JPH07247428A - Heat-resistant resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition containing a specific polyimide resin, an epoxy compound and a coupling agent, excellent in low temperature processability, high-temperature adhesiveness and reliability to heat resistance and useful for flexible printed-wiring boards, heat-resistant adhesive tapes, etc. CONSTITUTION:This composition contains (A) 100 pts.wt. of a polyimide resin soluble in organic solvents and having >=350 deg.C glass transition temperature and obtained by mixing a polyimidic acid which is obtained by reacting a diamine mixture consisting of (a) mols of a compound of the formula [(k) is 1-3] and (b) mols of other diamine with (c) mols of a tetracarboxylic acid dianhydride which is 4,4'-oxydiphthalic acid dianhydride, etc., at ratios of 0.02<=(a)/(a+b)<=0.10 and 0.96<=(c)/(a+b)<=1.04 with a polyimidic acid obtained by reacting a diamine mixture consisting of (a) mols of the compound of the formula and (b) mols of other diamine with (c) mols of the tetracarboxylic acid dianhydride at ratios of 0.20<(a)/(a+b)<=0.70 and 0.92<=(c)/(a+b)<=1.10 and imidating the mixed polyimidic acid, (B) 5-100 pts.wt. of a compound containing two or more epoxy groups in a molecule and (C) 0.1-50 pts.wt. of a coupling agent such as a silane coupling agent.

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 which is excellent in heat resistance, soluble in an organic solvent and excellent in moldability.

[0002]

2. Description of the Related Art Since polyimide resin has high heat resistance, flame resistance, and excellent electrical insulation, it is used as a film for base materials of flexible printed wiring boards and heat resistant adhesive tapes, and as a resin varnish for semiconductor interlayer insulation film. Widely used for surface protection film. However, conventional polyimide resins have high hygroscopicity and excellent heat resistance, but on the other hand, they are insoluble and infusible or have extremely high melting points, so that they cannot be said to be easy-to-use materials in terms of workability. It is also used as a mounting material for semiconductors in interlayer insulation films and surface protection films. These are applied to the surface of semiconductors with polyamic acid, a precursor of polyimide resin that is soluble in organic solvents, and the solvent is removed by heat treatment. Is used together with imidization. At this time, a high temperature drying step at 300 ° C. or higher is required to completely promote imidization and to volatilize the high boiling amide solvent. As a result, it is exposed to high temperatures, causing thermal damage to other members to be used and deterioration of the element, which deteriorates the yield of the assembly process. Further, since the film has a high hygroscopic property, there is a problem that the moisture absorbed at a high temperature evaporates at once and causes blisters and cracks.

As a method for improving the above-mentioned drawbacks, a method has been proposed in which a film adhesive is formed from a polyimide resin composition which is soluble in an organic solvent and has already been imidized, and which is thermocompression bonded to an adherend. (JP-A-5-105850,
See 112760, 112761). However, in such a case where a polyimide resin is used as a hot-melt type adhesive, if the glass transition temperature of the polyimide resin is high, an extremely 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 of the polyimide resin cannot be fully utilized.

[0004]

DISCLOSURE OF INVENTION Problems to be Solved by the Invention The present invention has been earnestly studied to obtain a heat-resistant resin having excellent heat resistance and excellent moldability at low temperature. When a coupling agent is added,
The inventors have found that the above problems can be solved and arrived at the present invention.

[0005]

The heat-resistant resin composition of the present invention contains at least two or more per molecule of 100 parts by weight of a polyimide resin soluble in an organic solvent having a glass transition temperature of 350 ° C. or less. 5 to 100 parts by weight of an epoxy compound having an epoxy group, and 0.1 to 50 parts by weight of a coupling agent as main components.

