JP2002167508A - Polyimide resin composition and film-shaped adhesive agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a film-shaped adhesive agent which is excellent in heat resistance as the property of a thermoplastic polyimide resin as well as adhesiveness to metal, a laminated sheet and a printed circuit board, and can be heated to press without bubbling foams. SOLUTION: The film-shaped adhesive agent comprises a polyimide resin of a specific structure, an epoxy compound, and a compound linkable with the epoxy compound to form a silane coupling.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyimide resin composition, and more specifically, to an adhesive for electronic parts. Further, the present invention relates to a film-like adhesive which is excellent in adhesiveness to metal, a laminated board, and a printed circuit board as a circuit board material and a semiconductor mounting material, and hardly foams when subjected to thermocompression bonding.

[0002]

2. Description of the Related Art In recent years, with the development of the electronic and electric equipment industries, communication, industrial and consumer equipment have been reduced in size and weight, and accordingly, the form of a semiconductor package (PKG) has been further increased. Chip scale packages (CSPs) have emerged as they have become lighter and smaller. There are various types of these PKGs, and a film adhesive for bonding various materials such as a flexible printed board, a circuit board, a semiconductor chip, and a lead frame has been required.

Conventionally, as a heat-resistant thermocompression-bondable film adhesive, a polyamide-based or polyamide-imide-based thermoplastic heat-resistant resin or an epoxy-based, phenol-based or acrylic-based heat-sensitive adhesive has been used. One using a curable resin is known. However, polyamide resins and polyamide-imide resins have a drawback that the water absorption is increased due to the hydrophilic nature of the amide group, and there is a limit in using them for electronic applications requiring reliability. In the case of thermosetting materials, thermocompression bonding can be performed at a relatively low temperature.
In order to obtain heat resistance, it is necessary to provide a long curing time, so that the productivity is low, and there are disadvantages such as a problem that a large amount of volatile components are generated during heat curing and a problem of an ionic impurity amount.

As a solution to these problems, a heat resistant adhesive using a thermoplastic polyimide resin has been developed. This adhesive mainly exhibits excellent adhesiveness and adhesive workability to inorganic materials such as metals and ceramics, but the adhesiveness to heat-resistant resins such as polyimide, polyamideimide, polyamide, epoxy and phenol is not necessarily sufficient. I couldn't say. Further, when thermocompression bonding is performed on a circuit board using these as a base material, there is a problem that the adhesive foams.

[0005]

SUMMARY OF THE INVENTION The present invention relates to a polyimide resin composition which has the heat resistance of the above-mentioned thermoplastic polyimide resin, has excellent adhesiveness to a circuit board, and is hardly foamed upon thermocompression bonding. To provide a film adhesive.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in view of the above problems, and have found that a resin composition mainly composed of a polyimide resin having a specific structure, an epoxy compound, and a coupling agent is bonded. The present inventors have found that a film-like adhesive having excellent adhesive properties and hardly foaming upon thermocompression bonding can be obtained by applying the composition to the agent, and the present invention has been completed.

That is, the present invention provides a compound of the formula (2) obtained by reacting an aromatic tetracarboxylic dianhydride component with a diaminopolysiloxane represented by the formula (1) and an aromatic or aliphatic diamine. (A), an epoxy compound (B) having at least two epoxy groups in one molecule and a silane coupling agent (C), wherein the diaminopolysiloxane is at least 10 to 50. Is a diaminopolysiloxane having a repeating unit k of the following formula, and based on 100 parts by weight of the component A, 0.01 to 100 parts by weight of the component B,
It is a polyimide resin composition characterized in that it is contained in an amount of 1 to 20 parts by weight.

[0008]

Embedded image

[0009]

Embedded image

In the formula, R ₁ and R ₂ represent a divalent aliphatic group or aromatic group having 1 to 4 carbon atoms, and R ₃ , R ₄ , R ₅ and R ₆ represent a monovalent aliphatic group or aromatic group. Group, R ₇ and R ₈ are tetravalent aliphatic or aromatic groups, R ₉ is divalent aliphatic or aromatic group, and m: n is 5-80: 95-20. k is
Equations (1) and (2) also represent the same integer.

[0011] The present invention is also a film adhesive characterized by being formed by casting a solution of the polyimide resin composition on one or both sides of a support, and then drying by heating.

