JPH05230368A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition, composed of maleimides, a methallylphenolic compound and a polyether imide, excellent in hot moldability, heat resistance and mechanical strength and useful as electrical and electronic materials, composite materials, etc. CONSTITUTION:The objective composition is obtained by blending (A) maleimides [preferably N,N'-(methylenedi-p-phenylene)dimaleimide, etc.] with (B) a methallylphenolic compound expressed by formula I (X is formula II, III or IV) and/or formula V (R<1> and R<2> are H, alkyl, etc.), (C) a polyether imide, having 3000-50000 number-average molecular weight and expressed by formula VI [(n) is a positive number] and (D) a radical polymerization initiator composed of an organic peroxide and/or an azo compound, etc.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel thermosetting resin composition. More specifically, the cured product has excellent heat resistance, mechanical strength and toughness.
It is particularly useful as a raw material for heat-resistant molded products, electric / electronic materials such as printed wiring boards, and composite materials.

[0002]

2. Description of the Related Art In recent years, in electric / electronic materials and aerospace materials, materials having high heat resistance, high mechanical strength and toughness have been demanded, and as high heat resistant materials that meet such demands, Bismaleimide resin was developed. However, a cured product obtained by curing bismaleimide alone is extremely brittle and cannot be used for the above applications.
Therefore, a resin composition comprising o, o'-diallyl bisphenol A and bismaleimide was developed as a means for improving the brittleness of the bismaleimide resin, and this resin composition also has the mechanical properties required for the above-mentioned applications. Properties such as dynamic strength and toughness have not yet been sufficiently satisfied. In the thermosetting resin composition such as epoxy resin,
As a method for improving the toughness of the cured product, a method of adding a liquid rubber to the thermosetting resin composition is known,
When liquid rubber is added, there is a problem that the heat resistance of the resin cured product is drastically reduced.

[0003]

SUMMARY OF THE INVENTION In view of the above situation, the present invention is a resin composition which can be easily thermoformed, and a cured product thereof has a high heat resistance and a thermosetting property which is excellent in mechanical strength. It is an object of the present invention to provide a water-soluble resin composition.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a resin composition containing a methallylphenol compound and a maleimide contains a specific polyetherimide containing a heat. It was found that a cured product having both excellent heat resistance and mechanical strength can be obtained by heat curing using a curable resin composition, and completed the present invention. That is, the present invention relates to a maleimide (a), a methallylphenol compound represented by the following general formula [1] and / or a methallylphenol compound (b) represented by the following general formula [2] and the following general formula [ 3], 3,000
A thermosetting resin composition comprising a polyetherimide (c) having a number average molecular weight of 0 to 50,000.

[0005]

[Chemical 4]

[0006]

[Chemical 5]

[0007]

[Chemical 6]

