JP2996872B2 - Heat resistant resin composition with excellent low temperature processability - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-resistant resin composition having excellent heat resistance, being soluble in an organic solvent, and having excellent moldability.

[0002]

2. Description of the Related Art Polyimide resin has high heat resistance, flame retardancy and excellent electrical insulation, so it is used as a film for a substrate of a flexible printed wiring board or a heat-resistant adhesive tape, and as a resin varnish, an interlayer insulating film of a semiconductor. Widely used for surface protection film. However, conventional polyimide resins have high hygroscopicity and excellent heat resistance, but are insoluble or infusible or have an extremely high melting point, and thus cannot be said to be materials which are easy to use in terms of workability. In addition, as a semiconductor mounting material, it is used for an interlayer insulating film, a surface protective film, and the like. For these, a polyimide resin precursor polyamic acid soluble in an organic solvent is applied to the semiconductor surface, and the solvent is removed by heat treatment. And is used after imidation. At this time, a high-temperature drying step of 300 ° C. or more is required to completely advance the imidization and to volatilize the amide-based solvent having a high boiling point. For this reason, it is exposed to a high temperature, which causes thermal damage to other members to be used and deterioration of the element, thereby deteriorating the yield of the assembly process. In addition, since the film has high hygroscopicity, there has been a problem that moisture absorbed at a high temperature evaporates at a stretch and causes swelling and cracks.

As a method for improving the above-mentioned drawbacks, there has been proposed a method of forming a film-like adhesive from a polyimide resin composition which is soluble in an organic solvent and has already been imidized, and thermocompression-bonds this to an adherend. (JP-A-5-105850,
112760, 112761). However, in such a case where the polyimide resin is used as a hot-melt type adhesive, if the glass transition temperature of the polyimide resin is high, a very high temperature is required for processing, and there is a great possibility that the adherend is thermally damaged. On the other hand, if the glass transition temperature of the polyimide resin is lowered to impart low temperature processability, there is a problem that the heat resistance characteristic of the polyimide resin cannot be fully utilized.

[0004]

The present invention has been made as a result of intensive studies to obtain a heat-resistant resin having excellent heat resistance and excellent moldability at low temperatures. The inventors have found that the above problem can be solved by adding a compound having an active hydrogen group capable of reacting with the epoxy compound and a coupling agent, and have reached the present invention.

[0005]

The heat-resistant resin composition of the present invention has a glass transition temperature of at least two per molecule per 100 parts by weight of a polyimide resin soluble in an organic solvent having a glass transition temperature of 350 ° C. or lower. Epoxy compound 5 having an epoxy group
100 parts by weight, 0.1 to 20 parts by weight of a compound having an active hydrogen group capable of reacting with the epoxy compound, and 0.1 to 50 parts by weight of a coupling agent as main components. It is a resin composition.

The component (A) of the heat-resistant resin composition of the present invention is characterized in that the polyimide resin is obtained by mixing a polyamic acid having a low silicone content and a polyamic acid having a high silicone content in a solution and then imidizing the mixture. And
This is because, in a mixed polyimide resin obtained by mixing two types of polyamic acids, the heat resistance, especially the excellent mechanical strength when hot, the silicone derived from the low silicone content polyamic acid with low water absorption and adhesiveness It is characterized in that a trade-off property is realized by imparting a portion derived from a polyamic acid having a high silicone content to an excellent property of modification. Furthermore, by mixing and then imidizing in the amic acid state, separation of the two components can be prevented and solvent solubility can be obtained.

More specifically, 4,4'-oxydiphthalic dianhydride is used as an amine component with a mole of silicon diamine represented by the general formula (1) and b mole of another diamine;
One or more kinds selected from the group consisting of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and 3,3', 4,4'-benzophenonetetracarboxylic dianhydride Polyamic acid A having a low silicone content of 0.02 ≦ a / (a + b) ≦ 0.10 and 0.960 ≦ c / (a + b) ≦ 1.04 using c mol of tetracarboxylic dianhydride as an acid component And d, 4,4′-oxydiphthalic dianhydride using d mol of silicon diamine represented by the general formula (1) and e mol of other diamine as an amine component,
One or more kinds selected from the group consisting of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and 3,3', 4,4'-benzophenonetetracarboxylic dianhydride Polysilicic acid B having a high silicone content satisfying 0.20 ≦ d / (d + e) ≦ 0.70 and 0.920 ≦ f / (d + e) ≦ 1.10. Using f mol of tetracarboxylic dianhydride as an acid component And 0.1 in solution
The polyimide resin is manufactured by mixing the mixture so that 2 ≦ (a + d) / (a + b + d + e) ≦ 0.50 and then imidizing the mixture.

