JPH0253826A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition suitable for adhesive film having excellent heat resistance, mechanical properties and moldability by mixing a polymer having specific repeating unit and specific N,N'-4,4'-diphenylmethane bismaleimide in specific ratio. CONSTITUTION:100 pts.wt. a polymer having repeating unit expressed by formula I (R1 is group expressed by formula II or formula III; X is bifunctional 1-10C hydrocarbon group, etc.; Z is group expressed by formula IV and/or formula V; Y is tetrafunctional aromatic group of non-fused ring bonded with >=2C aliphatic group or alicyclic group, etc.) is mixed with 5-100 pts.wt., preferably 10-80 pts.wt. N,N'-4,4'-diphenylmethane bismaleimide expressed by formula VI and polymerizing catalyst such as benzoyl peroxide, as necessary, preferably in a ratio of 0.1-5wt.% of total weight of the polymer to afford the aimed composition suitable for adhesive of electric or electronic devices, laminating board or molding material.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a thermosetting resin composition with excellent heat resistance that can be used for adhesive films, laminated materials, molding materials, and the like.

[Conventional technology]

Polyimide resins have been widely used in industry since they have excellent heat resistance, electrical insulation, and chemical resistance.

Among polyimide resins, many of the condensed polyimide resins obtained through the reaction of tetracarboxylic dianhydride and diamine via polyamic acid exhibit excellent properties.
It has the drawbacks of high softening temperature and poor workability. Thermoplastic polyetherimide (trade name: Ultem, manufactured by General Electric Company) is also known, which has improved processability at the expense of some heat resistance, but it is not sufficient in terms of heat resistance and chemical resistance. It wasn't something.

On the other hand, addition-type polyimide resins in which a bismaleimide compound is polymerized alone have excellent thermal properties, but
Due to its poor mechanical strength, it could not be cast into a film.

[Problems to be solved by the invention] The present invention was made in view of these drawbacks, and it can be formed into a film etc. before heat curing, and after curing, it has strong, flexible, adhesive and heat resistant properties. The present invention provides an excellent thermosetting resin composition.

[Means for solving problems]

As a result of intensive research to achieve the above object, the present inventors discovered that the thermosetting resin composition described below has excellent heat resistance, mechanical properties, and processability, and completed the present invention. This is what I did.

That is, the thermosetting resin composition of the present invention represents a divalent group consisting of one of the general formula (I), where X is a direct bond, a divalent hydrocarbon group having 1 to 10 carbon atoms, and a hexafluorinated isopropylene group. 5 to 100 parts by weight of N,N'-4,4'-diphenylmethane bismaleimide, which represents a group selected from the group consisting of lydene group, carbonyl group, thio group, sulfinyl group, sulfonyl group, or oxide, and is represented by It is a thermosetting resin composition consisting of.

The polymer used in the present invention has the formula (I[[),
Y is an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, a fused polycyclic aromatic group, or a non-fused cyclic group in which aromatic groups are bonded to each other directly or through a bridge member. Represents a tetravalent group selected from the group consisting of aromatic groups. ) represents a divalent group consisting of 100 parts by weight of a polymer having a repeating unit represented by formula (II), where X is a direct bond, a divalent hydrocarbon group having 1 to 10 carbon atoms, a hexafluorinated Represents a group selected from the group consisting of an isopropylidene group, a carbonyl group, a thio group, a sulfinyl group, a sulfonyl group, or an oxide.

) A polyamic acid obtained by reacting the diamine compound shown in the following with one or more tetracarboxylic dianhydrides by a commonly known method, and/or a polyimide obtained by further cyclodehydration of this.

