JPH115829A - Thermosetting resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition stable for a long period of time at a normal temperature, rapidly curing in molding by heating, useful as electric and electronic parts, by including a specific tetrasubstituted phosphonium tetrasubstituted borate. SOLUTION: This composition contains a tetrasubstituted phosphonium tetrasubstituted borate of formula I (R1 to R4 are each independently a monofunctional aliphatic group or an organic group containing an aromatic ring or a heterocycle; Ar is an aromatic ring formula substituent groups X and Y in the molecule, etc.; X and Y are each a group in which a monofunctional proton releases a proton, and the substituent groups X and Y in the same molecule are bound with a boron atom to form a chelate ring) [e.g. tetraphenylphosphonium-bis(catecholato) borate].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a thermosetting resin composition. More specifically, it can be stably stored at room temperature for a long time,
Further, the present invention relates to a resin composition which is quickly cured when heated at the time of molding and can provide a molded article having good moldability and high quality, and is particularly useful for electric and electronic parts.

[0002]

2. Description of the Related Art A thermosetting resin is generally used by blending a catalyst in order to accelerate the curing of the resin during molding. For example, in the case of epoxy resin, as a curing catalyst,
Various compounds such as amines, imidazole compounds, nitrogen-containing heterocyclic compounds such as diazabicycloundecene, organosilicone compounds, organophosphine compounds, quaternary ammonium, phosphonium or arsonium compounds are used. .

[0003] A maleimide resin can be radically cured only by heating, but the properties of a molded product obtained by curing are generally better when cured using a catalyst. As a curing catalyst for the maleimide resin,
Various compounds such as azo compounds, radical polymerization initiators such as organic peroxides, amines, imidazole compounds, organophosphine compounds, quaternary ammonium, and ion catalysts such as phosphonium compounds are used. .

[0004] Catalysts that are usually used often exhibit a curing acceleration effect even at a relatively low temperature such as room temperature. For example, heating or heat generation when mixing the resin with other compounding components may cause the resin to harden. In addition to allowing the curing to proceed, the curing reaction also proceeds while the resin composition is stored at room temperature after mixing, so that the quality of the resin composition tends to deteriorate. Therefore, when using such a catalyst, it is necessary to strictly control the quality when mixing with various components, keep the temperature low during storage and transportation, and furthermore, strictly control the molding conditions and the like. Was inevitable.

[0005] Therefore, in recent years, many studies have been made to develop a so-called latent catalyst, in which the curing reaction of a resin does not proceed at a relatively low temperature such as normal temperature, and the curing reaction is accelerated only when heated during molding. Has been made. As one of the methods of making the catalyst latent, there is a latent catalyst in which the active site of the catalyst is ion-paired and capped with a protecting group. For example, JP
JP 1-24399 describes that tetraphenylphosphonium tetraphenylborate is effective for improving room temperature storage stability and curability. But,
Tetraphenylphosphonium tetraphenylborate has a strong ionic bond between a cationic tetraphenylphosphonium group and an anionic tetraphenylborate group, has a melting point of 300 ° C. or more, and is uniform even when kneaded with a thermosetting resin composition. , The catalyst activity is low, and good curing reactivity cannot be exhibited during molding.

On the other hand, the ionic bond between the anion portion and the cation portion has a moderate strength, and as a latent catalyst, exhibits favorable behavior in which both room temperature stability and curability during molding are compatible.
Research has been conducted on a catalyst that can be dry-blended with a thermosetting resin. Japanese Patent Publication No. 5-76490 proposes a tetra-substituted phosphonium tetra-substituted borate as a latent catalyst. The substituent on the boron side of this compound is a hydrocarbon group, at least one of which is an alkyl group having 1 to 6 carbon atoms. Japanese Patent Application Laid-Open No. 8-295721 proposes a tetra-substituted phosphonium tetra-substituted borate in which the boron side is a tetraorganic acid borate, and a method for synthesizing the same. Similar to Japanese Patent Publication No. 5-76490, it is said that the latent catalyst exhibits favorable behavior in which storage stability at room temperature and curability during molding are compatible.

[0007]

DISCLOSURE OF THE INVENTION The present invention can be stably stored at room temperature for a long period of time,
At the same time, another object of the present invention is to provide a thermosetting resin composition which exhibits excellent curability by heating at the time of molding and can provide a molded article having good moldability and high quality.

