JP2595038B2 - Thermosetting resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a thermosetting resin composition having excellent heat resistance, which can be used for an adhesive film, a laminated material, a molding material or the like.

[Conventional technology]

2. Description of the Related Art Conventionally, polyimide resins have been widely used in industry because they have excellent heat resistance, electrical insulation properties, and chemical resistance.

Polyimide resins obtained via polyamic acid by the reaction of tetracarboxylic dianhydride and diamine among polyimide resins often have excellent properties, but their softening temperature is high and their workability is poor. There is a disadvantage that. Also known is a thermoplastic polyetherimide (trade name "Ultem" manufactured by General Electric Co., Ltd.) with improved workability at the expense of heat resistance to some extent, but which has sufficient heat resistance and chemical resistance. Was not.

On the other hand, an addition type polyimide resin obtained by polymerizing a bismaleimide compound alone is excellent in thermal properties, but poor in mechanical strength, and thus could not be cast into a film.

[Problems to be solved by the invention]

The present invention has been made in view of these drawbacks, and provides a thermosetting resin composition that can be formed into a film or the like before thermosetting, and that is tough after curing and has excellent flexibility, adhesiveness, and heat resistance. Is what you do.

[Means for solving the problem]

The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that the thermosetting resin composition described below has excellent heat resistance, mechanical properties, and workability, and have completed the present invention. It was done.

That is, the thermosetting resin composition of the present invention has the general formula (I) (Where R ₁ is X represents a direct bond, Represents a group selected from the group consisting of -S-, -SO- or -O-,
Z is And Y is Represents a tetravalent group selected from the group consisting of 100 parts by weight of a polymer having a repeating unit represented by the formula (II): (Where R ₂ is X represents a direct bond, Represents a group selected from the group consisting of -S-, -SO- or -O-. A thermosetting resin composition comprising 5 to 100 parts by weight of a bismaleimide compound represented by the formula:

The polymer used in the present invention has the formula (III) (Where R ₁ is X represents a direct bond, Represents a group selected from the group consisting of -S-, -SO- or -O-. Polyamide acid obtained by reacting one or more tetracarboxylic dianhydrides with the diamine compound shown in (1) by a generally known method and / or polyimide obtained by further dehydrating the polyamic acid.

Diamine compound which is one component of the polymer is specifically,
1,3-bis (3-aminophenoxy) benzene, bis [4- (3-aminophenoxy) phenyl] methane,
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) phenyl] butane, 2,2-bis [4-
(3-Aminophenoxy) phenyl] -1,1,1,3,3,3-
Hexafluoropropane, 4,4'-bis (3-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfoxide, bis [4-
(3-Aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ether, etc., and these may be used alone or as a mixture of two or more.

The other component, tetracarboxylic dianhydride, has the formula (IV) (Where Y is Represents a tetravalent group selected from the group consisting of And specifically, ethylene tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, (cyclopentane tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 ′, 4, 4'-benzophenonetetracarboxylic dianhydride, 2,2 ', 3,3'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl)
Propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone Dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-carboxyphenyl) methane dianhydride 4,4 '-(p-phenylenedioxy) diphthalic dianhydride, 4,4'-(m-phenylenedioxy) diphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid Dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,2,3,4, -benzenetetracarboxylic dianhydride Anhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic Dianhydride, 1,2,7,8 a-phenanthrene tetracarboxylic dianhydride, and these tetracarboxylic dianhydrides may be used alone or in combination.

As the bismaleimide compound (II) used in the present invention, specifically, 1,3-bis (3-maleimidophenoxy) benzene, bis [4- (3-maleimidophenoxy) phenyl] methane, 1,1-bis [4- (3-maleimidophenoxy) phenyl] ethane, 1,2-bis [4-
(3-maleimidophenoxy) phenyl] ethane, 2,2
-Bis [4- (3-maleimidophenoxy) phenyl]
Propane, 2,2-bis [4- (3-maleimidophenoxy) phenyl] butane, 2,2-bis [4- (3-maleimidophenoxy) phenyl] -1,1,1,3,3,3-hexa Fluoropropane, 4,4'-bis (3-maleimidophenoxy) biphenyl, bis [4- (3-maleimidophenoxy) phenyl] ketone, bis [4- (3-maleimidophenoxy) phenyl] sulfide, bis [4- ( 3-
Maleimidephenoxy) phenyl] sulfoxide, bis [4- (3-maleimidophenoxy) phenyl] sulfone, bis [4- (3-maleimidophenoxy) phenyl] ether and the like, and these may be used alone or as a mixture of two or more. Can be

These bismaleimide compounds can be easily produced by subjecting the corresponding diamine compound and maleic anhydride to condensation and dehydration reactions.

