JP2000230038A - Cure catalyst, resin composition, resin-sealed semiconductor device, and coating material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition which is quickly cured at a specified temperature higher than room temperature and is excellent in storage stability, electrical insulation properties, and mechanical strengths by incorporating, into the same, a cure catalyst which comprises a cation polymerization catalyst component and/or an organometallic compound and of which at least one component can be reversibly dissolved or precipitated in the composition by heating or cooling. SOLUTION: A cure catalyst which comprises at least one component selected from among a cation polymerization catalyst component which is a 10C or higher optionally substituted hydrocarbon or a compound having at least one organic ring structure having a 10C or higher optionally substituted hydrocarbon group and an organometallic compound selected from among compounds of formulas I, II, and III is incorporated in an amount of 0.01-20 wt.% into a resin composition provided at least one component contained in the catalyst can be reversibly dissolved or precipitated in the composition by heating or cooling. In the formulas, R21 to R24 are each H or a 1-30C optionally substituted hydrocarbon group provided that in one ligand, at least one group which is selected from among the groups: R21 to R24 and has at least 10 carbon atoms is present; M is Al, Ti, Cr, Fe, Co, Ni, Cu, Zr, Zn, Ba or the like; and n is 2-4.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an epoxy resin or the like,
The present invention relates to a curing catalyst used for curing a cationically polymerizable compound and a resin composition containing the curing catalyst. The present invention also relates to a resin-sealed semiconductor device using such a resin composition, and a coating material containing such a resin composition.

[0002]

2. Description of the Related Art In general, epoxy resins have excellent electrical insulation properties, mechanical strength, adhesiveness, water resistance and the like. It is used in a wide range such as the electric field, civil engineering / architecture, and adhesive field. 2. Description of the Related Art Conventionally, epoxy resins are widely used in a two-part system mixed with an amine compound or a carboxylic anhydride as a curing agent. However, 2 using these curing agents
The operation of a liquid system is complicated because the components must be mixed immediately before use. There are also restrictions such as the necessity of storage and transportation at a low temperature, and the fact that the product must be used within a certain period after production. Thus, for many years, an epoxy resin composition that can be stored at room temperature with one liquid has been desired, and many methods have been studied.

Conventionally, in a thermosetting composition in which a curing reaction is accelerated by an acid catalyst or a base catalyst, in order to improve storage stability, the latentification of these catalysts is carried out by using a physical method or a chemical method. Are being considered. For example, as a physical method, for example, a microcapsule in which an organic phosphine compound is wrapped in a particle shape with a polymer (JP-A-6-7316)
No. 3) or by adsorbing on a compound having pores such as zeolite to achieve one-pack storage stability. However, these catalyst systems have insufficient potential, and their uses are limited, for example, they cannot be used for processing methods such as impregnation because they are heterogeneous systems. In addition, it has a disadvantage that the cured resin tends to be non-uniform.

On the other hand, as a chemical method, a method using a so-called thermal latent catalyst, which temporarily suppresses the activity of an acid catalyst and shows the activity again by cleaving it during heat curing, has been widely studied. . Examples of such a heat latent catalyst include those in which active protons are blocked by using an acid-base neutralization reaction and those in which active protons are blocked by using an esterification reaction with alcohols. (Japanese Patent Publication No. 52-770). Also,
A benzylsulfonium salt type or a benzylpyridinium salt type is known as a heat-latent acid catalyst for generating an active benzyl cation by thermal decomposition of an onium salt (Japanese Patent Application Laid-Open No. 62-192427). Further, examples of commercially available heat-latent acid catalysts include a monoethylamine complex of boron trifluoride, which is a Lewis acid, and a pyridine complex of boron trifluoride.

However, those utilizing an acid-base neutralization reaction and those utilizing an esterification reaction with alcohols are known as heat-latent acids having both an appropriate dissociation temperature and the thermal stability of the catalyst itself. It is difficult to obtain a catalyst. Also,
The benzylsulfonium salt type and the benzylpyridinium salt type have relatively excellent storage stability but are not sufficient. Particularly, storage stability is poor for highly reactive alicyclic epoxies. Further, commercially available monoethylamine complex of boron trifluoride and pyridine complex of boron trifluoride generally have a tendency that the dissociation temperature is too high.

[0006]

As described above, when a conventional catalyst is used, the reaction gradually proceeds immediately after mixing the catalyst with the epoxy resin as a curable resin component even at room temperature. proceed. That is, the reaction proceeds and the epoxy resin composition is cured even if it is simply stored. Therefore, the storage period of the epoxy resin composition is limited to a certain limited period, and the epoxy resin composition must be used within that period.

Further, since the conventional curing reaction using a catalyst is caused by an ionic reaction, there is a problem that the ionic catalyst after the reaction remains in the cured resin and greatly reduces the electrical insulation of the resin.

On the other hand, cation polymerization catalysts for cation polymerization vinyl compounds include BF ₃ , AlCl ₃ , AlRC
Although such a Lewis acid such as l ₂ are known, such polymerization catalyst, occurs reaction even at about room temperature, the storage stability is extremely poor. Further, the polymerization reaction cannot be controlled well, and the degree of polymerization is small. In order to polymerize a vinyl compound, usually, a monomer dissolved in an appropriate solvent is cooled to a predetermined cryogenic temperature, and then a catalyst is added to perform polymerization. However, industrially performing the polymerization reaction in a low temperature range is complicated and expensive, and is not a good method.

The present invention relates to a curing catalyst for a resin composition, particularly an epoxy resin composition, which reacts rapidly at a predetermined temperature higher than room temperature to cure the resin, but the reaction does not proceed so much at room temperature. The purpose of the present invention is to provide a hardening catalyst that does not have a high temperature.

In addition, the present invention maintains high storage stability at about room temperature without a curing reaction proceeding, and cures rapidly at a predetermined temperature higher than room temperature, and furthermore, has an electrical insulating property and mechanical strength. An object of the present invention is to provide a resin composition having excellent workability and capable of obtaining an excellent cured product.

Further, the present invention provides a resin-encapsulated semiconductor device which is encapsulated with an epoxy resin composition having excellent storage stability, fluidity and filling properties, and has high thermal shock resistance and high moisture resistance reliability. Aim.

Still another object of the present invention is to provide a coating material containing the above-mentioned curing catalyst, having excellent storage stability and exhibiting high hardness characteristics after curing.

[0013]

In order to solve the above-mentioned problems, the present invention comprises a cationic polymerization catalyst component and at least one component of an organometallic compound, wherein at least one of the components is heated and cooled. The present invention provides a curing catalyst characterized by being capable of reversibly dissolving and precipitating.

The present invention also comprises a cationic polymerization catalyst component and at least one component of an organometallic compound, wherein the cationic polymerization catalyst component is a substituted or unsubstituted hydrocarbon having 10 or more carbon atoms, or a carbon atom having 10 or more carbon atoms. It is a compound having at least one cyclic organic structure having 10 or more substituted or unsubstituted hydrocarbon groups in a molecule, and at least one of the components can be reversibly dissolved and precipitated by heating and cooling. A curing catalyst is provided, characterized in that it is possible.

Further, the present invention provides a compound represented by the following general formula (III-1 ′):
And a curing catalyst containing at least one compound selected from the group consisting of compounds represented by (III-2).

[0016]

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(In the above general formula (III-1 ′), R ¹ ,
R ² and R ³ may be the same or different and each represent a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, an aromatic group having a substituted or unsubstituted hydrocarbon group, or a heteroaromatic group. Group. However, if the carbon number is 10
It has at least one aromatic or heteroaromatic group having the above-mentioned substituted or unsubstituted hydrocarbon group, or a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms. )

[0018]

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(In the above formula (III-2), R ³² ,
R ³³ , R ³⁴ and R ³⁵ may be the same or different,
Each is a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms. However, R ³² , R ³³ , R ³⁴
And at least two of R ³⁵ are hydrocarbon groups having 10 or more carbon atoms. In addition, the present invention provides compounds represented by the following general formulas (III-1) and (III-
A curing catalyst containing at least one compound selected from the group consisting of the compounds represented by 2) is provided.

[0020]

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(In the above formula (III-1), R ³¹ may be the same or different and each represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms. At least one of R ³¹ has 10 or more carbon atoms, and h, i and j are h + i + j =
3 is an integer satisfying 3, and m is an integer of 1 to 5. )

[0022]

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(In the above formula (III-2), R ³² ,
R ³³ , R ³⁴ and R ³⁵ may be the same or different,
Each is a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms. However, R ³² , R ³³ , R ³⁴
And at least two of R ³⁵ are hydrocarbon groups having 10 or more carbon atoms. Further, the present invention provides a resin composition containing the above-described curing catalyst and a cationically polymerizable resin component.

Further, the present invention comprises a semiconductor element and a resin layer for encapsulating the semiconductor element, wherein the resin layer is obtained by curing the above resin composition. A semiconductor device is provided.

Further, the present invention provides a coating material containing the above-mentioned curing catalyst.

Hereinafter, the present invention will be described in detail.

[0027] The first curing catalyst of the present invention contains at least one of a cationic polymerization catalyst component and an organometallic compound. In addition, at least one of these has the property that it can be dissolved and deposited reversibly by heating and cooling. In the present invention, heating means room temperature or higher, specifically from 40 ° C. or higher to the curing temperature,
Cooling means a temperature range below the curing temperature, specifically below 80 ° C, preferably below 60 ° C. In addition, precipitation means that the catalyst is a colloid or micelle in the epoxy resin,
This means that the active site of the catalyst is in a state of being isolated from an epoxy resin, a curing agent, or the like, which means that the active site of the catalyst is in the form of a crystal or the like. Furthermore, as long as the potential of the catalyst can be confirmed by a storage stability test or the like, any size may be used. Preferably, the catalyst has an average particle diameter of 0.1 μm or more. The dissolution means that the catalyst in the form described above may be partially dissolved, for example, by collecting the catalyst precipitated in the epoxy resin together with the resin in a glass plate, and then observing it with a microscope while heating. It suffices if the precipitated and cloudy catalyst is dissolved to become transparent. Furthermore, it is more preferable that an endothermic peak derived from dissolution of the catalyst in the epoxy resin be confirmed by DSC (differential scanning calorimetry) or the like.

Examples of the cationic polymerization catalyst component blended in the first curing catalyst include a substituted or unsubstituted hydrocarbon having 10 or more carbon atoms or a cyclic hydrocarbon having a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms. Compounds having one or more organic structures in the molecule are exemplified. 16 carbon atoms
The above is more preferable. These hydrocarbons and cyclic organic structures may be present as a substituent or may be present as a part of a ligand. As the cyclic organic structure,
Aromatic, heteroaromatic, condensed aromatic, condensed heteroaromatic and the like can be mentioned.

Examples of the element serving as a cation of the cationic polymerization catalyst component include S, I, Fe, N, O, P, and M.
g, Mn, and Si can be exemplified.

A specific description will be given. Examples of the cationic polymerization catalyst component include a sulfonium salt represented by the following formula (I-1), an iodonium salt represented by the following formula (I-2), and a formula represented by the following formula (I-3). Onium salts such as iron aromatic compounds; organic silicon compounds represented by the following general formula (I-4); and compounds represented by the following general formula (I-5).

The onium salts include, in addition to the above, ammonium salts, diazonium salts, pyrrolium salts, pyrylium salts, quinolium salts, anilium salts, pyridium salts, benzylammonium salts, benzothiazolium compound salts, benzylpyridium salts, benzyl salts A sulfonium salt, a benzylphosphonium salt or the like may be used.

[0032]

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In the above formula, R ¹¹ , R ¹² and R ¹³ are
They may be the same or different and are each a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, a substituted or unsubstituted aromatic group or a heteroaromatic group. However, the compound has at least one cyclic organic structure having a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms or a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms in the molecule. More specifically, a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms, or
It has at least one aromatic or heteroaromatic group having the above-mentioned substituted or unsubstituted hydrocarbon group. X is Sb
F ₆ , AsF ₆ , PF ₆ , BF _4, these anion derivatives wherein at least one fluorine atom is substituted by a hydroxyl group,
And CF ₃ SO ₃ , ClO ₄ , a halogen atom, R ¹ −
An anion selected from the group consisting of COO and R ² —SO ₃ is shown. Here, R ¹ and R ² represent an alkyl group, a halogen atom, a nitro group, a cyano group, an alkyl group which may be substituted with an alkoxy group or the like, or a phenyl group.

[0034]

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In the above formula, R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ may be the same or different and each represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, An unsubstituted aromatic or heteroaromatic group. However, a cyclic organic structure having a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms or a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms in one molecule.
Have more than one. More specifically, it has at least one aromatic or heteroaromatic group having a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms. p, q and r are 0 to
In the integer of 3, p + q + r is 3 or less.

[0036]

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In the above formula, Ar ¹ is a substituted or unsubstituted aromatic group or a heteroaromatic group, and R ¹⁸ may be the same or different and each represents a hydrogen atom or a substituted or unsubstituted carbon atom having 1 to 30 carbon atoms. Alternatively, it is an unsubstituted hydrocarbon group, a substituted or unsubstituted aromatic group or a heteroaromatic group. Note that the molecule has at least one cyclic organic structure having a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms or a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms. k represents an integer of 1 to 7, and n represents an integer of 1 to 7, respectively.

In the above general formula, examples of the hydrocarbon group introduced as R ^{11 to} R ¹⁸ include methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane and tridecane , Tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, icosane, henicosan, docosan, trichosane, tetracosane, pentacosane, hexacosane, branched or straight-chain substituents such as heotacosane, octacosan, nonacosan, triacosane, and steroid skeletons such as cholesterol. Can be used.

Further, the above-mentioned hydrocarbon groups are represented by F, Si,
Heteroatoms such as O, N, and S may be contained.

In the above formula, the substituted or unsubstituted aromatic or heteroaromatic group introduced as R ^{11 to} R ¹⁸ includes, for example, phenyl, benzyl, methylbenzyl, dimethylbenzyl, Two or three benzene rings such as trimethylbenzyl, chlorobenzyl, dichlorobenzyl, trichlorobenzyl, nitrobenzyl, dinitrobenzyl, trinitrobenzyl, naphthylmethyl; naphthyl, anthracenyl and phenanthrenyl Condensed condensed aromatic ring group; furanyl, thiophenyl, pyrrolyl, pyrrolinyl,
Pyrrolidinyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, imidazolinyl, imitazolidinyl, pyrazolyl, pyrazolidinyl,
Triazolyl, flazanil, tetrazolyl, pyranyl,
Thiynyl, pyridinyl, piperidinyl, oxazinyl,
Monocyclic heteroaromatic groups such as morpholinyl, thiadinyl, pyridazinyl, pyrimidinyl, pyrazinyl, piperazinyl and triazinyl groups; benzofuranyl, isobenzofuranyl, benzothiophenyl, indolyl, indolinyl, isoindolyl, benzoxazolyl, benzothiazolyl, indazolyl , Imidazolyl, chromenyl, chromanyl, isochromanyl, quinolyl, isoquinolyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, dibenzofuranyl, carbazolyl, xanthenyl, acridinyl, phenanthrinyl, phenanthrolinyl, phenazinyl, phenoxinyl, thianthinyl, thianthinyl Fused heterogenes such as quinuclidinyl, naphthyridinyl, prenyl and pteridinyl groups Kowamoto; and hydrogen atoms may include one or more substituent these groups substituted with a group.

Examples of the substituents of these substituted aromatic groups or heteroaromatic groups include organic groups having one or more carbon atoms. May be.

Examples of the sulfonium salt represented by the general formula (I-1) include tris (p-octadecyloxyphenyl) sulfonium hexafluoroantimonate and bis (p-octadecyloxyphenyl) phenylsulfonium hexafluoroantimonate , (P−
Octadecyloxyphenyl) diphenylsulfonium hexafluoroantimonate, tris (p-hexadecyloxyphenyl) sulfonium hexafluoroantimonate, bis (p-hexadecyloxyphenyl)
Phenylsulfonium hexafluoroantimonate,
(P-hexadecyloxyphenyl) diphenylsulfonium hexafluoroantimonate, benzyl-4-
Octadecyloxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-octadecyloxyphenylethylsulfonium hexafluoroantimonate, benzyl-4-octadecyloxyphenylsulfonium hexafluoroantimonate, tris (p-octadecyloxyphenyl) sulfonium hexafluorophosphate, Bis (p-octadecyloxyphenyl) phenylsulfonium hexafluorophosphate, (p-octadecyloxyphenyl) diphenylsulfonium hexafluorophosphate, tris (p-hexadecyloxyphenyl) sulfonium hexafluorophosphate, bis (p-hexadecyloxyphenyl) Phenylsulfonium hexafluorophosphate, (p- Xadecyloxyphenyl) diphenylsulfonium hexafluorophosphate, benzyl-4-octadecyloxyphenylmethylsulfonium hexafluorophosphate, benzyl-4-octadecyloxyphenylethylsulfonium hexafluorophosphate, benzyl-4-octadecyloxyphenylsulfonium hexafluorophosphate, tris (P-octadecyloxyphenyl) sulfonium hexafluoroarsenate, bis (p-octadecyloxyphenyl) phenylsulfonium hexafluoroarsenate, (p-octadecyloxyphenyl) diphenylsulfonium hexafluoroarsenate, tris (p-hexadecyloxyphenyl) ) Sulfonium hexafluoroarsenate, bis ( -Hexadecyloxyphenyl) phenylsulfonium hexafluoroarsenate, (p-hexadecyloxyphenyl) diphenylsulfonium hexafluoroarsenate, benzyl-4-octadecyloxyphenylmethylsulfonium hexafluoroarsenate, benzyl-4-octadecyloxyphenylethyl Sulfonium hexafluoroarsenate, benzyl-4-octadecyloxyphenylsulfonium hexafluoroarsenate, tris (p-octadecyloxyphenyl) sulfonium tetrafluoroborate, bis (p-octadecyloxyphenyl) phenylsulfonium tetrafluoroborate, (p-octadecyl Oxyphenyl) diphenylsulfonium tetrafluoroborate, tris (p-f Xadecyloxyphenyl) sulfonium tetrafluoroborate, bis (p-hexadecyloxyphenyl)
Phenylsulfonium tetrafluoroborate, (p-
(Hexadecyloxyphenyl) diphenylsulfonium tetrafluoroborate, benzyl-4-octadecyloxyphenylmethylsulfonium tetrafluoroborate, benzyl-4-octadecyloxyphenylethylsulfonium tetrafluoroborate, benzyl-4
-Octadecyloxyphenylsulfonium tetrafluoroborate, tris (p-octadecyloxyphenyl) sulfonium trifluoromethanesulfonate, bis (p-octadecyloxyphenyl) phenylsulfonium trifluoromethanesulfonate, (p-octadecyloxyphenyl) diphenylsulfonium trifluoromethanesulfonate, tris (P-hexadecyloxyphenyl) sulfonium trifluoromethanesulfonate, bis (p-hexadecyloxyphenyl) phenylsulfonium trifluoromethanesulfonate,
(P-hexadecyloxyphenyl) diphenylsulfonium trifluoromethanesulfonate, benzyl-4
-Octadecyloxyphenylmethylsulfonium trifluoromethanesulfonate, benzyl-4-octadecyloxyphenylethylsulfonium trifluoromethanesulfonate, benzyl-4-octadecyloxyphenylsulfonium trifluoromethanesulfonate, p-octadecyloxybenzyltetramethylenesulfonium hexafluoroantimonate, (4 -Octadecyloxyphenyl) cinnamylmethylsulfonium hexafluoroantimonate, (4-octadecyloxyphenyl) (3-methyl-2-butenyl) methylsulfonium hexafluoroantimonate, 4-octadecyloxyphenyl- (α-naphthylmethyl) methyl Sulfonium hexafluoroantimonate, 4
-Octadecyloxyphenyl-9-fluorenylmethylsulfonium hexafluoroantimonate, tris (4-octadecyloxyphenylmethyl) sulfonium hexafluoroantimonate, o-nitrobenzyl-4-octadecyloxyphenylmethylsulfonium hexafluoroantimonate, α -Phenylbenzyl-4-octadecyloxyphenylmethylsulfonium hexafluoroantimonate, α-methylbenzyl-4-octadecyloxyphenylmethylsulfonium hexafluoroantimonate, dibenzyl-
4-octadecyloxyphenylsulfonium hexafluoroantimonate, 4-octadecyloxyphenylmethylsulfonium hexafluoroantimonate, and the like.