The component (A) polyimide resin of the heat-resistant resin composition of the present invention is obtained by mixing a polyamic acid having a low silicone content and a polyamic acid having a high silicone content in a solution state and then imidizing the mixture. And
This is a mixed polyimide resin obtained by mixing two types of polyamic acid, which has high heat resistance, particularly excellent mechanical strength at the time of heat treatment, due to the low silicone content polyamic acid-derived portion having low water absorption and adhesiveness. It is characterized in that a trade-off characteristic is realized by allowing the portion derived from a high silicone content polyamic acid to have excellent modification characteristics. Furthermore, by mixing in the amic acid state and then imidizing, separation of the two components can be prevented and solvent solubility can be obtained.

In more detail, 4,4'-oxydiphthalic acid dianhydride is prepared by using a mol of silicon diamine represented by the formula (1) and another mol of diamine as an amine component.
One or two or more tetra selected from the group of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride 0.02 ≦ a / (a + b) ≦ 0.10 with c mole of carboxylic acid dianhydride as an acid component, and
A polyamic acid A having a low silicone content of 0.960 ≦ c / (a + b) ≦ 1.04, silicon diamine represented by the formula (1) d mole, and another diamine e mole as amine components, '-Oxydiphthalic acid dianhydride, 3,
One or two or more tetracarboxylic acids selected from the group of 3 ', 4,4'-biphenyltetracarboxylic dianhydride and 3,3', 4,4'-benzophenonetetracarboxylic dianhydride 0.20 ≦ d / (d + e) ≦ 0.70 with f mole of dianhydride as an acid component and 0.
920 ≦ f / (d + e) ≦ 1.10 with a high silicone content polyamic acid B in solution 0.12 ≦ (a
+ D) / (a + b + d + e) ≦ 0.50, and then is imidized to produce a polyimide resin.

[0008]

[Chemical 1] (In the formula, k: 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 represented by the formula (2) and one or more kinds of diamine hmol and the formula (3). I mol of one or two or more diamines, and in the polyamic acid B, the other diamine component used in combination with the silicone diamine is one mol or more of the diamine represented by Formula (2) and a formula. One or two or more kinds of diamines represented by (3) are kmol, and 0.1 ≦ (h + j)
The polyimide resin is characterized in that / (i + k) ≦ 10.

[0010]

[Chemical 2]

[0011]

[Chemical 3]

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

The silicone diamine represented by the formula (1) used in the present invention is α, ω-bis (3-aminopropyl) polydimethylsiloxane, and k = 1 to 1
3 is preferable, and a value of k in the range of 4 to 10 is particularly preferable from the viewpoint of glass transition temperature, adhesiveness, and heat resistance. K =
It is preferable to use 1 and the above k = 4 to 10 in a blend for use in which importance is attached to the adhesiveness.

The diamine represented by the general formula (2) is 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) phenyl sulfone, bis-4- (3-aminophenoxy) phenyl sulfone, 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'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,
4'-diaminodiphenylmethane, 4,4'-bis (4
-Aminophenoxy) biphenyl and the like. Among them, diamines having an aminophenoxy structure are preferable in the application field where the adhesiveness is important.

The diamine represented by the general formula (3) is o-
They are phenylenediamine, m-phenylenediamine, p-phenylenediamine, and monoalkyl and dialkyl nuclear substitution products thereof. Especially when importance is attached to heat resistance, a diamine having a p-phenylenediamine skeleton is preferable. Amount ratio of diamines represented by formulas (2) and (3) (h +
j) / (i + k) is 0.1 ≦ (h + j) / (i + k) from the balance of processability such as solubility, heat resistance and adhesiveness.
It is desirable to be in the range of ≤10. Outside of this range, the solubility of the solvent is lost and the effect of improving heat resistance is not recognized, which is not preferable.

The composition molar ratio of these diamines and acids is 0.02≤a in the polyamic acid having a low silicone content.
/(A+b)≦0.10 and 0.960 ≦ c /
It must be (a + b) ≦ 1.04. When the molar ratio of silicone diamine is less than 0.02, the solvent-soluble characteristics of the obtained mixed polyimide resin are lost,
When it exceeds 0.10, the heat resistance of the obtained mixed polyimide resin is deteriorated, which is not preferable. If the acid / amine molar ratio deviates from the above range, the molecular weight of the obtained polyimide resin decreases, and the purpose of bearing mechanical strength is not achieved, which is not preferable.

