example 11, to obtain 1.8 g of a pale yellow solid. 1 H-NMR, 19 F-NMR confirmed that this pale yellow solid was the above-mentioned PAG-8 (yield 80%).

[0132] Example 9 Preparation of (4-isopropylphenyl)tolyliodonium tetrakis(3-pentafluorosulfanylphenyl)borate (PAG-9) 0.75 g of (4-isopropylphenyl) tolyliodonium chloride was dissolved in 30 mL of dichloromethane, and 30 g of an aqueous solution containing 1.7 g of the anion precursor (A-4) obtained in Preparation Example 4 was added thereto at room temperature, and the mixture was stirred for 5 hours. The aqueous layer was removed by a separation operation, and the dichloromethane layer was washed five times with water, and then transferred to a rotary evaporator to distill off the solvent. This resulted in an oily product. The resulting oily product was recrystallized with a dichloromethane-cyclohexane mixture to obtain 1.9 g of a pale yellow solid. 1 H-NMR, 19 F-NMR confirmed that this pale yellow solid was the above-mentioned PAG-9 (yield 82%).

[0133] Example 10 Preparation of (4-isopropylphenyl)tolyliodonium tris(3,5-bis(pentafluorosulfanyl)phenyl)phenylborate (PAG-10) The same procedure as in Example 9 was repeated, except that 1.7 g of the anion precursor (A-4) obtained in Preparation Example 4 was replaced with 2.1 g of the anion precursor (A-9) obtained in Preparation Example 7, to obtain 2.1 g of a pale yellow solid. 1 H-NMR, 19 F-NMR confirmed that this pale yellow solid was the above-mentioned PAG-10 (yield 73%).

[0134] Example 11 Preparation of (4-isopropylphenyl)tolyliodonium tetrakis(4-pentafluorosulfanylphenyl)gallate (PAG-11) The same procedure as in Example 9 was repeated, except that 1.7 g of the anion precursor (A-4) obtained in Preparation Example 4 was replaced with 1.8 g of the anion precursor (A-13) obtained in Preparation Example 9, to obtain 2.1 g of a pale yellow solid. 1 H-NMR, 19 F-NMR confirmed that this pale yellow solid was the above-mentioned PAG-11 (yield 86%).

[0135] Example 12 Preparation of (4-isopropylphenyl)tolyliodonium (4-fluorophenyl)tris(4-pentafluorosulfanylphenyl)gallate (PAG-12) The same procedure as in Example 9 was repeated, except that 1.7 g of the anion precursor (A-4) obtained in Preparation Example 4 was replaced with 1.8 g of the anion precursor (A-22) obtained in Preparation Example 12, to obtain 1.5 g of a pale yellow solid. 1 H-NMR, 19 F-NMR confirmed that this pale yellow solid was the above-mentioned PAG-12 (yield 68%).

[0136] Example 13 Preparation of di(4-tert-butylphenyl)iodonium tetrakis[3,5-bis(pentafluorosulfanyl)phenyl]borate (PAG-13) 0.86 g of di(4-tert-butylphenyl)iodonium chloride was dissolved in 30 mL of dichloromethane, and 30 g of an aqueous solution containing 2.7 g of the anion precursor (A-3) obtained in Preparation Example 1 was added and mixed at room temperature, followed by stirring for 5 hours. The aqueous layer was removed by a separation operation, and the dichloromethane layer was washed five times with water, then transferred to a rotary evaporator to distill off the solvent. This resulted in an oily product. The resulting oily product was recrystallized with a dichloromethane-cyclohexane mixture to obtain 3.8 g of a pale yellow solid. 1 H-NMR, 19 F-NMR confirmed that this pale yellow solid was the above-mentioned PAG-13 (yield 90%).

[0137] Example 14 Preparation of di(4-tert-butylphenyl)iodonium tris(3,5-bis(pentafluorosulfanyl)phenyl)(4-pentafluorosulfanylphenyl)borate (PAG-14) The same procedure as in Example 13 was repeated, except that 2.7 g of the anion precursor (A-3) obtained in Preparation Example 1 was changed to 1.6 g of the anion precursor (A-12) obtained in Preparation Example 8, to obtain 2.7 g of a pale yellow solid. 1 H-NMR, 19 F-NMR confirmed that this pale yellow solid was the above-mentioned PAG-14 (yield 85%).