[0008]

Embedded image

(Where k is an integer of 1 to 13) More preferably, in the polyamic acid A, the other diamine component used in combination with the silicone diamine is one or two types represented by the general formula (2). The above diamine h
Mol and one or more kinds of diamines represented by the general formula (3), and the other diamine component used in combination with the silicone diamine in the polyamic acid B is 1 mol represented by the general formula (2). The kind or two or more kinds of diamines and the one or two or more kinds of diamines represented by the general formula (3) are k moles, and 0.1 ≦ (h + j) /
A polyimide resin, wherein (i + k) ≦ 10.

[0010]

Embedded image

[0011]

Embedded image

The tetracarboxylic dianhydride used in the present invention is 4,4′-tetrahydrofuran from the viewpoint of compatibility between solvent solubility and heat resistance.
Oxydiphthalic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4 ′
Preference is given to using benzophenonetetracarboxylic dianhydride. These tetracarboxylic dianhydrides may be used alone or in combination of two or more. Also,
The tetracarboxylic dianhydrides constituting the two kinds of polyamic acids to be mixed and the constitutional molar ratio thereof may be the same or different.

The silicone diamine represented by the general formula (1) used in the present invention is α, ω-bis (3-aminopropyl) polydimethylsiloxane, and
13 is preferable, and a value of k in the range of 4 to 10 is particularly preferable in terms of glass transition temperature, adhesiveness, and heat resistance. Also k
= 1 and the above k = 4 to 10 are preferably used in a blended manner, especially in applications where adhesion is important.

The diamine represented by the general formula (2) is 2,2
2-bis (4- (4-aminophenoxy) phenyl) propane, 2,2-bis (4- (4-aminophenoxy)
Phenyl) hexafluoropropane, 2,2-bis (4
-Aminophenoxy) hexafluoropropane, bis-
4- (4-aminophenoxy) phenylsulfone, bis-4- (3-aminophenoxy) phenylsulfone, 1,3-bis (3-aminophenoxy) benzene,
1,4-bis (3-aminophenoxy) benzene, 1,
4-bis (4-aminophenoxy) benzene, 1,4-
Bis (3-aminophenoxy) benzene, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, 4,
4'-diaminodiphenylmethane, 4,4'-bis (4
-Aminophenoxy) biphenyl and the like. Among them, a diamine having an aminophenoxy structure is preferable in an application field in which adhesion is emphasized.

The diamine represented by the general formula (3) is
Phenylenediamine, m-phenylenediamine, p-phenylenediamine, and monoalkyl and dialkyl nucleus substituted products thereof. Particularly, when importance is attached to heat resistance, a diamine having a p-phenylenediamine skeleton is preferable. The amount ratio (h) of the diamine represented by the general formulas (2) and (3)
+ J) / (i + k) is 0.1 ≦ (h + j) / (i +) from the balance of workability such as solubility, heat resistance and adhesiveness.
k) It is desirable to be in the range of ≤10. Outside of this range, the solvent solubility is lost and the effect of improving heat resistance is not preferred.

In the polyamic acid having a low silicone content, the constituent molar ratio of these diamine and acid is 0.02 ≦ a
/(A+b)≦0.10 and 0.960 ≦ c /
(A + b) ≦ 1.04. When the molar ratio of the silicone diamine is less than 0.02, the resulting mixed polyimide resin loses its solvent solubility characteristics,
If it exceeds 0.10, the heat resistance of the obtained mixed polyimide resin is undesirably reduced. If the acid / amine molar ratio deviates from the above range, the molecular weight of the resulting polyimide resin is reduced, and the object of imparting mechanical strength is not achieved, which is not preferable.