[0012]

DETAILED DESCRIPTION OF THE INVENTION The polyimide resin (A) used in the present invention is an aromatic tetracarboxylic dianhydride and a diaminopolysiloxane represented by the formula (1). A resin containing a certain diaminopolysiloxane, and a thermoplastic polyimide resin obtained by reacting with an aromatic or aliphatic diamine to obtain a polyamic acid and then heating or chemically imidizing the resin.

The diaminopolysiloxane represented by the formula (1) used in the present invention includes ω, ω′-bis (2-aminoethyl) polydimethylsiloxane and ω, ω′-bis (4-aminophenyl) polydimethylsiloxane. Dimethylsiloxane, α,
ω-bis (3-aminopropyl) polydimethylsiloxane, and particularly when the value of k in the formula (1) is 10 to 50,
Preferably, those having 15 to 25 are used,
It is preferable in terms of suppressing foaming. When the value of k is less than 10, the glass transition temperature of the obtained polyimide resin increases, the bonding temperature increases, and the adhesive film is easily foamed. On the other hand, when the value of k is larger than 50, the resin tends to flow when thermocompression bonding is performed, air is involved, and the adhesive film is easily foamed.

The diaminopolysiloxane having a repeating unit k value of 10 to 50 may be used alone or in combination with a compound in which k is out of the above range, as long as the properties are not impaired. In order to improve the adhesiveness, in addition to using k = 1 to 50, it is preferable to use k = 1 to 9 in combination without foaming.

The aromatic or aliphatic diamine used in the present invention includes 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,6-dimethyl-m-phenylenediamine, and 2,5-dimethyl-p-diamine. Phenylenediamine,
2,4-diaminomesitylene, 4,4'-methylenedi-
o-Toluidine, 4,4'-methylenediamine-2,6
-Xylidine, 4,4'-methylene-2,6-diethylaniline, 2,4-toluenediamine, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylpropane, 3,3'-diaminodiphenyl Propane, 4,4'-diaminodiphenylethane, 3,
3'-diaminodiphenylethane, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 3,
3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, benzidine, 3 , 3′-Diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminobiphenyl, 3,3′-dimethoxybenzidine, bis (p-aminocyclohexyl) methane, bis (p-β-amino-t-butyl) Phenyl) ether, bis (p-β-methyl-δ-aminopentyl)
Benzene, p-bis (2-methyl-4-aminopentyl) benzene, 1,5-diaminonaphthalene, 2,6-
Diaminonaphthalene, 2,4-bis (β-amino-t-
Butyl) toluene, 2,4-diaminotoluene, m-xylene-2,5-diamine, p-xylene-2,5-diamine, m-xylylenediamine, p-xylylenediamine, 2,6-diaminopyridine, 2,5-diaminopyridine, 2,5-diamino-1,3,4-oxadiazol, 1,4-diaminocyclohexane, piperazine,
Methylenediamine, ethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 2,5-dimethylhexamethylenediamine, 3
-Methoxyhexamethylenediamine, heptamethylenediamine, 2,5-dimethylheptamethylenediamine, 3
-Methylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, octamethylenediamine, nonamethylenediamine, 5-methylnonamethylenediamine,
Decamethylenediamine, 1,3-bis (3-aminophenoxy) benzene, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,3-bis (4-aminophenoxy) benzene, bis- 4- (4-aminophenoxy) phenylsulfone, bis-4- (3-aminophenoxy) phenylsulfone and the like can be mentioned. Among them, 2,2-bis [4- (4-aminophenoxy) phenyl] propane and 1,3-bis (3-aminophenoxy) benzene are preferable in terms of adhesiveness. The above diamines may be used alone or in combination of two or more.

The ratio of the diaminopolysiloxane to the aromatic or aliphatic diamine is not particularly limited, but the ratio of the diaminopolysiloxane to the total number of moles of the diaminopolysiloxane and the aromatic or aliphatic diamine is not limited. It is preferably 20 to 80 mol%. 2
If the amount is less than 0 mol%, the solubility in an organic solvent and the adhesiveness decrease. If it exceeds 80 mol%, the glass transition temperature is remarkably lowered, causing a problem in heat resistance, or the film-like adhesives adhere to each other at room temperature, causing a problem in operation.