[0008]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have found that a tetra-substituted phosphonium tetra-substituted borate having a specific structure is blended into a thermosetting resin. Thus, the present invention has been found to exhibit excellent storage stability at room temperature and excellent curability during heat molding, and that the final cured product gives a high-quality molded product. Was completed.

That is, the present invention provides at least one resin selected from the group consisting of an epoxy resin, a maleimide resin and the like.
It is characterized in that a tetra-substituted phosphonium tetra-substituted borate represented by the general formula [1] is blended as a latent catalyst of one or more thermosetting resins.

[0010]

Embedded image In the formula, R _{1 to} R ₄ are an organic group having an aromatic ring or a hetero ring or a monovalent aliphatic group, which may be the same or different. Ar is a group containing an aromatic ring or a heterocyclic ring having substituents X and Y in the molecule. X
And Y are groups in which a monovalent proton-donating substituent emits a proton, and the substituents X and Y in the same Ar molecule
Binds to a boron atom to form a chelate ring.

Furthermore, among the tetrasubstituted phosphonium tetrasubstituted borates represented by the general formula [1], XA
r-Y represents a group formed by the proton donor releasing two protons, and in particular, a polyfunctional aromatic carboxylic acid or a polyhydric phenol compound is a group formed by releasing two protons. .

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The thermosetting resin composition of the present invention comprises
This is a composition obtained by blending a latent catalyst comprising the tetra-substituted phosphonium tetra-substituted borate represented by the general formula [1] with a thermosetting resin.

In the general formula [1], R _{1 to} R ₄ are an organic group having an aromatic ring or a heterocyclic ring or a monovalent aliphatic group, which may be the same or different. Examples of such a group include a methyl group, an ethyl group, a butyl group, an allyl group, a phenyl group, a tolyl group, a benzyl group, an ethylphenyl group, a phenoxy group, and a naphthyl group. Examples of the phosphonium group constituting the general formula [1] include, for example, a tetraphenylphosphonium group, a tetratolylphosphonium group, a tetraethylphosphonium group, a tetramethoxyphosphonium group, a tetranaphthylphosphonium group, a tetrabenzylphosphonium group, and an ethyltriphenylphosphonium group , N-butyltriphenylphosphonium group, 2-hydroxyethyltriphenylphosphonium group, trimethylphenylphosphonium group, methyldiethylphenylphosphonium group,
Methyl diallyl phenyl phosphonium group, tetra-n-
A butylphosphonium group and the like can be mentioned.

In the formula, Ar is an aromatic or heterocyclic group having substituents X and Y in the molecule. X and Y
Is a group in which a monovalent proton donating substituent emits a proton, and the substituents X and Y in the same Ar molecule are bonded to a boron atom to form a chelate ring. Examples of the proton donor that provides such an organic group X—Ar—Y include Ar
Has any of the substituents X and Y, the other substituents are not particularly limited, and a trivalent or higher valent proton donor can be used. Among them, aromatic or heterocyclic polyfunctional carboxylic acids or polyphenols are particularly preferred. In this case, the polyhydric phenol is a general term for compounds in which two or more hydrogen atoms bonded to a benzene ring, a naphthalene ring, or another aromatic ring are substituted with a hydroxyl group.

Examples of such polyfunctional carboxylic acids and polyhydric phenols include catechol, salicylic acid, o-phthalic acid, 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 1-hydroxy-2-naphthoic acid , 3-hydroxy-
2-naphthoic acid, 2,3-naphthalenedicarboxylic acid, 3,4-biphenol, 2-hydroxybiphenyl-3-carboxylic acid, 4-
Hydroxybiphenyl-3-carboxylic acid, 2,3-pyridinedicarboxylic acid, 2,2′-biphenol, 1,8-naphthalic acid, 2,
And divalent aromatic organic acids such as 2′-binaphthol.
Also, resorcinol, trimellitic acid, pyromellitic acid,
A trivalent or higher aromatic polyvalent organic acid such as 2,2'-biphenol-3-carboxylic acid and 1,4,5,8-naphthalenetetracarboxylic acid may be used. The above compounds are mentioned as an example, but are not limited to them. The above compounds can be used alone or in combination of two or more.

In a latent catalyst comprising a tetra-substituted phosphonium tetra-substituted borate represented by the general formula [1], an organic group represented by X-Ar-Y is bonded to a boron atom to form a chelate ring structure. By combining
Suppression of catalytic activity at low temperatures becomes more effective than in the case of a proton donor that does not form a cyclic chelate structure,
At room temperature, the resin composition can be stably stored for a longer period of time.