Hexafluoroantimonate, which forms the anion portion of the above-mentioned sulfonium salt, is hexafluorophosphate, hexafluoroarsenate, tetrafluoroborate, these anions having at least one fluorine atom substituted by a hydroxyl group, and trifluoromethanesulfonate; Perchlorate, halogen, R ¹ -CO
A compound converted to an anion selected from the group consisting of O and R ² —SO ₃ can also be used as the curing catalyst component of the present invention. R ¹ and R ² represent an alkyl group, a halogen atom, a nitro group, a cyano group, an alkyl group which may be substituted with an alkoxy group, or a phenyl group.

Further, benzyl-4-octadecyloxyphenylmethylhexafluoroantimonate, benzyl-4-octadecyloxyphenylmethylhexafluoroarsenate, benzyl-4-octadecyloxyphenylmethylhexafluorophosphate, benzyl-4-octadecyloxyphenyl Methyltetrafluoroborate, benzyl-4-octadecyloxyphenylmethyltrifluoromethanesulfonate, and the like can also be used.

Examples of the iodonium salt represented by the general formula (I-2) include bis (p-octadecyloxyphenyl) iodonium hexafluoroantimonate, (p-octadecyloxyphenyl) phenyliodonium hexafluoroantimonate, Bis (p-hexadecyloxyphenyl) iodonium hexafluoroantimonate, (p-hexadecyloxyphenyl) phenyliodonium hexafluoroantimonate, benzyl-4-octadecyloxyphenylmethyliodonium hexafluoroantimonate, benzyl-4-octadecyloxy Phenylethyliodonium hexafluoroantimonate, benzyl-4-octadecyloxyphenyliodonium hexafluoroantimonate, bis ( - octadecyloxyphenyl)
Iodonium hexafluorophosphate, (p-octadecyloxyphenyl) phenyliodonium hexafluorophosphate, bis (p-hexadecyloxyphenyl) iodonium hexafluorophosphate,
(P-hexadecyloxyphenyl) phenyliodonium hexafluorophosphate, benzyl-4-octadecyloxyphenylmethyliodonium hexafluorophosphate, benzyl-4-octadecyloxyphenylethyliodonium hexafluorophosphate, benzyl-4-octadecyloxyphenyliodonium hexafluoro Phosphate, bis (p-octadecyloxyphenyl) iodonium hexafluoroarsenate, (p-octadecyloxyphenyl) phenyliodonium hexafluoroarsenate, bis (p-hexadecyloxyphenyl) iodonium hexafluoroarsenate, (p-hexadecyl) Oxyphenyl) phenyliodonium hexafluoroarsenate, benzyl-4 Octadecyloxyphenylmethyliodonium hexafluoroarsenate, benzyl-4-octadecyloxyphenylethyliodonium hexafluoroarsenate, benzyl-4-octadecyloxyphenyliodonium hexafluoroarsenate, bis (p-octadecyloxyphenyl) iodonium tetrafluoroborate, (P-octadecyloxyphenyl) phenyliodonium tetrafluoroborate, bis (p-hexadecyloxyphenyl) iodonium tetrafluoroborate, (p-hexadecyloxyphenyl) phenyliodonium tetrafluoroborate, benzyl-4-octadecyloxyphenylmethyliodonium Tetrafluoroborate, benzyl-4-octadecyloxyphenyl Tyliodonium tetrafluoroborate, benzyl-4-octadecyloxyphenyliodonium tetrafluoroborate, bis (p-octadecyloxyphenyl) iodonium trifluoromethylsulfonate, (p-octadecyloxyphenyl) phenyliodonium trifluoromethylsulfonate, bis (p- (Hexadecyloxyphenyl) iodonium trifluoromethylsulfonate, (p-hexadecyloxyphenyl) phenyliodonium trifluoromethylsulfonate, benzyl-
4-octadecyloxyphenylmethyliodonium trifluoromethylsulfonate, benzyl-4-octadecyloxyphenylethyliodonium trifluoromethylsulfonate, benzyl-4-octadecyloxyphenyliodonium trifluoromethylsulfonate, and p-octadecyloxybenzyltetramethyleneiodonium hexafluoro Antimonate, (4
-Octadecyloxyphenyl) cinnamylmethyliodonium hexafluoroantimonate, (4-octadecyloxyphenyl) (3-methyl-2-butenyl) iodonium hexafluoroantimonate, 4
-Octadecyloxyphenyl- (α-naphthylmethyl) iodonium hexafluoroantimonate, 4
-Octadecyloxyphenyl-9-fluorenyliodonium hexafluoroantimonate, bis (4-
Octadecyloxyphenylmethyl) iodonium hexafluoroantimonate, o-nitrobenzyl-4
-Octadecyloxyphenyliodonium hexafluoroantimonate, α-phenylbenzyl-4-octadecyloxyphenyliodonium hexafluoroantimonate, α-methylbenzyl-4-octadecyloxyphenyliodonium hexafluoroantimonate, benzyl-4-octadecyloxyphenyliodonium Hexafluoroantimonate, 4-octadecyloxyphenylmethyliodonium hexafluoroantimonate, and the like.

Hexafluoroantimonate, which is an anion part of the above-mentioned iodonium salt, is obtained by converting hexafluorophosphate, hexafluoroarsenate, tetrafluoroborate, these anions having at least one fluorine atom substituted with a hydroxyl group, and trifluoromethanesulfonate; Perchlorate, halogen, R ¹ -CO
A compound converted to an anion selected from the group consisting of O and R ² —SO ₃ can also be used as the curing catalyst component of the present invention. R ¹ and R ² represent an alkyl group, a halogen atom, a nitro group, a cyano group, an alkyl group which may be substituted with an alkoxy group, or a phenyl group.

Further, the following onium salts can be used.

Examples of the pyrylium salt include those represented by the following general formula.

[0049]

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In the above formula, R may be the same or different and each represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, a substituted or unsubstituted aromatic group or a heteroaromatic group. It is. However, it is a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms, or an aromatic group or a heteroaromatic group having a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms. R also includes a halogen atom, a nitro group, and a cyano group. N is an integer of 1 to 5.

X is SbF ₆ , AsF ₆ , PF ₆ , BF
_4, these anionic derivatives in which at least one fluorine atom is substituted by a hydroxyl group, CF ₃ SO ₃ , Cl
An anion selected from the group consisting of O ₄ , a halogen atom, R—COO, and R—SO ₃ is shown. Here, R is an alkyl group or a phenyl group which may be substituted with an alkyl group, a halogen atom, a nitro group, a cyano group, an alkoxy group, or the like.

The pyrylium salt represented by the above general formula includes 2,6-dimethyl-4-octadecyloxyphenylpyrylium hexafluoroantimonate,
Dimethyl-3- (4-octadecyloxyphenyl) propylpyrylium hexafluoroantimonate and the like can be mentioned.

The amount is usually from 0.01 to 20% by weight, preferably from 0.1 to 5% by weight, based on the epoxy resin of the composition. If the amount is less than 0.01% by weight,
Curing may be insufficient. Although it is possible to use it in an amount exceeding 20% by weight, it is not preferable because high cost and decomposition products of the catalyst component may cause problems.

Examples of the benzylsulfonium salt include those represented by the following general formula.

[0055]

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In the above formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be the same or different and each represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, It is a substituted or unsubstituted aromatic or heteroaromatic group. However, it is a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms, or an aromatic group or a heteroaromatic group having a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms. R ⁴ also includes a halogen atom, a nitro group, and a cyano group. N is an integer of 1 to 5.

X is SbF ₆ , AsF ₆ , PF ₆ , BF
_4, these anionic derivatives in which at least one fluorine atom is substituted by a hydroxyl group, CF ₃ SO ₃ , Cl
An anion selected from the group consisting of O ₄ , a halogen atom, R—COO, and R—SO ₃ is shown. Here, R is an alkyl group or a phenyl group which may be substituted with an alkyl group, a halogen atom, a nitro group, a cyano group, an alkoxy group, or the like.

Examples of the benzylphosphonium salt represented by the above general formula include benzyltris (4-octadecyloxyphenyl) phosphonium hexafluoroantimonate, α-phenylbenzyltris (4-octadecyloxyphenyl) phosphonium hexafluoroantimonate and the like. Can be mentioned.

Hexafluoroantimonate, which is an anion part of the above-mentioned benzylphosphonium salt, is hexafluorophosphate, hexafluoroarsenate, tetrafluoroborate, these anions having at least one fluorine atom substituted by a hydroxyl group, and trifluoromethanesulfonate. , Perchlorate, halogen, R
¹ -COO, compounds were converted to an anion selected from the group consisting of R ² -SO ₃ can also be used as the curing catalyst component of the present invention. R ¹ and R ² are an alkyl group,
It represents an alkyl group or a phenyl group which may be substituted with a halogen atom, a nitro group, a cyano group, an alkoxy group and the like.

The amount is usually 0.01 to 20% by weight, preferably 0.1 to 5% by weight, based on the epoxy resin of the composition. If the amount is less than 0.01% by weight, curing may be insufficient. Although it is possible to use it in an amount exceeding 20% by weight, it is not preferable because high cost and decomposition products of the catalyst component may cause problems.

Examples of the benzyl ammonium salt include those represented by the following general formula.

[0062]

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In the above formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵
And R ⁶ may be the same or different and are each a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, a substituted or unsubstituted aromatic group or a heteroaromatic group. However, it has at least one aromatic or heteroaromatic group having a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms or a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms. Further, R ⁵ and R ⁶ are both hydrogen atoms, one is a hydrogen atom and the other is an alkyl group or a halogen atom, or both are an alkyl group or a halogen atom. When R ⁵ and R ⁶ are both hydrogen atoms, at least one of R ¹ , R ² and R ³ is preferably an aromatic group or a heteroaromatic group. Here, R ⁴ contains a halogen atom, a nitro group, and a cyano group. n is an integer of 1 to 5.

X is SbF ₆ , AsF ₆ , PF ₆ , BF
_4, these anionic derivatives in which at least one fluorine atom is substituted by a hydroxyl group, CF ₃ SO ₃ , Cl
An anion selected from the group consisting of O ₄ , a halogen atom, R—COO, and R—SO ₃ is shown. Here, R is an alkyl group or a phenyl group which may be substituted with an alkyl group, a halogen atom, a nitro group, a cyano group, an alkoxy group, or the like.

The benzyl ammonium salt represented by the above general formula includes N- (p-octadecyloxybenzyl) -N, N-dimethylanilinium hexafluoroantimonate, N- (p-octadecyloxybenzyl) -N, N-dimethylanilinium hexafluorophosphate, N- (p-octadecyloxybenzyl)
-N, N-dimethylanilinium tetrafluoroborate, N- (α-methyl-p-octadecyloxybenzyl) -N, N-dimethylanilinium hexafluoroantimonate, N- (2-hydroxyethyl) -N-
(Α-methyl-p-octadecyloxybenzyl)-
N, N-dimethylammonium hexafluoroantimonate and the like can be mentioned.

The compounding amount is usually from 0.01 to 20% by weight, preferably from 0.1 to 5% by weight, based on the epoxy resin of the composition. If the amount is less than 0.01% by weight, curing may be insufficient. Although it is possible to use it in an amount exceeding 20% by weight, it is not preferable because high cost and decomposition products of the catalyst component may cause problems.

In the above benzylammonium salts, R
An anilium salt in which one of R ¹ , R ² and R ³ is a substituted or unsubstituted phenyl group has at least one of the remaining ^{two of} R ¹ , R ² and R ³ at the β-position carbon of the nitrogen atom. Those having an alkyl group having a substituent are also effective.

Examples of the benzylpyridinium salt include those represented by the following general formula.

[0069]

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In the above formula, R ¹ , R ² , and R ³ may be the same or different and each represents a hydrogen atom, a carbon number of 1 to 3,
It is 0 substituted or unsubstituted hydrocarbon group, substituted or unsubstituted aromatic group or heteroaromatic group. However, it has at least one aromatic or heteroaromatic group having a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms or a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms. However, R ^{1 also} includes a cyano group, and R ² also includes a halogen atom, a nitro group, and a cyano group. n is an integer of 1 to 5, m
Is an integer of 1 to 7.

X is SbF ₆ , AsF ₆ , PF ₆ , BF
_4, these anionic derivatives in which at least one fluorine atom is substituted by a hydroxyl group, CF ₃ SO ₃ , Cl
An anion selected from the group consisting of O ₄ , a halogen atom, R—COO, and R—SO ₃ is shown. Here, R is an alkyl group or a phenyl group which may be substituted with an alkyl group, a halogen atom, a nitro group, a cyano group, an alkoxy group, or the like.

The benzylpyridinium salt (A) represented by the above general formula includes 1- (p-octadecyloxybenzyl) -4-cyanopyridinium hexafluoroantimonate, 1- (p-octadecyloxybenzyl)
4-cyanopyridinium hexafluorophosphate, 1- (p-octadecyloxybenzyl) -4-cyanopyridinium tetrafluoroborate and the like.

The benzylpyridinium salt (B) exposed by the above general formula includes α-naphthylmethyl- (4-
Octadecyloxy) pyridinium hexafluoroantimonate, α-naphthylmethyl- (4-octadecyloxy) pyridinium hexafluorophosphate, α-naphthylmethyl- (4-octadecyloxy)
And pyridinium tetrafluoroborate.

The benzylpyridinium salt (C) represented by the above general formula includes cinnamyl- (4-octadecyloxy) pyridinium hexafluoroantimonate, 2-butenyl- (4-octadecyloxy) pyridinium hexafluoroantimonate, cinnamyl −
(4-octadecyloxy) pyridinium hexafluorophosphate, cinnamyl- (4-octadecyloxy) pyridinium tetrafluoroborate, and the like.

The compounding amount is usually 0.01 to 20% by weight, preferably 0.1 to 5% by weight, based on the epoxy resin of the composition. If the amount is less than 0.01% by weight, curing may be insufficient. Although it is possible to use it in an amount exceeding 20% by weight, it is not preferable because high cost and decomposition products of the catalyst component may cause problems.

Examples of the benzothiazolium salt include those represented by the following general formula.

[0077]

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In the above formula, R ¹ , R ² , and R ³ may be the same or different and each represents a hydrogen atom, a carbon number of 1 to 3,
It is 0 substituted or unsubstituted hydrocarbon group, substituted or unsubstituted aromatic group or heteroaromatic group. Note that the compound has one or more aromatic or heteroaromatic groups having a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms, or a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms. R ¹ and R ² contain a nitro group. R ⁴ is a hydrogen atom, an aromatic group or a heteroaromatic group, n is an integer of 1 to 5, and m is an integer of 1 to 4. The S atom of the thiazolium ring may be substituted with an O atom.

X is SbF ₆ , AsF ₆ , PF ₆ , BF
_4, these anionic derivatives in which at least one fluorine atom is substituted by a hydroxyl group, CF ₃ SO ₃ , Cl
An anion selected from the group consisting of O ₄ , a halogen atom, R—COO, and R—SO ₃ is shown. Here, R is an alkyl group or a phenyl group which may be substituted with an alkyl group, a halogen atom, a nitro group, a cyano group, an alkoxy group, or the like.

Further, a compound represented by the following general formula may be used.

[0081]

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In the above formula, R ¹ , R ² and R ³ may be the same or different and each represents a hydrogen atom, a halogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, a substituted or unsubstituted group. It is a substituted aromatic or heteroaromatic group. Note that the compound has one or more aromatic or heteroaromatic groups having a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms, or a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms. R1 and R2 contain a nitro group.
n is an integer of 1 to 5, and m is an integer of 1 to 4. The S atom of the thiazolium ring may be substituted with an O atom.

X is SbF ₆ , AsF ₆ , PF ₆ , BF
_4, these anionic derivatives in which at least one fluorine atom is substituted by a hydroxyl group, CF ₃ SO ₃ , Cl
An anion selected from the group consisting of O ₄ , a halogen atom, R—COO, and R—SO ₃ is shown. Here, R is an alkyl group or a phenyl group which may be substituted with an alkyl group, a halogen atom, a nitro group, a cyano group, an alkoxy group, or the like.

The benzothiazolium salt represented by the above general formula includes 3- (p-octadecyloxybenzyl)
Benzothiazolium hexafluoroantimonate, 3
-(P-octadecyloxybenzyl) -2-methylthiobenzothiazolium hexafluoroantimonate,
Examples thereof include 3- (p-octadecyloxybenzyl) benzothiazolium hexafluorophosphate and 3- (p-octadecyloxybenzyl) benzothiazolium tetrafluoroborate.

The compounding amount is usually from 0.01 to 20% by weight, preferably from 0.1 to 5% by weight, based on the epoxy resin of the composition. If the amount is less than 0.01% by weight, curing may be insufficient. Although it is possible to use it in an amount exceeding 20% by weight, it is not preferable because high cost and decomposition products of the catalyst component may cause problems.

Examples of the quinolinium salt include those represented by the following general formula.

[0087]

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In the above formula, R ¹ may be the same or different and each represents a hydrogen atom, a halogen atom, a nitro group, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, a substituted or unsubstituted aromatic group. Group or a heteroaromatic group. Note that the compound has one or more aromatic or heteroaromatic groups having a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms, or a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms. R ² is a group selected from the group consisting of an alkyl group substituted with an aromatic group or a heteroaromatic group and an alkyl group substituted with an unsaturated bond such as ethylene or acetylene. n is an integer of 1 to 7.

X is SbF ₆ , AsF ₆ , PF ₆ , BF
_4, these anionic derivatives in which at least one fluorine atom is substituted by a hydroxyl group, CF ₃ SO ₃ , Cl
An anion selected from the group consisting of O ₄ , a halogen atom, R—COO, and R—SO ₃ is shown. Here, R is an alkyl group or a phenyl group which may be substituted with an alkyl group, a halogen atom, a nitro group, a cyano group, an alkoxy group, or the like.

Examples of the quinolinium salt represented by the above general formula include N-benzyl- (5-octadecyloxy) quinolinium hexafluoroantimonate and N- (1-naphthylmethyl) -5-octadecyloxyquinolinium hexafluoroantimonate , N-cinnamyl-5
-Octadecyloxyquinolinium hexafluoroantimonate and the like.

The compounding amount is usually 0.01 to 20% by weight, preferably 0.1 to 5% by weight, based on the epoxy resin of the composition. If the amount is less than 0.01% by weight, curing may be insufficient. Although it is possible to use it in an amount exceeding 20% by weight, it is not preferable because high cost and decomposition products of the catalyst component may cause problems.

Examples of the pyrrolium salt include those represented by the following general formula.