The aromatic tetracarboxylic dianhydride used in the present invention includes 3,3,4,4-biphenyltetracarboxylic dianhydride, 3,3,4,4-benzophenonetetracarboxylic dianhydride, Pyromellitic dianhydride, 4,4
-Oxydiphthalic dianhydride, ethylene glycol bistrimellitic dianhydride and the like. Among them,
4-Oxydiphthalic dianhydride is preferred for adhesion. The above aromatic tetracarboxylic dianhydrides may be used alone or in combination of two or more.

The equivalent ratio between the acid component and the amine component in the polycondensation reaction for obtaining the polyimide resin (A) used in the present invention is an important factor for determining the molecular weight of the obtained polyimide resin. Further, it is well known that there is a correlation between the molecular weight and physical properties of the obtained polymer, particularly 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 polyimide resin (A) used in the present invention, the equivalent ratio r of the acid component to the amine component is in the range of 0.900 ≦ r ≦ 1.06, and more preferably 0.975 ≦ r ≦ 1.025. Is preferable in terms of both mechanical strength and heat resistance. Here, 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 material becomes brittle, so that the adhesive strength becomes weak. If it exceeds 1.06, unreacted carboxylic acid will be decarboxylated during heating, causing gas generation and foaming, which may be undesirable. Addition of a dicarboxylic anhydride or a monoamine for controlling the molecular weight of the polyimide resin does not particularly hinder the addition of the dicarboxylic anhydride or the monoamine as long as the molar ratio r of the acid / amine 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. As aprotic polar solvents, N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAC), N-methyl-2-pyrrolidone (N
MP), tetrahydrofuran (THF), diglyme,
Cyclohexanone, 1,4-dioxane (1,4-DO)
And so on. One type of aprotic polar solvent may be used alone, or two or more types may be mixed and used.

At this time, the above aprotic polar solvent and a compatible nonpolar 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 when the amount of the nonpolar solvent exceeds 30% by weight, the solvent power of the solvent decreases, and polyamic acid may precipitate.

The reaction between the aromatic tetracarboxylic dianhydride and the diamine is carried out by dissolving a well-dried diamine component in the above-mentioned reaction solvent dehydrated and purified, and adding a ring-closing rate of 98%, more preferably 99% or more. The reaction proceeds by adding well-dried tetracarboxylic dianhydride.

The polyamic acid solution thus obtained is subsequently heated and dehydrated in an organic solvent, cyclized and imidized to obtain a polyimide resin. Since water generated by the imidation reaction interferes with the ring closure reaction, an organic solvent that is incompatible with water is added to the system and azeotroped, and Dean-Stark (De
Discharge out of the system using an apparatus such as an-Stark tube. Dichlorobenzene is known as an organic solvent that is incompatible with water, but the above-mentioned aromatic hydrocarbon is preferably used for electronics because a chlorine component may be mixed therein. Further, it does not prevent the use of compounds such as acetic anhydride, β-picoline, and pyridine as a catalyst for the imidization reaction.

In the present invention, the higher the imidization ratio of the polyimide resin (A), the better. If the imidation rate is low, imidization occurs due to heat during use and water is generated, which is not preferable. Therefore, it is desirable that an imidization rate of 95% or more, more preferably 98% or more is achieved.

The epoxy compound (B) used in the present invention comprises:
It is not particularly limited as long as it has at least two epoxy groups in one molecule and is compatible with the polyimide resin (A), but is used when synthesizing the polyimide resin (A). A solvent having good solubility in a solvent is preferred. For example, diglycidyl ether of bisphenol A type, diglycidyl ether of bisphenol F type,
Bisphenol A-epichlorohydrin type epoxy compounds, diphenyl ether type epoxy compounds, phenol novolak type epoxy compounds, biphenyl type epoxy compounds, hydrogenated bisphenol A type epoxy compounds and the like can be mentioned.

The content of the epoxy compound (B) in the polyimide resin composition of the present invention is preferably 0.01 to 100 parts by weight based on 100 parts by weight of the polyimide resin (A). When the content is less than 0.01, the film strength at high temperature decreases, and the adhesive strength decreases. Content is 10
If the amount exceeds 0 parts by weight, the resin properties of the epoxy compound are affected, heat resistance and mechanical strength, properties of the polyimide resin, are impaired, and foaming tends to occur during thermocompression bonding.