For polyamic acids having a high silicone content, 0.20 ≦ d / (d + e) ≦ 0.70 and
0.920 ≦ f / (d + e) ≦ 1.10. When the molar ratio of the silicone diamine is less than 0.20, it becomes impossible to exhibit excellent properties of silicone modification in the obtained mixed polyimide resin.
If it exceeds 70, the mechanical strength of the obtained mixed polyimide resin is remarkably reduced, which is not preferable. If the acid / amine molar ratio deviates from the above range, the molecular weight of the resulting polyimide resin is reduced, and the heat resistance of the mixed polyimide resin is significantly reduced, which is not preferable.

Further, the two polyamic acids are combined with each other by a molar ratio of silicone diamine of 0.12 ≦ (a + d) /
(A + b + d + e) ≦ 0.50, more preferably
0.20 ≦ (a + d) / (a + b + d + e) ≦ 0.50
It is preferable to mix them so that It is important that the molar ratio is within the above range. When the molar ratio of the silicone diamine is less than 0.12, characteristics such as low water absorption, solubility, and adhesiveness, which are excellent characteristics of silicone modification, do not appear. .
If it exceeds 50, the mechanical strength at a high temperature is remarkably reduced, and a problem occurs in heat resistance.

The equivalent ratio between the acid component and the amine component in the polycondensation reaction is an important factor that determines the molecular weight of the resulting polyamic acid. It is well known that there is a correlation between the molecular weight and physical properties of a polymer, especially the number average molecular weight and mechanical properties. The higher the number average molecular weight, the better the mechanical properties. Therefore, in order to obtain practically excellent strength, it is necessary to have a high molecular weight to some extent. In the present invention,
The equivalent ratio r between the acid component and the amine component is preferably 0.900 ≦ r ≦ 1.060, more preferably 0.975 ≦ r ≦ 1.025. Here, r = [equivalent number of all acid components] / [equivalent number of all amine components]. When r is less than 0.900, the molecular weight is low and the polymer becomes brittle, so that the adhesive strength is weak. If it exceeds 1.06, unreacted carboxylic acid may be decarbonated during heating to cause gas generation and foaming, which may be undesirable.

In the present invention, the addition of a dicarboxylic anhydride or a monoamine for controlling the molecular weight does not hinder the addition, provided that the molar ratio of the acid / amine is in the above range. The reaction between the tetracarboxylic dianhydride and the diamine is
It is carried out in a known manner in an aprotic polar solvent. The aprotic polar solvent is N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMA
C), N-methyl-2-pyrrolidone (NMP), tetrahydrofuran (THF), diglyme, cyclohexanone, 1,4-dioxane (1,4-DO) and the like.
The aprotic polar solvent may be used alone,
Two or more kinds may be used as a mixture. At this time, a non-polar solvent compatible with the aprotic polar solvent may be mixed and used. Aromatic hydrocarbons such as toluene, xylene, and solvent naphtha are often used. The proportion of the non-polar solvent in the mixed solvent is preferably 30% by weight or less. This is because if the nonpolar solvent is 30% by weight or more, the solvent power of the solvent may be reduced and polyamic acid may be precipitated. The reaction between the tetracarboxylic dianhydride and the diamine is carried out by dissolving the well-dried diamine component in the above-mentioned reaction solvent that has been dehydrated and purified, and adding thereto the ring-closing rate of 98%, more preferably 99% or more. The reaction is allowed to proceed by adding the anhydride.

The polyamic acid solution thus obtained is subsequently heat-dehydrated and cyclized in an organic solvent to give an imidized polyimide. Since the water generated by the imidization reaction interferes with the ring closure reaction, an organic solvent incompatible with water is added to the system and azeotroped to form Dean-Stark (Dean-Stark).
k) Discharge out of the system using a device such as a pipe. Dichlorobenzene is known as an organic solvent that is not compatible with water, but the above-mentioned aromatic hydrocarbon is preferably used for electronics because a chlorine component may be mixed therein. Acetic anhydride, β-
It does not prevent the use of compounds such as picoline and pyridine.