The present invention will be described in detail below. -Component (a) The component (a) in this invention is a maleimide. Specific compounds include N-substituted maleimide compounds, N, N
There are -substituted maleimide compounds and prepolymers of these maleimide compounds, and the following compounds are specific examples of N-substituted maleimide compounds and N, N-substituted maleimide compounds. That is, N-methyl maleimide, N-ethyl maleimide, N-propyl maleimide, N-butyl maleimide, N-hexyl maleimide, N-octyl maleimide, N-dodecyl maleimide, N-cyclohexyl maleimide, N-phenyl maleimide, N-p. -Tolylmaleimide, N-α-naphthylmaleimide, N-benzylmaleimide, Nm-tolylmaleimide, N-o-tolylmaleimide, Np-xylylmaleimide, Nm-
Xylylmaleimide, N-o-xylylmaleimide,
N, N'-ethylene dimaleimide, N, N'-hexamethylene dimaleimide, N, N'-dodecamethylene dimaleimide, N, N'-m-phenylene dimaleimide, N,
N'-p-phenylenedimaleimide, N, N '-(oxydi-p-phenylene) dimaleimide, N, N'-(methylenedi-p-phenylene) dimaleimide, N, N'-
2,4-tolylene dimaleimide, N, N'-2,6-tolylene dimaleimide, N, N'-m-xylylene dimaleimide, N, N'-p-xylylene dimaleimide, N,
N'-oxydipropylene dimaleimide, ethylenedioxy-bis-N-propylmaleimide, oxy-bis-
N-ethylmaleimide, N, N'-p, p'-diphenylsulfone bismaleimide, N, N'-p, p'-diphenylether bismaleimide, N, N'-dicyclohexylmethane bismaleimide, N, N '-( 3,3'-
Dichloro-p, p'-bisphenylene) bismaleimide, 1,1,1,3,3,3-hexafluoro-2,2
-Bis (4-maleimidophenyl) propane, 1,1,
1,3,3,3-hexafluoro-2,2-bis [4-
(4-maleimidophenoxy) phenyl] propane and the like. If desired, two or more of these maleimide compounds may be used in combination. Further, two or more kinds of tri-substituted or tetra-substituted maleimide compounds, poly (phenylmethylene) polymaleimide compounds or these various maleimide compounds can be appropriately used in combination. Preferred maleimides include N, N '-(methylenedi-p-phenylene) dimaleimide and N, N'-p-phenylene dimaleimide.

Component (b) The component (b) in the present invention is a methallylphenol compound represented by the general formula [1] and / or a methallylphenol compound represented by the general formula [2]. .. The methallylphenol compound represented by the above general formula [1] is specifically the following three types of compounds. That is, 2,
2-bis (4-hydroxy-3-methallylphenyl) propane, 1,1-bis (4-hydroxy-3-methallylphenyl) cyclohexane and [1,1-bis (4-hydroxy-3-methallylphenyl) propane ) Ethyl] benzene.

The following compounds are preferred specific examples of the methallylphenol compound represented by the general formula [2]. That is, 2-methallylphenol, 4-methallylphenol, 2-methallyl-4-methylphenol, 2-methallyl-6-methylphenol, 2-methallyl-5-methylphenol, 2-methallyl-4-ethylphenol, 2-methallyl-6-ethylphenol, 2-methallyl-4-tert-butylphenol, 2-methallyl-
4-methoxyphenol, 2-methallyl-6-methoxyphenol, 2-methallyl-5-methoxyphenol,
2-methallyl-4-ethoxyphenol and 2-methallyl-6-ethoxyphenol. In the present invention, one kind or two or more kinds of the methallylphenol compounds represented by the above general formula [1] or [2] can be used in combination.

Of the above methallylphenol compounds,
[1,1-Bis (4-hydroxy-3-methallylphenyl) ethyl] benzene is a novel compound and can be used as the component (b) in the present invention like other compounds. This compound is, for example, [1,1-bis- (4
-Methallyloxyphenyl) ethyl] benzene, which is soluble in it and has a polymerizable functional group in the molecule or a base having an N atom in the molecule is 0.0
It can be easily synthesized by performing Claisen rearrangement in the presence of 1 to 10 mol%. Examples of the base that can be used in the above production method include the following compounds. That is, m-aminodiphenyl, 4-aminodiphenyl ether, 4,4'-diaminodiphenylmethane,
N, N-dimethylphenylenediamine, diallylamine, diallylbutylamine, N, N-diallylaniline, N, N, N ′, N′-tetramethallyl-bis- (4
-Aminophenyl) methane and propargylamine. The reaction temperature and the reaction time are usually 150 to 300 ° C.
At a temperature of 0.5 to 20 hours, preferably 180 to 250
Suitably, the temperature is in the range of 1 to 10 hours.