The latent catalyst comprising the tetra-substituted phosphonium tetra-substituted borate represented by the general formula [1] is represented by the general formula [3] and the tetra-substituted phosphonium tetra-substituted borate represented by the general formula [2]. A divalent or higher valent aromatic or heterocyclic proton donor capable of forming a chelate ring structure is used in bulk or organic solvent for 150 to 25.
It is possible to synthesize by reacting at 0 ° C.

[0018]

Embedded image In the formula, R _{5 to} R ₁₂ are an organic group having an aromatic ring or a hetero ring or a monovalent aliphatic group, which may be the same or different.

[0019]

Embedded image In the formula, Ar is a group comprising an aromatic ring or a heterocyclic ring having substituents X and Y in the molecule, and X and Y are groups formed by a monovalent proton donating substituent releasing a proton. . Further, n represents an integer of (n ≧ 2).

The latent catalyst comprising the tetra-substituted phosphonium tetra-substituted borate represented by the general formula [1] does not show catalytic activity at room temperature when mixed with the thermosetting resin. The curing reaction does not proceed, and the catalytic activity is exhibited at a high temperature during molding, and once developed, the catalytic activity is stronger than that of a conventional curing accelerator, and the thermosetting resin is highly cured.

The latent catalyst used in the present invention can be used not only alone, but also in combination of two or more. Further, it can be used in combination with other curing accelerators as long as the object of the present invention is not impaired.

The latent catalyst comprising a tetra-substituted phosphonium tetra-substituted borate in the present invention is effective for all thermosetting resins whose curing reaction is accelerated by the latent catalyst. It is particularly effective for thermosetting resins in which a salt catalyst is effective. Examples of such a thermosetting resin include an epoxy resin, particularly an epoxy resin containing a phenol resin or a carboxylic anhydride curing agent, and a maleimide resin. In addition to these resins, cyanate resins, isocyanate resins, acrylate resins, alkenyl resins and the like can be mentioned.

Particularly effective epoxy resins for which a latent catalyst comprising a tetra-substituted phosphonium tetra-substituted borate is effective are bisphenol A epoxy resin, bisphenol F epoxy resin, brominated bisphenol epoxy resin, biphenyl epoxy resin, phenol novolak epoxy resin. Epoxy resin, cresol novolak epoxy resin, alicyclic epoxy resin, glycidyl ester epoxy resin, glycidylamine epoxy resin, heterocyclic epoxy resin, stilbene epoxy resin, 4,4'-bis (1,2-epoxy Ethyl) diphenyl ether, 4,4′-bis (1,2-epoxyethyl) biphenyl and the like can be mentioned, and they can be used alone or in combination of two or more kinds. In addition, these epoxy compounds, further as a curing agent,
Phenols, acid anhydrides and amines can be used in combination.

A maleimide resin in which a latent catalyst comprising a tetra-substituted phosphonium tetra-substituted borate is particularly effective includes, for example, N, N'-m-phenylenebismaleimide,
N, N'-p-phenylenebismaleimide, N, N'-m-toluylenebismaleimide, N, N'-4,4'-biphenylenebismaleimide, N, N'-4,4 '-[3, 3'-dimethylbiphenylene] bismaleimide, N, N'-4,4 '-[3,3'-dimethyldiphenylmethane] bismaleimide, N, N'-4,4'-[3,3'-diethyldiphenylmethane] Bismaleimide, N, N'-4,4'-diphenylmethanebismaleimide, N, N'-4,4'-diphenylpropanebismaleimide, N, N'-4,4'-diphenylether bismaleimide, N, N '-4,4'-diphenylsulfone bismaleimide, N, N'-3,3'-diphenylsulfone bismaleimide,
2,2-bis- (4- (4-maleimidophenoxy) phenyl)
Propane, 2,2-bis- (4- (4-maleimidophenoxy)
Phenyl) hexafluoropropane, 2,2-bis- (4- (4
Maleimide compounds such as-(maleimidophenoxy) phenyl) sulfone and 2,2-bis- (4- (3-maleimidophenoxy) phenyl) sulfone or amines obtained by modifying these maleimide compounds with aromatic amine compounds or aromatic allyl compounds; An allyl-modified maleimide resin can be mentioned, and it is also possible to use one or a combination of two or more.