The silane coupling agent (C) used in the present invention has compatibility with the polyimide resin (A) and the epoxy compound (B) and solubility in a solvent used when synthesizing the polyimide resin (A). Are preferred.
Examples include vinyltrichlorosilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane,
γ-mercaptopropyltrimethoxysilane, N-β
(Aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane and the like. And N-phenyl-γ-aminopropyltrimethoxysilane are preferred in terms of adhesiveness.

The content of the silane coupling agent (C) in the polyimide resin composition of the present invention is preferably 0.01 to 20 parts by weight based on 100 parts by weight of the polyimide resin (A). If it is less than 0.01, sufficient adhesive properties cannot be obtained. If the amount is more than 20 parts by weight, crosslinking between the polyimide resins is likely to occur, and when thermocompression bonding is performed, the wettability to the adherend decreases, and the adhesive strength decreases.

The polyimide resin composition of the present invention is obtained by adding the epoxy compound (B) and the silane coupling agent (C) to the polyimide resin (A) and mixing them. To the polyimide resin composition of the present invention, in addition to the above components, various additives such as a leveling agent for improving surface smoothness, a leveling agent, and a defoaming agent can be added as necessary. Further, in order to adjust the evaporation rate of the solvent in the polyimide resin solution, an aromatic hydrocarbon-based solvent can be used as long as the solvent can be uniformly dissolved.

In the present invention, the polyimide resin composition comprises:
Used as an adhesive, a film adhesive is obtained by casting or applying a solution of the polyimide resin composition, for example, using a heat-resistant film substrate as a support, A resin layer is formed by casting or coating on one or both sides of the body, and a film adhesive together with the support, or a roll or metal sheet, or a release sheet such as a polyester sheet, a flow coater, A film composed of a resin layer is formed by a roll coater or the like, dried by heating, and then peeled off to obtain a film adhesive.

In particular, in order to avoid the problem of foaming of the film adhesive, which is an object of the present invention, the residual amount of the solvent is preferably 0.2% by weight or less of the adhesive.

As the heat-resistant film substrate used for the support in the film adhesive of the present invention, a polyimide resin film has a small coefficient of thermal expansion, excellent dimensional stability against temperature change, and flexibility. This is preferred because it is easy to handle and easy to handle, and has excellent adhesion to the polyimide resin composition of the present invention. Particularly, the glass transition temperature is 350 ° C.
The above polyimide resin film is excellent in workability and safety in the step of drying the coating solution.

The heat-resistant film substrate used for producing a single-layered film adhesive is required to have the heat resistance of the release agent and the substrate not lower than the drying temperature of the polyimide resin composition layer. . The substrate is preferably a polyethylene terephthalate film, a polyethylene naphthalate film, a polyimide film, a polyethylene sulfide film, an aluminum foil, or a stainless steel film. The release agent of hydrocarbon type is insufficient in heat resistance and silicone,
Heat-resistant resins such as silicone-modified epoxy and fluororesin are preferred. In particular, when a solvent having a high boiling point is used or a polyimide resin having a high glass transition temperature is formed into a film, 25
A drying temperature of 0 ° C. or higher may be required. In such a case, it is preferable to use an aluminum foil for the base material in terms of heat resistance and cost. At this time, the release agent is preferably a fluororesin such as polytetrafluoroethylene (PTFE) from the viewpoint of heat resistance and releasability, and is preferably a silicone-modified epoxy from the viewpoint of adhesion between the aluminum foil and the release agent.

The application and drying of the solution of the polyimide resin composition can be performed by using an apparatus in which an application facility such as a flow coater or a roll coater is combined with a hot air drying oven. After applying the resin varnish to the support, the resin varnish is introduced into a hot air drying oven and dried at a temperature and air volume sufficient to volatilize the solvent of the polyimide resin composition solution.

The method of using the film adhesive of the present invention is as follows.
Although not particularly limited, it can be used as an adhesive tape, for example, by cutting into a predetermined shape and bonding by thermocompression bonding with a heated heat block.

The film-like adhesive of the present invention is a film-like adhesive containing a substantially completely imidized polyimide resin having a specific structure as a main component. By introducing a cyclohexane ring into the molecule, excellent adhesion to heat-resistant resins such as polyimide, polyamideimide, polyamide, epoxy, and phenol can be stated.

