JPH05239155A - Low viscousity thermosetting resin composition - Google Patents

Abstract

PURPOSE:To provide the subject composition having a low viscosity, excellent in the workability and thermal moldability and giving heat-resistant cured products by adding a specific phenol derivative to an imide compound and a dimethacrylbisphenol A. CONSTITUTION:The objective composition comprises (A) an imide compound of formula I (D is divalent organic group having a C=C bond; Z is >=di-valent organic residue; (n) is >=2), (B) a dimethacrylbisphenol A of formula II (X is group of formula III or IV), and (C) an alkenylphenol compound of formula V (R<1> is H, methyl; R<2>, R<3> are H, alkyl, etc.,), the content of the component C being 10-100 moles per 100 moles of the component B. The component A includes N,N'-(methyl-di-p-phenylene)-dimaleimide. The component C is preferably 2-allylphenol, etc. The component A is employed so that the equivalent ratio of the imide groups of the component A is 0.1-1.5 to the total equivalent of the methacryl groups of the component B and the alkenyl groups of component C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel thermosetting resin composition having a resin composition with reduced viscosity and excellent workability. More specifically, the cured product has excellent heat resistance. The present invention relates to a composition which has properties and is particularly useful as a resin composition for obtaining 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, materials having high heat resistance have been demanded for electric / electronic materials and aerospace materials, and a bismaleimide resin has been developed as a high heat resistance material that meets such a demand. However, the resin obtained by curing bismaleimide alone is extremely brittle and cannot be used for the above applications. Therefore, a resin composition composed of o, o'-dimethallyl bisphenol A and bismaleimide was developed as a means for improving the brittleness of the bismaleimide resin (Japanese Patent Laid-Open No. 128908/1990). Although it has excellent physical and chemical heat resistance and electrical properties, it has a relatively low temperature (50-70 ° C)
However, there is a problem that the viscosity of the resin composition is high and the workability is poor. Further, when the resin composition is heated in order to reduce the viscosity of the resin composition, the addition reaction between o, o′-dimethallyl bisphenol A and bismaleimide proceeds, so that the pot life (low Viscosity retention time)
There is also a problem that is very short. On the other hand, as a method for decreasing the viscosity of the resin composition, a method of adding a ring-opening polymerizable monomer is known (Japanese Patent Laid-Open No. 61-23300).
No. 9) and the ring-opening polymerizable monomer are added, there is a problem that the heat resistance of a cured product obtained is lowered.

[0003]

DISCLOSURE OF THE INVENTION In view of the above situation, the present invention is directed to an imide compound and dimethallyl bisphenol A.
By lowering the viscosity of the resin composition consisting of, it is a resin composition having improved workability of heat molding, and the cured product thereof is to provide a thermosetting resin composition having high heat resistance. To do.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a resin composition comprising dimethallyl bisphenol A and an imide compound has one alkenyl group in one molecule. The present inventors have found that it is extremely effective to contain the specific phenol derivative, and have completed the present invention. That is, the present invention provides an imide compound (a) represented by the following general formula [1], dimethallyl bisphenol A (b) represented by the following general formula [2], and an alkenyl represented by the following general formula [3]. Consists of a phenolic compound (c), and the content of the component (c) is the component (b)
It is a low-viscosity thermosetting resin composition, characterized in that it is 10 to 100 mol per 100 mol.

[0005]

[Chemical 4] (In the formula, D represents a divalent organic group having a carbon-carbon double bond, Z is a divalent or higher valent organic group residue, and n is an integer of 2 or more.)