[0025] The thermosetting resin composition of the present invention may contain, if necessary, inorganic fillers such as alumina, fused silica, crystalline silica, clay, and talc, and mold release agents, flame retardants, and coupling agents. May be added.

[0026]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. The chemical structures and abbreviations of the catalysts (curing accelerators) used in the examples and comparative examples are summarized below.

[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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Various catalysts were mixed in a thermosetting resin to prepare a molding material, and the latency was evaluated. For evaluation of the material, spiral flow, curing torque, and storage stability (remaining rate of spiral flow) were measured. (1) Spiral flow Using a mold for spiral flow measurement according to EMMI-I-66, mold temperature 175 ° C, injection pressure 70 kg / c
The measurement was performed under the conditions of m ² and curing time of 2 minutes. Spiral flow is a parameter of fluidity, with higher values indicating better fluidity.

(2) Curing torque Curast meter (manufactured by Orientec Co., Ltd., JSR
(Curastometer PS type), and the torque after 175 ° C. and 90 seconds was determined. The torque in the curast meter is a parameter of curability, and the larger the value, the better the curability.

(3) Storage Property (Spiral Flow Residual Rate) After storing the molding material at 25 ° C. for 7 days and 30 days,
The spiral flow was measured again, and the percentage (spiral flow residual ratio) of the initial value of the spiral flow measured immediately after the preparation of the material was determined and used as an index of storage stability. The higher the value of the residual spiral flow, the better the storage stability.

Example 1 Orthocresol novolak type epoxy resin having a softening point of 65 ° C. and an epoxy equivalent of 210 (EOCN-1025-65, manufactured by Nippon Kayaku Co., Ltd.) 67
Phenol novolak resin having a softening point of 105 ° C and a hydroxyl equivalent of 104 by weight (PR-51, manufactured by Sumitomo Durez Co., Ltd.)
470) 33 parts by weight, 3.5 parts by weight of 4PPB-CT (tetraphenylphosphonium-bis (catecholate) borate) represented by the general formula [4] as a latent catalyst, 300 parts by weight of fused silica, and 2 parts by weight of carnauba wax Parts were blended and roll-kneaded at 90 ° C. for 8 minutes to obtain a molding material. The spiral flow of this molding material was 77 cm, and the curing torque was 77 kgf · cm. In addition, 25 ℃ ・ 7
Spiral flow retention after storage for 95 days is 95%, 25 ° C
-The residual ratio after 30 days was 90%.

Example 2 Same as Example 1 except that 3.8 parts by weight of 4PPB-SA (tetraphenylphosphonium-bis (salicylate) borate) represented by the general formula [5] was blended as a latent catalyst. A molding material was prepared by blending and operation. The spiral flow of the obtained material was 80 cm, and the curing torque was 81 kgf · cm. The spiral flow residual ratio after storage at 25 ° C. for 7 days was 96%, and the residual ratio after storage at 25 ° C. for 30 days was 92%.

(Example 3) Except that 4.1 parts by weight of 4PPB-DHN (tetraphenylphosphonium-bis (2,3-dioxynaphthalene) borate) represented by the general formula [6] was blended as a latent catalyst. A molding material was prepared by the same blending and operation as in Example 1. The spiral flow of the obtained material is 77 cm, and the curing torque is 80 kgf.
Cm. The spiral flow residual rate after storage at 25 ° C. for 7 days was 96%, and the residual rate after storage at 25 ° C. for 30 days was 91%.

(Example 4) Except that 4.4 parts by weight of 4PPB-HNA (tetraphenylphosphonium-bis (3-oxy-2-naphthoate) borate) represented by the general formula [7] was blended as a latent catalyst. A molding material was prepared by the same blending and operation as in Example 1. The spiral flow of the obtained material is 81 cm, and the curing torque is 78 kg.
f · cm. The spiral flow residual rate after storage at 25 ° C. for 7 days was 97%, and the residual rate after storage at 25 ° C. for 30 days was 93%.

Example 5 Except for blending 4.4 parts by weight of 4PPB-OBP (tetraphenylphosphonium-bis (2,2'-dioxybiphenyl) borate) represented by the general formula [8] as a latent catalyst. Prepared a molding material by the same blending and operation as in Example 1. The spiral flow of the obtained material is 80 cm, and the curing torque is 75 kgf.
Cm. The spiral flow residual rate after storage at 25 ° C for 7 days was 96%, and the residual rate after storage at 25 ° C for 30 days was 90%.