The preferable blending ratio of the methallylphenol compound is appropriately determined depending on the purpose of use of the molded article to be obtained, but the imide group 1 of the maleimides is 1
The methallyl group of the methallylphenol compound is in the range of 0.05 to 10 equivalents relative to the equivalent amount, and the more preferable blending ratio is 0.1 to 10 of the methallyl group of the methallylphenol compound.
It is in the range of 1.5 equivalents. If the blending ratio of the methallylphenol compound is less than 0.05 equivalents, the cured product becomes brittle and the viscosity of the thermosetting resin composition increases, so that the heat moldability may decrease. On the other hand, when the amount of the methallylphenol compound is more than 10 equivalents, the heat resistance may decrease.

Component (c) The component (c) in the present invention is a polyetherimide represented by the above general formula [3] and having a number average molecular weight of 3,000 to 50,000. The preferable mixing ratio of the component (c) is 1 to 15 parts by weight, and the more preferable mixing ratio is 3 to 10 parts by weight, per 100 parts by weight of the total amount of the components (a) and (b). If the mixing ratio of the component (c) is less than 1 part by weight, the effect of significantly increasing the mechanical strength may not be sufficiently exerted, and if it exceeds 15 parts by weight, the thermosetting resin composition may be obtained. The viscosity of the product increases, the blended polyetherimide may not be uniformly dispersed, and on the contrary, the tensile strength may decrease. In the resin composition of the present invention, a radical polymerization initiator such as an organic peroxide and / or an azo compound can be used in order to shorten the curing time. Specific examples of preferable radical polymerization initiators include the following compounds. That is, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, p-chlorobenzoyl peroxide, caprylyl peroxide, lauroyl peroxide, acetyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, dicumyl peroxide, bis ( 1-hydroxyheptyl) peroxide, t-butyl hydroperoxide, p-menthane hydroxyperoxide, t-butyl perbenzoate, t-butyl peracetate, t-butyl peroctoate, t-butyl peroxyisobutyrate, di- -T-butyl perphthalate and 2,2'-azobisisobutyronitrile. These can be used alone or in combination of two or more. The amount of these radical polymerization initiators used is in the range of about 0.1 to 10 parts with respect to 100 parts by weight of the total amount of the components (a) and (b) of the present invention (hereinafter simply referred to as "part"). Is preferred.

In addition to the above-mentioned components, the composition of the present invention may be in the form of fine particles, fibers, glass beads, quartz glass, glass fibers, paper, organic fiber cloth, mica, carbon fibers, etc., depending on the application. A dispersion material having various shapes such as a plate shape or a reinforcing material such as glass cloth may be uniformly contained,
In addition, a flame retardant can be added if necessary.

The resin composition of the present invention can be easily obtained by uniformly mixing the above various components at room temperature or under mild heating.

The conditions for curing the resin composition of the present invention vary somewhat depending on the type and blending amount of the radical polymerization initiator, but generally the treating temperature is 100 ° C. to 300 ° C. and the treating time is 2 to 25 hours. Is preferred. However, the curing treatment conditions are not limited, and curing can be performed at a temperature of 100 ° C. or lower by appropriately adjusting the type and blending amount of the radical polymerization initiator.

[0017]

EXAMPLES Next, the present invention will be described more specifically by way of Examples and Comparative Examples. Example 1 2 parts by weight of bismaleimidediphenylmethane as component (a), 10 parts by weight of 2,2-bis [4-hydroxy-3- (2-methyl-2-propenyl) phenyl] propane as component (b) and As a component (c), 1 part by weight of powdered polyetherimide (Ultem 1000, trade name, manufactured by General Electric Company) was mixed at 150 ° C. to obtain a uniform mixture. Furthermore, in this mixture, the bismaleimidodiphenylmethane of the component (a), 8.
A uniform thermosetting resin composition was obtained by adding 7 parts by weight and mixing at 150 ° C. This resin composition was placed in a molding die made of ethylene tetrafluoride and
2 hours at 0 ° C, then 2 hours at 200 ° C, then 2 hours at 220 ° C
A resin cured product was obtained by heat molding for a period of time. As a result of thermogravimetric analysis (temperature rising rate: 20 ° C./min), this resin cured product was stable with no weight change up to 425 ° C. in air. In addition, the tensile strength of the cured resin is 580 kgf / cm ² ,
The fracture toughness value (K _IC ) measured according to the ASTM E399-83 method was 1.32 MN / m ^3/2 .