The mixing ratio of the polymer of the formula (I) and the bismaleimide compound of the formula (II) is 5 to 100 parts by weight, preferably 10 to 100 parts by weight of the bismaleimide compound (II) per 100 parts by weight of the polymer (I). 80 parts by weight can be used. If the amount of the bismaleimide compound is less than 5 parts by weight, there is no effect on the improvement of the processability and mechanical properties aimed at by the present invention, and if it is more than 100 parts by weight, the resin composition becomes brittle and moldability is lost.

The mixing of the polymer (I) and the bismaleimide compound (II) may be carried out in powder form, but usually, the bismaleimide compound (II) is added and dissolved in the polyamic acid and (slush) or polyimide varnish or suspension. It is done by doing.

The resin composition thus obtained can be used as a prepreg by impregnating and drying a substrate such as glass cloth and carbon cloth, or cast on a glass plate, a stainless steel plate, or the like.
It can be dried and used as a film adhesive containing no substrate for various uses. In this case, the drying temperature and time vary depending on the type of solvent and bismaleimide used,
The temperature must be kept below the temperature at which the polymerization of the bismaleimide compound becomes noticeable, and the time must be such that the amount of residual solvent does not impair the object of the invention.

Further, it can be used as a molding material in powder form. The curing temperature varies depending on the type of bismaleimide, but by heating and curing these, a tough heat-resistant molded article can be obtained.

The thermosetting resin composition of the present invention may optionally contain a polymerization catalyst. The amount of the catalyst used is not particularly limited, but is 0.001 to 10% by weight, especially 0.1 to 10% by weight based on the total weight of the polymer.
A range of 5% by weight is preferred. As the polymerization catalyst, known free radical catalysts such as benzoyl peroxide, t-butyl hydroperoxide, dicumyl peroxide, azobisisobutyronitrile, and azobiscyclohexanecarbonitrile are effective. The polymerization catalysts may be used in appropriate combination.

〔Example〕

 Hereinafter, the present invention will be described with reference to examples.

Examples 1 to 4 In a container equipped with a stirrer, a reflux condenser and a nitrogen inlet tube
7,4 g of 4,4'-bis (3-aminophenoxy) biphenyl
(0.2 mol) and 467.2 g of N, N-dimethylacetamide, and pyromellitic dianhydride 43.2 at room temperature under a nitrogen atmosphere.
g (0.198 mol) was added in portions while paying attention to the rise in solution temperature, and the mixture was stirred at room temperature for about 20 hours to obtain a polyamic acid varnish having a resin content of 20.0% and a solution viscosity at 25 ° C of 64 poise. The logarithmic viscosity of the obtained polyamic acid at 35 ° C. and 0.5% concentration is 0.8.
It was 2 dl / g.

To 100 g of the polyamic acid varnish, 4,4'-bis (3-maleimidophenoxy) biphenyl was added in the amount shown in Table 1, and N, N-dimethylacetamide was added so that the resin content was 20.0%. Was dissolved. This resin composition was cast on a glass plate, and placed at 150 ° C. for 1 hour in a nitrogen atmosphere.
Further drying at 200 ° C. for 2 hours gave a soft brown transparent uncured film having a thickness of 25 μm. This uncured film is 25
By heating at 0 ° C. for 30 minutes, a tough cured film was obtained. Softening point of uncured film (TMA penetration method) and pre-heated uncured film steel (cold rolled steel,
JIS-3141, SPEC / SD, 25 × 100 × 1.6mm), 250
℃, 20kg / cm ² for 30 minutes pressure bonding, but 25 ℃ and
Tensile shear force at 240 ° C high temperature (JIS-K-6848
And K-6850. ) Are shown in Table 1.

Example 5 41.0 g (0.10 mol) of 2,2-bis [4- (3-aminophenoxy) phenyl] propane as a diamine compound and 3,3 ', 4,4'-benzophenonetetracarboxylic acid as a tetracarboxylic dianhydride The same operation as in Examples 1 to 4 was performed using 30.6 g (0.095 mol) of the acid dianhydride to obtain a polyamic acid varnish. This was further reacted at 150 to 160 ° C. for 16 hours and subjected to dehydration condensation to obtain a polyimide varnish having a resin content of 19.2% and a solution viscosity at 25 ° C. of 74 poise.

To 100 g of this polyimide varnish, 2,2-bis [4- (3-
Maleimidophenoxy) phenyl] propane 9.6g and N, N
-20.0 g of dimethylacetamide was added and dissolved at room temperature.