Example 6 As a latent catalyst, 5.6 parts by weight of 4PPB-BNP (tetraphenylphosphonium-bis (1,1′-bi-2-oxynaphthalene) borate) represented by the general formula [9] was used. Except for blending, a molding material was prepared by the same blending and operation as in Example 1. The resulting material has a spiral flow of 85 cm and a curing torque of 8
It was 1 kgf · cm. The spiral flow residual rate after storage at 25 ° C. for 7 days was 97%, and the residual rate after storage at 25 ° C. for 30 days was 91%.

Comparative Example 1 A molding material was prepared in the same manner as in Example 1, except that 0.8 parts by weight of triphenylphosphine represented by the general formula [10] was blended as a catalyst. The spiral flow of the material obtained is 71c
m, the curing torque was 73 kgf · cm. Also, 2
Spiral flow retention after storage at 5 ° C for 7 days is 64
%, And the residual ratio after 30 days at 25 ° C. was 53%.

Comparative Example 2 The same as Example 1 except that 0.3 part by weight of 1,8-diazabicyclo [5.4.0] -7-undecene represented by the general formula [11] was blended as a catalyst. A molding material was prepared by blending and operation. The resulting material has a spiral flow of 70 cm and a curing torque of 71 kg.
f · cm. The spiral flow residual rate after storage at 25 ° C. for 7 days was 60%, and the residual rate after storage at 25 ° C. for 30 days was 48%.

Comparative Example 3 A molding material was prepared in the same manner as in Example 1, except that 0.3 parts by weight of 2-methylimidazole represented by the general formula [12] was blended as a catalyst. The spiral flow of the obtained material is 73c
m, the curing torque was 75 kgf · cm. Also, 2
The residual spiral flow after storage at 5 ° C for 7 days is 67
%, And the residual ratio after 30 days at 25 ° C. was 58%.

Comparative Example 4 A molding material was prepared in the same manner as in Example 1, except that 4.0 parts by weight of tetraphenylphosphonium-tetraphenylborate represented by the general formula [13] was blended as a catalyst. . The resulting material has a spiral flow of 78 cm and a curing torque of 61 kg.
f · cm. The spiral flow residual rate after storage at 25 ° C. for 7 days was 95%, and the residual rate after storage at 25 ° C. for 30 days was 83%.

(Comparative Example 5) As a catalyst, 4PPB-ICA (tetraphenylphosphonium-tetrakis (isocyanurate) borate) represented by the general formula [14] was 3.3.
A molding material was prepared by the same blending and operation as in Example 1 except that it was blended in parts by weight. The spiral flow of the obtained material was 70 cm, and the curing torque was 73 kgf · cm. The spiral flow residual rate after storage at 25 ° C. for 7 days was 93%, and the residual rate after storage at 25 ° C. for 30 days was 76%.

(Comparative Example 6) 4PPB-BZ (tetraphenylphosphonium-tetrakis (benzotriazolate) borate) represented by the general formula [15] was used as a catalyst.
A molding material was prepared by the same blending and operation as in Example 1, except that 7 parts by weight were blended. The spiral flow of the obtained material was 74 cm, and the curing torque was 70 kgf · cm. The residual ratio of the spiral flow after storage at 25 ° C. for 7 days was 91%, and the residual ratio after storage at 25 ° C. for 30 days was 71%.

The results of Examples 1 to 6 and Comparative Examples 1 to 6 were
The results are summarized in Tables 1 and 2, respectively.

[Table 1]

[0055]

[Table 2]

Each of the resin compositions of Examples 1 to 6 had appropriate and good fluidity immediately after production, and all of the resin compositions were 90% even after storage at 25 ° C. for 30 days as well as at 25 ° C. for 7 days. The above spiral flow values are shown, and it is understood that the long-term storage stability is excellent. In addition, the curing torque also showed a high value and was good.

On the other hand, the resin compositions of Comparative Examples 1 to 3 exhibited good curing torque values equivalent to those of the Example, but had a spiral flow residual rate of 60% or less after 30 days at 25 ° C. Even after 7 days at 70 ° C, it remained at a low level of 70% or less. Further, in Comparative Example 4, although the spiral flow and the residual ratio of the spiral flow exhibited relatively good values, the curing torque was lower than in the examples, and the curability was poor. Furthermore, Comparative Examples 5 to 6 show relatively good values in spiral flow, curing torque, and residual ratio of spiral flow after 25 days at 25 ° C., however, compared with Examples in spiral flow residual ratio after 25 days and 30 days. Was low.