[0138] Example 15 Preparation of di(4-tert-butylphenyl)iodonium tetrakis[3,5-bis(pentafluorosulfanyl)phenyl]gallate (PAG-15) The same procedure as in Example 13 was repeated, except that 2.7 g of the anion precursor (A-3) obtained in Preparation Example 1 was changed to 2.8 g of the anion precursor (A-15) obtained in Preparation Example 10, to obtain 2.8 g of a pale yellow solid. 1 H-NMR, 19 F-NMR confirmed that this pale yellow solid was the above-mentioned PAG-15 (yield 79%).

[0139] Example 16 Preparation of di(4-tert-butylphenyl)iodonium tris(3-pentafluorosulfanylphenyl)phenyl gallate (PAG-16) The same procedure as in Example 13 was repeated, except that 2.7 g of the anion precursor (A-3) obtained in Preparation Example 1 was changed to 1.6 g of the anion precursor (A-20) obtained in Preparation Example 11, to obtain 1.7 g of a pale yellow solid. 1 H-NMR, 19 F-NMR confirmed that this pale yellow solid was the above-mentioned PAG-16 (yield 74%).

[0140] Comparative Example 1 Preparation of [4-(phenylthio)phenyl]sulfonium tetrakis(pentafluorophenyl)borate (PAG-H1) The same procedure as in Example 1 was repeated except that 2.7 g of the anion precursor (A-3) obtained in Preparation Example 1 was changed to 1.4 g of sodium tetrakis(pentafluorophenyl)borate (H-1), to obtain 1.8 g of a slightly yellow solid. 1 H-NMR, 19 F-NMR confirmed that this pale yellow solid was the above-mentioned PAG-H1 (yield 86%).

[0141] Comparative Example 2 Preparation of (4-isopropylphenyl)tolyliodonium tetrakis(pentafluorophenyl)borate (PAG-H2) The same procedure as in Example 9 was repeated except that 1.7 g of the anion precursor (A-4) obtained in Preparation Example 4 was changed to 1.4 g of sodium tetrakis(pentafluorophenyl)borate (H-1), to obtain 1.9 g of a white solid. 1 H-NMR, 19 F-NMR confirmed that this white solid was the above-mentioned PAG-H2 (yield 94%).

[0142] [Table 3]

[0143] <Preparation of Thermal Acid Generator> Example 17 Preparation of 4-hydroxyphenyl-methyl-benzylsulfonium tetrakis[3,5-bis(pentafluorosulfanyl)phenyl]borate (TAG-1) 0.53 g of 4-hydroxyphenyl-methyl-benzylsulfonium chloride was dissolved in 30 mL of dichloromethane, and 30 g of an aqueous solution containing 2.7 g of the anion precursor (A-3) obtained in Preparation Example 1 was added and mixed at room temperature, followed by stirring for 5 hours. The aqueous layer was removed by a separation operation, and the dichloromethane layer was washed five times with water, then transferred to a rotary evaporator to distill off the solvent. This resulted in a pale yellow solid. The resulting pale yellow solid was recrystallized with a dichloromethane-cyclohexane mixture to obtain 2.6 g of a white solid. 1 H-NMR, 19 F-NMR confirmed that this white solid was the above-mentioned TAG-1 (yield 84%).

[0144] Example 18 Preparation of 4-hydroxyphenyl-methyl-benzylsulfonium tetrakis[3,5-bis(pentafluorosulfanyl)phenyl]gallate (TAG-2) The same procedure as in Example 17 was repeated, except that 2.7 g of the anion precursor (A-3) obtained in Preparation Example 1 was changed to 2.1 g of the anion precursor (A-9) obtained in Preparation Example 7, to obtain 2.3 g of a white solid. 1 H-NMR, 19 F-NMR confirmed that this white solid was the above-mentioned TAG-2 (yield 88%).

[0145] Example 19 Preparation of 4-hydroxyphenyl-methyl-benzylsulfonium tetrakis(4-pentafluorosulfanylphenyl)gallate (TAG-3) The same procedure as in Example 17 was repeated, except that 2.7 g of the anion precursor (A-3) obtained in Preparation Example 1 was changed to 1.8 g of the anion precursor (A-13) obtained in Preparation Example 9, to obtain 2.0 g of a white solid. 1 H-NMR, 19 F-NMR confirmed that this white solid was the above-mentioned TAG-3 (yield 90%).