[0093]

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In the above general formula, R ¹ , R ² and R ³ may be the same or different and each represents a hydrogen atom, a halogen atom, a nitro group, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, It is a substituted or unsubstituted aromatic or heteroaromatic group. Note that the compound has one or more aromatic or heteroaromatic groups having a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms, or a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms. R ⁴ is a hydrogen atom or an alkyl group. n is an integer of 1 to 7.

X is SbF ₆ , AsF ₆ , PF ₆ , BF
_4, these anionic derivatives in which at least one fluorine atom is substituted by a hydroxyl group, CF ₃ SO ₃ , Cl
An anion selected from the group consisting of O ₄ , a halogen atom, R—COO, and R—SO ₃ is shown. Here, R is an alkyl group or a phenyl group which may be substituted with an alkyl group, a halogen atom, a nitro group, a cyano group, an alkoxy group, or the like.

The pyrrolium salts represented by the above general formula include N- (4-octadecyloxybenzyl-N-methylpyrrolinium hexafluoroantimonate,
-Benzyl-N-4-octadecyloxyphenylpyrrolinium hexafluoroantimonate, N- (4-
Octadecyloxybenzyl-N-methylpyrrolinium hexafluorophosphate and the like.

The amount is usually 0.01 to 20% by weight, preferably 0.1 to 5% by weight, based on the epoxy resin of the composition. If the amount is less than 0.01% by weight, curing may be insufficient. Although it is possible to use it in an amount exceeding 20% by weight, it is not preferable because high cost and decomposition products of the catalyst component may cause problems.

Examples of the organosilicon compound represented by the general formula (I-4) include tris (p-hexadecyloxyphenyl) silanol, tris (p-octadecyloxyphenyl) silanol, and tris (p-docosyl). Oxyphenyl) silanol, tris (m-hexadecyloxyphenyl) silanol, tris (m-octadecyloxyphenyl) silanol, tris (m-docosyloxyphenyl) silanol, bis (p-hexadecyloxyphenyl) silanediol, bis (P-octadecyloxyphenyl) silanediol, bis (p-docosyloxyphenyl) silanediol, bis (m-hexadecyloxyphenyl) silanediol, bis (m
-Octadecyloxyphenyl) silanediol, bis (m-docosyloxyphenyl) silanediol, bis (p-hexadecyloxyphenyl) methylsilanol, bis (p-hexadecyloxyphenyl) ethylsilanol, bis (p-hexadecyl) Oxyphenyl) propylsilanol, bis (m-hexadecyloxyphenyl) methylsilanol, bis (m-hexadecyloxyphenyl) ethylsilanol, bis (m-hexadecyloxyphenyl) propylsilanol, tris (6-
Hexadecyloxynaphthyl) silanol, tris (6
-Octadecyloxynaphthyl) silanol, tris (6-docosyloxynaphthyl) silanol, bis (6
-Hexadecyloxynaphthyl) silanediol, bis (6-octadecyloxynaphthyl) silanediol,
And bis (6-docosyloxynaphthyl) silanediol.

Further, the organosilicon compound represented by the above general formula (I-4) may be substituted with a hydrolyzable group instead of a hydroxyl group. Alternatively, the above general formula (I-
The organosilicon compound represented by 4) may have a substituent capable of generating silanol upon irradiation with light. In each case, one of the first curing catalysts of the present invention
It can be used as a component.

Here, the “hydrolyzable group” is a residue directly bonded to silicon, and is hydrolyzed in the presence of water at a certain temperature or higher to form a silanol hydroxyl group represented by the following chemical formula. Residue.

[0101]

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Examples of such groups include alkoxyl groups having 1 to 5 carbon atoms; aryls such as phenoxy, tolyloxy, paramethoxyphenoxy, paranitrophenoxy, benzyloxy, parachlorophenoxy and the like. Oxy group; acetoxy group, propionyloxy group, butanoyloxy group, benzoyloxy group, phenylacetoxy group, formyloxy group and other acyloxy group; vinyloxy group, allyloxy group and other carbon atoms 2
To 12 alkenyloxy groups; aralkyloxy groups such as a benzyloxy group and a phenethyloxy group; and groups represented by the following formulas.

[0103]

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(In the formula, R ′ and R ″ may be the same or different and represent an alkyl group having 1 to 5 carbon atoms.) On the other hand, silicon having a substituent capable of generating silanol upon irradiation with light As the compound, a silicon compound having any of a peroxysilano group, an o-nitrobenzyloxy group, and an α-ketosilyl group is preferable.

The silicon compound having a peroxysilano group can be represented by the following general formula (SI-PO).

[0106]

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(Wherein R ⁴¹ , R ⁴² and R ⁴³ may be the same or different and each represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, a substituted or unsubstituted An aromatic group or a heteroaromatic group, provided that a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms, or a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms, .R ⁴⁴ having one or more aromatic groups represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an aryl group or an aralkyl group, p, q, r Are each an integer of 0 to 3 and 1 ≦ p + q + r ≦ 3.) In the above general formula, a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted hydrocarbon group which can be introduced as R ⁴¹ , R ⁴² and R ⁴³ . Good The group or heteroaromatic group, those enumerated as groups that can be introduced into R ¹¹ to R ¹⁸ in the general formula (I-1) ~ (I -5) can be mentioned.

In the above general formula, chlorine and bromine atoms are exemplified as halogen atoms which can be introduced as R ⁴⁴ , and methyl, ethyl, n-propyl and the like as alkyl groups having 1 to 5 carbon atoms. Isopropyl, n
-Butyl, isobutyl, sec-butyl, tert-butyl, n
-Pentyl, isopentyl and neopentyl groups as C1-C5 alkoxy groups, for example, methoxy, ethoxy, n-propoxy, n-butoxy, sec-butoxy, tert-butoxy and n-pentyloxy groups, aryl Examples of the group include phenyl, naphthyl and anthranyl groups, and examples of the aralkyl group include a benzyl and phenethyl group. These groups may have a substituent such as a halogen atom, a nitro group, a cyano group, and a methoxy group.

Specific examples of the silicon compound having a peroxysilano group include a compound represented by the following formula.

[0110]

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[0111]

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[0112]

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The silicon compound having an o-nitrobenzyloxy group can be represented by the following general formula (SI-NB).

[0114]

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(Wherein R ⁴⁵ , R ⁴⁶ and R ⁴⁷ may be the same or different and each represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, a substituted or unsubstituted group, Wherein a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms, or an aromatic group having a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms, or 1 heteroaromatic group
Have more than one. R ⁴⁸ represents a hydrogen atom, an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, a phenyl group or a substituted phenyl group, and R ⁴⁹ , R ⁵⁰ , R ⁵¹ and R ⁵² may be the same or different. Respectively, a hydrogen atom, a nitro group, a cyano group, a hydroxyl group, a mercapto group, a halogen atom, an acetyl group, an allyl group, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, unsubstituted or substituted aryl A group or an aryloxy group,
p, q and r are each an integer of 0 to 3 and 0 ≦ p + q + r ≦ 3) In the above general formula, a substituted or unsubstituted hydrocarbon group which can be introduced as R ⁴⁵ , R ⁴⁶ and R ⁴⁷ Examples of the substituted or unsubstituted aromatic group or heteroaromatic group include those listed as groups that can be introduced into R ^{11 to} R ¹⁸ in the general formulas (I-1) to (I-5).

In the above general formula, examples of the unsubstituted or substituted alkyl group having 1 to 10 carbon atoms (or 1 to 5 carbon atoms) include a methyl group, an ethyl group, an n-propyl group, an n-butyl group and a tert. -Butyl group, n-pentyl group,
Examples include a chloromethyl group, a chloroethyl group, a fluoromethyl group, and a cyanomethyl group. Examples of the alkoxy group having 1 to 10 carbon atoms (or 1 to 5 carbon atoms) include a methoxy group, an ethoxy group, an n-propoxy group, and a -Butoxy group. Examples of the unsubstituted or substituted aryl group include a phenyl group, a p-methoxyphenyl group, a p-chlorophenyl group and a p-trifluoromethylphenyl group, and the aryloxy group includes
An example is a phenoxy group.

Specific examples of the silicon compound having an o-nitrobenzyloxy group include, for example, tris (p-hexadecyloxyphenyl) (o-nitrobenzyloxy) silane, bis (p-hexadecyloxyphenyl) ) (O-nitrobenzyloxy) methylsilane,
Vinylmethyl (p-hexadecyloxyphenyl) (o
-Nitrobenzyloxy) silane, t-butylmethyl (p-hexadecyloxyphenyl) (o-nitrobenzyloxy) silane, bis (p-hexadecyloxyphenyl) bis (o-nitrobenzyloxy) silane, bis (p- Hexadecyloxyphenyl) bis (o-nitrobenzyloxy) silane, methyl (p-hexadecyloxyphenyl) bis (o-nitrobenzyloxy) silane, t-butyl (p-hexadecyloxyphenyl)
Bis (o-nitrobenzyloxy) silane, tris (p
-Hexadecyloxyphenyl) (3,4,5-trimethoxy-2-nitrobenzyloxy) silane, tris (p-hexadecyloxyphenyl) (4,5,6-trimethoxy-2-nitrobenzyloxy) silane, tris (P-hexadecyloxyphenyl) (5-methyl-
4-methoxy-2-nitrobenzyloxy) silane, tris (p-hexadecyloxyphenyl) (4,5-dimethyl-2-nitrobenzyloxy) silane, and tris (p-hexadecyloxyphenyl) (2,6 -Dinitrobenzyloxy) silane and the like.

The silicon compound having an α-ketosilyl group can be represented by the following general formula (SI-KS).

[0119]

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(Wherein R ⁵³ , R ⁵⁴ and R ⁵⁵ may be the same or different and each represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, a substituted or unsubstituted An aromatic group or a heteroaromatic group, provided that a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms, or a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms, Having one or more aromatic groups, R ⁵⁶ represents a hydrogen atom, a vinyl group, an allyl group,
Alkyl group having 1 to 10 carbon atoms, 1 to 10 carbon atoms
Represents an alkoxy group, an aryl group or an aryloxy group, wherein p, q, and r are each an integer of 0 to 3,
And 1 ≦ p + q + r ≦ 3) In the above general formula, the substituted or unsubstituted hydrocarbon group, substituted or unsubstituted aromatic group or heteroaromatic group which can be introduced as R ⁵³ , R ⁵⁴ and R ⁵⁵ is Examples of the groups that can be introduced into R ^{11 to} R ¹⁸ of the above general formulas (I-1) to (I-5) include those mentioned above.

In the above general formula, examples of the alkyl group having 1 to 10 carbon atoms which can be introduced as R ⁵⁶ include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, a tert-butyl group and a n-butyl group. -A pentyl group, a neopentyl group, an n-hexyl group, an n-heptyl group and an n-octyl group, as an alkoxy group having 1 to 10 carbon atoms, for example, methoxy group, ethoxy group, n-propoxy group, n-
Butoxy group, tert-butoxy group, n-pentyloxy group, neopentyloxy group, n-hexyloxy group, n
Examples of the -heptyloxy group and n-octyloxy group, examples of the aryl group include a phenyl group and a naphthyl group, and examples of the aryloxy group include a phenoxy group and a naphthyloxy group. In addition, these groups may have a substituent such as a halogen atom, a nitro group, a cyano group, and a methoxy group in some cases.

More specific examples of the silicon compound having an α-ketosilyl group include compounds represented by the following formula.

[0123]

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The silicon compound which generates silanol upon irradiation with light is used alone or as a mixture of two or more kinds in the composition. The amount of the silicon compound added is usually 0.1 to the epoxy resin in the composition. It is 001 to 20% by weight, preferably 0.1 to 10% by weight. When the compounding amount is less than 0.001% by weight, curing may be insufficient. In addition, although it is possible to use more than 20% by weight, the cost is high and decomposition products of the catalyst component are reduced. This can be problematic and is not preferred.

Examples of the compound represented by the general formula (I-5) include bis (4-hydroxyphenyl) sulfone monooctadecyl ether, bis (4-hydroxy-3-octadecyloxyphenyl) sulfone, bis (4 -Hydroxyphenyl) sulfide monooctadecyl ether, (4-hydroxyphenyl) octadecyl sulfone, 4.4'-dihydroxydiphenyl ether monooctadecyl ether, and bis (2- (6-hydroxyphenyl)) sulfone monooctadecyl ether.

One or two of the above compounds may be contained in the composition.
More than one kind is used as a mixture, and its addition amount is usually 0.01 to 20% by weight, preferably 0.5 to 10% by weight based on the epoxy resin in the composition. If the amount is less than 0.01% by weight, curing may be insufficient, and it is possible to use more than 20% by weight. May give.

Among the above cationic polymerization catalyst components, the organosilicon compound represented by the general formula (I-4) and the compound represented by the general formula (I-5) are represented by the general formula (II-
It is used in combination with the metal compounds represented by 1), (II-2) and (II-3). In this case, if at least one of the components is repeatedly dissolved and precipitated reversibly in the heating and cooling processes, Well, the other component is not limited. Therefore, in this case, in the above general formulas (I-4) and (I-4
-5) a compound represented by general formula (II-1):
The organometallic compounds represented by (II-2) and (II-3)
A substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms, or an aromatic or heteroaromatic group having a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms
There is no need to have more than one.

Specifically, examples of the organosilicon compound represented by the general formula (I-4) include diphenylsilanediol, triphenylsilanol and the like. As the compound represented by the general formula (I-5), Is bis (4-hydroxyphenyl) sulfone, cyanophenol, nitrophenol, 2,2-dihydroxyphenylpropane,
Catechol, P, P'-biphenol, resorcinol and the like. Examples of the iron aromatic compound represented by the general formula (I-3) include compounds having a simple structure such as tris (ethylacetoacetate) aluminum, tris (acetylacetonato) aluminum, and tris (salicylaldehdate) aluminum. No.

Further, the sulfonium salt represented by the general formula (I-1) and the iodonium salt represented by the general formula (I-2) can be obtained by the above-mentioned general formulas (II-1) and (II-2) , (II
It can be used in combination with the organometallic compound represented by -3). In this case, as described above, the metal compound is not necessarily a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms, or an aromatic group or a heteroaromatic group having a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms. Need not be more than one.

The sulfonium salt represented by the general formula (I-1), the iodonium salt represented by the formula (I-2), and the iron aromatic compound represented by the formula (I-3) are heat-sensitive. In addition to increasing the activity, it has activity against radiation such as light and electron beams. In other words, these sulfonium salts, iodonium salts, and iron aromatic compounds excited by heat or electron beams are curing catalysts that promote the polymerization of cationically polymerizable substances. A resin composition of the invention is prepared.

In the present invention, when the cationically polymerizable substance is a vinyl compound or the like, the polymerization reaction is usually carried out by a solution polymerization method using an inert solvent for a catalyst, a monomer or the like. A polymerization method is also performed. Examples of the solvent include toluene, benzene, aromatic hydrocarbons such as xylene, n-hexane, aliphatic hydrocarbons such as n-heptane, alicyclic hydrocarbons such as cyclohexane, petroleum ether, Hydrocarbon mixtures such as ligroin, halogenated hydrocarbons such as chlorobenzene and dichloroethane can be used, and the polymerization reaction of these vinyl compounds is carried out under normal pressure or pressure, and the reaction temperature is 20 ° C. or higher. , Preferably 60 to 150 ° C, which is industrially easy to heat.

The iodonium salt, sulfonium salt, and iron aromatic compound used as the polymerization catalyst in the present invention do not initiate the cationic polymerization reaction at room temperature. It is also possible to save.

The sulfonium salt, iodonium salt and iron aromatic compound used in the present invention are used in an amount of 0.01 to 20 parts by weight, preferably 0.1 to 20 parts by weight, per 100 parts by weight of the resin.
5 parts by weight. If the amount is less than 0.01 parts by weight, a sufficient polymer cannot be obtained. On the other hand, if the addition amount exceeds 20 parts by weight, favorable properties cannot be obtained after polymerization.
It is not preferable in terms of cost.

Next, the organometallic compound as another component of the first curing catalyst of the present invention will be described in detail. Representative examples of the organometallic compound that can be blended include compounds represented by the following general formulas (II-1), (II-2) and (II-3).

[0135]

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(In the above formula, R ²¹ , R ²² , R ²³ and R ²⁴ may be the same or different and each is a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms.) However, in one ligand, R ²¹ , R ²² ,
It is assumed that at least one of R ²³ and R ²⁴ having 10 or more carbon atoms is included. M is Al, Ti, C
r, Mn, Fe, Co, Ni, Cu, Zr, Zn, B
It is selected from the group consisting of a, Ca, Ce, Pb, Mg, Sn, and V, where n is an integer of 2-4. Examples of the compounds represented by the general formulas (II-1), (II-2), and (II-3) include tris (octadecyl acetoacetate) aluminum, tris (hexadecyl acetoacetate) aluminum, and tris ( Examples include aluminum tetradecylacetoacetate, aluminum tris (dodecylacetoacetate), aluminum tris (octylsalicylaldehyde), aluminum tris (3-octadecylacetylacetate), and compounds represented by the following chemical formula.

[0137]

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[0138]

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[0139]

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Further, aluminum in the above chemical formula is represented by Ti, Cr, Zr, Mn, Fe, Co, Ni,
A chelate compound changed to a Cu, Zr or Zn atom can also be used as a component of the first curing catalyst of the present invention.

Incidentally, the above-mentioned general formulas (II-1) and (II-
2) In the compound represented by (II-3), all the bonds of the metal atom (M) need not be bonded to the ligand, and one alkoxy group may be used instead of the ligand. It may be bonded to a phenoxy group or an acyloxy group. Further, all the bonds may be bonded to these groups.

These organometallic compounds are contained in the composition in an amount of 1%.
Seeds or a mixture of two or more kinds are used, and the amount added is
Usually 0.01 to resin such as epoxy resin in the composition.
-20% by weight, preferably 0.5-10% by weight.
If the amount is less than 0.01% by weight, curing may be insufficient. Although it is possible to use more than 20% by weight, it is not preferable because the cost is high and the catalyst component may adversely affect the physical properties. When these organometallic compounds are used, the ionic substance hardly remains in the cured resin.

The first curing catalyst of the present invention contains at least one of the above-mentioned cationic polymerization catalyst component and the organometallic compound, and may not contain either one of the components. For example, organometallic compounds
The first curing catalyst of the present invention can be constituted by combining with other components such as the following. As the compound that can be used in combination with the organometallic compound, at least one selected from the group consisting of an organosilane having a hydroxyl group directly bonded to a silicon atom, an organosiloxane having a hydroxyl group directly bonded to a silicon atom, and a phenol compound Compounds.

Hereinafter, the organosilane having a hydroxyl group directly bonded to a silicon atom, the organosiloxane having a hydroxyl group directly bonded to a silicon atom, and a phenol compound will be described in detail.

An organic silicon compound having a hydrolyzable group directly bonded to a silicon atom, or a silicon compound capable of generating silanol by light irradiation is also used.
The first curing catalyst can be obtained in combination with the organometallic compound as described above.

Here, the “hydrolysable group” is a residue directly bonded to silicon as described above as a group which can be introduced into the general formula (I-4), and includes the same groups as described above. Can be

The organosilane that can be used can be represented by the following general formula (S-1).

