JP2002105176A - Anionic latent catalyst and thermosetting resin composition using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an anionic latent catalyst that realizes excellent resin- curing properties and storability of a thermosetting resin composition and a resin composition that includes the latent catalyst and is useful in the fields of the electric and electronic materials. SOLUTION: As a latent catalyst, is used an anionic compound bearing the structure represented by the following general formula (1). In addition, a compound bearing two or more epoxy groups in one molecule (A) and a compound bearing two or more phenolic hydroxy groups in one molecule (B) and the anionic latent catalyst (C) are used as the essential components to prepare the objective resin composition.

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 anionic 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 which realizes excellent curability and storage stability, and a resin composition which is useful in the field of electric and electronic materials using the same.

[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 a thermosetting resin comprising the anionic latent catalyst (C) as essential components. A composition.

[0005]

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In the formula, R ^{1 to} R ³ are at least one selected from the group consisting of an alkyl group, a substituted or unsubstituted (hereinafter, referred to as substituted / unsubstituted) aryl group, and a substituted / unsubstituted aralkyl group. Which may be the same or different from each other. R ⁴ is hydrogen, halogen, substituted
Represents at least one selected from the group consisting of an unsubstituted alkyl group, a substituted / unsubstituted aryl group, a substituted / unsubstituted aralkyl group, a substituted / unsubstituted acyl group, a substituted / unsubstituted aryloyl group, and a cyano group; May be the same or different from each other. X is a Group 3 element having Lewis acidity; L is hydrogen, a substituted / unsubstituted alkyl group, a substituted / unsubstituted aryl group, a substituted / unsubstituted aralkyl group, a substituted / unsubstituted alkoxy group, a substituted / unsubstituted alkoxy group; It represents at least one selected from the group consisting of a substituted aryloxy group, a substituted / unsubstituted acyloxy group, and a substituted / unsubstituted arylyloxy group, which may be the same or different.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The substituents R ^{1 to} R ³ of the anionic latent catalyst in the present invention are at least one selected from the group consisting of alkyl, substituted / unsubstituted aryl, and substituted / unsubstituted aralkyl. Specific examples include an alkyl group such as methyl, ethyl and butyl, an aryl group such as phenyl, naphthyl, tolyl and anisyl, and an aralkyl group such as benzyl.

Further, the substituent R ⁴ is hydrogen, halogen, substituted / unsubstituted alkyl group, substituted / unsubstituted aryl group, substituted / unsubstituted aralkyl group, substituted / unsubstituted acyl group, substituted / unsubstituted acyl group,
Unsubstituted aryloyl group, and at least one selected from the group consisting of cyano group, specifically, hydrogen, cyano group, fluorine, chlorine, bromine, halogen such as iodine, methyl, ethyl, butyl, Such as an alkyl group, or a corresponding perfluoroalkyl group, a substituted or unsubstituted aryl group such as phenyl, naphthyl, tolyl, anisyl, nitrophenyl, and cyanophenyl; a corresponding perfluoroaryl group such as pentafluorophenyl; and benzyl. Examples thereof include an aralkyl group, an acyl group such as formyl, acetyl, propionyl, benzoyl, naphthoyl, toluoyl, anisoyl, cyanobenzoyl, and nitrobenzoyl, and an aryloyl group.

X is an element exhibiting Group 13 Lewis acidity, and is boron, aluminum, gallium, indium, or thallium, with boron and aluminum atoms being particularly desirable. However, organoboranes and organoaluminums are
It is known that it has the property of easily meeting. For example, borane associates with dimer of dimer, and aluminum associates with dinuclear cluster. This has caused a decrease in the stability of the catalyst in the present invention. Therefore, in the present invention, in order to reduce the degree of association, a bulky substituent or a bidentate ligand is introduced into L to improve the stability of the catalyst. Specifically, as L, phenyl group, tolyl group, mesityl group, pentafluorophenyl group, benzoyl group, naphthyl group, naphthoyl group, phenoxy group, 2,6-dimethylphenoxy group, 2,6-di-t-butyl A phenoxy group, a normal propyl group, an isopropyl group, or a catechol group, an acetylacetonate group, a 2,2,6,6-tetramethyl-3,5-heptanedionate group having a cyclic structure bonded to each other, 3-hydroxy-2-methyl-4H-pyrano-4-ate group,
Examples thereof include a 9-bicyclo [3,3,1] nonyl group.

The anion-latent catalyst of the present invention is an ordinary anion-curable resin system and exhibits excellent catalytic activity. More specifically, 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, which is 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, it is manufactured by reacting epichlorohydrin with phenols such as biphenol, such as biphenyl type epoxy resin, novolak type epoxy resin, and naphthalene type epoxy resin, and phenolic resin and hydroxyl groups such as naphthols. In addition to the epoxy resin described above, epoxy resins such as an alicyclic epoxy resin obtained by oxidizing an olefin with a peracid and epoxidized, and epoxy resins 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. The resin composition containing as an essential component has extremely good curability and storage stability, and can realize excellent performance as a sealing material for electric / electronic use. 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.

