JP2003105199A - Polyimide resin composition solution and filmy adhesive agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyimide resin composition solution which can be heated at a relatively low temperature for a short time to produce a filmy adhesive agent that has performance to make adhesiveness compatible with heat resistance. SOLUTION: The polyimide resin composition solution comprises a polyimide resin solution, an epoxy compound having at least two epoxy groups in the molecule, and a silane coupling agent, wherein the polyimide resin solution can be obtained by polymerizing an aromatic tetracarboxylic acid dianhydride, a diaminopolysiloxane, and an aromatic diamine or an aliphatic diamine in diphenyl ether to use as the reaction solvent.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyimide resin composition solution and a film adhesive.
Specifically, it relates to a polyimide resin composition solution used for an adhesive for electronic parts, and more particularly, a film having excellent adhesiveness to a metal, a laminated board, a printed circuit board as a circuit board material or a semiconductor mounting material. -Shaped adhesive.

[0002]

2. Description of the Related Art A polyimide resin soluble in an organic solvent has hitherto been prepared by reacting a tetracarboxylic dianhydride and a diamine in an organic solvent at room temperature to prepare a polyamic acid solution, and then heating or chemically reacting the same. It was obtained by closing the ring.

However, in the above method, the tetracarboxylic acid dianhydride and the polyamic acid as a precursor are soluble only in a polar organic solvent having a high boiling point such as N-methyl-2-pyrrolidone. The polyimide resin could be produced only in these solvents. When using this resin as a film material, it was necessary to perform heat treatment at a high temperature for a long time or to replace the solvent with a low boiling point in order to completely remove the high boiling point solvent.

To use this resin as a film material, in order to completely remove the solvent of the polyimide resin, 15
Heat treatment at a high temperature of 0 ° C. to 250 ° C. is required, and the polyimide resin film could not be manufactured by the heat treatment at a low temperature. Therefore, in order to increase the heat resistance of the polyimide resin film, when an attempt is made to manufacture a film in which a thermosetting component such as an epoxy resin is mixed with a solution of this polyimide resin, a high temperature heat treatment results in a thermosetting property during the film manufacturing process. There is a problem that all the components react and the adhesiveness as a film adhesive is impaired.

In order to avoid this problem, it is possible to completely replace the solvent for producing the polyimide with a solvent having a low boiling point and to produce a polyimide resin solution capable of producing a polyimide resin film by heat treatment at a low temperature. However, at that time, there was a problem that a large amount of the solvent having a high boiling point used when the polyimide was produced was a waste liquid.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made as a result of intensive studies in view of the problems of the film adhesive using the polyimide resin, and a polyimide resin composition solution capable of forming a film at a low temperature. , And using it,
An object of the present invention is to provide a film adhesive which can be bonded at low temperature in a short time and has excellent adhesiveness.

[0007]

Means for Solving the Problems That is, according to the present invention, an aromatic tetracarboxylic dianhydride, a diaminopolysiloxane represented by the general formula (1), and an aromatic diamine or an aliphatic diamine are represented by the general formula A solution of a polyimide resin having a repeating unit represented by the general formula (3) and a repeating unit represented by the general formula (4) obtained by polymerization using phenyl ether represented by (2) as a reaction solvent. (A)
In addition, a polyimide resin composition solution containing an epoxy compound (B) having at least two epoxy groups in one molecule and a silane coupling agent (C), and the polyimide resin composition solution, It is a film-like adhesive obtained by casting and coating on one side or both sides and then coating and drying at 150 ° C. or less.

[0008]

[Chemical 5]

[0009]

[Chemical 6]

[0010]

[Chemical 7]

[0011]

[Chemical 8]

In the formula, R ₁ and R ₂ are divalent aliphatic groups or aromatic groups having 1 to 4 carbon atoms, and R ₃ , R ₄ , R ₅ and R ₆ are monovalent aliphatic groups or aromatic groups. Group R, R ₇ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, R ₈ is a monovalent hydrocarbon group having 1 to 6 carbon atoms, and R ₉ and R ₁₀ are tetravalent. Is an aliphatic group or an aromatic group, R ₁₁ is a divalent aliphatic group or an aromatic group, and k is an integer of 1 to 100. The ratio of m and n is 5 to 95 mol% and n is 5 to 95 mol% in 100 mol% of the total amount of each component.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The diaminopolysiloxane represented by the general formula (1) used in the present invention includes 1,3-bis (3-aminopropyl) tetramethylsiloxane and α,
ω-bis (3-aminopropyl) polydimethylsiloxane and the like can be mentioned. These may be soluble in the phenyl ether represented by the general formula (2).

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-. 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) phenyl sulfone, bis-4- (3-aminophenoxy) phenyl sulfone 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 solubility in phenyl ether. The above diamines may be used alone or in combination of two or more.

The reaction ratio of the above diaminopolysiloxane and the aromatic or aliphatic diamine is not particularly limited, but the reaction ratio of the diaminopolysiloxane is based on the total number of moles of the diaminopolysiloxane and the aromatic or aliphatic diamine. It is preferably 5 to 95 mol%. 5 mol%
When it is lower, the solubility of the obtained polyimide resin in phenyl ether is lowered, which may cause a problem in work. If it is higher than 95 mol%, the glass transition temperature of the film is remarkably lowered, and the strength of the film may not be maintained.