[0148]

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(In the formula, R ¹ represents a hydroxyl group or the above-mentioned hydrolyzable group, and X ¹ , X ² and X ³ may be the same or different and each has 1 to 12 carbon atoms. Alkyl groups; aryl groups such as phenyl, tolyl, paramethoxyphenyl, parachlorophenyl, and paranitrophenyl; aralkyl groups such as benzyl, phenethyl, paramethoxybenzyl, and paramethylbenzyl; vinyl An alkenyl group such as a group, an allyl group, a propenyl group or a butenyl group; or an acyl group such as an acetyl group, a benzoyl group or a trifluoroacetyl group, wherein p, q and r are each an integer of 0 to 3, and p + q + r Is 3 or less) Of the organosilanes, specific examples of the more preferable ones in the first curing catalyst include diphenylsilanediol, Liphenylsilanol, diphenyl (methyl) silanol, phenyl (vinyl) silanediol,
Tri (paramethoxyphenyl) silanol, triacetylsilanol, diphenyl (ethyl) silanol, diphenyl (propyl) silanol, tri (paranitrophenyl) silanol, phenyldivinylsilanol, 2-
Butenyldiphenylsilanol, di (2-pentenyl)
Phenylsilanol, phenyldipropylsilanol,
Examples thereof include silanols such as paramethylbenzyldimethylsilanol, triethylsilanol, trimethylsilanol, tripropylsilanol, tributylsilanol and triisobutylsilanol. Also,
Specific examples of the organosilane having a hydrolyzable group include triphenyl (methoxy) silane, diphenyldimethoxysilane, triphenyl (ethoxy) silane, diphenyl (methyl) methoxysilane, and phenyl (vinyl).
(Methyl) (methoxy) silane, diphenyldiethoxysilane, tri (paramethoxyphenyl) methoxysilane, triacetyl (methoxy) silane, diphenyl (ethyl) (ethoxy) silane, diphenyl (propyl)
(Ethoxy) silane, diphenyl (methyl) (acetoxy) silane, diphenyldipropionyloxysilane,
Diphenyl (methyl) (triphenylacetoxy) silane, tri (paranitrophenyl) (methoxy) silane,
Triacetyl (methoxy) silane, phenyldivinyl (propoxy) silane, 2-butenyldiphenyl (methoxy) silane, di (2-pentenyl) (phenyl) (ethoxy) silane, phenyldipropyl (methoxy) silane, tri (paramethoxy) silane Phenyl) (ethoxy) silane, paramethylbenzyltrimethoxysilane, trifluoroacetyltrimethoxysilane, di (parachlorophenyl) diethoxysilane, triethyl (methoxy) silane, trimethyl (methoxy) silane, tripropyl (methoxy) silane, Examples thereof include tributyl (ethoxy) silane, triisobutyl (acetoxy) silane, and compounds represented by the following chemical formula.

[0150]

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Further, in addition to the above examples, of course, an organosilane having both a hydroxyl group and a hydrolyzable group can also be used.

The organosilane having a hydroxyl group or a hydrolyzable group directly bonded to a silicon atom as described above is
One or more of them may be used in the composition. The amount is based on the epoxy resin in the composition.
Usually 0.001 to 20% by weight, preferably 0.01 to 1%
0% by weight. If the amount is less than 0.001%, curing may be insufficient. Although it is possible to use more than 20 parts by weight, it is not preferable because the cost may be high and the decomposition product of the catalyst component may become a problem.

The organosiloxane that can be suitably used as the first curing catalyst of the present invention is a bifunctional unit represented by the following formula (S-2) and / or the following formula (S-
It is a linear or cyclic siloxane which may have a branch and which comprises a trifunctional unit represented by 3), and may contain a tetrafunctional unit represented by the following formula (S-4) in some cases. Good. Further, this organosiloxane has the following formula (S) when the siloxane chain has a terminal.
It is sealed with a monofunctional unit represented by -5), and in particular, at least one of the structural units contains at least one hydroxyl group or hydrolyzable group.

[0154]

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(Wherein Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ and Y ⁶ may be the same or different;
A hydroxyl group or a hydrolyzable group; an alkyl group having 1 to 12 carbon atoms; an aryl group such as a phenyl group, a tolyl group, a paramethoxyphenyl group, a parachlorophenyl group, a paracyanophenyl group; a benzyl group, a phenethyl group, An aralkyl group such as a methoxybenzyl group and a paramethylbenzyl group; an alkenyl group such as a vinyl group, an allyl group, a propenyl group and a butenyl group; and an acyl group such as an acetyl group, a benzoyl group and a trifluoroacetyl group. Of which, the polymerization degree is 50 or less,
More preferably, the equivalent of the hydroxyl group and / or the hydrolyzable group is 1000 or less, and furthermore, the equivalent is 50 to 500.
Is preferred.

Specific examples of such preferred organosiloxanes include those having a hydroxyl group as 1,3-
Dihydroxy-1,3-dimethyl-1,3-diphenyldisiloxane, 1,5-dihydroxy-1,3,5-trimethyl-1,3,5-triphenyltrisiloxane,
1,7-dihydroxy-1,3,5,7-tetramethyl-1,3,5,7-tetraphenyltetrasiloxane,
1,3-dihydroxytetraphenyldisiloxane,
1,5-dihydroxyhexaphenyltrisiloxane,
1,7-dihydroxyoctaphenyltetrasiloxane, 1,5-dihydroxy-3,3-dimethyl-1,
1,5,5-tetraphenyltrisiloxane, 1,3-
Dihydroxytetra (dimethylphenyl) disiloxane, 1,5-dihydroxyhexaethyltrisiloxane, 1,7-dihydroxyoctapropyltetrasiloxane, 1,3,5-trihydroxy-3-ethyl-1,
1,5,5-tetramethyltrisiloxane, 1,5-dihydroxy-1,1,5,5-tetraphenyl-3,3
-Di-p-tolyltrisiloxane; and compounds represented by the following chemical formula.

[0157]

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Also, a silicone resin available under a trade name such as SH6018 (manufactured by Toray Silicone Co., Ltd .: methylphenylpolysiloxane having a hydroxyl equivalent of 400 and a molecular weight of 1600) can be used.

In general, polysiloxanes represented by the following general formula can also be used.

[0160]

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(In the above formula, R ⁶¹ , R ⁶² , R ⁶³ ,
R ⁶⁴ , R ⁶⁵ and R ⁶⁶ may be the same or different,
A hydroxyl group or a hydrolyzable group;
12 alkyl groups; aryl groups such as phenyl, tolyl, paramethoxyphenyl, parachlorophenyl, and paracyanophenyl; benzyl, phenethyl,
Aralkyl groups such as paramethoxybenzyl group and paramethylbenzyl group; alkenyl groups such as vinyl group, allyl group, propenyl group and butenyl group; acetyl group, benzoyl group,
The above-mentioned organosiloxane having a hydroxyl group directly bonded to a silicon atom is used alone or as a mixture of two or more kinds in the composition. The compounding amount is usually 0.001 to 20% by weight based on the epoxy resin in the composition,
Preferably it is 0.01 to 10% by weight. The blending amount is 0.
If it is less than 001%, curing may be insufficient. Although it is possible to use more than 20 parts by weight, it is not preferable because the cost may be high and the decomposition product of the catalyst component may become a problem.

Examples of the silicon compound which can be blended to generate silanol by light irradiation include a peroxysilano group, o
A silicon compound having either a -nitrobenzyloxy group or an α-ketosilyl group is preferred.

The silicon compound having a peroxysilano group is a compound represented by the general formula (SI-PO) as already described in the general formula (I-4). However,
In this case, R ⁴¹ , R ⁴² and R ⁴³ in the above general formula
A hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an aryl group or an aralkyl group. These may be the same or different.

[0164] As the halogen atoms and the like alkyl group having 1 to 5 carbon atoms include those listed as the group may be introduced into R ^44.

Specific examples of the silicon compound having a peroxysilano group include a compound represented by the following formula.

[0166]

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[0167]

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[0168]

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The silicon compound having an o-nitrobenzyloxy group is a compound represented by the general formula (SI-NB) as already described in the general formula (I-4). However, in this case, R ⁴⁵ , R ⁴⁶ and R ⁴⁷ represent a hydrogen atom, a halogen atom, a vinyl group, an allyl group,
A substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group, an aryloxy group or a siloxy group is introduced. These may be the same or different.

Examples of the halogen atom include chlorine and bromine atoms, and examples of the substituted or unsubstituted alkyl group having 1 to 10 carbon atoms include methyl, ethyl and n.
-Propyl group, n-butyl group, tert-butyl group, n-pentyl group, chloromethyl group, chloroethyl group, fluoromethyl group and cyanomethyl group;
Examples of the 10 alkoxy groups include a methoxy group, an ethoxy group, an n-propoxy group and an n-butoxy group. Examples of the unsubstituted or substituted aryl group include a phenyl group, a p-methoxyphenyl group, a p-chlorophenyl group and a p-trifluoromethylphenyl group, and examples of the aryloxy group include a phenoxy group.

The silicon compound having an o-nitrobenzyloxy group may be a compound having an o-nitrobenzyloxy group as a terminal group and having a main chain represented by the following formula.

[0172]

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(Wherein, s represents an integer of 1 or more;⁶⁷
And R⁶⁸May be the same or different,
Respectively, hydrogen atom, halogen atom, vinyl group, allyl group,
An unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, carbon
An alkoxy group of the formulas 1 to 10, unsubstituted or substituted aryl
X represents an aryl group, an aryloxy group or a siloxy group;
^FourRepresents an oxygen atom, an alkylene group or an aryldiyl group
Represents) the silicon compound having the o-nitrobenzyloxy group
As a specific example of trimethyl (o-nitrobenzyl)
Loxy) silane, dimethylphenyl (o-nitroben)
(Zyloxy) silane, diphenylmethyl (o-nitrobe)
Ndyloxy) silane, triphenyl (o-nitroben)
(Zyloxy) silane, vinylmethylphenyl (o-nito)
Robenzyloxy) silane, t-butylmethylphenyl
(O-nitrobenzyloxy) silane, triethyl (o
-Nitrobenzyloxy) silane, tri (2-chloroe
Tyl) -o-nitrobenzyloxysilane, tri (p-
Trifluoromethylphenyl-o-nitrobenzyloxy
B) silane, trimethyl [α- (o-nitrophenyl)
-O-nitrobenzyloxy] silane, dimethylphenyi
[Α- (o-nitrophenyl) -o-nitrobenzyl
Oxy] silane, methylphenyldi [α- (o-nitro
Phenyl) -o-nitrobenzyloxy] silane, tri
Phenyl (α-ethyl-o-nitrobenzyloxy)
Orchid, trimethyl (3-methyl-2-nitrobenzyl)
Xy) silane, dimethylphenyl (3,4,5-trime
Toxi-2-nitrobenzyloxy) silane, triphe
Nil (4,5,6-trimethoxy-2-nitrobenzyl
Oxy) silane, diphenylmethyl (5-methyl-4-
Methoxy-2-nitrobenzyloxy) silane, trif
Enyl (4,5-dimethyl-2-nitrobenzyloxy)
B) Silane, vinylmethylphenyl (4,5-dichloro
-2-nitrobenzyloxy) silane, triphenyl
(2,6-dinitrobenzyloxy) silane, diphenyl
Methyl (2,4-dinitrobenzyloxy) silane,
Triphenyl (3-methoxy-2-nitrobenzyloxy)
B) Silane, vinylmethylphenyl (3,4-dimethoxy)
C-2-nitrobenzyloxy) silane, dimethyldi
(O-nitrobenzyloxy) silane, methylphenyl
Di (o-nitrobenzyloxy) silane, vinylphenyl
Rudi (o-nitrobenzyloxy) silane, t-butyl
Phenyldi (o-nitrobenzyloxy) silane, die
Tildi (o-nitrobenzyloxy) silane, 2-chloro
Roethylphenyldi (o-nitrobenzyloxy) sila
Diphenyldi (o-nitrobenzyloxy) sila
Diphenyldi (3-methoxy-2-nitrobenzyl)
Oxy) silane, diphenyldi (3,4-dimethoxy-
2-nitrobenzyloxy) silane, diphenyldi
(2,6-dinitrobenzyloxy) silane, diphenyl
Rudi (2,4-dinitrobenzyloxy) silane, methyl
Rutri (o-nitrobenzyloxy) silane, phenyl
Tri (o-nitrobenzyloxy) silane, p-bis
(O-Nitrobenzyloxydimethylsilyl) benze
1,1,3,3-tetraphenyl-1,3-di (o
-Nitrobenzyloxy) disiloxane, 1,1,3,
3,5,5-hexaphenyl-1,5-di (o-nitro
Containing benzyloxy) trisiloxane and SiCl
Reaction between silicone resin and o-nitrobenzyl alcohol
And silicon compounds formed by the reaction.

The silicon compound having an α-ketosilyl group is a compound represented by the general formula (SI-KS) as already described in the general formula (I-4). However, in this case, R ⁵³ , R ⁵⁴ and R ⁵⁵ in the above general formula represent a hydrogen atom, a vinyl group, an allyl group, a carbon atom 1
An alkyl group having 10 to 10, an alkoxy group having 1 to 10 carbon atoms, an aryl group or an allyloxy group is introduced. These may be the same or different.

Examples of the alkyl group having 1 to 10 carbon atoms and the alkoxy group having 1 to 10 carbon atoms which can be introduced into R ⁵³ , R ⁵⁴ and R ⁵⁵ include those listed as the groups which can be introduced into R ^56. .

Specific examples of the silicon compound having an α-ketosilyl group include a compound represented by the following chemical formula.

[0177]

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The silicon compound which generates silanol upon irradiation with light as described above may be used alone or in the composition.
More than one species are used as a mixture, and the amount is usually 0.001 to 20% by weight, preferably 0.01 to 10% by weight, based on the epoxy resin in the composition. 0.0%
If it is less than 01% by weight, curing may be insufficient. Although it is possible to use it in an amount exceeding 20% by weight, it is not preferable because high cost and decomposition products of the catalyst component may cause problems.

Examples of the phenol compound that can be used include those represented by the following general formula (Ph-1).

[0180]

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(In the above general formula (Ph-1), Ar^TwoIs
Represents a substituted or unsubstituted aromatic or heteroaromatic group
And n is an integer of 1 to 10. In the above general formula (Ph-1), Ar^TwoRepresented by
A substituted or unsubstituted aromatic or heteroaromatic group
In the general formulas (I-1) to (I-5), ¹¹~ R¹⁸
Groups such as those that can be introduced into
it can. These substituted aromatic or heteroaromatic
Examples of the substituent of the group include an organic group having 1 or more carbon atoms.
And when there are a plurality of
May also be different. Specific examples of such substituents
Examples include the following organic groups.

[0182]

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[0183]

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More specific examples of the compound represented by formula (Ph-1) include the following compounds.

[0185]

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[0186]

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[0187]

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[0188]

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These phenol compounds can be used alone or in combination of two or more.

When the phenol compound as described above is blended in the first curing catalyst of the present invention, the blending amount is preferably about 0.1 to 50% by weight based on the resin. If the amount is less than 0.1% by weight, it is difficult to sufficiently promote the curing reaction. On the other hand, 50% by weight
If it exceeds, the cost tends to be high and the mechanical strength of the cured product tends to decrease.

Examples of the organosilicon compound having a hydrolyzable group directly bonded to a silicon atom include alkoxyl groups having 1 to 5 carbon atoms; phenoxy, tolyloxy, paramethoxyphenoxy, paranitrophenoxy, and benzyloxy. An aryloxy group such as a group or parachlorophenoxy group; an acyloxy group such as an acetoxy group, a propionyloxy group, a butanoyloxy group, a benzoyloxy group, a phenylacetoxy group or a formyloxy group; the number of carbon atoms such as a vinyloxy group or an allyloxy group 2 to 12 alkenyloxy groups; aralkyloxy groups such as benzyloxy group and phenethyloxy group; and organosilicon compounds having a group represented by the following formula.

[0192]

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(Wherein R ′ and R ″ may be the same or different and represent an alkyl group having 1 to 5 carbon atoms) Hydrolyzable directly bonded to a silicon atom as described above The organosilicon compound having a group is used alone or as a mixture of two or more in the composition, and the compounding amount is usually 0.001 to 20% by weight, preferably 0.001 to 20% by weight, based on the epoxy resin in the composition. If the amount is less than 0.001%, the curing may be insufficient, and it is possible to use more than 20 parts by weight. In some cases, high cost and decomposition products of the catalyst component may cause problems, which is not preferable.

Next, the second curing catalyst of the present invention will be described. The second curing catalyst of the present invention has the general formula (III)
-1 ') and at least one compound selected from the group consisting of compounds represented by (III-2).

In the general formula (III-1 ′), R ¹ ,
Examples of the hydrocarbon group that can be introduced as R ² and R ³ include the groups listed as those that can be introduced into R ^{11 to} R ¹⁸ in the general formulas (I-1) to (I-5). . It is more preferable that R ¹ , R ² , and R ³ each be an aromatic group or a heteroaromatic group having a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms.

Specifically, compounds represented by the above general formula (III-1 ′) include bis (p-octadecyloxyphenyl) butylphosphine, bis (m-octadecyloxyphenyl) butylphosphine, and bis (p-octadecyloxyphenyl) butylphosphine. -Octadecyloxyphenyl) decylphosphine, p-octadecyloxyphenyldibutylphosphine, p-octadecyloxyphenyloctadecylphosphine and the like.

As the compound represented by the general formula (III-1 ′), the compound represented by the general formula (III-1) can be used. The general formula (III-1)
And a hydrocarbon group which can be introduced as R ^{31 in the} general formula (III-2), R ³² , R ³³ , R ³⁴ and R ³⁵
Examples of the hydrocarbon group which can be introduced as R 1 include the groups listed as those which can be introduced into R ^{11 to} R ¹⁸ in the general formulas (I-1) to (I-5). Further, such a hydrocarbon group may contain a hetero atom such as F, Si, O, N, or S.

As the compound represented by the general formula (III-1), for example, the following compounds can be mentioned.

[0199]

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[0200]

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Examples of the compound represented by the formula (III-2) include the following.

[0202]

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The formula (III-1) or the formula (III-
Examples of the anionic catalyst used in the same manner as in 2) include the following compounds.

Specific anionic compounds include linear tertiary amines, piperazine, pyridine, picoline,
1,8-diazabicyclo [5.4.0] undecene-
Derivatives such as 1, benzylamine, 2- (aminomethyl) phenol, and 2,4,6-tris (aminomethyl) phenol can be used. These derivatives include halogen atoms, nitro groups, cyano groups, hydrogen atoms,
A substituted or unsubstituted hydrocarbon group having 30 or more substituted or unsubstituted hydrocarbon groups, an aromatic group or a heteroaromatic group having a substituted or unsubstituted hydrocarbon group, and further having 10 or more carbon atoms; or It has at least one aromatic or heteroaromatic group having a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms.

It is preferred that the above-mentioned second curing catalyst of the present invention is blended at a ratio of 0.01 to 20% by weight with respect to the resin component to prepare a resin composition. 0.01
When the amount is less than 20% by weight, it is difficult to sufficiently promote the curing reaction. On the other hand, when the amount exceeds 20% by weight, the cost tends to be high and the mechanical strength of the cured product tends to decrease.

The first curing catalyst of the present invention contains at least one of a cationic polymerization catalyst component and an organometallic compound, and has the property that it can be dissolved and deposited reversibly by heating and cooling. are doing. The second curing catalyst contains at least one atom selected from the group consisting of P and N atoms, has a property of being uniformly dissolved by heating in an epoxy resin, and further being precipitated in a cooling process. I have. Precipitation in this case means that the curing catalyst takes the form of colloids, micelles, crystals, and the like in the epoxy resin.
This shows a state in which the P atom portion is shielded from a reactive site such as an epoxy group, an ester group, or a phenolic hydroxyl group by taking the above-described form. In order to create this state, for example, a compound having a substituted or unsubstituted hydrocarbon group having a large number of carbon atoms is effective.