[0014]

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

(Synthesis of an anion-latent catalyst) In the synthesis of an anion-latent catalyst according to the present invention, usually, first, an organic phosphinimine is synthesized, and then contacted with a Lewis acid to form an adjacent carbon of anionic phosphorus. To a Lewis acid. A typical synthesis example is shown below.

(Synthesis Example) In a 100 ml eggplant-shaped flask equipped with a cooling tube equipped with a calcium chloride tube, 5.2 g of methylaminotriphenylphosphonium bromide and 50 ml of diethyl ether were placed, and cooled to 0 ° C. while stirring with a magnetic stirrer. Then, a phenyllithium solution is added dropwise so as to be 1.1 times the molar amount of methyltriphenylphosphonium bromide. Thereafter, the precipitate was returned to room temperature, and the formed precipitate was filtered, and the obtained filtrate was put into a 100 ml eggplant-shaped flask equipped with a cooling tube equipped with a calcium chloride tube.
Further, 50 ml of diethyl ether was added, the mixture was cooled and stirred at 0 ° C., and a trifluoroborane diethyl ether solution was slowly added dropwise so as to be equimolar to the formed phosphinimine. Then, after returning to room temperature and continuing stirring for 1 hour, the produced | generated precipitate was filtered and dried. The obtained compound is designated as D.

Further, according to the above synthesis method, compound E
~ H was synthesized. The chemical structures of Compounds D to H are as shown below.

[0018]

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[0019]

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[0020]

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[0021]

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[0022]

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(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, the anionic latent catalyst (C) (compounds D to H) prepared in the above synthesis example is pulverized and mixed, melt-kneaded on a hot plate at 100 ° C. for 5 minutes, and then cooled and pulverized to prepare a resin composition sample. did. For each sample, a curing torque (curability) and a residual rate of heat generation after curing (preservability) were measured for characteristic evaluation. Each evaluation method was as follows.

1. Curing Torque (Evaluation of Curability) Using the resin composition prepared by the above method, determine the torque after heating at 175 ° C. for 45 seconds with a curastometer (JSR Curastometer PS, manufactured by Orientec). . Torque in a 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 above method, 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 measurement was performed by differential thermal analysis in “in”, and the 100% ratio of the curing heat generation value after the preservation treatment to the initial curing heat generation value (residual rate of curing heat generation) was determined. A larger value indicates better storage stability.

The evaluation results are shown in Table 1. In Examples, both the curability and the preservability were good. In particular, while the residual ratio of the heat generated by curing maintained 90% or more, the comparative example 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%.

[0027]

[Table 1]

[0028]

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 storage stability 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.

Claims (4)

[Claims] 1. An anion latent catalyst for a thermosetting resin, having a structure represented by the general formula (1). Embedded image In the formula, R ^{1 to} R ³ are at least one selected from the group consisting of an alkyl group, a substituted or unsubstituted (hereinafter, referred to as substituted / unsubstituted) aryl group, and a substituted / unsubstituted aralkyl group.
Represent species, which may be the same or different from each other. R ⁴ is selected from the group consisting of hydrogen, halogen, substituted / unsubstituted alkyl group, substituted / unsubstituted aryl group, substituted / unsubstituted aralkyl group, substituted / unsubstituted acyl group, substituted / unsubstituted aryloyl group, and cyano group Represents at least one selected kind, which may be the same or different from each other. X is a Group 13 element having Lewis acidity, and L is a hydrogen atom, a substituted / unsubstituted alkyl group, a substituted / unsubstituted aryl group, a substituted / unsubstituted aralkyl group, a substituted / unsubstituted alkoxy group, a substituted / unsubstituted alkoxy group, At least one selected from the group consisting of an unsubstituted aryloxy group, a substituted / unsubstituted acyloxy group, and a substituted / unsubstituted arylyloxy group
Represent species, which may be the same or different from each other. 2. The substituent L of the element X having a group 13 Lewis acidity having a Lewis acidity is a phenyl group, a tolyl group, a mesityl group, a pentafluorophenyl group, a benzoyl group, a naphthyl group, a naphthoyl group, a phenoxy group, a 2,6- 2. The anionic latent catalyst according to claim 1, wherein the catalyst is at least one selected from the group consisting of a dimethylphenoxy group, a 2,6-di-t-butylphenoxy group, a normal propyl group, and an isopropyl group. . 3. A catechol group, an acetylacetonate group, and a 2,2,6,6-tetramethyl group in which the substituent L of the element X having a group 13 Lewis acidity is an intramolecular bidentate substituent. At least one selected from the group consisting of a -3,5-heptanedionate group, a 3-hydroxy-2-methyl-4H-pyrano-4-ate group, and a 9-bicyclo [3,3,1] nonyl group The anionic latent catalyst according to claim 1, wherein 4. 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 according to claim 1. A thermosetting resin composition comprising a catalyst (C) as an essential component.