In the present invention, the higher the degree of imide ring closure, the better the degree of imidization. If the rate of imidization is low, imidation occurs due to heat during use and water is not generated, which is not preferable. Is preferably achieved.

The component (B) epoxy compound used in the heat-resistant resin composition of the present invention is not particularly limited as long as it has at least two epoxy groups in one molecule. Those having good solubility in a solvent are preferred. For example, bisphenol A type diglycidyl ether, bisphenol F type diglycidyl ether, phenol novolak type epoxy resin, biphenyl type epoxy compound and the like can be mentioned.

The amount ratio of the epoxy compound is 5 to 100 parts by weight with respect to 100 parts by weight of the component (A) polyimide resin.
In particular, it is preferably in the range of 10 to 70 parts by weight. 5
If the amount is less than 10 parts by weight, the effect of adding an uncured epoxy compound to lower the softening temperature of the resin composition and increase the low-temperature processability is unlikely to be exerted.

The component (C) having an active hydrogen group capable of reacting with the epoxy compound used in the heat-resistant resin composition of the present invention includes a polyimide resin of the component (A) and an epoxy compound of the component (B). And those having good compatibility with the polyimide resin and solubility of the polyimide resin in the solvent. For example, resol, novolak, amino compound and the like can be mentioned.
The mixing ratio of the component (C) is polyimide resin 1 of the component (A).
The amount is 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight based on 00 parts by weight. If less than 0.1 parts by weight,
The reaction rate of the uncured epoxy compound becomes extremely low, and the effect desired in the present invention does not appear. In addition, it is difficult to control the resin flow when the elastic modulus of the resin at high temperatures is low. If the amount is more than 20 parts by weight, a gel is likely to be formed in a resin solution state, whereby processability is impaired, and heat resistance of the resin composition is impaired, which is not preferable.

The component (D) coupling agent used in the heat-resistant resin composition of the present invention is compatible with the polyimide resin of the component (A) and the epoxy compound of the component (B), and dissolves the polyimide resin in a solvent. Those having good properties are preferred.
For example, a silane-based coupling agent, a titanium-based or zircon-based coupling agent, and the like can be given. In particular, a silane coupling agent is preferable in terms of compatibility and solubility. The mixing ratio of the coupling agent is 100% of the polyimide resin of the component (A).
It is 0.1 to 50 parts by weight, more preferably 0.5 to 30 parts by weight based on parts by weight. If the amount is less than 0.1 part by weight, it is difficult to control the resin flow when the elastic modulus of the resin at a high temperature is low, and when the resin composition is used for bonding, the resin adheres to an adherend. The effect of improving the performance does not appear. If the amount exceeds 50 parts by weight, the heat resistance of the resin composition is impaired, which is not preferable.

The heat-resistant resin composition of the present invention may contain a fine inorganic filler as long as its workability and heat resistance are not impaired.

In the present invention, a component (B) epoxy compound and other components (C) and (D) can be directly added to the obtained polyimide solution to obtain a heat-resistant resin composition solution. Further, the polyimide solution may be poured into a poor solvent to reprecipitate the polyimide resin, remove unreacted monomers, purify, and dry to use as a solid polyimide resin. In applications that dislike the high-temperature process, or particularly in applications where impurities or foreign matter becomes a problem, it is preferable to dissolve again in an organic solvent to obtain a filtration and purification varnish. The solvent used at this time can be selected from solvents having a low boiling point in consideration of workability.

In the polyimide resin of the present invention, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone are used as ketone solvents, and 1,4-dioxane, tetrahydrofuran, and diglyme are used as ether solvents. It can be used as a low boiling point solvent. These solvents may be used alone or in combination of two or more. Alternatively, these low-boiling solvents may be added to a polyimide resin solution for use.

