JPH07165836A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:To obtain a composition having a high Tg and excellent workability, adhesiveness and toughness. CONSTITUTION:This composition comprises a bismaleimide (a), a bisoxazoline compound (b) and a dicarboxylic acid (c) in such amounts as to give 5-99 pts.wt. component (a), total of components (b) and (c) of 95-1 pt.wt., and an equivalent ratio of component (b) to component (c) of 1/1 to 5/1.

Description

Detailed Description of the Invention

[0001]

The present invention has a glass transition point (hereinafter referred to as T
g)) and is excellent in workability, adhesiveness and toughness.

[0002]

2. Description of the Related Art Conventionally, as a high heat resistant thermosetting resin,
Bismaleimide resin, amine-modified maleimide resin, and allyl-modified maleimide resin are well known. Although these resins have excellent heat resistance, they have insufficient adhesiveness and fracture toughness. On the other hand, a thermosetting resin composed of bisoxazoline and a dicarboxylic acid, a bisphenol compound, or a diamine has excellent adhesiveness, but has insufficient heat resistance.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a thermosetting resin composition having a high Tg and excellent workability, adhesiveness and toughness.

[0004]

The present invention comprises a bismaleimide compound (a), a bisoxazoline compound (b) and a dicarboxylic acid (c), and the weight ratio of each is 5 to 99 parts by weight of the component (a). , The total of the component (b) and the component (c) is 95 to 1 part by weight, and the equivalent ratio of the component (b) and the component (c) is 1/1 to 5/1. Is a thermosetting resin composition.

Examples of the bismaleimide compound used in the present invention include N, N'-m-phenylene bismaleimide, N, N'-p-phenylene bismaleimide, N, N'-m-
Toluylene bismaleimide, N, N'-4,4'-biphenylene bismaleimide, N, N'-4,4 '-[3,3'-dimethyl-
Biphenylene] bismaleimide, N, N'-4,4 '-[3,3'
-Dimethyldiphenylmethane] bismaleimide, N, N'-
4,4 '-[3,3'-Diethyldiphenylmethane] bismaleimide, N, N'-4,4'-diphenylmethane bismaleimide, N, N'-4,4'-diphenylpropane bismaleimide, N, N'-4,4'-diphenyl ether bismaleimide, N, N'-3,3'-diphenyl sulfone bismaleimide, N, N'-4,4'-diphenyl sulfone bismaleimide, 2,2-bis [4- (4 -Maleimidophenoxy) phenyl] nonane, 2,2-bis [3-tertiarybutyl-4- (4
-Maleimidophenoxy) phenyl] propane, 2,2-bis [3-secondary-butyl-4- (4-maleimidophenoxy) phenyl] propane, 1,1-bis [4- (4-maleimidophenoxy) phenyl] decane, 1 , 1-bis [2-methyl-
4- (4-maleimidophenoxy) -5-tertiarybutylphenyl] -2-methylpropane, 4,4′-cyclohexylidene-bis [1- (4-maleimidophenoxy) -2- (1,1-
Dimethylethyl) benzene], 4'-methylene-bis [1-
(4-maleimidophenoxy) -2,6-bis (1,1-dimethylethyl) benzene], 4,4'-methylene-bis [1- (4-maleimidophenoxy) -2,6-di-secondarybutylbenzene ], 4,4'-Cyclohexylidene-bis [1- (4-maleimidophenoxy) -2-cyclohexylbenzene],
4,4'-methylene-bis [1- (maleimidophenoxy) -2-
Nonylbenzene], 4 '-(1-methylethylidene) -bis
[1- (maleimidophenoxy) -2,6-bis (1,1-dimethylethyl) benzene, 4,4 '-(2-ethylhexylidene)-
Bis [1- (maleimidophenoxy) -benzene], 4,4'-
(1-Methylheptylidene) -bis [1- (maleimidophenoxy) -benzene], 4,4′-cyclohexylidene-bis [1
-(Maleimidophenoxy) -3-methylbenzene], bismaleimides represented by the general formulas (1) and (2), and the like. There is no problem even if two or more of these are included.

