JPH0574581B2 - - Google Patents

Description

[Detailed description of the invention]

[Field of Application of the Invention] The present invention relates to a novel epoxy ester resin composition. [Background of the Invention] Epoxy ester resin compositions are useful for electrical equipment, such as insulating materials for insulated windings, casting materials, various fiber-reinforced resin molded products, impregnating materials, surface covering materials for decorative paper or decorative boards, and synthetic resin laminations. Applicable to impregnated resins for boards or decorative boards, paints, adhesives, prepreg resins, etc. In addition, in recent years, applications have begun to be considered as materials for covering elements of semiconductor devices, sealing materials, and the like. By the way, in the fields of electrical equipment and semiconductor devices, there is a trend toward smaller size, lighter weight, higher performance, and higher reliability, and there is a strong demand for heat resistance to be added to the epoxy ester resins (compounds) used for these applications. It is being Conventionally, as a countermeasure against this problem, an epoxy ester resin obtained by reacting a polyglycidyl ether of novolac phenol with a polymerizable unsaturated monocarboxylic acid has been known as an effective means for imparting heat resistance. However, this system has poor stability during storage (large viscosity change), and in order to improve this,
Addition of various inhibitors has the disadvantage of causing problems such as deterioration of heat resistance and electrical properties. [Object of the Invention] An object of the present invention is to provide a novel epoxy ester resin composition having excellent heat resistance and stability during storage. [Summary of the invention] The present invention has been made in view of the above situation, and
The first gist is a resin composition containing an epoxy ester resin characterized by having a tris(hydroxyphenyl)methane skeleton and a polymerizable compound. The epoxy ester resin is a resin obtained by reacting a tris(hydroxyphenyl)methane-based epoxy compound with a polymerizable unsaturated monocarboxylic acid, and has the following formula:

It is characterized by being represented by: (wherein, m is 0 to 10). In the present invention, the epoxy ester resin is manufactured by the following reaction formula.

[ka]

[Chemical formula] (In the formula, m is 0 to 10.) In other words, a tris(hydroxyphenyl)methane-based polyfunctional epoxy compound and a polymerizable unsaturated monocarboxylic acid compound are coexisted in the presence of an esterification accelerator. It can be obtained by reacting in the same state. To explain in more detail, in the present invention, the tris(hydroxyphenyl)methane-based polyfunctional epoxy compound has the following formula:

It is represented by [ ]. Examples of these include Dow Chemical's XD-9053 (epoxy equivalent, 225, softening point, 85°C), XD-7342 (epoxy equivalent, 162,
softening point, 55℃). Furthermore, examples of the polymerizable unsaturated monocarboxylic acid compound that can be used in the present invention include acrylic acid, methacrylic acid, and crotonic acid. These unsaturated monocarboxylic acid compounds may be used in combination. Further, in order to impart flexibility, a saturated dicarboxylic acid such as adipic acid, sebacic acid, phthalic acid, etc. may be used in combination. The tris(hydroxyphenyl)methane-based epoxy compound and the polymerizable unsaturated monocarboxylic acid compound are produced by the method described in JP-A-50-14617. For example, 10 parts by weight of a polyfunctional epoxy compound based on tris(hydroxyphenyl)methane, 10 parts by weight of a polymerizable unsaturated monocarboxylic acid compound.
It is obtained by blending the mixture in an amount within the range of 100 parts by weight, adding a known esterification accelerator such as an imidazole compound, and reacting at 60 to 130°C for several hours. When the blending ratio of the polymerizable unsaturated monocarboxylic acid compound is within the range of 30 to 60 parts by weight, the oxidation of the epoxy ester resin is 5 to 20 parts by weight, and when the blending ratio is 10 to 30 parts by weight. In some cases, epoxy groups remain. The effects of the present invention can also be achieved with such resins. In addition, in the present invention, as the polymerizable compound, a compound having an N-substituted maleimide group, celoxide diacrylate, unsaturated polyester resin,
There are polyfunctional epoxy compounds, and one or more of them can be used in combination. As a compound having an N-substituted maleimide group, for example, the following formula