[0030]

The heat-resistant resin composition obtained by adding an epoxy compound, a compound having an active hydrogen group capable of reacting with the epoxy compound, and a coupling agent to the polyimide resin of the present invention has an apparent glass transition temperature of the polyimide resin. Lower than the glass transition temperature, and the low temperature processability is improved. on the other hand,
The adhesive strength at a temperature higher than the glass transition temperature is higher than that of the polyimide resin, and the physical properties at a high temperature such as no peeling even when subjected to a thermal shock such as IR reflow are improved. Although the detailed mechanism for this peculiar phenomenon is still unclear, the epoxy compound and a compound having an active hydrogen group, or a low-molecular-weight product obtained by the reaction of a coupling agent, may not react with a polyimide resin having a specific structure. As a result, it acts as a plasticizer and lowers the elastic modulus at a temperature lower than the glass transition temperature of the polyimide resin, thereby improving workability at a low temperature such as adhesiveness and workability. On the other hand, in the region higher than the glass transition temperature, it is considered that a three-dimensional network structure is formed by the applied heat, and the fluidity of the polyimide resin is reduced, and thus the heat resistance of the polyimide resin is maintained or improved. With the above mechanism, both low-temperature workability and high-temperature heat-reliability can be achieved. Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.

[0031]

【Example】

(Synthesis of polyimide resin PI-1) (1) Preparation of polyamic acid A １３ Put 213 g of dehydrated and purified NMP into a four-necked flask equipped with a dry nitrogen gas inlet tube, a cooler, a thermometer, and a stirrer, and flow nitrogen gas. Stir vigorously for 10 minutes. Next, 2,2-bis (4-
(4-aminophenoxy) phenyl) propane (BAP
P) 25.4519 g (0.0620 mol) and 2,5-
Dimethyl-p-phenylenediamine (DPX) 4.22
4. 21 g (0.0310 mol) and α, ω-bis (3-aminopropyl) polydimethylsiloxane (APPS)
8590 g (average molecular weight 837, 0.0070 mol)
And heat the system to 60 ° C. and stir until uniform. After dissolving uniformly, the system was cooled to 5 ° C in an ice water bath,
4'-oxydiphthalic dianhydride (ODPA) 31.0
222 g (0.1000 mol) was added over 10 minutes in the form of a powder, and thereafter stirring was continued for 5 hours to obtain a polyamic acid solution. During this time, the flask was kept at 5 ° C.

(2) Preparation of Polyamic Acid B As in the case of Polyamic Acid A, 303.6 g of NMP is vigorously stirred for 10 minutes while flowing nitrogen gas. Next, 2,2-bis (4- (4-aminophenoxy) phenyl) propane 1
1.4944 g (0.0280 mol) and 2,5-dimethyl-p-phenylenediamine 1.9067 g (0.01
40 mol) and 48.5460 g of α, ω-bis (3-aminopropyl) polydimethylsiloxane (average molecular weight 83
7, 0.0580 mol), and heat the system to 60 ° C. and stir until uniform. After homogeneously dissolving, the system was cooled to 5 ° C. in an ice water bath, and 31.0222 g (0.1000 mol) of 4,4′-oxydiphthalic dianhydride was added as a powder over 10 minutes, and then 5 hours Stirring was continued. During this time, the flask was kept at 5 ° C.

(3) Preparation of Polyimide Resin Polyamic acid A and polyamic acid B are weighed in the same weight and placed in a flask. At this time, the average amount of silicone diamine was 32.5 mol% based on all amine components. The nitrogen gas introduction tube and the condenser were removed, a Dean-Stark tube filled with xylene was attached to the flask, and xylene was added to the system. The system was heated by replacing the ice water bath with an oil bath, and the generated water was removed from the system. After heating for 4 hours, no water was generated from the system. After cooling, the reaction solution was poured into a large amount of methanol to precipitate a polyimide resin. After filtering the solid content, the solid was dried under reduced pressure at 80 ° C. for 12 hours to obtain a solid resin. K
When an infrared absorption spectrum was measured by a Br tablet method, an absorption of 5.6 μm derived from the cyclic imide bond was observed.
No absorption at 6.06 μm due to the amide bond could be observed, confirming that the resin was almost 100% imidized. At this time, the molar ratios of the acid and the amine are b = h + i, a / (a + b) = 0.07, and c / (a
+ B) = 1, e = j + k, d / (d + e) = 0.58,
(H + j) / (i + k) = 2, g / (d + e) = 1,
(A + d) / (a + b + d + e) = 0.325.
The polyimide resin thus obtained was prepared using dimethylformamide (DMF), 1,4-dioxane (1,4-D
O) and tetrahydrofuran (THF). The glass transition temperature was 166 ° C. and the tensile modulus was 215 kgf / mm ² .