[0146] Example 20 Preparation of 4-hydroxyphenyl-methyl-benzylsulfonium (4-fluorophenyl) tris(4-pentafluorosulfanylphenyl) gallate (TAG-4) The same procedure as in Example 17 was repeated, except that 2.7 g of the anion precursor (A-3) obtained in Preparation Example 1 was changed to 1.8 g of the anion precursor (A-22) obtained in Preparation Example 12, to obtain 2.0 g of a white solid. 1 H-NMR, 19 F-NMR confirmed that this pale yellow solid was the above-mentioned TAG-4 (yield 75%).

[0147] Example 21 Preparation of N-(4-methoxybenzyl)-N,N-dimethylanilinium tetrakis(3-pentafluorosulfanylphenyl)borate (TAG-5) 50g of N,N-dimethylaniline, 65g of 4-methoxybenzyl chloride, and 25mL of acetonitrile were mixed in a reaction vessel and reacted at 50°C for 5 hours. 320mL of acetone was added to the reaction solution, cooled to below 10°C, and stirred for 1 hour. The precipitated solid was then separated to obtain 81g of N-(4-methoxybenzyl)-N,N-dimethylanilinium chloride. 0.56 g of N-(4-methoxybenzyl)-N,N-dimethylanilinium chloride and 30 mL of dichloromethane were added to a reaction vessel and dissolved, and 30 g of an aqueous solution containing 1.7 g of the anion precursor (A-4) obtained in Preparation Example 4 was added and mixed at room temperature, followed by stirring for 5 hours. The aqueous layer was removed by a separation operation, and the dichloromethane layer was washed five times with water, then transferred to a rotary evaporator to distill off the solvent. This resulted in a pale yellow solid. Recrystallization was performed with methanol-water to obtain 1.7 g of a pale yellow solid. 1 H-NMR, 19F-NMR confirmed that this pale yellow solid was the above-mentioned TAG-5 (yield 80%).

[0148] Example 22 Preparation of N-(4-methoxybenzyl)-N,N-dimethylanilinium tris(3,5-bis(pentafluorosulfanyl)phenyl)(4-pentafluorosulfanylphenyl)borate (TAG-6) The same procedure as in Example 21 was repeated, except that 1.7 g of the anion precursor (A-4) obtained in Preparation Example 4 was changed to 1.6 g of the anion precursor (A-12) obtained in Preparation Example 8, to obtain 2.2 g of a slightly yellow solid. 1 H-NMR, 19 F-NMR confirmed that this pale yellow solid was the above-mentioned TAG-6 (yield 77%).

[0149] Example 23 Preparation of N-(4-methoxybenzyl)-N,N-dimethylanilinium tetrakis[3,5-bis(pentafluorosulfanyl)phenyl]gallate (TAG-7) The same procedure as in Example 21 was repeated, except that 1.7 g of the anion precursor (A-4) obtained in Preparation Example 4 was changed to 2.8 g of the anion precursor (A-15) obtained in Preparation Example 10, to obtain 2.4 g of a slightly yellow solid. 1 H-NMR, 19 F-NMR confirmed that this pale yellow solid was the TAG-7 (yield 74%).

[0150] Example 24 Preparation of N-(4-methoxybenzyl)-N,N-dimethylanilinium tris(3-pentafluorosulfanylphenyl)phenyl gallate (TAG-8) The same procedure as in Example 21 was repeated, except that 1.7 g of the anion precursor (A-4) obtained in Preparation Example 4 was replaced with 1.6 g of the anion precursor (A-20) obtained in Preparation Example 11, to obtain 1.6 g of a pale yellow solid. 1 H-NMR, 19 F-NMR confirmed that this pale yellow solid was the above-mentioned TAG-8 (yield 80%).

[0151] Comparative Example 3 Preparation of 4-hydroxyphenyl-methyl-benzylsulfonium tetrakis(pentafluorophenyl)borate (TAG-H1) The same procedure as in Example 17 was repeated except that 2.7 g of the anion precursor (A-3) obtained in Preparation Example 1 was changed to 1.4 g of sodium tetrakis(pentafluorophenyl)borate (H-1), to obtain 1.6 g of a white solid. 1 H-NMR, 19 F-NMR confirmed that this white solid was the above-mentioned TAG-H1 (yield 90%).

[0152] Comparative Example 4 Preparation of N-(4-methoxybenzyl)-N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (TAG-H2) The same procedure as in Example 21 was repeated, except that 1.7 g of the anion precursor (A-4) obtained in Preparation Example 4 was changed to 1.4 g of sodium tetrakis(pentafluorophenyl)borate (H-1), to obtain 1.6 g of a white solid. 1 H-NMR, 19 F-NMR confirmed that this white solid was the above-mentioned TAG-H2 (yield 87%).