[0037]

The present invention will be described in detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

The abbreviations in the examples and comparative examples are as follows. PI: polyimide APPS-9 (k = 9 in formula (2)): α, ω-bis (3-aminopropyl) polydimethylsiloxane (average molecular weight 837) APPS-20 (k = 20 in formula (2)): α, ω
-Bis (3-aminopropyl) polydimethylsiloxane (average molecular weight 1548) APB: 1,3-bis (3-aminophenoxy) benzene ODPA: 4,4'-oxydiphthalic dianhydride NMP: N-methyl-2- Pyrrolidone Ep-A: Bisphenol A-epichlorohydrin type epoxy resin (manufactured by Yuka Shell Co., Ltd., trade name: Epicoat 1)
004, epoxy equivalent 910) Ep-B: hydrogenated bisphenol A type epoxy resin (manufactured by Toto Kasei Co., Ltd., trade name ST5080, epoxy equivalent 63)
0) Si-A: N-phenyl-γ-aminopropyltrimethoxysilane (trade name: KBM57, manufactured by Shin-Etsu Chemical Co., Ltd.)
3)

(Synthesis of PI-A) Dry nitrogen gas inlet tube,
NMP in a three-necked flask equipped with a cooler, thermometer and stirrer
521.05 g was charged, and nitrogen gas was flown. Next, 52.62 g (0.18 mol) of APB, which is an amine component, and A
207.18 g (0.248 mol) of PPS-9, AP
Then, 34.83 g (0.023 mol) of PS-20 was added, and the mixture was stirred until it became uniform. After uniformly dissolving, the system was kept at 20 ° C. in an ice water bath while ODPA 13
9.60 g (0.45 mol) was added over 10 minutes while keeping the powdery state, and then stirring was continued for 2 hours to obtain a polyamic acid solution. During this time, the flask was kept at 20 ° C. Then, remove the nitrogen gas inlet tube and cooler, attach a Dean-Stark tube filled with toluene to the flask, and add toluene
130.26 g were added. 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 3 hours, the mixture was cooled to obtain a polyimide solution A (PI-A).

(Synthesis of PI-B) Dry nitrogen gas inlet tube,
NMP in a three-necked flask equipped with a cooler, thermometer and stirrer
456.04 g was charged, and nitrogen gas was flown. Next, 78.93 g (0.27 mol) of APB, which is an amine component, and A
89.54 g (0.107 mol) of PPS-9, APP
78.82 g (0.051 mol) of S-20 was charged,
Stir until uniform. After uniformly dissolving, the system was kept at 20 ° C. in an ice-water bath, and ODPA 132.
74 g (0.428 mol) was added over 10 minutes in the form of a powder, and thereafter stirring was continued for 2 hours to obtain a polyamic acid solution. During this time, the flask was kept at 20 ° C. Thereafter, the nitrogen gas inlet tube and the condenser were removed, a Dean-Stark tube filled with toluene was attached to the flask, and toluene 1 was added to the system.
14.01 g was added. 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 3 hours, the mixture was cooled to obtain a polyimide solution B (PI-B).

(Synthesis of PI-C) Dry nitrogen gas inlet tube,
NMP in a three-necked flask equipped with a cooler, thermometer and stirrer
552.41 g were charged, and nitrogen gas was flown. Next, 73.08 g (0.25 mol) of APB, which is an amine component, and A
258.00 g (0.167 mol) of PPS-20 was added thereto, and the mixture was stirred until it became uniform. After dissolving uniformly, the acid component ODPA 1
29.26 g (0.417 mol) was added over 10 minutes while keeping the powdery state, and then stirring was continued for 2 hours to obtain a polyamic acid solution. During this time, the flask was kept at 20 ° C. Thereafter, the nitrogen gas inlet tube and the condenser were removed, a Dean-Stark tube filled with toluene was attached to the flask, and 138.10 g of toluene 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 3 hours, the mixture was cooled to obtain a polyimide solution C (PI-C).