[0006]

[Chemical 5]

[0007]

[Chemical 6] [Wherein R ¹ represents a hydrogen atom or a methyl group, and R ² and R
³ represents a hydrogen atom, an alkyl group or an alkoxy group. ]

The present invention will be described in detail below. Component (a) The component (a) in the present invention is a component for imparting heat resistance to the cured resin, and is an imide compound represented by the above general formula [1]. The valence of the compound means the number of functional groups bonded to the compound, as is already known. Specific compounds of the component (a) include
There are N, N-substituted maleimide compounds, tri-substituted substituted maleimide compounds, tetra-substituted maleimide compounds, poly (phenylmethylene) polymaleimide compounds and the like, and two or more of these various maleimide compounds can be used in combination as appropriate. Specific examples of the N, N-substituted maleimide compound include the following compounds. That is, N, N'-ethylene dimaleimide, N, N'-hexamethylene dimaleimide, N, N'-dodecamethylene dimaleimide, N,
N'-m-phenylenedimaleimide, 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
3-hexafluoro-2,2-bis [4- (4-maleimidophenoxy) phenyl] propane and prepolymers of these imide compounds. As the preferred imide compound in the present invention, N, N ′-(methylenedi-p-phenylene) dimaleimide and N, N′-m-xylenedimaleimide are used because of their excellent melting temperature and heat resistance of the cured product. You can

Component (b) Component (b) in the present invention is dimethallyl bisphenol A represented by the above general formula [2], and its specific name is 1,1-bis (4-hydroxy-3). -Methallylphenyl) cyclohexane and [1,1-bis (4-hydroxy-3-methallylphenyl) ethyl] benzene. Due to the two methallyl groups in these compounds,
In addition to high polymerizability, the resin composition has the property of being heat moldable, that is, capable of being molded into a desired shape without distortion. These compounds may be used alone or as a mixture.

Component (c) The component (c) in the present invention is an alkenylphenol compound represented by the above general formula [3], and is an extremely effective component for reducing the viscosity of the composition of the present invention. is there. Specific preferred examples of the alkenylphenol compound in the present invention include the following compounds. That is, 2-allylphenol, 4-allylphenol, 2-methallylphenol, 4-methallylphenol, 2-allyl-4
-Methylphenol, 2-allyl-6-methylphenol, 2-methallyl-4-methylphenol, 2-methallyl-6-methylphenol, 2-allyl-4-ethylphenol, 2-allyl-6-ethylphenol, 2 -Methallyl-5-methylphenol, 2-methallyl-4-ethylphenol, 2-methallyl-6-ethylphenol, 2-allyl-4-tert-butylphenol, 2
-Methallyl-4-tert-butylphenol, 2-allyl-4,6-dimethylphenol, 2-methallyl-
4,6-dimethylphenol, 2-allyl-4-methoxyphenol, 2-allyl-5-methoxyphenol,
2-allyl-6-methoxyphenol, 2-methallyl-
4-methoxyphenol, 2-methallyl-6-methoxyphenol, 2-methallyl-5-methoxyphenol,
2-allyl-4-ethoxyphenol, 2-allyl-6
-Ethoxyphenol, 2-methallyl-4-ethoxyphenol, 2-methallyl-6-ethoxyphenol, and the like, and one or more of these can be used.

The blending ratio of the component (c) in the resin composition of the present invention is 10 to 1 per 100 mol of the component (b).
It is necessary to set it to 00 mol, and the preferable blending ratio is 20
~ 70 mol. When the component (c) is more than 100 mol, the property that it can be molded into a desired shape without distortion, that is, the heat moldability is deteriorated, and when it is less than 10 mol,
The effect of the present invention that the viscosity of the resin composition is lowered to remarkably improve the workability cannot be sufficiently exerted. In a composition having component (a) and component (b) as constituent components and having a rotational viscosity at 70 ° C. of 100,000 cp, 10 mol or more of component (c) per 100 mol of component (b) is blended to prepare a composition of the present invention. With the composition, the rotational viscosity at 70 ° C. can be easily adjusted to 30,000 cp or less. The blending amount of the component (a) in the composition of the present invention may be appropriately set depending on the purpose of use of the molded article to be obtained, and the methallyl group of the component (b) and the alkenyl group of the component (c), that is, the allyl group, / Or the equivalent equivalent of the imide group of the component (a) to the total equivalent (MF) of the methallyl group (I)
When the above blending amount is represented by the ratio of F), it is (MF) / (IF)
The ratio is preferably adjusted to be in the range of 0.05 to 5, more preferably 0.1 to 1.5. If (MF) / (IF) is less than 0.05, the cured resin product may become brittle, whereas if it is more than 5, the heat resistance of the cured resin product may be reduced.