Example 7 52 parts by weight of a tetramethylbiphenyl type epoxy resin having a melting point of 105 ° C. and an epoxy equivalent of 185 (YX-4000H manufactured by Yuka Shell Epoxy Co., Ltd.), a softening point of 95 ° C. and a hydroxyl equivalent of 177 Xylene type phenol resin (manufactured by Mitsui Toatsu Chemicals, Inc., XL-22)
5), 48 parts by weight, 3.5 parts by weight of 4PPB-CT represented by the general formula [4] as a latent catalyst, fused silica 80
0 parts by weight and 2 parts by weight of carnauba wax, 9
Roll kneading was performed at 0 ° C. for 8 minutes to prepare a molding material. The spiral flow of this molding material was 97 cm, and the curing torque was 91 kgf · cm. The residual spiral flow after storage at 25 ° C. for 7 days was 91%, and the residual rate after storage at 25 ° C. for 30 days was 83%.

Example 8 A molding material was prepared in the same manner as in Example 7, except that 3.8 parts by weight of 4PPB-SA represented by the general formula [5] was blended as a latent catalyst. The spiral flow of the material obtained is 105c
m, the curing torque was 88 kgf · cm. Also, 2
Spiral flow retention after storage at 5 ° C for 7 days is 90
%, And the residual ratio after 30 days at 25 ° C. was 83%.

Example 9 A molding material was prepared in the same manner as in Example 7, except that 4.1 parts by weight of 4PPB-DHN represented by the general formula [6] was blended as a latent catalyst. The spiral flow of the material obtained is 110
cm, and the curing torque was 90 kgf · cm. Also,
Spiral flow residual rate after storage at 25 ° C for 7 days is 92
%, And the residual ratio after 30 days at 25 ° C. was 87%.

Example 10 A molding material was prepared in the same manner as in Example 7, except that 4.4 parts by weight of 4PPB-HNA represented by the general formula [7] was blended as a latent catalyst. The spiral flow of the material obtained is 109
cm, and the curing torque was 86 kgf · cm. Also,
Spiral flow retention after storage at 25 ° C for 7 days is 94
%, And the residual ratio after 30 days at 25 ° C. was 86%.

Example 11 A molding material was prepared in the same manner as in Example 7, except that 4.4 parts by weight of 4PPB-OBP represented by the general formula [8] was blended as a latent catalyst. The spiral flow of the material obtained is 99c
m, the curing torque was 90 kgf · cm. Also, 2
Spiral flow residual rate after storage at 5 ° C for 7 days is 91
%, And the residual ratio after 30 days at 25 ° C. was 81%.

Example 12 A molding material was prepared in the same manner as in Example 7, except that 5.6 parts by weight of 4PPB-BNP represented by the general formula [9] was blended as a latent catalyst. The spiral flow of the resulting material is 104
cm, and the curing torque was 91 kgf · cm. Also,
Spiral flow retention after storage at 25 ° C for 7 days is 94
%, The residual ratio after 30 days at 25 ° C. was 82%.

Comparative Example 7 A molding material was prepared in the same manner as in Example 7, except that 0.8 parts by weight of triphenylphosphine represented by the general formula [10] was blended as a catalyst. The spiral flow of the material obtained is 86c
m, the curing torque was 89 kgf · cm. Also, 2
The residual spiral flow after storage at 5 ° C for 7 days is 59.
%, And the residual ratio after 30 days at 25 ° C. was 43%.

Comparative Example 8 The same formulation as in Example 7 except that 1,8-diazabicyclo [5.4.0] -7-undecene represented by the general formula [11] was used in an amount of 0.3 part by weight as a catalyst. -A molding material was prepared by the operation. The resulting material has a spiral flow of 84 cm and a curing torque of 84 kgf ·
cm. The residual spiral flow after storage at 25 ° C. for 7 days was 51%, and the residual ratio after storage at 25 ° C. for 30 days was 40%.

Comparative Example 9 A molding material was prepared in the same manner as in Example 7, except that 0.3 parts by weight of 2-methylimidazole represented by the general formula [12] was blended as a catalyst. The spiral flow of the obtained material is 81c
m, the curing torque was 88 kgf · cm. Also, 2
Spiral flow residual rate after storage at 5 ° C for 7 days is 55
%, And the residual ratio after 30 days at 25 ° C. was 41%.