[0153] [Table 4]

[0154] Examples 25 to 49, Comparative Examples 5 to 8 Each component was charged into a beaker according to the formulation shown in Tables 5 and 6 below (units are parts by weight), and a stirrer was added and the mixture was stirred at 20° C. and 100 rpm to obtain a photocurable composition.

[0155] The solubility, curability, adhesiveness, heat-resistant adhesiveness, and insulating properties of the photocurable compositions obtained in the Examples and Comparative Examples were evaluated by the following methods. The results are summarized in Tables 5 and 6 below.

[0156] [Solubility evaluation] The stirring time required until the acid generator was completely dissolved was measured, and the solubility was evaluated according to the following criteria. <Evaluation criteria> ◎ (Excellent): Dissolves with stirring for less than 1 minute ○ (Good): Dissolves after stirring for 1 minute or more but less than 5 minutes △(OK): Dissolves after stirring for 5 to 10 minutes × (Fail): Not dissolved even after stirring for 10 minutes or more

[0157] [PAG curability] A 30 μmm spacer was placed on both ends of a slide glass (product name "S9112", manufactured by Matsunami Glass Industrial Co., Ltd.), and the photocurable composition obtained in the Examples and Comparative Examples was dropped in the center. The photocurable composition was spread using a squeegee to a thickness of 0.03 mm, and light was irradiated using a high-pressure mercury lamp under the following conditions. After light irradiation, the material was left at room temperature for 60 minutes to obtain a cured product. <Light irradiation conditions of high pressure mercury lamp> Irradiation device: Product name "LC-8" (manufactured by Hamamatsu Photonics K.K.) Irradiation intensity: 100mW / cm Accumulative irradiation dose: 500~1000mJ / cm 2

[0158] The cured product thus obtained was evaluated for curability according to the following criteria. The presence or absence of tackiness was judged by touching with a finger. Evaluation criteria ◎: Irradiation amount 1000mJ / cm 2 The cured surface had no tackiness and the surface shape of the cured product did not change when touched with a finger. ○: Irradiation amount 1000mJ / cm 2 There was no tackiness on the surface and no change in the surface shape of the cured product. However, with an irradiation dose of 1000 mJ / cm 2 At less than this temperature, the cured product had no surface tackiness, but the surface shape of the cured product changed when touched with a finger. △: Irradiation amount 1000mJ / cm 2 The cured product had no tackiness on the surface, but the surface shape of the cured product changed when touched with the fingers. ×: Irradiation amount 1500mJ / cm 2 However, the cured surface had tackiness.

[0159] [PAG adhesiveness] A 40 μm spacer was placed on both ends of a slide glass, and the photocurable composition obtained in the Examples and Comparative Examples was dropped in the center. The photocurable composition was spread using a squeegee to a thickness of 40 μm, and an epoxy resin cube (outer diameter: 4 mm × 4 mm × 1 mm, inner diameter: 3.7 mm × 3.7 mm × 0.8 mm, adhesive area: 2.3 mm) was placed on top. 2 ) was set and irradiated with light in the same manner as in the evaluation of [PAG curability] above. After irradiating with light, it was left at room temperature for 60 minutes or more. As a result, a structure was obtained in which the cured product of the photocurable composition and the epoxy resin cube were closely attached to each other. Five of the obtained structures were prepared.

[0160] The peel load (kgf) of the epoxy resin cube from the cured product was determined using a die shear tester (product name "4000PXY", manufactured by Nordson DAGE) under the following conditions. The peel load of the five structures was evaluated as the average value. The larger the load, the better the adhesion. <Die shear tester measurement conditions> Shear height: 0.65mm Shear speed: 0.5mm / s

[0161] [PAG heat resistant adhesion] For the structures obtained in the same manner as in the above [PAG adhesion] evaluation, a heat resistance test was performed three times in succession using a benchtop reflow oven (manufactured by Synapec) based on the reflow temperature profile (maximum temperature: 270°C) specified in the JEDEC standard. The average peel load was then calculated in the same manner as in the above [PAG adhesion] evaluation (number of samples: 5), and this was used as the peel load after the heat resistance test. The difference between the peel load determined in the PAG adhesion evaluation (= peel load before heat resistance test) and the peel load after heat resistance test was determined. The smaller the difference, the better the thermal stability.