A radical polymerization initiator such as an organic peroxide and / or an azo compound may be used in the resin composition of the present invention 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- −
Examples thereof include t-butyl perphthalate and 2,2′-azobisisobutyronitrile, which may be used alone or in combination of two or more. The amount of these radical polymerization initiators used is in the range of 0.1 to 10 parts with respect to 100 parts by weight (hereinafter simply abbreviated as parts) of the total amount of the components (b) and (c) in the present invention. Preferably.

In addition to the above-mentioned components, the resin composition of the present invention may further include fillers such as glass powder, fused silica, calcium carbonate and talc, glass cloth, quartz glass cloth, carbon fiber cloth, depending on the intended use. A dispersion material having various shapes such as paper, organic fiber cloth and mica, having various shapes such as fine particle shape, fiber shape, plate shape, or a reinforcing material such as glass cloth may be contained, and if necessary, a flame retardant may be added. You can also do it.

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 are somewhat different depending on the type and blending amount of the radical polymerization initiator, but generally the treatment temperature is 100 ° C. to 300 ° C., and the treatment time is 2 to 25 hours. Preferably. 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.

[0016]

EXAMPLES Next, the present invention will be described more specifically by way of Examples and Comparative Examples. Example 1 11.22 parts (0.031 mol) of N, N '-(methylenedi-p-phenylene) dimaleimide as component (a) and 10 parts (0.025 mol) of [1,1- Bis (4-hydroxy-3-methallylphenyl) ethyl] benzene and 1.9 parts as component (c) [0.013 mol. This corresponds to 50 mol% of the component (b). ] 2-Methallylphenol was mixed at 150 ° C. to obtain a uniform mixture. After cooling this mixture to room temperature, the rotational viscosity at 70 ° C. was measured using a B-type viscometer, and the result was 6,500 cp. or,
0.5 parts of dicumyl peroxide was added to this mixture and stirred to obtain a uniform low-viscosity thermosetting resin composition. The resin composition thus obtained was put into a molding die made of tetrafluoroethylene and heated at 120 ° C. using a hot press.
A resin cured product was obtained by heat molding for 2 hours and then at 200 ° C. for 2 hours. This resin cured product has a glass transition temperature of 300 ° C or higher and is subjected to thermogravimetric analysis (heating rate of 20 ° C).
As a result, there was no change in weight up to 438 ° C. in air and it was stable.

Examples 2 to 6 In Example 1, except that the types of the components (b) and (c), the amounts of the components (a) and (c), and the amount of dicumyl peroxide added were changed. In the same manner as in Example 1,
Each low viscosity thermosetting resin composition of Examples 2-5 was obtained. The rotational viscosity of these resin compositions was measured in the same manner as in Example 1. Further, these resin compositions were heat-molded under the same conditions as in Example 1, and the resin cured products obtained were measured for glass transition temperature and decomposition temperature by thermogravimetric analysis. The results are shown in Table 1 below together with the results of Example 1.

[0018]

[Table 1]

Note) Upper: compound Lower: compounding amount (part)

The symbols in the table indicate the following compounds. (a); maleimides (a) 1; N, N '-(methylenedi-p-phenylene) dimaleimide (b); methallylphenol compound (b) 1; [1,1-bis (4-hydroxy-3- Methallylphenyl) ethyl] benzene (b) 2; 1,1-bis [4-hydroxy-3- (2-methyl-2-propenyl) phenyl] cyclohexane (c); alkenylphenol compound (c) 1; 2- Methallylphenol (c) 2; 2-allyl-4-tert-butylphenol (c) 3; 2-allylphenol (c) 4; 2-methallyl-4-tert-butylphenol (c) 5; 4-methoxy-2 -Methallylphenol (d); radical polymerization initiator (d) 1; dicumyl peroxide The blending ratio of the component (c) to the component (b) in Examples 2, 3, 4, 5 and 6 is as follows. On the street. Example 2: 27 mol% Example 3: 73 mol% Example 4: 50 mol% Example 5: 18 mol% Example 6: 49 mol%