Thereafter, the same operation as in Examples 1 to 4 was performed, and the results in Table 1 were obtained.

Examples 6 to 9 and Comparative Examples 1 and 2 The diamine compounds and the tetracarboxylic dianhydrides shown in Table 1 were each used in the number of moles shown in Table 1 to obtain Examples 1 to 4.
By performing the same operation as above, a polyamic acid dope was obtained. The bismaleimide compound was dissolved therein in the amount shown in Table 1,
A resin composition varnish was obtained.

Hereinafter, the same operation as in Examples 1 to 4 was performed, and the results in Table 1 were obtained.

Example 1B In a container equipped with a stirrer, a reflux condenser and a nitrogen inlet tube
736 g of 4,4'-bis (3-aminophenoxy) biphenyl
(2 moles) and 4688 g of N, N-dimethylacetamide, and under a nitrogen atmosphere, pyromellitic dianhydride 43
6 g (2 mol) was added in portions, paying attention to the rise in solution temperature, and the mixture was stirred at room temperature for about 20 hours. To the polyamic acid solution thus obtained, 60.6 g of triethylamine and 61.
2 g of acetic anhydride was added over about 60 minutes, followed by stirring for about 60 minutes. 4000 g of methanol was added to this solution, and the polyimide powder was filtered off at 30 ° C. After washing the obtained polyimide powder with methanol and acetone, it was dried at 200 ° C. for 16 hours under a nitrogen atmosphere to obtain 1091 g (96% yield) of polyimide powder. 1.0 g of 4,4'bis (3-maleimidophenoxy) biphenyl was added to 10 g of the above-mentioned polyimide powder, mixed uniformly, and then heated to 250 ° C. and 125 × 12.5 × 3.2 × mm.
And press-molded at 350 ° C. × 50 kg / cm ² × 5 min to obtain a bending test piece. The obtained test piece was subjected to ASTM D-63.
According to 8, the flexural strength and flexural modulus at room temperature were measured.

The molded product was heated in air at a heating rate of 10 ° C./min using a thermobalance, and the temperature at which the weight was reduced by 5% was measured.
Further, the obtained resin composition powder was subjected to a vertical flow tester CRT-500 (manufactured by Shimadzu Corporation) at 420 ° C. under a load of 100.
The melt viscosity was measured under the conditions of kgf and a preheat time of 10 seconds.

 These measurement results are also shown in Table-2.

Examples 2B to 9B and Comparative Examples 1B to 4B A diamine compound and a tetracarboxylic dianhydride shown in Table 2 were obtained in the same manner as in Example 1B by using the moles shown in Table 2 and polyimide powders were obtained. To the obtained polyimide powder, bismaleimide compounds shown in Table 2 were mixed at the weight ratios shown in the same table by exactly the same operation as in Example 1B, and by the same operation, flexural strength, flexural modulus, melt viscosity and 5% The weight loss temperature was measured. The results are shown in Table 2.

However, in Comparative Examples 3B and 4B, the bismaleimide component was not mixed, and the measurement was performed on the polyimide powder obtained from the raw materials in Table 2.

〔The invention's effect〕

The thermosetting resin composition of the present invention has adhesiveness, It is excellent in heat resistance, flexibility, and heat resistance and is expected to be widely used as an adhesive, a laminate, and a molding material for electric and electronic devices, and has a great industrial application effect.

Claims (4)

(57) [Claims] 1. The compound of the general formula (I) (Where R ₁ is X represents a direct bond, Represents a group selected from the group consisting of -S-, -SO- or -O-, wherein Z is And Y is Represents a tetravalent group selected from the group consisting of 100 parts by weight of a polymer having a repeating unit represented by the formula (II): (Where R ₂ is X represents a direct bond, Represents a group selected from the group consisting of -S-, -SO- or -O-. A thermosetting resin composition comprising 5 to 100 parts by weight of a bismaleimide compound represented by the formula: 2. The polymer of formula (I) according to claim 1, wherein Z in the formula is the following formula (A): (Wherein, Y is the same as defined above). The thermosetting resin composition according to claim 1, wherein: 3. The polymer of formula (I) according to claim 1, wherein Z in the formula is the following formula (B): (Wherein, Y is the same as defined above). The thermosetting resin composition according to claim 1, wherein: 4. The polymer represented by the general formula (I) according to claim (1), wherein the polymer represented by the following formula (C) and (D): (Wherein R ₁ and Y have the same definitions as above). The thermosetting resin composition according to claim 1, wherein