(Synthesis of PI-D) Dry nitrogen gas inlet tube,
NMP in a three-necked flask equipped with a cooler, thermometer and stirrer
454.35 g was charged, and nitrogen gas was flown. Next, 58.47 g (0.200 mol) of APB as an amine component and 251.10 g (0.300 mol) of APPS-9 were added, and the mixture was stirred until it became uniform. After dissolving uniformly, the acid component ODPA 1
55.11 g (0.500 mol) was added over 10 minutes while keeping the powdery state, and then stirring was continued for 2 hours to obtain a polyamic acid solution. During this time, the flask was kept at 20 ° C. Thereafter, the nitrogen gas inlet tube and the condenser were removed, a Dean-Stark tube filled with toluene was attached to the flask, and 113.59 g of toluene 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 3 hours, the mixture was cooled to obtain a polyimide solution D (PI-D).

Examples 1-6 and Comparative Examples 1-4 Adhesive solutions of Examples 1-6 and Comparative Examples 1-4 were prepared by mixing the above-obtained polyimide solution with each component according to the formulation shown in Table 1. Was prepared.

[0044]

[Table 1]

Next, each adhesive solution obtained above was applied to a commercially available release film (polyester film) with a roll coater to a thickness of 25 μm.
After drying at 120 ° C. for 2 minutes and at 180 ° C. for 2 minutes, a film adhesive with a release film was obtained.

Next, an adhesive strength test and an appearance test of the obtained film adhesive were performed, and the results are shown in Table 1. 1. Adhesion test A film adhesive was punched out to a size of 5 mm 2, and this was sandwiched between a 4 × 4 mm silicon chip and a 42 alloy lead frame, and a load of 500 g was applied at 200 ° C.
After pressing for 1 second, the shear adhesion was measured. 2. Appearance test After sandwiching between a 4 × 4 mm glass chip and a 42 alloy lead frame, applying a load of 500 g, pressing at 200 ° C. for 1 second, and visually observing film foaming from the glass chip side, an appearance test. Was done.

[0047]

[Table 2]

[0048]

According to the present invention, a film exhibiting excellent adhesiveness to a heat-resistant resin such as polyimide, polyamide-imide, polyamide, epoxy, phenol or the like in a short time of thermocompression bonding, and hardly foaming upon thermocompression bonding. An adhesive can be provided. For this reason, it is extremely useful industrially as a material for electronics requiring high reliability and heat resistance.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C09J 7/02 C09J 163/00 163/00 179/08 Z 179/08 183/04 183/04 183/04 C08K 5 / 54 F-term (reference) 4J002 CD022 CD052 CD062 CM041 EX026 EX036 EX066 EX076 EX086 FD146 4J004 AA11 AB01 AB05 CA06 CC02 EA05 FA05 4J040 EC062 EC072 EH031 EK032 EK052 EK082 EK111 GA03 GA04 GA14 HD31 KA08 PA04 QB26 QB31 QB32 RA35 SA06 SA42 SA43 SA44 SA72 SB02 TA13 TA14 TA22 UA041 UA121 UA131 UA132 UA141 UA261 UA361 UA381 UA531 UA761 UA771 UB011 UB021 VAUB XA VA12A1A

Claims (3)

[Claims] 1. A compound represented by the formula (2) obtained by reacting an aromatic tetracarboxylic dianhydride, a diaminopolysiloxane represented by the formula (1), and an aromatic or aliphatic diamine.
(A) an epoxy compound having at least two epoxy groups in one molecule (B)
And the silane coupling agent (C), wherein the diaminopolysiloxane is a diaminopolysiloxane having at least 10 to 50 repeating units k, and the component (B) is added to 100 parts by weight of the component (A). )
A polyimide resin composition comprising 0.01 to 100 parts by weight and 0.01 to 20 parts by weight of the component (C). Embedded image Embedded image In the formula, R ₁ and R _{2 each} represent a divalent aliphatic or aromatic group having 1 to 4 carbon atoms, and R ₃ , R ₄ , R ₅ and R ₆ represent a monovalent aliphatic or aromatic group; R ₇ and R ₈ represent a tetravalent aliphatic group or an aromatic group; R ₉ represents a divalent aliphatic or aromatic group;
n is 5-80: 95-20. k represents the same integer in formulas (1) and (2). 2. The polyimide resin composition according to claim 1, wherein the diaminopolysiloxane is a diaminopolysiloxane having 1 to 9 and 10 to 50 repeating units k. 3. A solution of the polyimide resin composition according to claim 1 or 2, which is applied to one or both sides of the support by casting.
A film adhesive formed by heating and drying.