JP2002265614A - Anionic latent catalyst and thermosetting resin composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an anionic latent catalyst that can achieve the excellent hardening properties and storability of thermosetting resin composition and a resin composition that is useful in the fields of electric and electronic materials using the latent catalyst. SOLUTION: An anionic compound having a chemical structure represented by general formula (1) is used as an objective latent polymerization catalyst. The objective resin composition is produced by using as the essential components (A) a compound bearing two or more epoxy groups in the molecule, (B) a compound bearing two or more phenolic hydroxyls in the molecule and (C) the anionic latent catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an anionic latent catalyst for realizing excellent curability and storage stability of a thermosetting resin composition, and a resin composition using the same which is useful in the field of electric and electronic materials. Things.

[0002]

2. Description of the Related Art Electric and electronic materials, especially epoxy resin ICs
The anionic curing catalysts used so far, such as imidazoles, bicyclic amidines such as DBU (diazabicycloundecene), and tri-substituted phosphines have poor storage stability, and epoxy resin sealing materials When these catalysts are used, the reaction proceeds at room temperature, and there is a possibility of causing molding failure due to a decrease in fluidity. Therefore, it is essential to store and transport the catalyst at a low temperature. In recent years,
Low molecular weight crystalline epoxy resins such as biphenyl type epoxy resins have been used as epoxy resins, and with the spread of automatic molding, faster curing properties have been required. Increasingly, the problem of its preservation is becoming more important.

[0003]

In view of such circumstances, the present inventors have conducted intensive studies to propose an anion-latent catalyst for thermosetting resins having a novel structure and function. A novel anion-latent catalyst was found, and the present invention was completed. An object of the present invention is to provide an anionic latent catalyst that achieves excellent curability and storage stability, and a resin composition using the same that is useful in the field of electric and electronic materials.

[0004]

That is, the present invention provides an anionic latent catalyst for a thermosetting resin having a structure represented by the general formula (1), and further comprises an epoxy group in one molecule. (A), a compound (B) having two or more phenolic hydroxyl groups in one molecule, and the anionic latent catalyst (C) as essential components. A composition.

[0005]

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In the formula, substituents R ^{1 to} R ⁶ are halogen, substituted or unsubstituted (hereinafter, referred to as substituted / unsubstituted) alkyl groups, substituted / unsubstituted aryl groups, substituted / unsubstituted alkoxide groups, substituted / unsubstituted alkoxide groups, Unsubstituted aryloyl group, represents at least one selected from the group consisting of substituted and unsubstituted amino groups,
They may be the same or different from each other.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The component (C) which is an anion latent catalyst is represented by the above-mentioned general formula (1). Although it is stable at room temperature due to its six-membered ring structure, it is decomposed by high-temperature heating during molding, which makes it possible to achieve both storage stability at room temperature and rapid curing at high temperatures. Wherein the substituents R ^{1 to} R
⁶ is a halogen, a substituted / unsubstituted alkyl group, a substituted / unsubstituted aryl group, a substituted / unsubstituted alkoxide group,
At least one selected from the group consisting of unsubstituted aryloyl groups and substituted / unsubstituted amino groups, specifically, fluoride, chloride, bromide, phenyl, tolyl, naphthyl, methoxide, ethoxide, phenoxide , Naphthoxide, catecholate, amino group, dimethylamino group and the like.

The anion-latent catalyst of the present invention is an ordinary anion-curable resin system and exhibits excellent catalytic activity. Specific examples include epoxy resins, maleimide resins, cyanate resins, isocyanate resins, acrylate resins, and the like, but include all those that undergo a curing reaction with a tertiary amine, tertiary phosphine, or a quaternary salt thereof.

Next, the compound (A) having two or more epoxy groups in one molecule used in the resin composition of the second invention is a compound having two or more epoxy groups in one molecule. There is no limitation, for example, biphenyl type epoxy resin, novolak type epoxy resin, naphthalene type epoxy resin, etc., phenols such as biphenol, phenolic resin, hydroxyl groups such as naphthols, manufactured by reacting epichlorohydrin. In addition to the above epoxy resins, epoxy resins such as alicyclic epoxy resins, which are obtained by oxidizing an olefin with a peracid and epoxidized, and those obtained by epoxidizing dihydroxybenzenes such as hydroquinone with epichlorohydrin are also included.