[0162] [PAG insulation] The photocurable compositions obtained in the examples and comparative examples were coated on a polyphenylene ether substrate using a bar coater to a thickness of 50 μm. Then, light irradiation was performed in the same manner as in the above-mentioned [PAG curability] evaluation. After light irradiation, the composition was left at room temperature for 60 minutes to obtain a cured product. The obtained cured product was peeled off from the polyphenylene ether substrate, and about 0.2 g was precisely weighed to obtain a test piece. The thus obtained test piece and a Teflon (registered trademark) PCT container containing 10 g of ion-exchanged distilled water were placed in a SUS pressure vessel, sealed, and left to stand under conditions of 141°C and 2 atm for 20 hours, and then allowed to cool to room temperature. Thereafter, the moisture in the PCT container was removed, the electrical conductivity was measured, and the insulation was evaluated according to the following criteria. <Evaluation criteria> ◎(Excellent): Conductivity is less than 25μS / cm ○(Good): Conductivity is 25μS / cm or more and less than 50μS / cm △(Acceptable): Conductivity is 50μS / cm or more and less than 100μS / cm × (Not acceptable): Conductivity is 100μS / cm or more

[0163] [Table 5]

[0164] [Table 6]

[0165] Examples 50 to 66, Comparative Examples 9 to 12 Each component was charged into a beaker according to the formulation shown in Tables 7 and 8 below (units are parts by weight), and a stirrer was placed in the beaker and the mixture was stirred at 20° C. and 100 rpm to obtain a thermosetting composition.

[0166] The solubility, thermosetting property, adhesive property, heat-resistant adhesive property, and insulating property of the thermosetting compositions obtained in the Examples and Comparative Examples were evaluated by the following methods. The results are summarized in Tables 7 and 8 below.

[0167] [Solubility evaluation] The stirring time required until the acid generator was completely dissolved was measured, and the solubility was evaluated according to the following criteria. <Evaluation criteria> ◎ (Excellent): Dissolves with stirring for less than 1 minute ○ (Good): Dissolves after stirring for 1 minute or more but less than 5 minutes △(OK): Dissolves after stirring for 5 to 10 minutes × (Fail): Not dissolved even after stirring for 10 minutes or more

[0168] [TAG curability] A 40 μm spacer was placed on both ends of a slide glass, and the thermosetting composition obtained in the examples and comparative examples was dropped in the center. The thermosetting composition was spread using a squeegee to a thickness of 40 μm, and heated at 120° C. for 5 to 10 minutes using a hot plate. After that, it was left at room temperature for 60 minutes or more to obtain a cured product.

[0169] The cured product thus obtained was evaluated for curability according to the following criteria. The presence or absence of tackiness was judged by touching with a finger. Evaluation criteria ⊚: After heating for less than 10 minutes, the surface had no tackiness and the surface shape of the cured product did not change when touched with a finger. ○: After 10 minutes of heating, the surface had no tackiness and the surface shape of the cured product did not change when touched with a finger. However, after heating for less than 10 minutes, the surface of the cured product had no tackiness, but the surface shape of the cured product changed when touched with a finger. Δ: After heating for 10 minutes, there was no tackiness on the surface, but the surface shape of the cured product changed when touched with a finger. ×: The surface had tack even after heating for 10 minutes or more.

[0170] [TAG adhesiveness] A 40 μm spacer was placed on both ends of a slide glass, and the thermosetting composition obtained in the Examples and Comparative Examples was dropped in the center. The thermosetting composition was spread using a squeegee to a thickness of 40 μm, and an epoxy resin cube (outer diameter: 4 mm × 4 mm × 1 mm, inner diameter: 3.7 mm × 3.7 mm × 0.8 mm, adhesive area: 2.3 mm) was placed on top. 2) was set and heated in the same manner as in the above [TAG curability] evaluation. After heating, it was left at room temperature for 60 minutes or more. As a result, a structure was obtained in which the cured product of the thermosetting composition and the epoxy resin cube were closely attached to each other. Five of the obtained structures were prepared.

[0171] The adhesion of the five structures was evaluated by finding the average peel load in the same manner as in the evaluation of the [TAG adhesion] of the photocurable composition.

[0172] [TAG heat resistant adhesion] For structures (number of samples: 5) obtained using the same method as in the above [TAG adhesion] evaluation, the difference in peel load after the heat resistance test was determined using the same method as in the [PAG heat resistance adhesion] evaluation, and the difference from the peel load determined in the [TAG adhesion] evaluation (= peel load before heat resistance test) was calculated.