The hydrocarbon group having a large number of carbon atoms specifically means a hexadecyl group, an octadecyl group, a docosyl group and the like.

Next, the resin composition of the present invention will be described in detail. The resin composition of the present invention contains the above-described first or second curing catalyst of the present invention and a curable resin component. As the curable resin component, a cationic polymerizable resin component can be used, and specific examples include an epoxy resin, a resin having a vinyl ether group, a resin containing lactone, styrene, or vinyl thioether.

Hereinafter, the epoxy resin will be described in detail using an example. The epoxy resin that can be used is not particularly limited. For example, a glycidyl ether type epoxy resin which is a reaction product of a novolak compound and epichlorohydrin, a diallyl bisphenol compound having an allyl group at the ortho position of each hydroxyl group of bisphenol A Glycidyl ether type epoxy resin, which is a reaction product of phenol and epichlorohydrin, can be used. Among these compounds, an epoxy resin obtained using bisphenol A is preferable in order to maintain the flexibility of the cured product. Furthermore, the molecular weight is 300-5000,
Those having an epoxy equivalent of 150 to 2500 are preferred.

The epoxy resin used in the resin composition according to the present invention may be an alicyclic epoxy compound. The alicyclic epoxy compound is an alicyclic compound in which a ring is directly epoxidized, and examples thereof include those represented by the following structural formula.

[0211]

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In the above general formula, R is an organic group containing an alkyl group, an ether bond, an ester bond, a thioether bond, or a spiro ring, and binds two or more epoxidized rings. Further, n is an integer of 1 or more.

The following are specific examples of the alicyclic epoxy compound.

[0214]

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For example, Chissonox 221 (trade name,
(Chisso). The epoxy equivalent of the alicyclic epoxy compound is not particularly limited, but the epoxy equivalent is preferably 200 or less from the viewpoint of increasing the curing speed.

Further, as the epoxy resin used in the resin composition according to the present invention, an epoxy compound having an epoxy group and an unsaturated double bond in the molecule can also be used. As the epoxy group in this epoxy compound,
For example, groups represented by the following formula can be mentioned.

[0219]

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The group having an unsaturated double bond in this epoxy compound includes, for example, a group represented by the following formula.

[0219]

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[0220]

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The number of the epoxy group and the number of unsaturated double bonds present in one molecule of the epoxy compound may be any number as long as it is at least one, but may be in the range of two to five. preferable. When there are a plurality of groups having an epoxy group and an unsaturated double bond, they do not necessarily have to be the same, and two or more kinds may be mixed.

In the epoxy group and the group having an unsaturated double bond, a hydrogen atom bonded to a carbon atom may be, for example, a halogen atom such as a chlorine atom, a bromine atom or a fluorine atom or a carbon atom. It may be substituted with 1 to 12 alkyl groups. Examples of such an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, Examples include a neopentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a dodecyl group.

The structure of the epoxy compound having an epoxy group and an unsaturated double bond is arbitrarily selected depending on the use. An epoxy compound having a desired structure is, for example, an unsaturated carboxylic acid and a normal epoxy compound,
It can be obtained by reacting in an organic solvent in the presence of a catalyst such as choline chloride.

As the unsaturated carboxylic acid used herein, for example, acrylic acid, methacrylic acid, cinnamic acid, maleic acid and derivatives thereof can be mentioned.
Further, as the epoxy compound, at least one
Any one having two epoxy groups may be used, and any of a monofunctional epoxy compound and a polyfunctional epoxy compound may be used.

The monofunctional epoxy compound includes, for example, ethylene oxide, propylene oxide, butylene oxide, styrene oxide, phenyl glycidyl ether and butyl glycidyl ether.

The polyfunctional epoxy compound is not particularly limited as long as it is generally known as an epoxy resin. For example, bisphenol A type epoxy resin; bisphenol F type epoxy resin; phenol novolak type Epoxy resin; Alicyclic epoxy resin; Heterocyclic epoxy resin such as triglycidyl isocyanurate and hydantoin epoxy; Hydrogenated bisphenol A type epoxy resin; Aliphatic such as propylene glycol-diglycidyl ether and pentaerythritol-polyglycidyl ether Epoxy resin; glycidyl ester type epoxy resin obtained by reaction of aromatic, aliphatic or alicyclic carboxylic acid with epichlorohydrin;
Spiro ring-containing epoxy resin; glycidyl ether type epoxy resin which is a reaction product of o-allyl-phenol novolak compound and epichlorohydrin; A glycidyl ether type epoxy resin which is a reaction product can be exemplified.

Specific examples of the epoxy compound having an epoxy group and an unsaturated double bond include the following compounds.

[0228]

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[0229]

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[0230]

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Further, an acryl group in the above formula: —COO
CH = CH ₂ is, methacryl group: -COOC (CH ₃₎ = CH compound which is converted to _2.

In the resin composition according to the present invention, a compound having an unsaturated double bond such as a methacrylic resin or an acrylic resin can be optionally compounded according to the purpose. Further, maleimides can be blended to increase the mechanical strength at high temperatures. As such maleimides, the following general formula

[0233]

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(In the formula, X is a divalent hydrocarbon group such as an alkylene group, a cycloalkylene group, a monocyclic or polycyclic arylene group, or —CH ₂ —, —CO—, —S
N, N'-substituted bismaleimide represented by the following general formula: which is a divalent hydrocarbon group bonded by a divalent atomic group such as O ₂ -or -CONH-

[0235]

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In the formula, poly (phenylmethylene) polymaleimide represented by the formula: More specifically, for example, N, N′-phenylenebismaleimide, N, N′-hexamethylenebismaleimide, N, N′-diphenylmethanebismaleimide,
N, N'-oxy-di-p-phenylenebismaleimide, N, N'-4,4'-benzophenonebismaleimide, N, N'-p-diphenylsulfonebismaleimide, N, N '-(3,3 '-Dimethyl) methylene-di-
p-phenylenebismaleimide, poly (phenylmethylene) polymaleimide, 2,2-bis (4-phenoxyphenyl) propane-N, N′-bismaleimide, bis (4-phenoxyphenyl) sulfone-N, N′-bis Maleimide, 1,4-bis (4-phenoxy) benzene-N, N′-bismaleimide, 1,3-bis (4-phenoxy) benzene-N, N′-bismaleimide, 1,3
-Bis (3-phenoxy) benzene-N, N'-bismaleimide.

It is preferable that the maleimide is blended in a range of 1 to 70% by weight based on a resin such as an epoxy resin. If the amount exceeds 70% by weight, the cured product tends to become brittle and the curing properties tend to deteriorate. If the amount is less than 1% by weight, the effect of adding the maleimide is not sufficiently exhibited.

An inorganic filler may be added to the resin composition according to the present invention according to the purpose. The inorganic filler that can be used is not particularly limited as long as it can be generally combined with a resin, and examples thereof include fused silica, crystalline silica, alumina, silicon nitride, and aluminum nitride.

Further, the mixing ratio of the inorganic filler is preferably in the range of 40 to 90% by volume in the whole resin composition. If the compounding ratio is less than 40% by volume, the thermal expansion coefficient increases and the thermal stress increases, and if it exceeds 90% by volume, the fluidity of the resin composition tends to decrease.

The resin composition of the present invention may further contain a photosensitizer to further promote curing. The photosensitizer is not particularly limited as long as it can photosensitize the compound, and is appropriately selected according to the type of the compound used, the light source, and the like. Specifically, for example, aromatic hydrocarbons and derivatives thereof, benzophenone and derivatives thereof, o-benzoyl benzoate and derivatives thereof, acetophenone and derivatives thereof, benzoin and benzoin ether and derivatives thereof, xanthones and derivatives thereof,
Thioxanthone and its derivatives, disulfide compounds, quinone compounds, halogenated hydrocarbon-containing compounds and amines can be used as photosensitizers.

More specifically, examples of aromatic hydrocarbons and derivatives thereof include benzene, benzene-d6, toluene, p-xylene, fluorobenzene, chlorobenzene, bromobenzene, iodobenzene, naphthalene,
-Methylnaphthalene, 2-methylnaphthalene, 1-fluoronaphthalene, 1-chloronaphthalene, 2-chloronaphthalene, 1-bromonaphthalene, 2-bromonaphthalene, 1-iodonaphthalene, 2-iodonaphthalene, 1
-Naphthol, 2-naphthol, biphenyl, fluorene, p-terphenyl, acenaphthene, p-quaterphenyl, triphenylene, phenanthrene, azulene,
Fluoranthene, chrysene, pyrene, 1,2-benzpyrene, anthracene, 1,2-benzanthracene,
Mention may be made of 9,10-dichloroanthracene, 9.10-dibromoanthracene, 9,10-diphenylanthracene, perylene, tetracene and pentacene.

Examples of benzophenone and its derivatives include benzophenone, 2,4-dimethylbenzophenone, 2,4-dichlorobenzophenone and 4,4'-
Bis (dimethylamino) benzophenone can be mentioned.

Examples of o-benzoyl benzoate and its derivatives include o-benzoyl benzoate methyl ester, o-benzoyl benzoate ethyl ester, o-benzoyl benzoate ethyl ester
-Benzoylbenzoic acid phenyl ester and a compound represented by the following formula.

[0244]

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Examples of acetophenone and its derivatives include acetophenone, 4-methylacetophenone,
-Methylacetophenone and 3-methoxyacetophenone.

Examples of benzoin, benzoin ether and derivatives thereof include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin triphenylsilyl ether and compounds represented by the following chemical formula. it can.

[0247]

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Examples of xanthone and its derivatives include xanthone, 2,4-dimethylxanthone and 2,4-dichloroxanthone.

Examples of thioxanthone and its derivatives include thioxanthone, 2,4-dimethylthioxanthone and 2,4-dichlorothioxanthone.

Examples of the disulfide compound include a compound represented by the following formula.

[0251]

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(Here, Et represents an ethyl group, and is similarly abbreviated hereinafter.) Examples of quinone compounds include benzoquinone, naphthoquinone, anthraquinone, 5,12-naphthacenedione and 2,7-pyrenedione. be able to.

Examples of the halogenated hydrocarbon-containing compound include carbon tetrachloride, hexachloroethane, carbon tetrabromide and compounds represented by the following formula.

[0254]

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[0255]

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Examples of the amines include diphenylamine, carbazole, triphenylamine and compounds represented by the following formula.

[0257]

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Further, specific examples of the photosensitizer other than those described above include propiophenone, anthrone, benzaldehyde, butyrophenone, 2-naphthylphenylketone,
-Naphthaldehyde, 2-acetonaphthone, 1-naphthyl phenyl ketone, 1-acetonaphthone, 1-naphthaldehyde, fluorenone, 1-phenyl-1,2-propanedione, benznitrile, acetone, biacetyl,
Examples thereof include acridine orange, acridine, rhodamine B, eosin, fluorescein, and a compound represented by the following formula.

[0259]

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These photosensitizers can be used alone or in combination of two or more, and the amount thereof is usually 0.001 to 10% by weight, preferably 0.1 to 10% by weight, based on the resin.
01 to 5% by weight. When the amount is less than 0.001% by weight, the effect of adding the photosensitizer is not sufficiently exhibited, and when it exceeds 10% by weight, the mechanical strength of the cured product tends to decrease.

In the resin composition of the present invention, curing agents such as acid anhydrides, phenols, aromatic amine compounds and cyanate ester compounds may be further added.

Specific examples of the acid anhydride that can be used as a curing agent include phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl-tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride,
Nadic anhydride, methylnadic anhydride, chlorendic anhydride, dodecyl succinic anhydride, methyl succinic anhydride, benzophenone tetracarboxylic anhydride, pyromellitic anhydride, and maleic anhydride .

The compounding amount of these acid anhydrides is preferably an amount equivalent to 0.1 to 1.1 times the equivalent of the epoxy resin. If the equivalent of the acid anhydride exceeds 1.1 times, unreacted acid anhydride may be left in the system and deteriorate the properties of the cured product. The effect of adding the anhydride is not sufficiently exhibited.

Specific examples of phenols that can be used as a curing agent include, for example, phenol resins, phenol novolak resins, cresol novolak resins, and polyvinyl phenol.

The compounding amount of these phenols is preferably an amount equivalent to 0.1 to 1.1 times the equivalent of the epoxy resin. If the equivalent of phenols exceeds 1.1 times, unreacted phenols may be left in the system and deteriorate the properties of the cured product,
If it is less than 0.1 times, the effect of adding phenols is not sufficiently exhibited.

Further, examples of the aromatic amine compound which can be used as a curing agent include 4,4'-diaminodicyclohexylmethane, 1,4-diaminocyclohexane, 2,6-diaminopyridine, m-phenylenediamine, -Phenylenediamine, 4,4'-diaminodiphenylmethane, 2,2'-bis (4-aminophenyl) propane, 4,4'-diaminodiphenyl oxide, 4,4'-diaminodiphenylsulfone, bis (4
-Aminophenyl) methylphosphine oxide, bis (4-aminophenyl) methylamine, 1,5-diaminonaphthalene, m-xylylenediamine, 1,1-bis (p-aminophenyl) furatan, p-xylylenediamine, Hexamethylenediamine, 6,6'-diamino-
2,2′-dipyridyl, 4,4′-diaminobenzophenone, 4,4′-diaminoazobenzene, bis (4-aminophenyl) phenylmethane, 1,1-bis (4-aminophenyl) cyclohexane, 1,1- Bis (4-aminophenyl-3-methylphenyl) cyclohexane,
2,5-bis (m-aminophenyl) -1,3,4-oxadiazole, 2,5-bis (p-aminophenyl)
-1,3,4-oxadiazole, 2,5-bis (m-
Aminophenyl) thiazolo (4,5-d) thiazole,
5,5'-di (m-aminophenyl) -2,2'-bis (1,3,4-oxadiazolyl), 4,4'-diaminodiphenyl ether, 4,4'-bis (p-aminophenyl)- 2,2′-dithiazole, m-bis (4-p
-Aminophenyl-2-thiazolyl) benzene, 4,
4'-diaminobenzanilide, 4,4'-diaminophenylbenzoate, N, N'-bis (4-aminobenzyl) -p-phenylenediamine, 4,4'-methylenebis (2-chloroaniline), 2,2 -Bis [4- (4
-Aminophenoxy) phenyl] propane, bis [4-
(4-aminophenoxy) phenyl] sulfone, 1,4
-Bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, and 1,3-bis (3-aminophenoxy) benzene can be mentioned.

The amounts of these aromatic amine compounds are as follows:
Preferably, the equivalent is 0.1 to 1.1 times the epoxy equivalent. If the equivalent of the amine compound exceeds 1.1 times, unreacted amine compound may be left in the system and the properties of the cured product may be deteriorated.
If it is less than 1, the effect of adding the amine compound is not sufficiently exhibited.

Examples of the cyanate ester compound which can be used as a curing agent include phenol novolak cyanate, hexafluorobisphenol A dicyanate, ethylidene bis-4,4-phenylenediocyanate, and 4,4 '-(1,3-phenylenediisopropylate). Ridene) diphenyl cyanate, tetrafluoromethylbisphenol F dicyanate, tetraorthomethylbisphenol A dicyanate and the like. Also, at least one cyanate ester compound selected from the group consisting of cyanate esters in which 50% or less of a cyanate group derived from these cyanate ester compounds is polymerized can be used.

Since the cyanate ester compound is ethylidene-4,4-phenylenediocyanate and the cyanate ester obtained by polymerizing 50% or less of a cyanate group derived from the cyanate ester compound is a liquid at room temperature, it has a low viscosity curing agent. Can be suitably used.
Therefore, it is preferable to use in combination with a liquid epoxy resin.

The compounding amount of the cyanate ester compound is preferably 0.30 to 0.70 with respect to the total amount of the liquid epoxy resin and the cyanate ester compound.
When heated, the cyanate ester group alone trimerizes to form a triazine ring, giving a cured product having excellent heat resistance, but has insufficient adhesion to metals, printed wiring boards, etc., and has a high temperature and high humidity. The water absorption at the bottom was large and the moisture resistance was not sufficient. Such disadvantages can be remedied by curing in combination with an epoxy resin.
If the compounding ratio of the cyanate ester compound exceeds 0.70, the heat resistance represented by the glass transition temperature decreases, and the reliability in the thermal cycle test decreases, which is not preferable. It is not preferable because the adhesion to a metal or an organic substrate is reduced, and the moisture resistance reliability in a PCT test is lowered.

The resin composition of the present invention can be polymerized and cured by heat treatment or irradiation, and in some cases, heating and irradiation can be used in combination.
At the time of polymerization, a solvent can be used if necessary.

Particularly, when the resin composition according to the present invention contains a compound which accelerates curing by irradiation with light, such as a compound which generates an acid or an acidic substance upon irradiation with light or a photosensitizer, the resin composition Irradiation when curing. The wavelength of the radiation varies depending on the compound and the composition of the contained compound, but is usually 180 to 700 nm,
In particular, ultraviolet light having a wavelength of 250 to 400 nm is most efficient.

The light source may be any light source that is generally used for photocuring, such as a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, a xenon lamp, a carbon arc lamp, and a metal lamp. a halogen lamp, a xenon - mercury lamp, a xenon lamp, a hydrogen discharge tube, a tungsten lamp, a halogen lamp, sodium discharge tubes, neon discharge tube, argon discharge tube, the He-Ne laser, Ar ion laser, N ₂ laser, Cd ion laser, He-Cd lasers and dye lasers can be mentioned. Furthermore, the resin composition of the present invention is polymerized by irradiation with an electron beam,
Can be cured. At the time of curing, one or more kinds selected from the group consisting of these light sources are appropriately used.

The curing catalyst according to the invention is usually activated at a temperature of from 60 to 250 ° C. Therefore, curing of the resin composition according to the present invention containing the curing catalyst is performed in the above temperature range for several minutes to several hours.

The resin composition of the present invention contains a curing catalyst having the property of being uniformly dissolved in a resin by heating and of being precipitated during a cooling process. The curing catalyst of the present invention does not exhibit catalytic activity at room temperature because the active site is shielded.

For example, when an epoxy resin composition containing a first curing catalyst containing an organometallic compound and a specific organosilane or the like is cured, first, the organometallic compound is heated as described above. It loses its shape and dissolves completely in the epoxy resin. Thus, an active site appears, and then an epoxy group is polymerized by interacting with a compound such as a specific organosilane or a phenol compound.

In the case of an epoxy resin composition containing the first cationic polymerization catalyst, the above-mentioned form is broken by heat and completely dissolved in the epoxy resin. Next, at around 150 ° C., cationic species such as protons are generated from the cationic polymerization catalyst, and polymerization of the epoxy group is started.

In the case of an epoxy resin composition containing a second curing catalyst, the above-mentioned form is broken by heat and completely dissolved in the epoxy resin. Next, the reaction is started by acting on the epoxy group, the carbonyl group of the curing agent and the phenolic hydroxyl group.

As described above, all of the curing catalysts of the present invention do not exhibit catalytic activity at room temperature because the active sites are blocked at room temperature, and the reaction does not proceed at all. However, once dissolved by heat, the reaction proceeds rapidly. For this reason, the above-mentioned curing catalyst has a potential. Therefore, the curing catalyst of the present invention has both high storage stability and excellent curing characteristics. That is, the curing catalyst according to the present invention enhances the storage stability of the resin composition at about room temperature, enables long-term storage, and does not deteriorate the electrical insulation of the resin.