Example 7 The rotational viscosity at 70 ° C. was 6 in the same manner as in Example 1 except that dicumyl peroxide was removed.
A low-viscosity thermosetting resin composition having a viscosity of 500 cp was obtained. Put this resin composition in a molding die made of ethylene tetrafluoride,
A resin cured product was obtained by hot molding at 120 ° C. for 2 hours, then at 200 ° C. for 2 hours, and at 250 ° C. for 3 hours. The glass transition temperature of this cured resin is 30.
The temperature was 0 ° C. or higher, and thermogravimetric analysis (temperature rising rate 20 ° C./min) showed that there was no weight change up to 431 ° C. in air and it was stable.

Comparative Example 1 Component (c) was not blended, and 9 parts (0.0) were added as component (a).
25 mol) of N, N '-(methylenedi-p-phenylene) dimaleimide and 10 parts (0.0) as component (b).
25 mol) of [1,1-bis (4-hydroxy-3-)
A uniform mixture was obtained by mixing methallylphenyl) ethyl] benzene at 150 ° C. After cooling this mixture to room temperature, the rotational viscosity at 70 ° C. was measured using a B-type viscometer, and it was found to be 105,000 cp. Further, dicumyl peroxide 0.
A uniform thermosetting resin composition was obtained by adding 4 parts and stirring. This resin composition was placed in a molding die made of tetrafluoroethylene and was heat-molded using a hot press at 120 ° C. for 2 hours and then at 200 ° C. for 2 hours to obtain a resin cured product. The glass transition temperature of this cured resin is 300 ° C.
The above is the result of the thermogravimetric analysis (temperature rising rate 20 ° C./min),
It was stable with no change in weight up to 430 ° C in air.

Comparative Example 2 9.5 parts (0.027 mol) of N, N '-(methylenedi-p-) was used as the component (a) without blending the component (c).
By mixing phenylene) dimaleimide and 10 parts (0.027 mol) of 1,1-bis [4-hydroxy-3- (2-methyl-2-propenyl) phenyl] cyclohexane as component (b) at 150 ° C. A homogeneous mixture was obtained. After cooling the mixture to room temperature, 70 ° C
As a result of measuring the rotational viscosity in B using a B-type viscometer,
It was 165,000 cp. Further, 0.4 parts of dicumyl peroxide was added to this resin composition and stirred to obtain a uniform thermosetting resin composition. This resin composition was placed in a molding die made of tetrafluoroethylene and was heat-molded using a hot press at 120 ° C. for 2 hours and then at 200 ° C. for 2 hours to obtain a resin cured product. The glass transition temperature of this cured resin was 300 ° C. or higher, and as a result of thermogravimetric analysis (heating rate 20 ° C./min), there was no weight change up to 436 ° C. in air and it was stable.

[0024]

The resin composition of the present invention has a low rotational viscosity at 70 ° C. of 30,000 cp or less, and therefore,
It has excellent workability and heat moldability, and the cured product after heat molding has excellent heat resistance, so heat resistant molded products, electric / electronic materials such as printed wiring boards, other heat resistant composite materials, heat resistance As a resin composition for obtaining a filler, a heat resistant coating agent, etc., its industrial value is extremely large.

 ─────────────────────────────────────────────────── ─── 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. An imide compound (a) represented by the following general formula [1], dimethallyl bisphenol A (b) represented by the following general formula [2], and an alkenyl represented by the following general formula [3]. Consists of a phenol compound (c), and the content of the component (c) is 10 to 100 m per 100 mol of the component (b).
and a low-viscosity thermosetting resin composition. [Chemical 1] (In the formula, D represents a divalent organic group having a carbon-carbon double bond, Z is a divalent or higher valent organic group residue, and n is an integer of 2 or more.) [Chemical 3] [Wherein R ¹ represents a hydrogen atom or a methyl group, and R ² and R
³ represents a hydrogen atom, an alkyl group or an alkoxy group. ]