[0173] [TAG insulation] The thermosetting compositions obtained in the examples and comparative examples were coated on a polyphenylene ether substrate using a bar coater to a thickness of 50 μm. Then, the substrate was heated for 10 minutes in a hot air dryer at 120° C., and then left at room temperature for 60 minutes or more to obtain a cured product. The electrical conductivity of the obtained cured product was measured in the same manner as in the [PAG insulation] evaluation, and the insulation was evaluated.

[0174] [Table 7]

[0175] [Table 8]

[0176] The compound names of the components in Tables 5 to 8 are as follows. <Cationic curing compound> CELLOXIDE 2021P: 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate, epoxy equivalent 127g / eq, manufactured by Daicel Corporation THI-DE: Diepoxidized tetrahydroindene, manufactured by JXTG Nippon Oil & Energy Corporation jER 828: Bisphenol A diglycidyl ether, epoxy equivalent 189g / eq, manufactured by Mitsubishi Chemical Corporation jER YX8000: Hydrogenated bisphenol A diglycidyl ether, epoxy equivalent 205g / eq, manufactured by Mitsubishi Chemical Corporation VG3101L: 2-[4-(2,3-epoxypropoxy)phenyl]-2-[4-[1,1-bis[4-[2,3-epoxypropoxy]phenyl]ethyl]phenyl]propane, product name "TECHMORE VG3101L", manufactured by Printec Co., Ltd. SR-NPG: Neopentyl glycol diglycidyl ether, manufactured by Sakamoto Pharmaceutical Co., Ltd. OXT-121: Xylylene bisoxetane, oxetane equivalent 167g / eq, manufactured by Toagosei Co., Ltd. OXT-221: 3-ethyl-3{[(3-ethyloxetan-3-yl)methoxy]methyl}oxetane, manufactured by Toagosei Co., Ltd. X-22-169: Epoxy-modified silicone oligomer with alicyclic ends, manufactured by Shin-Etsu Chemical Co., Ltd. Denacol EX-146: p-tert-butylphenyl glycidyl ether, manufactured by Nagase ChemteX Corporation <Photoacid generator> PAG-1 to 16, PAG-H1, H2: The compounds obtained in Examples 1 to 16 and Comparative Examples 1 and 2 were used. <Thermal acid generator> TAG-1 to 8, TAG-H1, H2: The compounds obtained in Examples 17 to 24 and Comparative Examples 3 and 4 were used. <Coupling Agent> KBM-403: 3-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd. <Antifoaming agent> BYK-1790: Non-silicone polymeric defoamer, manufactured by BYK Japan Co., Ltd. <Leveling agent> LS-460: Polyether modified silicone, manufactured by Kusumoto Chemicals Co., Ltd.

[0177] It can be seen from Tables 5 to 8 that the acid generators of the present invention are superior in solubility in cationic curable compounds and superior in cationic polymerization initiation ability as compared with the acid generators of the comparative examples. It can also be seen that when the acid generator of the present invention is used in a photocurable composition, it can be cured with less light energy, and when the acid generator of the present invention is used in a thermosetting composition, it can be cured with less heat energy. Furthermore, it is clear that the acid generator of the present invention provides a cured product having excellent adhesiveness and insulating properties.

Claims

1. An acid generator comprising a compound represented by the following formula (1): 【Chemistry 1】 (In the formula, Ct represents a monovalent cation. Ar represents an aromatic hydrocarbon group or an aromatic heterocyclic group. M represents a boron atom, an aluminum atom, or a gallium atom. R 1 represents a fluorine atom, an aromatic hydrocarbon group, or an aromatic heterocyclic group; m represents an integer of 1 or more, and n represents an integer of 1 to 4.

2. 2. The acid generator according to claim 1, wherein the monovalent cation in Ct is a cation selected from the group consisting of a sulfonium ion, an iodonium ion, a selenium ion, an ammonium ion, and a phosphonium ion.

3. A curable composition comprising the acid generator according to claim 1 or 2 and a cationic curable compound.

4. A cured product of the curable composition according to claim 3.

5. A compound represented by the following formula (1-1): 【Chemistry 2】 (In the formula, Ct represents a monovalent cation. Ar represents an aromatic hydrocarbon group or an aromatic heterocyclic group. M' represents a boron atom or a gallium atom. R 1 represents a fluorine atom, an aromatic hydrocarbon group, or an aromatic heterocyclic group. m represents an integer of 1 or more, and n represents an integer of 1 to 4. However, when M' is a boron atom, R 1 is an aromatic hydrocarbon group or an aromatic heterocyclic group)

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