Specifically, the diamine compound that is one component of the polymer is 1
, 3-bis(3-aminophenoxy)benzene, bis(
4-(3-aminophenoxy)phenylcomethane, 1,
1-bis(4-(3-aminophenoxy)phenyl]ethane, 1.2-bis(4-(3-aminophenoxy)phenyl)ethane, 2.2-bis(4-(3-aminophenoxy)phenyl) Propane, 2,2-bis(4-(3
aminophenoxy)phenylcobutane, 2,2-bis(
4-(3-aminophenoxy)phenyl)-1,1,l
, 3,3.3-hexafluoropropane, 4.4°-bis(3-aminophenoxy)biphenyl, bis(4-(
3-aminophenoxy)phenylkoketone, bis(4-
(3-aminophenoxy)phenyl sulfide, bis[4(3-aminophenoxy)phenyl]sulfoxide, bis(4-(3-aminophenoxy)phenyl)sulfone, bis(1-(3-aminophenoxy)phenyl)
Examples include ether, and these may be used alone or in a mixture of two or more.

In addition, the other component, tetracarboxylic dianhydride, has the formula (IV) (wherein, Y is an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group,
It represents a tetravalent group selected from the group consisting of a monocyclic aromatic group, a fused polycyclic aromatic group, and a non-fused cyclic aromatic group in which aromatic groups are mutually bonded directly or through a bridge member. ), specifically, ethylenetetracarboxylic dianhydride, butanetetracarboxylic dianhydride, cyclopenkune tetracarboxylic dianhydride, pyromellitic dianhydride, 3.3°, 4 .4'-benzophenonetetracarboxylic dianhydride, 2.23.3'-benzophenonetetracarboxylic dianhydride, 3.3', 4.4'-biphenyltetracarboxylic dianhydride, 2.2°, 3.3'
-Biphenyltetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propanihydride, 2,2-bis(2,3-dicarboxyphenyl)propanihydride, bis(3,4 -dicarboxyphenyl)
Ether dianhydride, bis(34-carboxyphenyl)
Sulfone dianhydride, 1.1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, 4.4'-(p-phenylenedioxy)cyphthalic dianhydride, 4.4"-(
m-phenylenedioxy)cyphthalic dianhydride, 2,3
, 6.7-naphthalenetetracarboxylic dianhydride, 1,
4,5.8-naphthalenetetracarboxylic dianhydride, 1
．． 2. 5. 6 naphthalenetetracarboxylic dianhydride, 1,2°3.4. -Benzenetetracarboxylic dianhydride, 3.4,9.10-perylenetetracarboxylic dianhydride, 2,3,6.7-anthracenetetracarboxylic dianhydride, 1,2,7.8-phenanthrene Tetracarboxylic dianhydrides, etc., and these tetracarboxylic dianhydrides may be used alone or in a mixture of two or more.

The N,N'-4,4'' diphenylmethane bismaleimide represented by the formula (n) can be prepared in 4. by a commonly known method.
It can be easily produced by condensing and dehydrating 4''-diaminodiphenylmethane and maleic anhydride.

The mixing ratio of the polymer of the formula (I) and the bismaleimide compound of the formula (n) is 5 to 100 parts by weight, preferably 10 to 100 parts by weight of the bismaleimide compound (n) per 100 parts by weight of the polymer (I). 80 parts by weight can be used. If the blending amount of the bismaleimide compound is less than 5 parts by weight, it will not be effective in improving the processability and mechanical properties that are the objectives of the present invention.
If the amount exceeds 1 part by weight, the cured product will become brittle and moldability will deteriorate.

The polymer (I) and the bismaleimide compound (II) may be mixed in powder form, but usually the bismaleimide compound (n) is added and dissolved in the polyamic acid and/or polyamide foam or suspension. It is carried out by

The resin composition thus obtained can be impregnated into a base material such as glass cloth or carbon cloth and dried to be used as a Bripreg, or it can be cast onto a glass plate, stainless steel plate, etc. and dried to impregnate the base material. It can also be used for various purposes as a film-like adhesive. In this case, the drying temperature must be kept lower than the temperature at which polymerization of the bismaleimide compound becomes noticeable, and the drying time must be set such that the amount of residual solvent does not impair the purpose of the present invention.