[Formula] [In the formula, R represents an alkylene group, an arylene group, or a divalent organic group substituted thereof], and specifically, N,
N'-ethylene bismaleimide, N,N'-hexamethylene bismaleimide, N,N'-dodecamethylene bismaleimide, N,N'-m-phenylene bismaleimide, N,N'-4,4'-diph enyl ether bismaleimide, N,N'-4,4'-diphenylmethane bismaleimide, N,N'-4,4'-dicyclohexylmethane bismaleimide, N,
N'-4,4'-methaxylene bismaleimide, N,
N'-4,4'-diphenylcyclohexane bismaleimide, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, 2,2-bis[3-methyl-4-(4-maleimide) phenoxy)
phenyl]propane, 2,2-bis[3-chloro-4-(4-maleimidophenoxy)phenyl"
Propane, 2,2-bis[3-bromo-4-(4
-maleimidophenoxy)phenyl]propane,
2,2-bis[3-ethyl-4-(4-maleimidophenoxy)phenyl]propane, 2,2-bis[3-propyl-4-(4-maleimidophenoxy)phenyl]propane, 2, 2-bis [3-
Isopropyl-4-(4-maleimidophenoxy)
phenyl]propane, 2,2-bis[3-butyl-4-(4-maleimidophenoxy)phenyl]
Propane, 2,2-bis[3-sec-butyl-4
-(4-maleimidophenoxy)phenyl]propane, 2,2-bis[3-methoxy-4-(4-
maleimidophenoxy)phenyl]propane,
1,1-bis[4-(4-maleimidophenoxy)
phenyl]ethane, 1,1-bis[3-methyl-
4-(4-maleimidophenoxy)phenyl]ethane, 1,1-bis[3-chloro-4-(maleimidophenoxy)phenyl]ethane, 1,1-bis[3-bromo-4-(4 -maleimidophenoxy)phenyl]ethane, bis[4-(4-maleimidophenoxy)phenyl]methane, bis[3-
Methyl-4-(4-maleimidophenoxy)phenyl]methane, bis[3-chloro-4-(4-maleimidophenoxy)phenyl]methane, bis[3-bromo-4-(4-maleimidophenoxy)phenyl]methane C)
phenyl]methane, 1,1,1,3,3,3-hexafluoro-2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, 1,1,
1,3,3,3-hexachloro-2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, 3,3-bis[4-(4-maleimidophenoxy)phenyl]pentane, 1,1-bis[4-(4-maleimidophenoxy)phenyl]propane, 1,1,1,3,3,3-hexafluoro-2,2-bis[3,5-dibromo-4(4 −
maleimidophenoxy)phenyl]propane,
1,1,1,3,3,3-hexafluoro-2,
Examples include 2-bis[3-methyl-4(4-maleimidophenoxy)phenyl]propane, and one or more of these can be used. Furthermore, mixtures of mono-substituted maleimide, tri-substituted maleimide, tetra-substituted maleimide and the above-mentioned substituted bismaleimide can also be used as appropriate. In addition, reaction products accompanying the Deers-Alda addition reaction can also be used, including the amine adducts, phenol adducts, and thiol adducts of the above-mentioned compounds having an N-substituted maleimide group.
Among these adducts, amine adducts are useful. Examples of primary diamines include m-phenylene diamine, p-phenylene diamine, benzidine, 3,3'-dimethyl-4,
4-diaminobiphenyl, 3,3'-dichlorobenzidine, 3,3'dimethoxybenzidine, 4,4'diaminodiphenylmethane, 1,1-bis(4-aminophenyl)ethane, 2,2-bis(4- aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-
bis(4-aminophenyl)-1,3-dichloro-1,1,3,3-tetrafluoropropane,
4,4'-diaminodiphenyl ether, 4,4'-
Diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenylsulfoxide, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 3,3'-diaminodibenzophenone, 4,4-diaminobenzophenone, 3,4'-
Diaminobenzophenone, N,N-bis(4-aminophenyl)aniline, N,N-bis(4-aminophenyl)methylamine, N,N-bis(4-aminophenyl)
-aminophenyl)-n-butylamine, N,N
-bis(4-aminophenyl)amine, m-aminobenzoyl-p-aminoanilide, 4-aminophenyl-3-aminobenzoate, 4,4'-diaminoazobenzene, 3,3'-diaminoazobenzene, bis(3-aminophenyl) ) diethylsilane, bis(4-aminophenyl)phenylphosphine oxide, bis(4-aminophenyl)ethylphosphine oxide, 1,5-diaminonaphthalene, 2,6-diaminopyridine, 2,5-
Diamino-1,3,4-oxadiazole, m-
xylylene diamine, p-xylylene diamine,
2,4-(p-β-amino-tert-butylphenyl)ether, p-bis-2-(2-methyl-4
-aminopentyl)benzene, p-bis(1,1
-dimethyl-5-aminobentyl)benzene, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, 2,11-diaminododecane, 1,12-diaminooctadecane, 2,
2-dimethylpropylenediamine, 2,5-dimethylhexamethylenediamine, 3-methylheptamethylenediamine, 2,5-dimethylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, 5-methynonamethylenediamine, 1,
4-diaminocyclohexane, bis(p-aminocyclohexyl)methane, 3-methoxyhexamethylenediamine, 1,2-bis(3-aminopropoxy)ethane, bis(3-aminopropyl)sulfide, N,N-bis(3 -aminopropyl) methylamine, and the like. Further, examples of N-aryl substituted aromatic triamines include 2,4-diaminodiphenylamine,
2,4-diamino-5-methyl-diphenylamine, 2,4-diamino-4'-methyl-diphenylamine, 1-anilino-2,4-diaminonaphthalene, 3,3'-diamino-4-anilinobenzophenone and so on. In the present invention, celoxide diacrylate is represented by the following formula:

[ka] or

[Embodiments of the invention]