For high silicone content polyamic acid, 0.20≤d / (d + e) ≤0.70 and
It should be 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, so that it is not possible to achieve
When it exceeds 70, the mechanical strength of the obtained mixed polyimide resin is remarkably lowered, which is not preferable. Further, if the acid / amine molar ratio deviates from the above range, the molecular weight of the obtained polyimide resin decreases, and the heat resistance of the mixed polyimide resin remarkably decreases, which is not preferable.

Furthermore, the molar ratio of the two polyamic acids to the total silicone diamine is 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 so that. It is important that the amount ratio is within the above range. If the molar ratio of the silicone diamine is less than 0.12, the excellent characteristics of silicone modification such as low water absorption, solubility and adhesiveness do not appear, and ．
When it exceeds 50, the mechanical strength at high temperature is remarkably reduced and a problem occurs in heat resistance.

The equivalent ratio of the acid component and the amine component in the polycondensation reaction is an important factor that determines the molecular weight of the polyamic acid obtained. It is well known that there is a correlation between polymer molecular weight and physical properties, especially number average molecular weight and mechanical properties. The larger the number average molecular weight, the better the mechanical properties. Therefore, in order to obtain practically excellent strength, it is necessary that the polymer has a high molecular weight to some extent. In the present invention,
The equivalent ratio r of the acid component and the amine component is more preferably 0.900 ≤ r ≤ 1.060, and more preferably 0.975 ≤ r ≤ 1.025. However, r = [equivalent number of all acid components] / [equivalent number of all amine components]. If r is less than 0.900, the molecular weight is low and the composition becomes brittle, so that the adhesive strength becomes weak. On the other hand, if it exceeds 1.06, unreacted carboxylic acid may be decarboxylated during heating to cause gas generation and foaming, which is not preferable.

In the present invention, addition of a dicarboxylic acid anhydride or a monoamine for controlling the molecular weight of the polyimide resin is not particularly hindered as long as the acid / amine molar ratio is within the above range.

The reaction between the tetracarboxylic dianhydride and the diamine is carried out by a known method in an aprotic polar solvent. The aprotic polar solvent is N, N-dimethylformamide (DMF), N, N-dimethylacetamide (D
MAC), 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 or in combination of two or more. 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 nonpolar solvent in the mixed solvent is preferably 30% by weight or less. This is because if the amount of the nonpolar solvent is 30% by weight or more, the solvent's dissolving power may decrease and polyamic acid may precipitate. The reaction between the tetracarboxylic acid dianhydride and the diamine is carried out by dissolving a well-dried diamine component in the dehydrated and purified reaction solvent described above and adding a ring closure ratio of 98%, more preferably 99% or more to the well-dried tetracarboxylic acid dianhydride. Anhydrous is added to drive the reaction.

The polyamic acid solution thus obtained is subsequently heated and dehydrated in an organic solvent to form an imidized polyimide. Since the water generated by the imidization reaction interferes with the ring-closing reaction, an organic solvent that is incompatible with water is added to the system to azeotrope the mixture, and then Dean-Stark (Dean-Star).
k) Discharge to the outside of the system using a device such as a pipe. Dichlorobenzene is known as an organic solvent which is incompatible with water, but for electronics use, the aromatic hydrocarbon is preferably used since chlorine components may be mixed therein. In addition, acetic anhydride, β-
It does not prevent the use of compounds such as picoline, pyridine.

In the present invention, the higher the degree of imide ring closure, the better, and if the imidization ratio is low, imidization occurs due to heat during use and water is not generated, which is not preferable. Therefore, 95% or more, more preferably 98% or more. It is desirable that the imidization ratio of is 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, but it is not limited to polyimide resins. Those having good solubility in a solvent are preferable. Examples thereof include bisphenol A type diglycidyl ether, bisphenol F type diglycidyl ether, phenol novolac type epoxy resin, and biphenyl type epoxy compound.