The compound (B) having two or more phenolic hydroxyl groups in one molecule includes phenol novolak resin, cresol novolak resin, alkyl-modified novolak resin, phenol aralkyl resin, naphthols and phenols together with carbonyl group-containing compounds. Examples thereof include a condensed resin, and any compound may be used as long as two or more hydrogen atoms bonded to an aromatic ring in one molecule are substituted with a hydroxyl group.

The compound (A) having two or more epoxy groups, the compound (B) having two or more phenolic hydroxyl groups, and the anionic latent catalyst (C) represented by the general formula (1) of the present invention are The resin composition as an essential component has extremely good curability and storage stability, and can realize excellent performance as a sealing material for electric and electronic applications. In addition, if necessary, additives and secondary materials known to those skilled in the art such as an inorganic filler, a release agent, and a coupling agent may be combined with the resin composition.

[0012]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.

(Examples 1 to 5 and Comparative Examples 1 and 2) Compounds having two or more epoxy groups (A), compounds having two or more phenolic hydroxyl groups (B), And an anionic latent catalyst (C) (compound D
To H) were pulverized and mixed, melt-kneaded on a hot plate at 100 ° C. for 5 minutes, and then cooled and pulverized to prepare a sample of a resin composition. The chemical structural formulas of the five types of curing accelerators used in Examples 1 to 5 are shown in Formulas (D) to (H). In addition, for each sample, the characteristic evaluation was performed by setting the curing torque (curability),
And the measurement of the residual heat generation value (preservability) was performed.
Each evaluation method was as follows.

[0014]

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[0015]

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[0016]

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[0017]

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[0018]

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1. Curing Torque (Evaluation of Curability) Using the resin composition prepared by the above method, the torque after heating at 175 ° C. for 45 seconds with a curastometer (JSR Curastometer PS type, manufactured by Orientec) is determined. . Torque in the curast meter is a parameter of curability, and a larger value indicates higher curability.

2. Residual Curing Calorific Value (Evaluation of Storage Stability) For the resin composition prepared by the method described above, the initial curing calorific value (mj / mg) and the curing calorific value (mj / mg) after storage treatment at 40 ° C. for 3 days are as follows: Heating rate 10 ° C / m
The ratio was measured by differential thermal analysis in "in", and the percentage of the heat generated by the curing after the preservation treatment relative to the initial heat generated by the curing was determined as 100% (residual rate of the heat generated by the curing). The larger the value, the better the storage stability.

The evaluation results are shown in Table 1. In the examples, both the curability and the preservability were good. In this case, the curing torque was 0, the curability was low, and the residual rate of heat generation after curing was as low as about 60%.

[0022]

[Table 1]

[0023]

When the anionic latent catalyst of the present invention and the thermosetting resin composition using the same are used for electric and electronic materials, a product having good curability and preservability can be obtained. The advantages in the electric and electronic industries, such as being transportable and not causing curing failure during molding, are greatly useful.

 ──────────────────────────────────────────────────続 き Continued on front page F term (reference) 4J015 EA04 4J031 CA04 CB06 4J036 AD07 AF05 AF06 AJ08 DA05 DA10 FA12 FB07 4M109 AA01 EA11

Claims (3)

[Claims] 1. An anion latent catalyst for a thermosetting resin, having a structure represented by the general formula (1). Embedded image In the formula, the substituents R ^{1 to} R ⁶ are a halogen, a substituted or unsubstituted (hereinafter, referred to as “substituted / unsubstituted”) alkyl group, a substituted / unsubstituted aryl group, a substituted / unsubstituted alkoxide group, a substituted / unsubstituted alkoxide group,
Represents at least one selected from the group consisting of an unsubstituted aryloyl group and a substituted / unsubstituted amino group, which may be the same or different. 2. The substituents R ^{1 to} R ⁶ are selected from the group consisting of fluoride, chloride, bromide, phenyl, tolyl, naphthyl, methoxide, ethoxide, phenoxide, naphthoxide, catecholate, amino and dimethylamino. 2. The anion-latent catalyst according to claim 1, wherein the catalyst is at least one selected from the group. 3. A compound having two or more epoxy groups in one molecule (A), a compound having two or more phenolic hydroxyl groups in one molecule (B), and the anion latency described in claim 1. A thermosetting resin composition comprising a catalyst (C) as an essential component.