[0006]

[Chemical 1]

[0007]

[Chemical 2]

Examples of the bis (2-oxazoline) compound used in the present invention include 1,2-bis (2-oxazolinyl-2) ethane, 1,4-bis (2-oxazolinyl-2) butane, 1,6 -Bis (2-oxazolinyl-2) hexane,
1,8-bis (2-oxazolinyl-2) octane, 1,4-bis (2-oxazolinyl-2) cyclohexane and other compounds in which an oxazoline ring is bonded to an alkyl chain, for example, 1,2-
Bis (2-oxazolinyl-2) benzene, 1,3-bis (2-
Oxazolinyl-2) benzene, 1,4-bis (2-oxazolinyl-2) benzene, 5,5'-dimethyl-2,2'-bis (2
-Oxazolinyl-2) benzene, 4,4,4 ', 4'-tetramethyl-2,2'-bis (2-oxazolinyl-2) benzene,
1,2-Bis (5-methyl-2-oxazolinyl-2) benzene, 1,3-bis (5-methyl-2-oxazolinyl-2) benzene, 1,4-bis (5-methyl-2-oxazolinyl- 2) Two oxazoline rings bonded to an aromatic nucleus such as benzene and 2,2'-bis (2-oxazoline), 2,2'-bis (4-methyl-2-oxazoline), 2,2 ' -Bis (5-methyl-2-oxazoline) and the like. There is no problem even if two or more of these are included.

Examples of the dicarboxylic acid used in the present invention include aliphatic dicarboxylic acids such as adipic acid, dodecanenic acid, eicosannic acid, malonic acid, succinic acid, pimelic acid, speric acid and azelaic acid, phthalic acid, isophthalic acid, terephthalic acid. Examples thereof include acids, naphthalene dicarboxylic acid, diphenyl sulfone dicarboxylic acid, diphenyl methane dicarboxylic acid, aromatic dicarboxylic acids such as 4,4′-biphenyl dicarboxylic acid and diphenyl ether dicarboxylic acid. There is no problem even if two or more of these are included.

If the amount of the bismaleimide compound is less than 5 parts by weight, the heat resistance will decrease, and if it exceeds 99 parts by weight, the adhesiveness and toughness will decrease. If the equivalent ratio of the component (b) and the component (c) is less than 1, the heat resistance will decrease, and if it exceeds 5, the composition will be hard and brittle. In the present invention, in order to obtain the composition, three components may be mixed, or a method of reacting the components (b) and (c) and then adding and mixing the bismaleimide may be adopted. Good.

As the curing catalyst, for example, in addition to phosphite esters, organic acids, organic acid salts, radical catalysts, anion catalysts, organic phosphorus compounds, etc. can be used, and they can be used alone or in combination. I don't care.

The thermosetting resin composition of the present invention has a high Tg and is excellent in workability and toughness.
It can be advantageously used for a multilayer printed wiring board, a sealing material and the like.

[0013]

EXAMPLES The present invention will be described in more detail by way of examples.

(Examples 1 to 5) 1 according to the formulation of Table 1
Melt mix at 50 ° C, degas under reduced pressure, and then 150 ° C in advance.
After pouring it into a glass mold (with or without copper foil set) heated to 1, heat it at 150 ° C for 2 hours, then 20 more
It was cured at 0 ° C. for 4 hours to obtain a cast plate. From this, a test piece for measuring fracture toughness (K _1c ) and a copper foil peel strength test piece were cut out and used for measurement. Fracture toughness is ASTM E399-
From 83, the copper foil peel strength was determined according to JIS C6481. The glass transition temperature (Tg) was determined by viscoelasticity test. The results are summarized in Table 1.

(Comparative Examples 1 to 4) According to the formulations shown in Table 1, test pieces were prepared in the same manner as in the examples. Comparative Example 1 was brittle and had a low copper foil peel strength. Comparative Examples 2 and 3 have low Tg,
It was inferior in heat resistance. Comparative Example 4 was brittle and had a slightly low copper foil peel strength. In the present invention shown in Examples 1 to 5, fracture toughness, copper foil peel strength, and Tg are improved as a whole as compared with Comparative Examples.

[0016]

[Table 1]

[0017]

The thermosetting resin composition according to the present invention has Tg
Has high workability, adhesiveness, and toughness.
It can be advantageously used as an adhesive, a multilayer printed wiring board, a sealing material, and the like.

Claims (1)

[Claims] 1. A bismaleimide compound (a), a bisoxazoline compound (b) and a dicarboxylic acid (c),
The weight ratio of each component (a) is 5 to 99 parts by weight,
The total of the component (b) and the component (c) is 95 to 1 parts by weight, and the equivalent ratio of the component (b) and the component (c) is 1/1 to 1
It is 5/1, The thermosetting resin composition characterized by the above-mentioned.