The amount ratio of the epoxy compound is 5 to 100 parts by weight based on 100 parts by weight of the component (A) polyimide resin,
It is particularly preferably in the range of 10 to 70 parts by weight. 5
If it is less than 100 parts by weight, the effect of adding an uncured epoxy compound to lower the softening temperature of the resin composition and improving the low-temperature processability is difficult to appear. If it exceeds 100 parts by weight, the heat resistance of the polyimide resin is impaired.

The component (C) coupling agent used in the heat resistant resin composition of the present invention is compatible with the component (A) polyimide resin and the component (B) epoxy compound,
It is preferable that the polyimide resin has good solubility in a solvent. For example, a silane-based coupling agent, a titanium-based coupling agent, a zircon-based coupling agent, or the like may be used. Particularly, a silane coupling agent is preferable in terms of compatibility and solubility. The mixing ratio of the coupling agent is the polyimide resin 1 of the component (A).
The amount is 0.1 to 50 parts by weight, more preferably 0.5 to 30 parts by weight, relative to 00 parts by weight. Below 0.1 parts by weight,
It is difficult to control the resin flow when the elastic modulus of the resin at a high temperature is lowered, and when the resin composition is used for bonding, the effect of improving the adhesion to the adherend does not appear. If it 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 the processability and heat resistance thereof are not impaired.

In the present invention, an epoxy compound or a coupling agent may be added as it is to the obtained polyimide solution to prepare a heat resistant resin composition solution. It is also possible to use the polyimide solution as a solid polyimide resin by pouring the polyimide solution into a poor solvent to reprecipitate and precipitate the polyimide resin to remove unreacted monomers, and to refine and dry the polyimide resin. In applications where high-temperature processes are disliked or where impurities and foreign substances are particularly problematic, it is preferable to dissolve them again in an organic solvent to obtain a filtration / purification varnish. Considering the workability of the solvent used at this time,
It is possible to select a solvent with a low boiling point.

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 having a boiling point of 200 ° C. or less. It can be used as a low boiling point solvent. These solvents may be used alone or in combination of two or more. Alternatively, the low boiling point solvent may be added to the polyimide resin solution for use.

[0030]

The heat-resistant resin composition obtained by adding the epoxy compound and the coupling agent to the polyimide resin of the present invention has an apparent glass transition temperature lower than the glass transition temperature of the polyimide resin, thus improving the low temperature processability. On the other hand, the adhesive strength in a temperature range higher than the glass transition temperature is higher than that of the polyimide resin, and the physical properties in a high temperature area such as no peeling observed even when a thermal shock such as IR reflow is applied are improved. Although the detailed mechanism for this peculiar phenomenon is not yet clear, the low molecular weight product obtained by reacting the epoxy compound with the coupling agent acts as a plasticizer for the polyimide resin having a specific structure, It lowers the elastic modulus in a temperature range lower than the glass transition temperature of, thus improving workability at low temperatures such as adhesiveness and processability. On the other hand, it is considered that in a temperature range higher than the glass transition temperature, a heat applied thereto forms a three-dimensional network structure, which lowers the fluidity of the polyimide resin and thus maintains or improves the heat resistance of the polyimide resin. By the above mechanism, both low temperature processability and heat resistance reliability at high temperature can be achieved.
The present invention is described in detail below 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 ... Putting 213 g of dehydrated and refined NMP into a four-necked flask equipped with a dry nitrogen gas introduction tube, a cooler, a thermometer, and a stirrer, and flowing nitrogen gas. Stir vigorously for 10 minutes. Next, 2,2-bis (4-
(4-aminophenoxy) phenyl) propane (BAP
P) 25.419 g (0.0620 mol) and 2,5-
Dimethyl-p-phenylenediamine (DPX) 4.22
21 g (0.0310 mol) and α, ω-bis (3-aminopropyl) polydimethylsiloxane (APPS) 5.
8,590 g (average molecular weight 837, 0.0070 mol,)
, And the system is heated to 60 ° C. and stirred until uniform. After uniform dissolution, the system was cooled to 5 ° C in an ice water bath,
4'-oxydiphthalic acid dianhydride 31.0222 g
(0.1000 mol) was added as a powder over 10 minutes, and then 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: Like the polyamic acid A, 303.6 g of NMP is vigorously stirred for 10 minutes while flowing nitrogen gas. Then 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 α, ω-bis (3-aminopropyl) polydimethylsiloxane 48.5460 g (average molecular weight 83
7, 0.0580 mol), and the system is heated to 60 ° C. and stirred until uniform. After being uniformly dissolved, 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 for 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 is 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 ice water bath was replaced with an oil bath to heat the system and remove the generated water outside the system. After heating for 4 hours, generation of water from the system was not observed. After cooling, this reaction solution was poured into a large amount of methanol to precipitate a polyimide resin. The solid content was filtered and then dried under reduced pressure at 80 ° C. for 12 hours to obtain a solid resin. K
When the infrared absorption spectrum was measured by the Br tablet method, an absorption of 5.6 μm derived from a cyclic imide bond was observed.
Absorption at 6.06 μm derived from an amide bond could not be observed, and it was confirmed that this resin was almost 100% imidized. At this time, the molar ratio of the acid and the amine is b = h + i, a / (a + b) = 0.07, 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 is dimethylformamide (DMF), 1,4-dioxane (1,4-D
It was confirmed that it was well dissolved in 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 the synthesis of the polyimide resin PI-1. Table 1 shows the evaluation results obtained for these polyimide resins.