Examples 2 to 4 Examples 2 to 4 were carried out except that the kinds and amounts of the components (a) and (b) were changed, and the amount of the polyetherimide as the component (c) was changed. Similar to Example 1,
Each thermosetting resin composition of Examples 2-4 was obtained. Physical properties of resin cured products obtained by heat-molding these resin compositions under the same conditions as in Example 1 were evaluated. The results are shown in Table 1 below together with the results of Example 1.

[0019]

[Table 1]

Note) Top: compound; bottom: compounding amount (parts by weight)

The symbols in the table indicate the following compounds. (a); maleimides (a) 1; bismaleimidediphenylmethane (b); methallylphenol compound (b) 1; 2,2-bis [4-hydroxy-3- (2-methyl-2-propenyl) phenyl] Propane (b) 2; 1,1-bis [4-hydroxy-3- (2-methyl-2-propenyl) phenyl] cyclohexane (b) 3; {1,1-bis [4-hydroxy-3- (2 -Methyl-2-propenyl) phenyl] ethyl} benzene (c); polyetherimide (c) 1; product name Ultem 10 manufactured by General Electric Company
00

Example 5 2 parts by weight of bismaleimidediphenylmethane as the component (a) and 8 parts by weight of 2,2-bis [4] as the component (b).
-Hydroxy-3- (2-methyl-2-propenyl) phenyl] propane and 2 parts by weight of 2- (2-methyl-2)
-Propenyl) pheninol, 1.1 as component (c)
A uniform mixture was obtained by mixing parts by weight of powdered polyetherimide (Ultem 1000, trade name, manufactured by General Electric Company) at 150 ° C. Further, 8.9 parts by weight of bismaleimidediphenylmethane which is the component (a) was added to this mixture and mixed at 150 ° C. to obtain a uniform thermosetting resin composition. This resin composition was placed in a molding die made of ethylene tetrafluoride, and heated at 120 ° C for 2 hours, then at 200 ° C for 2 hours, and then 220
A resin cured product was obtained by heat molding at 2 ° C. for 2 hours. This resin cured product was subjected to thermogravimetric analysis (heating rate 20 ° C /
As a result, there was no weight change up to 423 ℃ in air,
It was stable. Also, the tensile strength of the cured resin is 595 kgf / cm ²
The fracture toughness value (K _IC ) measured according to the ASTM E399-83 method was 1.28 MN / m ^3/2 .

Comparative Example A thermosetting resin composition was obtained in the same manner as in Example 1 except that the polyetherimide was not added in Example 1. Moreover, about this thermosetting resin composition, Example 1
Heat molding was carried out in the same manner as above to evaluate the physical properties. The results are shown in Table 1 above.

[0024]

EFFECTS OF THE INVENTION The resin composition of the present invention can exhibit excellent heat resistance, mechanical strength and toughness in a cured product after heat molding.・ Electronic materials, other heat resistant composite materials,
Its industrial value is remarkably great as a resin composition for obtaining a heat resistant filler, a heat resistant coating agent and the like.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kaoru Kimura 1-1 Funami-cho, Minato-ku, Nagoya-shi, Aichi Toagosei Chemical Industry Co., Ltd. Nagoya Research Institute

Claims (1)

[Claims] 1. A maleimide (a), a methallylphenol compound represented by the following general formula [1] and / or a methallylphenol compound (b) represented by the following general formula [2] and the following general formula []. 3], 3,000 to 50,000
A thermosetting resin composition comprising a polyetherimide (c) having a number average molecular weight of 0. [Chemical 1] [Chemical 2] [In the formula, R ¹ and R ² represent a hydrogen atom, an alkyl group or an alkoxy group. ] [Chemical 3]