(Comparative Example 10) A general formula [13] as a catalyst
A molding material was prepared by the same blending and operation as in Example 7, except that 4.0 parts by weight of tetraphenylphosphonium tetraphenylborate represented by the formula (1) was blended. The resulting material has a spiral flow of 204 cm and a curing torque of 38 k.
gf · cm. The spiral flow residual rate after storage at 25 ° C. for 7 days was 98%, and the residual rate after storage at 25 ° C. for 30 days was 86%.

(Comparative Example 11) A catalyst represented by the general formula [14]
A molding material was prepared by the same blending and operation as in Example 7, except that 3.3 parts by weight of 4PPB-ICA represented by. The spiral flow of the obtained material is 101 cm,
The curing torque was 90 kgf · cm. 25 ° C
-Spiral flow residual rate after storage for 7 days is 91%, 2
The residual rate after 30 days at 5 ° C. was 76%.

(Comparative Example 12) A catalyst represented by the general formula [15]
A molding material was prepared by the same blending and operation as in Example 7, except that 2.7 parts by weight of 4PPB-BZ represented by the following formula was blended. The spiral flow of the obtained material was 96 cm, and the curing torque was 87 kgf · cm. In addition, 25 ℃ ・ 7
Spiral flow retention after storage for 89 days is 89%, 25 ° C
-The residual ratio after 30 days was 70%.

The results of Examples 7 to 12 and Comparative Examples 7 to 12 are summarized in Tables 3 and 4, respectively.

[Table 3]

[0071]

[Table 4]

All of the resin compositions of Examples 7 to 12 had appropriate and good fluidity immediately after production, and had a temperature of 25 ° C.
After storage for 30 days at 25 ° C, of course,
All of them show a spiral flow value of 80% or more, which indicates that they have excellent long-term storage stability. In addition, the curing torque also showed a high value and was good.

On the other hand, the resin compositions of Comparative Examples 7 to 9 exhibited good curing torque equivalent to that of the Example, but had a residual spiral flow of 50% or less after 25 days at 25 ° C. Even after 7 days at ℃, it remained at a low level of 60% or less. In Comparative Example 11, although the spiral flow and the residual ratio of the spiral flow exhibited relatively good values, the curing torque was lower than in the examples, and the curability was poor. In Comparative Examples 11 to 12, although the spiral flow, the curing torque, and the residual ratio of the spiral flow after 7 days at 25 ° C. show relatively good values, 25 ° C./30
The spiral flow residual rate after the day was a lower value than in the examples.

[0074]

According to the present invention, the latent catalyst used in the present invention does not exhibit a catalytic action at room temperature but exhibits an excellent catalytic action when heated. The thermosetting resin composition using this can be stably stored for a long period of time, and is quickly cured by heating during molding,
Provides good moldability and high quality molded products. The epoxy resin and maleimide resin compositions containing the latent catalyst according to the present invention are particularly useful for electronic and electrical parts.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Akiko Okubo 2-58-8 Higashishinagawa, Shinagawa-ku, Tokyo Sumitomo Bakelite Co., Ltd. (72) Inventor Minoru Kobayashi 2-5-2-8 Higashishinagawa, Shinagawa-ku, Tokyo Sumitomo Bakelite Co., Ltd.

Claims (3)

[Claims] 1. A thermosetting resin composition comprising a tetra-substituted phosphonium tetra-substituted borate represented by the general formula [1] as a latent catalyst for accelerating the curing of the thermosetting resin. . Embedded image In the formula, R _{1 to} R ₄ are an organic group having an aromatic ring or a hetero ring or a monovalent aliphatic group, which may be the same or different. Ar is a group containing an aromatic ring or a heterocyclic ring having substituents X and Y in the molecule. X and Y are groups in which a monovalent proton-donating substituent emits a proton, and the substituents X and Y in the same Ar molecule combine with a boron atom to form a chelate ring. 2. The thermosetting resin according to claim 1, wherein the thermosetting resin is at least one resin selected from the group consisting of an epoxy resin and a maleimide resin. Composition. 3. A group obtained by releasing two protons from a proton donor represented by X—Ar—Y in a tetra-substituted phosphonium tetra-substituted borate represented by the general formula [1] is a polyfunctional aromatic compound. The thermosetting resin composition according to claim 1 or 2, wherein the aromatic carboxylic acid or the polyhydric phenol compound is a group that releases two protons.