[0035]

[Table 1]

APB and BPDA in the Monomer column are 1,3-
Bis (3-aminophenoxy) benzene, 3,3'4
Represents 4'-biphenyltetracarboxylic dianhydride, respectively. S in the solubility column 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 and a tensile speed of 5 mm / min.

Example 1 100 g of polyimide resin PI-1 and 355 g of DMF were placed in a glass flask and sufficiently stirred at room temperature to completely dissolve the polyimide. After being uniformly dissolved, 40 g of a bisphenol A type epoxy compound (Epicoat 828, manufactured by Yuka Shell Epoxy Co., Ltd.) was added and stirred at room temperature for 2 hours. After confirming that the silane coupling agent is uniformly dissolved, the silane coupling agent (N-phenyl-γ-aminopropyltrimethoxysilane, KBM5
No. 73, manufactured by Shin-Etsu Chemical Co., Ltd.) was gradually added with stirring. Subsequently, the mixture was stirred for 2 hours to prepare a heat resistant resin solution.
This solution composition did not gel even after standing at room temperature for 10 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 to give a thickness of 50 μm.
m film was obtained. The maximum drying temperature was 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 side of a polyimide film (trade name Upilex SGA, thickness 50 μm, Ube Industries, Ltd.) with a reverse roll coater to obtain an adhesive tape having an adhesive layer thickness of 30 μm. The drying temperature was up to 200 ° C. and the drying time was 15 minutes. This adhesive tape was thermocompression-bonded to a 35 μm copper foil to prepare a test piece (thermocompression-bonded to the treated surface of the copper foil at 250 ° C. for 2 seconds, and after releasing the pressure, at 3 ° C. at 250 ° C.
Annealed for 0 seconds. The pressure applied to the bonding surface was 4 kgf / cm ^{2 as} a result of calculation from the gauge pressure and the bonding area. ), And the results of measuring the 180 degree peel strength with a tensile tester are shown in Table 2. The adhesive strength is a value obtained by measuring a 180 degree peel strength at room temperature and 240 ° C. after treatment with a normal state and a pressure cooker (125 ° C., 48 hours, 100% saturation) (pulling speed 50 mm / min). On the fracture surface of the test piece, the adhesive resin layer was cohesively broken, 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 to prepare a film,
An adhesive tape was obtained. Table 2 shows the obtained evaluation results.