Further, the resin composition of the present invention containing such a curing catalyst has not only high storage stability and excellent curing properties, but also properties such as excellent electrical insulation properties and mechanical strength after curing. I have.

Further, the composition containing a cationically polymerizable vinyl compound enables one-pack storage of a monomer and a catalyst, which has been difficult in the past, and further enables a cationic polymerization reaction at room temperature or higher and a simple heating method. Thus, it became possible to obtain a polymer having a high degree of polymerization which was practical.

In the resin composition of the present invention, a liquid epoxy resin is used, and as a curing catalyst, the organometallic compounds represented by the above general formulas (II-1) to (II-3) and a specific organosilane are used. And a phenolic compound or the like, or a second curing catalyst represented by the above general formula (III-1) or (III-2) as a curing catalyst, or a second curing catalyst represented by the above general formula (I-1) ), (I-2), (I
When the curing catalyst represented by -3) is blended, a liquid epoxy resin composition that can be suitably used for manufacturing a resin-sealed semiconductor device is obtained. That is, the general formula (II-
1) selected from the group consisting of organometallic compounds represented by (II-3), an organosilane having a hydroxyl group directly bonded to a silicon atom, an organosiloxane having a hydroxyl group directly bonded to a silicon atom, and a phenol compound. A liquid epoxy resin composition comprising a first curing catalyst containing at least one compound. The amount of each component is as described above.

Further, the liquid epoxy resin composition contains an inorganic filler as an essential component. Although the liquid epoxy resin composition can be prepared by blending the above-mentioned curing agent, it is most preferable to use an acid anhydride.

The inorganic filler is not particularly limited as long as it is an inorganic filler in which the viscosity, fluidity and filling properties of the obtained liquid epoxy resin composition are sufficiently considered. .

Thus, fused silica, crystalline silica, glass, talc, alumina, calcium silicate, calcium carbonate, barium sulfate, magnesia, silicon nitride, boron nitride, aluminum nitride, magnesium oxide, beryllium oxide, mica, magnesium titanate , Barium titanate, and others can be used, and these can be used alone or in combination of two or more (regardless of the same type or different types). Particularly, fused silica and crystalline silica are preferable.

As the shape of the inorganic filler, crushed, spherical, subspherical, fibrous, scale pen-shaped and other shapes can be used, and one or more of these shapes may be used. You may mix and use.

Of these, the average particle diameter is 10 μm in consideration of the filling property of the liquid epoxy resin composition into the fine gaps.
Below, spherical and sub-spherical fillers are particularly preferred.

Incidentally, aiming at the reinforcing effect of crack resistance,
A fibrous material can also be used.

As the fibrous inorganic filler, titania,
Aluminum borate, silicon carbide, silicon nitride, potassium titanate, basic magnesium, zinc oxide, graphite, magnesia, calcium sulfate, magnesium borate, titanium diboride, α-alumina, chrysotile, wollastonite, and other Whiskers, E glass fiber, silica alumina fiber, silica glass fiber, and other amorphous fibers, silicon carbide fiber, zirconia fiber, γ-alumina fiber, α-alumina fiber, PAN-based carbon fiber, pitch-based carbon fiber, And other crystalline fibers, and other fibers can be used. These fibers can be used alone or in combination of two or more (regardless of the same type or different types). Among the above-mentioned inorganic fillers, acidic or neutral ones are preferably used.

As the fibrous inorganic filler, an average fiber diameter of 5
μm or less and a maximum fiber length of 10 μm or less are preferable from the viewpoint of filling property to details.

The inorganic filler can be used in a range of 30% by weight or more and 80% by weight or less based on the total amount of the liquid epoxy resin composition. 30% by weight of inorganic filler
If it is less than 1, the thermal expansion coefficient of the cured product becomes large and the thermal shock resistance becomes insufficient. On the other hand, when the content exceeds 80% by weight, the fluidity of the epoxy resin composition for resin encapsulation is insufficient, and the filling property into the gap is reduced, which may cause unfilling.

As described above, other inorganic fillers can be used in combination with the inorganic filler that can be used in the present invention. However, the fluidity and storage stability of the liquid epoxy resin composition, the semiconductor element and the substrate It is desired to determine the blending amount and the like so as not to impair the filling property of the gap between the two.

In addition to the above-described components, the liquid epoxy resin composition of the present invention may further contain the following optional components.

(1) Thermoplastic resins, rubber components, various oligomers, and others Others are added for the purpose of lowering the modulus of elasticity of the liquid epoxy resin composition of the present invention in order to improve crack resistance. is there. Specific examples of the thermoplastic resin include polyamide resin, aromatic polyester resin, phenoxy resin, butyral resin, MBS resin, ABS resin, silicone resin, silicone rubber, fluoro rubber, and others.

(2) Various plastic powders, for example, various engineering plastic powders, and others These are added to impart low stress. The maximum particle size of the above component imparting low stress properties is 10 μm or less, preferably 5 μm or less. When the particle size is larger than the particle size of each component in the liquid epoxy resin composition of the present invention, unfilling occurs at the time of filling.

(3) If necessary, silane coupling agents, other surface treating agents for fillers, adhesion promoters, natural waxes, synthetic waxes, linear fatty acids and metal salts thereof, acid amides, Paraffins, and other release agents, carbon black, titanium dioxide, and other pigments, halogen compounds, phosphorus compounds, and other flame retardants, antimony trioxide, and other flame retardants, silicone compounds, Organic rubber and other low stress imparting agents, hydrotalcites, and other ion scavengers, petroleum resins, rosins, terpenes, indene resins, other tackifiers, and other various additives are appropriately compounded. May be.

[0297] The liquid epoxy resin composition of the present invention can be produced by a generally well-known method using predetermined raw materials. More specifically, the liquid epoxy resin composition of the present invention provides a predetermined amount of each component as a raw material,
A universal mixer, a method of mixing and stirring by supplying to a mixer such as a concentric twin-screw mixer, or after pre-mixing, further using a three-roll, a ball mill, a mill, a homogenizer, and a filler component and a resin component. Can be obtained by a method of uniformly mixing, and one or a combination of two or more of these methods.

The resulting liquid epoxy resin composition of the present invention has a viscosity at 60 ° C. of preferably 200 poise or less, particularly preferably 100 poise or less.

If the poise exceeds 200 poise, the fillability of the gap between the flip-chip connected chip and the substrate becomes poor, and the moldability of the semiconductor device may be reduced.

The obtained liquid epoxy resin composition of the present invention can be used not only as a resin sealing composition for semiconductor elements but also for other uses.

Typically, precision electronic parts, precision electric parts, automobile parts, aerospace materials, sliding materials, heat-resistant laminates, mounting agents, casting materials, heat-resistant adhesives, heat-resistant paints, and other fields Can also be used.

The liquid epoxy resin composition of the present invention produced as described above is filled in a dispenser which is a part of a semiconductor resin sealing machine, and is filled with BGA, CSP, CO
G, COR and multi-chip modules, and others, are effectively used for resin sealing of semiconductor devices having chip semiconductor elements connected on a substrate by flip chip connection.

[0303] The resin-encapsulated semiconductor device of the present invention typically comprises a liquid epoxy resin composition filled in a dispenser in the gap between the flip-chip connected chip and the substrate as described above. After filling by discharging a certain amount, by a general resin sealing method such as heating and curing at a temperature of about 120 to 180 ° C. for about 0.5 to 10 hours,
It can be easily manufactured.

The semiconductor element (chip) resin-sealed with the liquid epoxy resin composition of the present invention is, for example, a diode, a transistor, a thyristor, an IC, an L
SI, VLSI, CCD, RAM, DRAM, ROM,
And other elements, but are not limited thereto.

Further, the resin-encapsulated semiconductor device according to the present invention includes a personal computer, an electronic calculator, a control machine, a liquid crystal display, a card, a calculator, a clock, an electronic thermometer, a tape recorder, a VTR, small and other mechanical and electronic devices. Used in the manufacture of appliances, home appliances, and other things, but is not limited to these. When the resin composition of the present invention has a light transmitting property, the
An optical semiconductor device such as an ED device can also be manufactured.

The resin composition of the present invention can be applied to various uses other than the semiconductor device sealing. Specifically, the resin composition of the present invention is preferably used as an electrical insulating material, an adhesive, a printed circuit board, a laminate, a paint, and further as a metal surface or a wooden product, a coating material on a surface of rubber or plastic, or the like. be able to.

[0307]

BEST MODE FOR CARRYING OUT THE INVENTION Example I Examples (I-1 to I-30) Epoxy resin compositions having the compositions shown in the following Tables 1 to 3 were mixed in the same amounts as shown in Tables 1 to 3. Prepared. In addition, the compounding amount in a table | surface is shown by a weight part, and it is the same also in a following table.

For each of the obtained compositions, the gelation time (150 ° C. in all of Examples I-1 to I-30), the storage stability at room temperature, and the mechanical strength after curing were measured. At this time, the time until the viscosity of the composition doubled was measured as the storage stability at room temperature, and the bending strength at room temperature was measured as the mechanical strength after curing. Further, the bending strength was measured at 120 ° C. 1 in Examples I-1 to I-6.
Time, 150 ° C. for 1 hour, and in Examples I-7 to I-12 and I-30, 80 ° C. for 1 hour, 150 ° C. for 1 hour, Example I
-13 to I-16, I-21 to I-24, 200C,
The cured product for 2 hours was prepared according to Examples I-7 to I-12 and I-17 to
For I-20, I-25 to I-28, a cured product at 200 ° C for 20 minutes, and for Example I-29, 120 ° C for 1 hour, 150 ° C
One hour was performed with each. The results are summarized in Table 4 below.

The details of each component represented by the following abbreviations are as follows.

EP1: Epicoat 828 Epibis type epoxy resin, manufactured by Yuka Shell Co., Ltd., epoxy equivalent 190-210 EP2: Epicoat 2021 alicyclic epoxy resin, manufactured by Daicel Chemical Industries, Ltd., epoxy equivalent 145

[0311]

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[0312]

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[0313]

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[0314]

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[0315]

[Table 1]

[0316]

[Table 2]

[0317]

[Table 3]

[0318]

[Table 4]

Comparative Examples I-1 to I-8 Epoxy resin compositions having the compositions shown in Table 5 below were prepared by mixing the same amounts shown in Table 5.
Here, compounds A6, A7, B2, B4, C2 and C
3 is a compound having no long substituent and cannot be reversibly dissolved and precipitated by heating and cooling.

[0320]

[Table 5]

For each of the obtained compositions, the gelation time (150 ° C. for Comparative Examples I-1 to I-4, Comparative Example I-5 to
The storage stability at room temperature and the mechanical strength after curing were measured. At this time, the time until the viscosity of the composition doubled was measured as the storage stability at room temperature, and the bending strength at room temperature was measured as the mechanical strength after curing. Further, the measurement of the bending strength was performed according to Comparative Example I-
1, I-2 at 120 ° C. for 1 hour, 150 ° C. for 1 hour, Comparative Examples I-3 and I-4 for 80 ° C. for 1 hour, 150 ° C. for 1 hour,
In Comparative Examples I-5 and I-7, a cured product at 200 ° C. for 2 hours was used.
In Comparative Examples I-6 and I-8, curing was performed using a cured product at 200 ° C. for 20 minutes. The results obtained are summarized in Table 6 below.

[0322]

[Table 6]

As is clear from the results shown in Tables 4 and 6, the epoxy resin composition of the present invention (Example I-1)
-I-30) has a high storage stability that is 12 months or more at room temperature, far exceeding the conventional epoxy resin compositions (Comparative Examples I-1 to I-8), while maintaining the curing properties of rapidly curing at high temperatures. have.

Further, the epoxy resin composition of the present invention shows good mechanical strength even after curing.

Example I-31 A composition was prepared by mixing 100 g of EP1 and 80 g of a compound (AA1) represented by the following chemical formula as an acid anhydride curing agent, 5 g of B1 and 2 g of C12.
It was heated at 00 ° C. for 2 hours to produce a cured product. The bending strength of the obtained cured product and the storage stability of the composition were measured.

[0326]

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As a result, the bending strength was 14 kg / m at room temperature.
m ² . Even when the composition was left at room temperature for one month, the increase in viscosity was about twice the initial value.

Comparative Example I-9 Example I-9 was repeated except that the curing catalyst B1 was changed to B2.
A composition was prepared in the same manner as in -31, and the flexural strength of the obtained cured product and the storage stability of the composition were measured.

As a result, the bending strength was 14 kg / mm ² . When the composition was left at room temperature for one month, the viscosity was increased to 10 times or more the initial value.

Example I-32 A composition was prepared by mixing 100 g of EP1, 80 g of a compound (AA1) represented by the above formula as an acid anhydride curing agent, and 2 g of C12, and the composition was prepared at 200 ° C. for 2 hours. Heating was performed for a time to produce a cured product. The bending strength of the obtained cured product and the storage stability of the composition were measured.

As a result, the bending strength was 14 kg / m at room temperature.
m ² . Even when the composition was left at room temperature for one week, the increase in viscosity was about twice the initial value.

Comparative Example I-10 Example I-10 was repeated except that the curing catalyst C1 was changed to C2.
A composition was prepared in the same manner as in -32, and the bending strength of the obtained cured product and the storage stability of the composition were measured.

As a result, the bending strength was 14 kg / mm ² . When this composition was allowed to stand at room temperature for one month, the viscosity increased to 10 times or more the initial value.

Example I-33 100 g of EP1, 20 g of a compound (DAM) represented by the following chemical formula as an aromatic amine curing agent and 2 g of C1
Is mixed to prepare a composition,
Heating was performed for a time to produce a cured product. The bending strength of the obtained cured product and the storage stability of the composition were measured.

[0335]

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As a result, the bending strength was 14 kg / m at room temperature.
m ² . Even when the composition was left at room temperature for one week, the increase in viscosity was about twice the initial value.

Comparative Example I-11 Example I-11 was repeated except that the curing catalyst C1 was changed to C2.
A composition was prepared in the same manner as in -33, and the bending strength of the obtained cured product and the storage stability of the composition were measured.

As a result, the bending strength was 14 kg / mm ² . When this composition was allowed to stand at room temperature, it gelled after one week.

Example I-34 A composition was prepared by mixing 100 g of EP1, 20 g of a compound represented by the above formula (DAM) as an aromatic amine curing agent, 5 g of B1 and 2 g of C1. For 2 hours to produce a cured product. The bending strength of the obtained cured product and the storage stability of the composition were measured.

As a result, the bending strength was 14 kg / m at room temperature.
m ² . Even when the composition was left at room temperature for one week, the increase in viscosity was about twice the initial value.

Comparative Example I-12 A curing catalyst C1 was changed to C2, and a curing catalyst B1 was changed to B2.
A composition was prepared in the same manner as in Example I-34 described above, and the bending strength of the obtained cured product and the storage stability of the composition were measured.

As a result, the bending strength was 14 kg / mm ² . When this composition was allowed to stand at room temperature, it gelled after one week.

As is evident from the above results, the storage stability of the epoxy resin composition could be significantly improved without impairing the mechanical strength by using the curing catalyst of the present invention.

Example I-35 1 g of Compound A2 as a curing catalyst and 100 g of EP1
And a mixture was prepared and applied on a 0.5 mm thick plate. After heating this at 60 ° C., an ultraviolet lamp (80
(W / cm high-pressure mercury lamp) from a distance of 10 cm for 2 minutes. After irradiation, the resin was completely gelled.

The mixture did not show any increase in viscosity when left at room temperature for 6 months.

Comparative Example I-13 The above-mentioned Example I-3 was repeated, except that the curing catalyst was changed to A6.
A mixture was prepared in the same manner as in No. 5. When this was irradiated with an ultraviolet lamp (80 W / cm high-pressure mercury lamp) from a distance of 10 cm for 2 minutes, the resin was completely gelled after the irradiation.

When this mixture was allowed to stand at room temperature for one month, the viscosity increased to 10 times or more the initial value.

Example II Examples II-1 to II-24 Epoxy resin compositions having the compositions shown in Tables 7 and 8 below were prepared by mixing the same amounts shown in Tables 7 and 8. . In addition, the compounding amount in a table | surface is shown by a weight part, and it is the same also in a following table. For each of the obtained compositions, the gelation time at 150 ° C., the storage stability at room temperature, the mechanical strength after curing, and the electrical insulation after curing were measured. At this time, the time until the viscosity of the composition doubled was measured as the storage stability at room temperature, and the bending strength at room temperature was measured as the mechanical strength after curing. Furthermore, the measurement of the volume resistivity and the bending strength was performed at 200 ° C. for 2 hours in Examples II-1 to II-12, and at 200 ° C. for 20 minutes in Examples II-13 to II-24. It was carried out using. The results are summarized in Table 9 below.

The details of each component represented by the following abbreviations are as follows.

[0350]

Embedded image

[0351]

Embedded image

[0352]

Embedded image

[0353]

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Note that EP1 and EP2 are the same epoxy resins as those used in Example I described above.

[0355]

[Table 7]

[0356]

[Table 8]

[0357]

[Table 9]

Comparative Examples II-1 to II-3 An epoxy resin composition having a composition shown in Table 10 below was used.
Similarly, it was prepared by mixing at the compounding amounts shown in Table 10. Here, the compounds Al5, Al6 and Al7 have a ligand with a short side chain.

[0359]

[Table 10]

With respect to each of the obtained compositions, Example II-1
The gelation time at 200 ° C. and the storage stability at room temperature were measured in the same manner as in Examples II to 24. The results are shown in Table 11 below.

[0361]

[Table 11]

As is clear from Tables 9 and 11, the epoxy resin compositions of the present invention (Examples II-1 to II-24)
Is a conventional epoxy resin composition (Comparative Examples II-1 to II-
It has high storage stability far exceeding 3). When Al1 to Al4 in which the central metal is aluminum is used, and when a phenol compound is used as the compound having a hydroxyl group, particularly high storage stability is obtained.

Further, the epoxy resin composition of the present invention shows good mechanical strength and electrical insulation even after curing.

Example II-25 A composition was prepared by mixing 100 g of EP1, 80 g of a compound (AA1) represented by the above formula as an acid anhydride curing agent, 5 g of OH1 and 2 g of Al1, and the composition was prepared at 200 ° C. A cured product was prepared by heating for 2 hours. The electrical insulation and bending strength of the obtained cured product, and the storage stability of the composition were measured.

As a result, the volume resistivity at 200 ° C. was 8 ×
10 ¹¹ Ω · cm, flexural strength 14 kg / m at room temperature
m ² . Even when the composition was left at room temperature for one month, the increase in viscosity was about twice the initial value.

Comparative Example II-4 Example II-4 described above was repeated except that the curing catalyst was changed to Al5.
A composition was prepared in the same manner as in Example 25, and the obtained cured product was measured for electrical insulation and bending strength, and storage stability of the composition.

As a result, the volume resistivity at 200 ° C. was 8 ×
It was 10 ¹¹ Ωcm, and the bending strength was 14 kg / mm ² . When the composition was left at room temperature for one month,
The viscosity increased to 10 times or more of the initial value.

Example II-26 A composition was prepared by mixing 100 g of EP1, 5 g of OH, 20 g of a compound represented by the above formula (DAM) as an aromatic amine curing agent, and 2 g of Al2. For 2 hours to produce a cured product. The electrical insulation and bending strength of the obtained cured product, and the storage stability of the composition were measured.