(Synthesis of polyimide resin PI-2) A polyimide resin PI-2 was obtained in the same manner as in the synthesis of the polyimide resin PI-1. Table 1 shows the evaluation results obtained for these polyimide resins.

[0035]

[Table 1]

APB in the monomer column is 1,3-bis (3-aminophenoxy) benzene, and BPDA is 3,
Represents 3 ', 4,4'-biphenyltetracarboxylic dianhydride.

S in the column of solubility indicates that the compound is soluble in the corresponding solvent. The glass transition temperature was determined by DSC measurement. The tensile test was performed at room temperature at a tensile speed of 5 mm / min. Young's modulus was determined using a viscoelastic spectrometer.

Example 1 A glass flask was charged with 100 g of polyimide resin PI-1 and 355 g of DMF, and thoroughly stirred at room temperature to completely dissolve the polyimide. After uniformly dissolving, 40 g of a bisphenol A type epoxy compound (Epicoat 828, manufactured by Yuka Shell Epoxy) was added, and the mixture was stirred at room temperature for 2 hours. After confirming that the silane coupling agent is uniformly dissolved, a silane coupling agent (trismethoxyethoxyvinylsilane, KBC1003, Shin-Etsu Chemical
1 g) and stirred at room temperature for 1 hour. After confirming that the resin is dissolved uniformly, resole resin (PR-5078)
1, 5 g of Sumitomo Durez Co., Ltd.) was gradually added while stirring the system. Subsequently, the mixture was stirred for 2 hours to prepare a heat-resistant resin solution. This solution composition did not gel even when left at room temperature for 5 days, and remained in a uniform solution state.

The resin solution thus obtained was applied to a mirror-polished stainless steel plate with a doctor blade, and the thickness was 50 μm.
m was obtained. The drying temperature was a maximum of 195 ° C. and the drying time was 20 minutes. Table 2 shows the solubility, glass transition temperature, and tensile properties.

This varnish was applied to one surface of a polyimide film (trade name: Upilex SGA, thickness: 50 μm, manufactured by Ube Industries, Ltd.) using a reverse roll coater to obtain an adhesive tape having an adhesive layer thickness of 30 μm. The drying temperature was a maximum of 200 ° C. and the drying time was 15 minutes. This adhesive tape was thermocompression bonded to a 42 alloy plate to prepare a test piece (2
After thermocompression bonding at 50 ° C. for 2 seconds, the pressure was released, and annealing was performed at 250 ° C. for 30 seconds. The pressure applied to the bonded surface was 4 kgf / cm ² calculated from the gauge pressure and the bonded area. ), And the results of measuring the 180 degree peel strength with a tensile tester are shown in Table 2. The adhesive strength was normal and pressure cooker (12
(180 ° peel strength at room temperature and 240 ° C. after treatment at 5 ° C., 48 hours, saturation 100%) (tensile speed 50 mm / min). In the fracture surface of the test piece, the adhesive resin layer was cohesively fractured, and no foaming was observed.

(Examples 2 to 4) In the same manner as in Example 1, a heat-resistant resin solution was prepared according to the formulation shown in Table 2, and a film,
An adhesive tape was obtained. Table 2 shows the obtained evaluation results.

[0042]

[Table 2]

With respect to the component (B) epoxy compound used, YX-4000H is a biphenyl type epoxy compound epicoat YX-4000H, Yuka Shell Epoxy Co., Ltd.
EOCN-1020 manufactured by Nippon Kayaku Co., Ltd. indicates a phenol novolak type epoxy compound EOCN-1020. About component (C) used, PR-
50781, 175, 53647 and 22193 are manufactured by Sumitomo Durez Corporation. About component (D) used, KBM5
73 (N-phenyl-γ-aminopropyltrimethoxysilane) and KBC1003 (trismethoxyethoxyvinylsilane) are silane coupling agents manufactured by Shin-Etsu Chemical Co., Ltd.