[0041]

[Table 2]

YX-4000H is a biphenyl type epoxy compound, Epicoat YX-4000H, manufactured by Yuka Shell Epoxy Co., Ltd., and EOCN-1020 is a phenol novolac type epoxy compound, manufactured by Nippon Kayaku Co., Ltd. KBC1
003 is trismethoxyethoxyvinylsilane, KBE
1003 is triethoxyvinylsilane (Shin-Etsu Chemical Co., Ltd.)
Manufactured). S in the solubility column 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 and a tensile speed of 5 mm / min.

(Comparative Examples 1 and 2) Polyimide resin PI-1
An adhesive tape containing only PI-2 and PI-2 was prepared in the same manner as in Example 1, and the adhesive strength with copper was measured. The results are shown in Table 3.

[0044]

[Table 3]

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

(Comparative Example 3) In the same manner as in Example 1, 100 g of polyimide resin PI-1 and 375 g of DMF were added,
Stir well at room temperature to completely dissolve the polyimide. After being uniformly dissolved, a bisphenol A type epoxy compound (Epicoat 828, manufactured by Yuka Shell Epoxy Co., Ltd.) 20
g was added and the mixture was stirred at room temperature for 2 hours. Then, after confirming that the titanate coupling agent (preneact KR44) was homogeneously dissolved, 5 g of the titanate coupling agent (preneact KR44) was gradually added with stirring, and immediately a gel was formed in the solution. The gel did not disappear even after stirring overnight, and a uniform solution could not be obtained even when diluted with NMP.

(Comparative Example 4) Polyimide resin PI-1, 1
The adhesive strength of the adhesive tape obtained from the resin prepared with only 00 g and Epicoat 828, 20 g was measured in the same manner as in the example, and the results are shown in Table 3.

The above examples show that the present invention can provide a film adhesive having excellent heat resistance and molding processability, which can prevent the adhesive strength from significantly lowering under heat of moisture absorption.

[0049]

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

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

Claims (3)

[Claims] 1. (A) A mol of silicon diamine represented by the formula (1) and b mol of another diamine as amine components,
4,4'-oxydiphthalic dianhydride, 3,3 ', 4
4'-biphenyltetracarboxylic dianhydride, and 3,
One or two or more tetracarboxylic acid dianhydrides cmol selected from the group of 3 ', 4,4'-benzophenone tetracarboxylic acid dianhydride as an acid component, and 0.02
≦ a / (a + b) ≦ 0.10, 0.960 ≦ c / (a +
b) 4,4′-oxydiphthalic acid dianhydride, wherein polyamic acid A reacted in a ratio of ≦ 1.04, silicon diamine represented by formula (1) d mole and other diamine e mole as amine components , 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, and one or more kinds selected from the group of 3,3', 4,4'-benzophenonetetracarboxylic dianhydride An acid component of tetracarboxylic acid dianhydride (f mole) and 0.20 ≦ d / (d + e) ≦ 0.7
0, 0.920 ≦ f / (d + e) ≦ 1.10 and polyamic acid B reacted at a ratio of 0.12 ≦ (a + d) /
100 parts by weight of an organic solvent-soluble polyimide resin having a glass transition temperature of 350 ° C. or lower, which is mixed and imidized at a ratio of (a + b + d + e) ≦ 0.50, and (B) at least two epoxies in one molecule. 5 to 100 parts by weight of epoxy compound having a group, and (C) coupling agent 0.1 to 5
A heat-resistant resin composition comprising 0 part by weight as a main component. [Chemical 1] (In the formula, k: an integer of 1 to 13) 2. The polyimide resin of component (A),
The other diamines in the polyamic acid A are one or more kinds of diamines represented by the formula (2), and one or more kinds of diamines represented by the formula (3).
And the other diamine in the polyamic acid B is one or more diamines represented by the formula (2).
Mol and one or two or more kinds of diamines represented by the formula (3), and 0.1 ≦ (h + j) / (i
The heat-resistant resin composition according to claim 1, wherein + k) ≦ 10. [Chemical 2] [Chemical 3] 3. The heat resistant resin composition according to claim 1, wherein the component (C) is a silane coupling agent.