As a result, the volume resistivity at 200 ° C. was 8 ×
10 ¹¹ Ω · cm, flexural strength 14 kg / m at room temperature
m ² . Even when the composition was left at room temperature for one week, the increase in viscosity was about twice the initial value.

Comparative Example II-5 Example II-5 was repeated except that the curing catalyst was changed to Al5.
A composition was prepared in the same manner as in No. 26, and the obtained cured product was measured for electrical insulation and bending strength, and storage stability of the composition.

As a result, the volume resistivity at 200 ° C. was 8 ×
It was 10 ¹¹ Ωcm, and the bending strength was 14 kg / mm ² . When this composition was allowed to stand at room temperature, it gelled after one week.

Example II-27 A composition was prepared by mixing 100 g of Ep1, 51 g of a phenol novolak resin (manufactured by Showa Polymer Co., BGR-556, OH equivalent: 103) and 1 g of P1. Heating was performed for 8 hours to produce a cured product. The obtained cured product was measured for electrical insulation, bending strength, and storage stability of the composition.

As a result, the volume resistivity at 200 ° C. was 7 ×
It was 10 ¹¹ Ωcm, and the bending strength was 14 kg / mm ² . In addition, even if this composition was left at room temperature for one month, the increase in viscosity was about twice.

Comparative Example II-6 A composition was prepared by mixing 100 g of Ep1, 51 g of a phenol novolak resin (manufactured by Showa Polymer Co., Ltd., BGR-556, OH equivalent: 103) and 1 g of P2, and the composition was prepared at 180 ° C. Heating was performed for 8 hours to produce a cured product. The obtained cured product was measured for electrical insulation, bending strength, and storage stability of the composition.

As a result, the volume resistivity at 200 ° C. was 7 ×
It was 10 ¹¹ Ωcm, and the bending strength was 14 kg / mm ² . However, when the composition was left at room temperature for one month, it was gelled.

As is clear from the above results, the storage stability of the epoxy resin composition can be significantly improved without impairing the electrical properties and mechanical strength by using the curing catalyst of the present invention. Was.

Example II-28 100 g of Ep1, AA110 as an acid anhydride curing agent
0 g and 0.3 g N1 to prepare a composition,
This composition was heated at 150 ° C. for 4 hours to prepare a cured product. The obtained cured product was measured for electrical insulation, bending strength, and storage stability of the composition.

As a result, the volume resistivity at 200 ° C. was 7 ×
It was 10 ¹¹ Ωcm, and the bending strength was 14 kg / mm ² . Even when the composition was left at room temperature for one month, the increase in viscosity was about twice. Also, JISK-6911-
The shrinkage was determined from the specific gravity of each of the cured product and the uncured resin according to 1970 and found to be 0.1%.

Comparative Example II-7 100 g of Ep1 and AA110 as an acid anhydride curing agent
0 g and 0.3 g N2 to prepare a composition,
This composition was heated at 150 ° C. for 4 hours to prepare a cured product. The obtained cured product was measured for electrical insulation, bending strength, and storage stability of the composition.

As a result, the volume resistivity at 200 ° C. was 7 ×
It was 10 ¹¹ Ωcm, and the bending strength was 14 kg / mm ² . However, when the composition was left at room temperature for one month, the increase in viscosity was quadrupled. Further, when the shrinkage was measured in the same manner as described above, it was 0.25%.

As is clear from the above results, the storage stability of the epoxy resin composition can be greatly improved without impairing the electrical properties and mechanical strength by using the curing catalyst of the present invention. Was. Further, since the shrinkage of the molded article can be reduced, a resin composition having excellent dimensional stability can be provided.

Example III In this example, a liquid epoxy resin composition was prepared, and a semiconductor element was encapsulated with the liquid epoxy resin composition to produce a resin-encapsulated semiconductor device, and its characteristics were examined.

First, the components used for preparing the liquid epoxy resin composition are shown below.

EP3: Epicoat 806 Epibis type epoxy resin, manufactured by Yuka Shell Co., Ltd., epoxy equivalent: 160 to 170 EP4: Celloxide 2021A alicyclic epoxy resin, manufactured by Daicel Chemical Industries, Ltd., epoxy equivalent: 135

[0385]

Embedded image

NN1: Microcapsules (imidazole, HX-3088, manufactured by Asahi Kasei Corporation, reaction start temperature 87)
℃) NN2: Boron trifluoride monoethylamine salt (manufactured by Tokyo Chemical Industry Co., Ltd.) BS: Aliphatic sulfonium salt of Bronsted acid (manufactured by Asahi Denka Kogyo Co., Ltd., Opton CP-66) PN1: MEH-8005 Phenol novolak resin Hydroxyl equivalent 135 , Viscosity 47.4 poise (25 ° C) AN: MH-700 acid anhydride Acid anhydride equivalent 166, viscosity 0.62 poise (25 ° C) F1: spherical silica, average particle size 3.3 μm, maximum particle size 15
μm F2: spherical silica, average particle size 1.5 μm, maximum particle size 5 μm
m Note that OH1, OH3, and Al1 are the same as those in the above-described embodiment.
Compounds similar to those used in II.

Each of the above components was blended according to the compositions shown in Tables 12 to 15 and mixed well by a universal mixer, and then kneaded for 10 minutes using a three-roll mill (at a rotation speed of 10).
0 rpm, room temperature) to obtain Examples III-1 to III-15,
And the liquid epoxy resin composition of Comparative Examples III-1 to III-10 was obtained.

[0388]

[Table 12]

[0389]

[Table 13]

[0390]

[Table 14]

[0391]

[Table 15]

The obtained epoxy resin compositions of Examples III-1 to III-15 and Comparative Examples III-1 to III-10 were measured for the following properties, and the results are summarized in Tables 16 to 23 below.

In the measurement of characteristics other than the viscosity, Examples III-1 to III-3, III-7, III-9,
III-11, III-15 and Comparative Examples III-1 to III-
In Examples III-4 to III-6, III-8 and Comparative Examples 3, 3, 7, and 9 were heat-treated at 150 ° C. for 15 hours to cure the epoxy resin composition to obtain test pieces. In III-4 to III-6, a test piece was obtained by performing a heat treatment at 150 ° C. for 2 hours to cure the epoxy resin composition. Examples III-10 and III-12
And in Comparative Examples III-8 and III-10,
For 8 hours at 150 ° C., Examples III-13 and III-1
In No. 4, a test piece was obtained by performing heat treatment at 120 ° C. for 1 hour and 150 ° C. for 2 hours to cure the epoxy resin composition. Each characteristic was measured as follows.

Viscosity: Measured at a temperature of 25 ° C. using an E-type viscometer manufactured by Toki Sangyo Co., Ltd.

Glass transition temperature and coefficient of thermal expansion: Test pieces were measured using TMA manufactured by Seiko Denshi Co., Ltd.

Flexural strength and flexural modulus: JIS K-
The test piece was measured according to the method of 6911.

Storage stability: The viscosity of the liquid epoxy resin composition immediately after production and the viscosity one month after the production were measured, and the viscosity increase ratio one month after the production immediately after the production was calculated. The storage temperature was 30 ° C., and the viscosity was measured using an E-type viscometer manufactured by Toki Sangyo Co., Ltd.
m at a temperature of 25 ° C.

[0398] A plastic substrate and a chip were bump-connected (100 solder bumps) to obtain a test semiconductor element (12 mm x 12 mm chip). In this test semiconductor device, the gap between the plastic substrate and the chip was 50 μm. Examples III-1 to III
III-15, each of the liquid epoxy resin compositions of Comparative Examples III-1 to III-10 was supplied to a dispenser, and a predetermined amount of the liquid epoxy resin composition was discharged into a gap between the test semiconductor elements, thereby sealing the resin. did. At this time, the substrate temperature was 80 ° C.

After the resin was completely sealed, each was cured for the same heat treatment time as when the test pieces were obtained. After the curing treatment, the obtained resin-encapsulated semiconductor device is subjected to an initial failure check under the following conditions, and then a cooling / heating cycle test and a moisture resistance reliability test are performed. The results are summarized in Tables 16 to 23 below. .

[0400]

[Table 16]

[0401]

[Table 17]

[0402]

[Table 18]

[0403]

[Table 19]

[0404]

[Table 20]

[0405]

[Table 21]

[0406]

[Table 22]

[0407]

[Table 23]

The initial failure check is performed before mounting a semiconductor element on a substrate and then performing a cooling / heating cycle test and moisture resistance reliability evaluation, and examines an open failure check and an operation check of a device. is there.

The thermal shock resistance of the obtained resin-encapsulated semiconductor device was evaluated by performing a thermal cycle test (TCT test). In this test, the obtained resin-encapsulated semiconductor device was cooled at −65 ° C. for 30 minutes, left at room temperature for 5 minutes, and further heated and cooled at 150 ° C. for 30 minutes. This is to check the operation rate of the device and check the defect occurrence rate.

[0410] The humidity resistance reliability was evaluated by performing a pressure cooker test (PCT test) on the obtained resin-encapsulated semiconductor device. This test was carried out by leaving the obtained resin-encapsulated semiconductor device in a saturated steam atmosphere at 121 ° C. and 2 atm, and examining the defect occurrence rate.

Further, using a glass chip having glass bumps as shown in FIG. 1, an epoxy resin-based adhesive was applied to the tips of the glass bumps and pressed and fixed to a glass substrate to form a glass semiconductor device for testing. (12mm × 12mm
Chip). In the test glass semiconductor device obtained, the distance of the gap between the glass substrate and the glass chip was 30 μm. Subsequently, the aforementioned Example III
-1 to III-15, Comparative Examples III-1 to III-10 were filled in the gap between the glass substrate and the glass chip by using the liquid epoxy resin compositions and sealed with a resin as shown in FIG. A prototype glass semiconductor device was fabricated.

In order to evaluate the filling property of the obtained resin-sealed glass semiconductor device, the following measurements and evaluations were performed, and the obtained results are summarized in Tables 16 to 23.

Appearance of injected resin: The uniformity of the liquid epoxy resin composition filled in the resin-sealed glass semiconductor device was observed under a microscope. In the case of uniformity, the evaluation was (（).

Presence / absence of voids: The presence / absence of voids in the liquid epoxy resin composition filled in the resin-sealed glass semiconductor device was observed by an ultrasonic flaw detector. When no occurrence occurred, it was marked as (○).

Presence or absence of flow marks: It was visually observed whether or not flow marks were generated in the liquid epoxy resin composition filled in the resin-sealed crow semiconductor device. When no occurrence occurred, it was marked as (○).

Measurement of filling time: When the above liquid epoxy resin composition is used to fill the gap (30 μm) between the glass substrate and the glass chip, the time until the filling amount reaches 15 μm (min) Was measured.

Presence / absence of peeled portion: Whether or not a peeled portion occurred in the resin-sealed glass semiconductor device was observed with a microscope or an ultrasonic flaw detector. When no occurrence occurred, it was marked as (○).

Adhesion: The adhesion was evaluated by measuring the distance (mm) of ink penetration into the interface between the glass chip and the glass substrate inside the resin-sealed glass semiconductor device.

Specifically, the test resin-sealed glass semiconductor device was housed in a pressure cooker, and was treated with red ink in a temperature of 128 ° C. and 2.5 atmospheres. Thereafter, the substrate was washed with water to wipe off the moisture, and the penetration of the ink between the layers of the glass chip and the glass substrate was observed and measured using a microscope.

The liquid epoxy resin composition of the present invention (Example
III-1 to III-15) contain a novel latent curing catalyst, and thus have excellent storage stability as compared with the case where a conventional liquid epoxy resin composition is used. . Microcapsule type catalyst (Comparative Example III-1)
In the case of (1), although the potential for the epibis type epoxy resin is sufficient, it does not react at all with the alicyclic epoxy resin. However, the latent catalysts of the present invention do not, and any type of epoxy resin can be cured.

A semiconductor device in which a semiconductor element is sealed with a resin using the liquid epoxy resin composition of the present invention has a failure rate of an initial check of 0%, and a failure count in a thermal cycle test and a humidity resistance reliability test. Not at all.
Therefore, it can be seen that they have excellent thermal shock resistance and humidity resistance reliability as compared with the comparative example.

The resin-encapsulated glass semiconductor device obtained by encapsulating a glass chip with the liquid epoxy resin composition of the present invention has a better appearance of the filled epoxy resin composition than the comparative example. , Also voids, flow marks,
No occurrence of peeling-off spots was observed. Further, it can be seen that the filling time is short, the adhesiveness is excellent, and the molding stability, the filling property, and the moisture resistance reliability are all excellent.

Next, a cyanate ester compound was blended as a curing agent, and Example III-
16 to III-20 and Comparative Examples III-11 to III-12
Of a liquid epoxy resin composition was prepared.

The components used are shown below.

CE1: Ethylidene-4,4-phenylenediocyanate Al10: Aluminum tris (ethyl acetoacetate) Other components are the same as those used above.

[0426]

[Table 24]

The obtained Examples III-16 to III-20,
The same general properties as described above were measured for the liquid epoxy resin compositions of Comparative Examples III-11 and III-12, and the results are summarized in Tables 25 and 26 below.

In the measurement of properties other than the viscosity, Examples III-16 to III-20 and Comparative Example III-
All of 11 to III-12 were treated at 120 ° C. for 1 hour for 16 hours.
A test piece was obtained by performing a heat treatment at 5 ° C. for 2 hours to cure the epoxy resin composition.

Also, a glass semiconductor element for testing similar to that described above is manufactured, and each liquid epoxy resin composition is filled in a gap between a glass substrate and a glass chip to manufacture a resin-sealed glass semiconductor device. did. About the filling property of the obtained resin-sealed glass semiconductor device, the same measurement as described above,
The evaluation was performed, and the obtained results are summarized in Tables 25 to 26 below.

[0430]

[Table 25]

[0431]

[Table 26]

The liquid epoxy resin composition of the present invention (Example
III-16 to III-20) contain a novel latent curing catalyst, so that they have excellent storage stability as compared with the case where a conventional liquid epoxy resin composition is used. Understand.

A semiconductor device in which a semiconductor element is resin-sealed using the liquid epoxy resin composition of the present invention has a failure rate of an initial check of 0%, and has been subjected to a thermal cycle test and a humidity resistance reliability test. There are no defective pieces. Therefore, it can be seen that they have excellent thermal shock resistance and humidity resistance reliability as compared with the comparative example.

The resin-encapsulated glass semiconductor device obtained by encapsulating a glass chip with the liquid epoxy resin composition of the present invention has a better appearance of the filled epoxy resin composition than the comparative example. , Also voids, flow marks,
No occurrence of peeling-off spots was observed. Further, it can be seen that the filling time is short, the adhesiveness is excellent, and the molding stability, the filling property, and the moisture resistance reliability are all excellent.

Example IV In this example, a coating material containing the epoxy resin composition of the present invention will be described. Each component used here is the same compound as that used in Example III described above.

Example IV-1 80 g of EP4, epoxidized polybutadiene (trade name: PB3600, manufactured by Daicel Chemical Industries, Ltd., epoxy equivalent: 20)
0, oxirane oxygen concentration 8% by weight, 1,4-bond 50
% Of liquid polybutadiene epoxidized) 2
0 g, OH1 5 g and Al1 1 g as curing catalyst
It was used. These resins were dissolved in a dilute solution of butyl alcohol to prepare a solution of an epoxy resin composition having a resin content of 80%.

A solution of the obtained epoxy resin composition was applied to a base material (galvanized sheet, 50 × 150 × 0.3 mm) with a bar coater to a thickness of 50 μm, and then applied in an oven.
The composition was cured at 20 ° C. for 20 minutes to form a coating material composed of a cured product of the epoxy resin composition.

The storage stability of the epoxy resin composition was examined.
The appearance of the cured product was visually observed. Further, a rubbing test, a pencil hardness and an impact test were performed on the cured product, and the obtained results are summarized in Table 27 below.

[0439] Each test method is as follows.

Rubbing test: xylene / 100 times, 無 for intact, 傷 for scratches, and x for all rubbed cloudiness.

Pencil hardness test: Measured according to JIS K5400.

Impact test: Measured according to JIS K5400 using a DuPont impact deformation tester. The unit of the numerical value in the table is (cm).

Example IV-2 The same procedure as in Example IV- except that the epoxidized polybutadiene as the flexible component was changed to an alicyclic epoxy resin (Ceroxide 2081, trade name, manufactured by Daicel Chemical Industries, Ltd., epoxy equivalent: 200) was used. An epoxy resin composition was obtained in the same manner as in Example 1, and a coating material was formed using this. The same evaluation was performed on the composition and its cured product, and the obtained results are summarized in Table 27 below.

Example IV-3 Example IV-3 was repeated except that the curing catalyst was changed to 1 g of A91.
An epoxy resin composition was obtained in the same manner as in IV-1, and a coating material was formed using this. The same evaluation was performed on the composition and its cured product, and the obtained results are summarized in Table 27 below.

Comparative Example IV-1 An epoxy resin composition was obtained in the same manner as in Example IV-1 except that the curing catalyst was changed to 1 g of aluminum isopropoxide, and a coating material was formed using the same. . The same evaluation was performed for the composition and its cured product. The results obtained are summarized in Table 27 below.

Comparative Example IV-2 EP3, epoxidized polybutadiene (PB4700),
Phenolic resin (PS manufactured by Gunei Chemical Industry Co., Ltd., PS
2980) to prepare an epoxy resin composition.
The curing agent was phenolic OH equivalent / epoxy equivalent = 1. These resins were dissolved in a mixed solvent containing ethylene glycol, 2-ethoxyethyl acetate and butyl alcohol (weight ratio: ethylene glycol: 2-ethoxyethyl acetate: butyl alcohol = 3: 3: 4), and the resin content was 50%. Was prepared. Further, 1 part by weight of 2-ethylimidazole was added to 100 parts by weight of the resin component. EP3 / PB4700 = 1/1.
Using the epoxy resin composition thus obtained, a coating material was formed in the same manner as described above. The same evaluation was performed for the composition and its cured product. The results obtained are summarized in Table 27 below.

[0447]

[Table 27]

As shown in Table 27, epoxy resin compositions containing the curing catalyst of the present invention (Examples IV-1 to IV-IV)
-3) all have excellent storage stability of 12 months or more. Furthermore, the coating material obtained by curing the resin composition of the present invention was used in any of the rubbing test, the pencil hardness test and the impact test to obtain the compositions of Comparative Examples IV-1 to IV-2 using a conventional catalyst or curing agent. It shows characteristics equal to or higher than those formed using a material.

Example V In this example, an epoxy resin composition having optical transparency was prepared, and an optical semiconductor device was manufactured using the epoxy resin composition.
Its characteristics were investigated. The abbreviations of the components used in the preparation of each epoxy resin composition are the same as those described in Example III above.

Example V-1 60 g of EP3, an alicyclic solid epoxy resin (trade name: EHPE3150, manufactured by Daicel Chemical Industries, Ltd., epoxy equivalent: 18)
5, softening point 85 ° C) 40 g, OH15 as curing catalyst
g and 1 g of Al1 were used to prepare an epoxy resin composition.

Example V-2 The same procedure as in Example V above was conducted except that the curing catalyst was changed to A9 1 g.
In the same manner as in -1, an epoxy resin composition was prepared.

Example V-3 30 g of EP3, 25 g of an alicyclic solid epoxy resin (manufactured by Daicel Chemical Industries, Inc., EHPE3150), a curing agent (acid anhydride, methylhexahydrophthalic anhydride, trade name: RIKACID MH-700, molecular weight) 168, manufactured by Shin Nippon Rika) 45
g, an epoxy resin composition was prepared using 5 g of OH1 and 1 g of Al1 as a curing catalyst.