Example 1 (Production method of epoxy ester resin) As a tris(hydroxyphenyl)methane-based polyfunctional epoxy compound, XD-7342 (epoxy equivalent, 162, softening point, 55
°C, Dow Chemical Company) XD-9053 (Epoxy equivalent, 220, Softening point, 85
℃) were selected. The above epoxy compound was reacted with acrylic acid and methacrylic acid, which are polymerizable unsaturated monocarboxylic acid compounds, by the following method to obtain the desired epoxy ester resin. Manufacturing method of epoxy ester resin A: Add 53 parts by weight of methacrylic acid and 0.5 parts by weight of 2-ethylimidazole to 100 parts by weight of XD-7342, and react at 80 to 110°C for 6 hours to prepare epoxy ester resin A. Manufactured. The acid value of this resin is
It is 10.8. Manufacturing method of epoxy ester resin B: 100 parts by weight of XD-9053, 32.7 parts by weight of acrylic acid, and 2-ethyl-4-methylimidazole,
Epoxy ester resin B was produced by adding 0.5 parts by weight and reacting at 80 to 110°C for 8 hours. The acid value of this resin is 11.5. Manufacturing method of epoxy ester resin C: 40 parts by weight of epoxy novolak resin manufactured by Dow Chemical Company (epoxy equivalent weight 190), 60 parts by weight of XD-9053, 41.6 parts by weight of methacrylic acid, and 0.5 parts by weight of 2-ethylimidazole. was added and reacted at 80 to 110°C for 7 hours to produce epoxy ester resin C. The acid value of this resin is 11.1. Conventional epoxy ester resin (comparative example): 100 parts by weight of epoxy novolak resin (epoxy equivalent: 190) manufactured by Dow Chemical Company, methacrylic acid
45.3 parts by weight, and 2-ethylimidazole, 0.5
Add parts by weight, react at 80-110℃ for 6 hours,
An epoxy ester resin with an oxidation of 10.0 was obtained. The above epoxy ester resins A to C and conventional resins contain 30 parts by weight of styrene per 70 parts by weight of the resin.
The following tests were performed by adding parts by weight, and the results are shown in Table 2. Examples 2 to 13; Comparative Example Predetermined amounts of epoxy ester resins A, B, and C shown in Table 2 were collected, and N,N'-4,4'-diphenylmethane bismaleimide and chemimide were added to these, respectively. K-601: Bismaleimide amine adduct (manufactured by Lorne-Poulenc) Celloxide diacrylate (manufactured by Daicel Chemical Co., Ltd., acid value 5 or less) Unsaturated polyester resin PS-508 (manufactured by Hitachi Chemical Co., Ltd., styrene content 40% by weight) %) Epoxy resin, XD-9053 triallyl isocyanurate (TAIC) diallyl phthalate (DAP) was blended in the prescribed amounts shown in Table 2. Each of the above formulations contained 2 parts by weight of dicumyl peroxide, 75% by weight of filler (mixed fused silica glass and calcium carbonate system), and Hoechstwax E.
(manufactured by Hoechst Japan), 2 parts by weight of an epoxy silane coupling agent KBM403, and 2 parts by weight of carbon black were added. These blends were then kneaded for 30 minutes using a pressure kneader to obtain a resin composition. Next, using each of the above compositions, 180℃, 70Kg
Samples for measuring various characteristics were transfer molded under the conditions of f/cm ² and 3 minutes. Cracking resistance test: Repeated immersion in a -196°C liquid nitrogen bath and +200°C silicone oil bath for 2 minutes each to determine whether cracks appeared on the appearance of the LSI (48 pin) molded product or abnormal operation of the LSI. It was expressed as the number of cooling and heating cycles when the percentage of defective specimens reached 10% of the specimens. In addition, the bending strength of the cured specimen (at 180℃), the retention rate of bending strength after being left at 200℃ for 30 days,
Heat resistance was evaluated based on the volume resistivity and glass transition point of the cured specimen at 140°C. Epoxy ester resin B, 40 parts by weight, N,
N'-4,4'-diphenylmethane dimaleimide, 60
After dissolving 3 parts by weight of dixyl peroxide (DCPO) in 120 ml of methyl ethyl ketone, the solution was impregnated into a glass cloth. Next, it was heated and dried at 80 to 85°C for 30 minutes to obtain a glass cloth impregnated with 45% by weight resin. Layer 7 pieces of this glass cloth, heat at 180℃, 70℃
A laminate was obtained by heat-pressing molding at Kgf/cm ² for 60 minutes. The temperature characteristics of the bending strength of the obtained laminate are
As shown in the table.

【table】

【table】

【table】

〔Effect of the invention〕

The novel epoxy ester compound and the resin composition of the present invention have excellent not only heat resistance but also stability during storage.

Claims (1)

[Scope of Claims] 1. An epoxy ester resin composition comprising at least an epoxy ester resin represented by the formula: (where m is 0 to 10) and a polymerizable compound. 2. The epoxy according to claim 1, wherein the polymerizable compound is any one of a compound having an N-substituted maleimide group, a ceroxide diacrylate, an unsaturated polyester resin, and a polyfunctional epoxy compound. Ester resin composition.