S in the column of solubility indicates that the compound is soluble in the corresponding solvent. The glass transition temperature was determined by DSC measurement. The tensile test was performed at room temperature at a tensile speed of 5 mm / min. Young's modulus was determined using a viscoelastic spectrometer.

(Comparative Examples 1 to 4) A resin composition containing only a polyimide resin or a resin composition obtained by adding one or two of components (B) to (D) was prepared. Next, an adhesive tape was prepared in the same manner as in the example, and the adhesive strength to a 42 alloy plate was measured. Table 3 shows the results.

[0046]

[Table 3]

From the results in Tables 2 and 3, the heat strength of the adhesive tape of the comparative example after treatment with a pressure cooker was as follows:
It is significantly lower than that of the tape obtained from the resin composition of the example.

From the above examples, it is shown that the present invention can prevent the adhesive strength at the time of moisture absorption from being greatly reduced, and can obtain a film adhesive excellent in heat resistance and moldability.

[0049]

According to the present invention, it is possible to provide a highly reliable film adhesive having both heat resistance and moldability. Since it is soluble in a low boiling point solvent, the residual solvent can be almost completely eliminated, and since it has already been imidized, a high temperature process for imidization is not required during processing, and no water is generated. Also, since it can be used as a tack-free film, it is very effective when continuous workability and a clean environment are required. For this reason, it is extremely useful industrially as a material for electronics requiring high reliability and heat resistance.

The method of using the resin composition of the present invention is not particularly limited. However, as a resin varnish in which all of the resin constituents are uniformly dissolved in an organic solvent, coating and dipping are performed by casting. The film can be used as an insulating material, an adhesive film, or the like that has both heat resistance and processability.

Continuation of the front page (56) References JP-A-7-247427 (JP, A) JP-A-7-247408 (JP, A) JP-A-7-247426 (JP, A) JP-A-6-256472 (JP, A) , A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 79/00-79/08 C08G 73/00-73/26

Claims (3)

(57) [Claims] (A) A mole of silicon diamine represented by the general formula (1) and b mole of another diamine are used as amine components, and 4,4′-oxydiphthalic dianhydride, 3,3 ′,
One or more tetracarboxylic dianhydrides selected from the group consisting of 4,4'-biphenyltetracarboxylic dianhydride and 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride C as an acid component, and 0.02 ≦ a / (a + b) ≦ 0.10, 0.960 ≦
Polyamide acid A reacted at a ratio of c / (a + b) ≦ 1.04, d mole of silicon diamine represented by the general formula (1) and e mole of other diamine as an amine component, and 4,4′-
Oxydiphthalic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, and 3,3 ′, 4
One or more kinds of tetracarboxylic dianhydrides (fmol) selected from the group consisting of 4'-benzophenonetetracarboxylic dianhydrides are used as acid components, and 0.20 ≦ d
/(D+e)≦0.70, 0.920 ≦ f / (d + e)
The polyamic acid B reacted at a ratio of ≦ 1.10.
100 parts by weight of a polyimide resin having a glass transition temperature of 350 ° C. or less soluble in an organic solvent and mixed and imidized in a ratio of 12 ≦ (a + d) / (a + b + d + e) ≦ 0.50;
(B) 5 to 100 parts by weight of an epoxy compound having at least two epoxy groups in one molecule, and (C) 0.1 to 100 parts by weight of a compound having an active hydrogen group capable of reacting with the epoxy compound.
A heat-resistant resin composition having excellent low-temperature processability, comprising 20 parts by weight and (D) 0.1 to 50 parts by weight of a coupling agent as main components. Embedded image (Where k is an integer of 1 to 13) 2. In the polyimide resin of the component (A),
The other diamines in the polyamic acid A are one or two or more kinds of diamines represented by the general formula (2) and one or two or more kinds of diamines represented by the general formula (3) i mol, The other diamine in the polyamic acid B is one or two or more kinds of diamines represented by the general formula (2) and one or two diamines represented by the general formula (3).
More than one kind of diamine, and 0.1 ≦ (h
The heat-resistant resin composition according to claim 1, wherein + j) / (i + k) ≦ 10. Embedded image Embedded image 3. The heat-resistant resin composition according to claim 1, wherein the component (D) is a silane coupling agent.