Example-4 50 g of EP4, 25 g of alicyclic solid epoxy resin (EHPE3150, manufactured by Daicel Chemical Industries, Ltd.), and O as a curing catalyst
An epoxy resin composition was prepared using 5 g of H1 and 1 g of Al1.

Comparative Example V-1 30 g of EP3, 25 g of an alicyclic solid epoxy resin (manufactured by Daicel Chemical Industries, EHPE3150), 45 g of a curing agent (acid anhydride, RIKACID MH-700), and 2-methyl-4- as a curing catalyst An epoxy resin composition was prepared using 1 g of methylimidazole.

Comparative Example V-2 40 g of EP4, novolak type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name: EOCN1027, epoxy equivalent: 20)
0) 20 g, curing agent (acid anhydride, RIKACID MH-70)
0) 40 g, and 1 g of 2-methyl-4-methylimidazole as a curing catalyst were used to prepare an epoxy resin composition.

The obtained epoxy resin compositions of Examples V-1 to V-4 and Comparative Examples V-1 and V-2 were subjected to transfer molding under the conditions of a temperature of 150 ° C., a pressure of 70 kg / cm ² and a duration of 5 minutes. Was performed to produce a cured product. A test piece was prepared by after-curing the cured product at 150 ° C. for 4 hours, and the following tests were performed. The results are summarized in Table 28 below.

Light transmittance: A test piece having a size of 10 × 50 × 1 mm was prepared and measured at 500 nm and 589 nm using an absorptiometer.
m and light transmittance at 700 nm were measured.

Moldability: 4 × 1 by transfer molding
When producing a 0 × 100 mm test piece, the degree of cracking in the test piece was evaluated in three stages. The evaluation criteria were as follows. A: No cracks B: Cracks occurred C: Cracks and chips occurred on the test piece during mold release Glass transition temperature and coefficient of thermal expansion: Measured by TMA at a heating rate of 5 ° C./min.

Storage stability: The epoxy resin composition was heated at 30 ° C.
The number of days until the melt viscosity after the elapse of a certain period of time at the temperature of doubles.

Gelling time: The epoxy resin composition was placed on a hot plate at 150 ° C., and the time required for the molten composition to start to gel was measured.

[0461]

[Table 28]

As shown in Table 28, epoxy resin compositions containing the curing catalyst of the present invention (Examples V-1 to V-
4) all have storage stability of 3 months or more, and they are good in moldability, curability, coefficient of thermal expansion, and light transmittance. On the other hand, Comparative Example V-
It can be seen that the storage stability of the epoxy resin compositions 1 to V-2 is insufficient.

Further, an LED device was manufactured using the light-transmitting epoxy resin composition of Example V-1. FIG.
FIG. In the figure, 11 is a light emitting element (gallium arsenide diode), 12 is a transparent resin formed by molding an epoxy resin, 13 is a glass epoxy base material, 14 is a lead wire, and 15 is an electrode. This LED device is
It had excellent light transmittance and high reliability.

[0464]

As described above, the curing catalyst according to the present invention does not show catalytic activity at a temperature around room temperature, but exhibits its activity by heat. Therefore, when this curing catalyst is blended with the resin composition, the resin composition maintains excellent curing characteristics at a predetermined temperature or more higher than room temperature of the resin composition, and the resin composition has high storage stability at room temperature. Give. That is, the resin composition containing the curing catalyst is stable for a long period of time without reaction at room temperature, and reacts and cures quickly by heating.

Further, the resin composition according to the present invention contains the above-mentioned curing catalyst, has a high storage stability that can be stored for a long period of time without the reaction proceeding at about room temperature, and has a high room temperature. If the temperature is higher than the predetermined temperature, the reaction proceeds rapidly to cure. Furthermore, the ionic substance does not remain after curing, and the cured product is excellent in electrical insulation and mechanical strength.

In particular, when a specific component is blended as a resin or a curing catalyst, a liquid resin composition having excellent fluidity, filling properties, thermal shock resistance and moisture resistance in addition to storage stability can be obtained. . Since such a resin composition is excellent in workability when filling the gap between the semiconductor element and the substrate,
By sealing the semiconductor element with this resin composition,
A resin-encapsulated semiconductor device that can support high-density packaging, high integration of electronic devices, high-density semiconductor devices, high-speed operation, high pin count, and small and thin packages. Is provided.

Further, according to the present invention, there is provided a coating material containing the above-mentioned resin composition, having excellent storage stability and exhibiting high hardness after curing.

The resin composition of the present invention can be suitably used for many uses such as sealing of semiconductor elements and coating materials, and its industrial value is enormous.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of a glass chip having glass bumps before resin sealing with a liquid epoxy resin composition of the present invention.

FIG. 2 is a schematic view of a resin-sealed glass semiconductor device sealed with a resin using the liquid epoxy resin composition of the present invention.

FIG. 3 is a longitudinal sectional view of the LED device used in the embodiment.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... The hardened | cured material of the liquid epoxy resin composition of this invention 2 ... Glass bump 3 ... Glass chip 4 ... Epoxy resin adhesive 5 ... Glass substrate 11 ... Light emitting element 12 ... Transparent resin 13 ... Glass epoxy base material 14 ... Lead wire 15 ... Electrode

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission Date] September 17, 1999 (1999.9.1)
7)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0316

[Correction method] Change

[Correction contents]

[0316]

[Table 2]

Continuing on the front page (72) Inventor Shinetsu Fujieda 1 Toshiba R & D Center, Komukai Toshiba-ku, Kawasaki-shi, Kanagawa Prefecture (72) Inventor Rumiko Hayase 1 Komukai Toshiba-cho, Sachi-ku, Kawasaki-shi, Kanagawa Address: Toshiba R & D Center (72) Inventor Yasuyuki Hotta 1: Komukai Toshiba-cho, Yuki-ku, Kawasaki-shi, Kanagawa Prefecture Toshiba R & D Center

Claims (32)

[Claims] 1. A composition comprising at least one of a cationic polymerization catalyst component and an organometallic compound, wherein at least one of the components can be reversibly dissolved and precipitated by heating and cooling. And a curing catalyst. 2. A cation polymerization catalyst component and at least one kind of an organometallic compound, wherein the cation polymerization catalyst component is a substituted or unsubstituted hydrocarbon having 10 or more carbon atoms, or a hydrocarbon having 10 or more carbon atoms. A compound having at least one cyclic organic structure having a substituted or unsubstituted hydrocarbon group in a molecule, and at least one of the components can be reversibly dissolved and precipitated by heating and cooling. Curing catalyst characterized by the following. 3. The cationic polymerization catalyst component includes a sulfonium salt represented by the following general formula (I-1), an iodonium salt represented by the following general formula (I-2),
-3), an iron aromatic compound represented by the following general formula (I-
The curing catalyst according to claim 1, wherein the curing catalyst is selected from the group consisting of an organosilicon compound represented by 4) and a compound represented by the following general formula (I-5). Embedded image (In the above general formula, R ¹¹ , R ¹² and R ¹³ may be the same or different and each represent a hydrogen atom or a carbon atom having 1 to 1 carbon atoms.
30 substituted or unsubstituted hydrocarbon groups, substituted or unsubstituted aromatic groups or heteroaromatic groups. However,
A substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms,
Alternatively, the compound has at least one cyclic organic structure having a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms in the molecule. X represents SbF ₆ , AsF ₆ , PF ₆ , BF _4, an anion derivative having at least one fluorine atom substituted with a hydroxyl group, CF ₃ SO ₃ , ClO ₄ , a halogen atom, R ¹ —COO, R ² — ₃ shows an anion selected from the group consisting of SO ₃ . Here, R ¹ and R ² represent an alkyl group, a halogen atom, a nitro group, a cyano group, an alkyl group which may be substituted with an alkoxy group or the like, or a phenyl group. ) (In the above general formula, R ¹⁴ , R ¹⁵ , R ¹⁶ , and R ¹⁷ may be the same or different, and each represents a hydrogen atom and a carbon atom number of 1 to 1.
30 substituted or unsubstituted hydrocarbon groups, substituted or unsubstituted aromatic groups or heteroaromatic groups. However,
A substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms,
Alternatively, the compound has at least one cyclic organic structure having a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms in the molecule. p, q and r are integers from 0 to 3, and p + q + r is 3
It is as follows. ) (In the above general formula, Ar ¹ is a substituted or unsubstituted aromatic group or a heteroaromatic group, and R ¹⁸ may be the same or different, and each represents a hydrogen atom, a substituted or unsubstituted group having 1 to 30 carbon atoms. A substituted hydrocarbon group, a substituted or unsubstituted aromatic group or a heteroaromatic group, provided that a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms, or a substituted or unsubstituted group having 10 or more carbon atoms Has at least one cyclic organic structure having a hydrocarbon group in the molecule. K represents an integer of 1 to 7, and n represents an integer of 1 to 7.) 4. The organic metal compound has the following general formula (II)
The compound according to any one of claims 1 to 3, which is selected from the group consisting of a compound represented by -1), a compound represented by (II-2), and a compound represented by (II-3). Curing catalyst. Embedded image (In the above general formula, R ²¹ , R ²² , R ²³ and R ²⁴ may be the same or different and each represent a hydrogen atom,
30 substituted or unsubstituted hydrocarbon groups. However, in one ligand, R ²¹ , R ²² , R ²³ and R
It is assumed that at least one compound having ²⁴ carbon atoms of 10 or more is included. M is Al, Ti, Cr, Mn, F
e, Co, Ni, Cu, Zr, Zn, Ba, Ca, C
It is selected from the group consisting of e, Pb, Mg, Sn and V, where n is an integer of 2-4. ) 5. An organometallic compound, an organosilane having a hydroxyl group directly bonded to a silicon atom, an organosiloxane having a hydroxyl group directly bonded to a silicon atom, a phenol compound, and an organic compound having a hydrolyzable group directly bonded to a silicon atom. The curing catalyst according to claim 1, comprising a silicon compound and at least one compound selected from the group consisting of a silicon compound capable of generating silanol by light irradiation. 6. A compound represented by the following general formulas (III-1 ′) and (III-
A curing catalyst comprising at least one compound selected from the group consisting of the compounds represented by 2). Embedded image (In the general formula (III-1 ′), R ¹ , R ² , and R ³ may be the same or different, and each represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, Or a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms, or a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms. It has at least one aromatic or heteroaromatic group having a hydrogen group.) (In the general formula (III-2), R ³² , R ³³ , R ³⁴ and R ³⁵ may be the same or different, and each represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms. However, at least two of R ³² , R ³³ , R ³⁴ and R ³⁵ are a hydrocarbon group having 10 or more carbon atoms.) 7. The following general formulas (III-1) and (III-
A curing catalyst comprising at least one compound selected from the group consisting of the compounds represented by 2). Embedded image (In the general formula (III-1), R ³¹ may be the same or different and each represents a hydrogen atom or a carbon atom having 1 to 30 carbon atoms.
Is a substituted or unsubstituted hydrocarbon group. However, 1
At least one R ³¹ in the molecule has 10 or more carbon atoms. h, i and j are integers satisfying h + i + j = 3, and m is an integer of 1 to 5. ) (In the general formula (III-2), R ³² , R ³³ , R ³⁴ and R ³⁵ may be the same or different, and each represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms. However, at least two of R ³² , R ³³ , R ³⁴ and R ³⁵ are a hydrocarbon group having 10 or more carbon atoms.) 8. The curing catalyst according to claim 7, wherein the compound represented by the general formula (III-1) is selected from the following group. Embedded image Embedded image 9. The curing catalyst according to claim 6, wherein the compound represented by the general formula (III-2) is selected from the following group. Embedded image 10. A curing catalyst containing a cationic polymerization catalyst component and at least one component of an organometallic compound,
A resin composition comprising a cationically polymerizable resin component, wherein at least one of the components in the curing catalyst is reversibly dissolved and precipitated by heating and cooling. 11. The cationically polymerizable resin component includes an epoxy resin, a resin having a vinyl ether group, a lactone,
The resin composition according to claim 10, which is selected from the group consisting of resins containing styrene and vinyl thioether. 12. The resin composition according to claim 11, wherein the cationically polymerizable resin component is an epoxy resin. 13. The resin composition according to claim 10, further comprising at least one selected from the group consisting of a methacrylic resin, an acrylic resin, and a maleimide resin. 14. The method according to claim 1, further comprising an inorganic filler.
14. The resin composition according to any one of 0 to 13. 15. The method according to claim 10, further comprising a photosensitizer.
15. The resin composition according to any one of items 14 to 14. 16. The method according to claim 10, further comprising at least one curing agent selected from the group consisting of acid anhydrides, phenols, aromatic amine compounds, and cyanate ester compounds. Resin composition. 17. The cationic polymerization catalyst component in the curing catalyst is a substituted or unsubstituted hydrocarbon having 10 or more carbon atoms or a cyclic organic structure having a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms. The resin composition according to any one of claims 10 to 16, which is a compound having one or more in a molecule. 18. The cationic polymerization catalyst component in the curing catalyst includes a sulfonium salt represented by the following general formula (I-1), an iodonium salt represented by the following general formula (I-2),
A group consisting of an iron aromatic compound represented by the following general formula (I-3), an organosilicon compound represented by the following general formula (I-4), and a compound represented by the following general formula (I-5) The resin composition according to any one of claims 10 to 17, which is selected from the group consisting of: Embedded image (In the above general formula, R ¹¹ , R ¹² and R ¹³ may be the same or different and each represent a hydrogen atom or a carbon atom having 1 to 1 carbon atoms.
30 substituted or unsubstituted hydrocarbon groups, substituted or unsubstituted aromatic groups or heteroaromatic groups. However,
A substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms,
Alternatively, the compound has at least one cyclic organic structure having a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms in the molecule. X represents SbF ₆ , AsF ₆ , PF ₆ , BF _4, an anion derivative having at least one fluorine atom substituted with a hydroxyl group, CF ₃ SO ₃ , ClO ₄ , a halogen atom, R ¹ —COO, R ² — ₃ shows an anion selected from the group consisting of SO ₃ . Here, R ¹ and R ² represent an alkyl group, a halogen atom, a nitro group, a cyano group, an alkyl group which may be substituted with an alkoxy group or the like, or a phenyl group. ) (In the above general formula, R ¹⁴ , R ¹⁵ , R ¹⁶ , and R ¹⁷ may be the same or different, and each represents a hydrogen atom and a carbon atom number of 1 to 1.
30 substituted or unsubstituted hydrocarbon groups, substituted or unsubstituted aromatic groups or heteroaromatic groups. However,
A substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms,
Alternatively, the compound has at least one cyclic organic structure having a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms in the molecule. p, q and r are integers from 0 to 3, and p + q + r is 3
It is as follows. ) (In the above general formula, Ar ¹ is a substituted or unsubstituted aromatic group or a heteroaromatic group, and R ¹⁸ may be the same or different, and each represents a hydrogen atom, a substituted or unsubstituted group having 1 to 30 carbon atoms. A substituted hydrocarbon group, a substituted or unsubstituted aromatic group or a heteroaromatic group, provided that a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms, or a substituted or unsubstituted group having 10 or more carbon atoms Has at least one cyclic organic structure having a hydrocarbon group in the molecule. K represents an integer of 1 to 7, and n represents an integer of 1 to 7.) 19. The organic metal compound is a group consisting of a compound represented by the following general formula (II-1), a compound represented by (II-2), and a compound represented by (II-3) The resin composition according to any one of claims 10 to 18, which is selected from the group consisting of: Embedded image (In the above general formula, R ²¹ , R ²² , R ²³ and R ²⁴ may be the same or different and each represent a hydrogen atom,
30 substituted or unsubstituted hydrocarbon groups. However, in one ligand, R ²¹ , R ²² , R ²³ and R
It is assumed that at least one compound having ²⁴ carbon atoms of 10 or more is included. M is Al, Ti, Cr, Mn, F
e, Co, Ni, Cu, Zr, Zn, Ba, Ca, C
It is selected from the group consisting of e, Pb, Mg, Sn, and V, where n is an integer from 2 to 4. ) 20. An organometallic compound, an organosilane having a hydroxyl group directly bonded to a silicon atom, an organosiloxane having a hydroxyl group directly bonded to a silicon atom, a phenol compound, and an organic compound having a hydrolyzable group directly bonded to a silicon atom. The resin composition according to any one of claims 10 to 16 and 19, comprising a silicon compound and at least one compound selected from the group consisting of a silicon compound capable of generating silanol by light irradiation. object. 21. The following general formulas (III-1 ′) and (I)
A resin composition comprising a curing catalyst containing at least one compound selected from the group consisting of compounds represented by II-2), and a cationic polymerizable compound. Embedded image (In the general formula (III-1 ′), R ¹ , R ² , and R ³ may be the same or different, and each represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, Or a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms, or a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms. It has at least one aromatic or heteroaromatic group having a hydrogen group.) (In the general formula (III-2), R ³² , R ³³ , R ³⁴ and R ³⁵ may be the same or different, and each represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms. However, at least two of R ³² , R ³³ , R ³⁴ and R ³⁵ are a hydrocarbon group having 10 or more carbon atoms.) 22. The following general formulas (III-1) and (III)
A resin composition containing a curing catalyst containing at least one compound selected from the group consisting of the compounds represented by -2) and a cationic polymerizable compound. Embedded image (In the general formula (III-1), R ³¹ may be the same or different and each represents a hydrogen atom or a carbon atom having 1 to 30 carbon atoms.
Is a substituted or unsubstituted hydrocarbon group. However, 1
At least one R ³¹ in the molecule has 10 or more carbon atoms. h, i and j are integers satisfying h + i + j = 3, and m is an integer of 1 to 5. Embedded image (In the general formula (III-2), R ³² , R ³³ , R ³⁴ and R ³⁵ may be the same or different, and each represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms. However, at least two of R ³² , R ³³ , R ³⁴ and R ³⁵ are a hydrocarbon group having 10 or more carbon atoms.) 23. The cationic polymerizable resin component includes an epoxy resin, a resin having a vinyl ether group, a lactone,
The resin composition according to claim 21 or 22, which is selected from the group consisting of resins containing styrene and vinyl thioether. 24. The resin composition according to claim 23, wherein the cationically polymerizable resin component is an epoxy resin. 25. The resin composition according to claim 21, further comprising at least one selected from the group consisting of a methacrylic resin, an acrylic resin, and a maleimide resin. 26. The method according to claim 2, further comprising an inorganic filler.
26. The resin composition according to any one of 1 to 25. 27. The method according to claim 21, further comprising a photosensitizer.
27. The resin composition according to any one of items 26 to 26. 28. The method according to claim 21, further comprising at least one curing agent selected from the group consisting of acid anhydrides, phenols, aromatic amine compounds, and cyanate ester compounds. Resin composition. 29. The resin composition according to claim 22, wherein the compound represented by the general formula (III-1) is selected from the group shown below. Embedded image Embedded image 30. The resin composition according to claim 21, wherein the compound represented by the general formula (III-2) is selected from the group shown below. Embedded image 31. A semiconductor device comprising: a semiconductor element; and a resin layer for encapsulating the semiconductor element, wherein the resin layer is formed by curing the resin composition according to claim 10. A resin-encapsulated semiconductor device. A coating material comprising the curing catalyst according to any one of claims 1 to 9.