Moreover, it can also be used as a molding material in powder form. A tough, heat-resistant molded article can be obtained by heating and curing the resin composition of the present invention.

The thermosetting resin composition of the present invention is not particularly limited if necessary, but it is preferably in the range of 0.001 to 10% by weight, particularly 0.1 to 5% by weight, based on the total weight of the polymer.

As the polymerization catalyst, known free radical catalysts such as benzoyl peroxide, L-butyl hydroperoxide, dicumyl peroxide, azobisisobutyronitrile, and azobiscyclohexanecarbonitrile are effective. Note that the polymerization catalysts may be used in appropriate combinations.

〔Example〕

The present invention will be explained below with reference to Examples.

Examples 1-4 In a container equipped with a stirrer, a reflux condenser and a nitrogen inlet tube, 4
, 4′-bis(3-aminophenoxy)biphenyl 73
．． 6 g (0.2 mol) and 467.2 g of N,N-dimethylacetamide were charged, and 43.2 g (0.198 mol) of pyromellitic dianhydride was added at room temperature under a nitrogen atmosphere to raise the temperature of the solution. Add carefully in portions and stir at room temperature for about 20 hours, resin content 20.0%, 25°C.
A polyamic acid varnish having a solution viscosity of 64 poise was obtained.

35°c1 of the obtained polyamic acid.

, the logarithmic viscosity at 5% concentration was 0.82 d1/g.

Add N to 100 g of this polyamic acid varnish, N"-44°-
Diphenylmethane bismaleimide was added in the amount shown in Table 1, N,N-dimethylacetamide was added so that the resin content was 20.0%, and the mixture was dissolved at room temperature. This resin composition was cast onto a glass plate and dried at 130°C for 1 hour in a nitrogen atmosphere and then for 2 hours at 180"C to a thickness of 25μ.
A soft brown transparent uncured film of m was obtained. A tough cured film was obtained by heating this uncured film at 250°C for 30 minutes. Softening point of uncured film (TMA Needle Co., Ltd. Steel with preheated uncured film (cold rolled steel, JIS-3141, 5PEC/
SD, 25X 100X1.6 am) inserted between
Tensile shear force at high temperatures of 25°C and 240°C (measured using JIS-6848 and -685
Based on 0. ) values are shown in Table 1.

Examples 5-8 and Comparative Examples 1-2 Polyamide Acid varnish was obtained. A bismaleimide compound was dissolved in this in the amount shown in Table 1 to obtain a resin composition varnish.

Hereinafter, the same operations as in Examples 1 to 4 were performed to obtain the results shown in Table 1.

〔Effect of the invention〕

The thermosetting resin composition of the present invention has excellent adhesiveness, moldability, flexibility, and heat resistance, and is widely used as an adhesive, laminate, and molding material in electrical and electronic devices. It is expected to have many uses and has great industrial effects.

Claims (1)

[Claims] General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R_1 is ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc. ▼ represents a divalent group consisting of a direct bond, a divalent hydrocarbon group having 1 to 10 carbon atoms, a hexafluorinated isopropylidene group, a carbonyl group, a thio group, a sulfinyl group, a sulfonyl group, or an oxide represents a group selected from the group consisting of
There are mathematical formulas, chemical formulas, tables, etc. Represents ▼, and Y is the number of carbon atoms 2
Consists of the above aliphatic groups, cyclic aliphatic groups, monocyclic aromatic groups, fused polycyclic aromatic groups, and non-fused cyclic aromatic groups in which aromatic groups are bonded to each other directly or through a bridge member. Represents a tetravalent group selected from the group. ) 100 parts by weight of a polymer having a repeating unit represented by formula (II) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (II) N,N'-4,4'-diphenylmethane bismaleimide 5 -100 parts by weight of a thermosetting resin composition.