The aromatic tetracarboxylic dianhydride used in the present invention is 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic acid. Dianhydride, pyromellitic dianhydride,
4,4'-oxydiphthalic acid dianhydride, ethylene glycol bistrimellitic acid dianhydride and the like can be mentioned. Among them, 4,4′-oxydiphthalic dianhydride is preferable for the solubility of the obtained polyimide resin in phenyl ether. The above-mentioned aromatic tetracarboxylic dianhydrides may be used alone or in combination of two or more kinds.

The equivalent ratio of the acid component and the amine component in the polycondensation reaction of the polyimide resin composition of the present invention is an important factor that determines the molecular weight of the obtained polyimide resin. It is also well known that there is a correlation between the molecular weight of a polymer and its physical properties, particularly the 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 production of the polyimide resin used in the present invention, the equivalent ratio r of the acid component and the amine component is in the range of 0.900 ≤ r ≤ 1.06 and 0.975 ≤ r ≤ 1.025. Are preferable from the viewpoint of both mechanical strength and heat resistance. 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 film becomes brittle. On the other hand, if it exceeds 1.06, unreacted carboxylic acid may be decarboxylated during heating, causing gas generation and foaming, which is not preferable in some cases. To control the molecular weight of the polyimide resin, adding dicarboxylic acid anhydride or monoamine,
If the acid / amine molar ratio r is within the above range, this is not particularly hindered.

The reaction solvent used in the present invention is represented by the general formula (2).
It is a phenyl ether represented by.

Here, typical examples of the phenyl ether represented by the general formula (2) include anisole, phenetole, methoxytoluene and the like, but since a polyimide resin film can be obtained by heat treatment at a lower temperature,
Anisole is most preferred.

At this time, as the azeotropic solvent, a nonpolar solvent compatible with the above phenyl ether may be mixed and used. The non-polar solvent is preferably an aromatic hydrocarbon such as toluene, xylene or solvent naphtha. The proportion of non-polar solvent in the mixed solvent is 50% by weight
The following is preferable. This is because if the amount of the nonpolar solvent exceeds 50% by weight, the solvent's dissolving power is reduced and the starting material diaminopolysiloxane and aromatic or aliphatic diamine or polyimide resin may be precipitated.

Polyimide resin solution (A) used in the present invention
As a method for obtaining the above, first, diaminopolysiloxane and an aromatic or aliphatic diamine are charged into a reaction solvent mainly containing phenyl ether and heated to about 70 to 80 ° C. to diamine the diaminopolysiloxane and the aromatic or aliphatic diamine. The group diamine is dissolved (solution A). Furthermore, an aromatic tetracarboxylic dianhydride is charged into another reactor in a solvent mainly composed of phenyl ether, and heated and heated until reflux occurs (Liquid B). Subsequently, the liquid A is added to the liquid B under reflux to cause polyamidation and dehydration ring closure reaction to proceed in a short time, and the repeating unit represented by the general formula (3) and the general unit represented by the general formula (4) are represented. A solution of a polyimide resin having a repeating unit is obtained. The water generated by the imidization reaction interferes with the ring closure reaction, so Dean Stark (De
It is discharged out of the system using a device such as an-Stark tube.

The epoxy compound (B) used in the present invention is
There is no particular limitation as long as it has at least two epoxy groups in one molecule and is compatible with the polyimide resin (A), but it is used when synthesizing the polyimide resin (A). Those having good solubility in the solvent are preferred. As an example, bisphenol A type diglycidyl ether, bisphenol F type diglycidyl ether,
Examples thereof include bisphenol A-epichlorohydrin type epoxy compounds, diphenyl ether type epoxy compounds, phenol novolac type epoxy compounds, cresol nevolac type epoxy compounds, biphenyl type epoxy compounds, hydrogenated bisphenol A type epoxy compounds and the like.

The content of the epoxy compound (B) in the polyimide resin composition solution of the present invention is 0.01 to 100 parts by weight (solid content) of the polyimide resin (A).
200 parts by weight is preferred. If the content is less than 0.01, the film strength at high temperature may be reduced and the adhesive force may be reduced. If the content exceeds 200 parts by weight, the resin characteristics of the epoxy compound may affect the heat resistance and mechanical strength of the polyimide resin.

The silane coupling agent (C) used in the present invention is compatible with the polyimide resin (A) and the epoxy compound (B) and the solubility in the solvent used when synthesizing the polyimide resin (A). Is preferable.
As examples, 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. , N-phenyl-γ-aminopropyltrimethoxysilane is preferable in terms of adhesiveness.

The content of the silane coupling agent (C) in the polyimide resin composition solution of the present invention is 0.01 to 100 parts by weight (solid content) of the polyimide resin (A).
It is preferably 50 parts by weight or less. If it is less than 0.01, sufficient adhesive properties may not be obtained. If the amount exceeds 50 parts by weight, crosslinking between the polyimide resins is likely to occur, and when the polyimide resin composition solution is prepared, the solution may be easily gelated. Also, when the film adhesive is used, thermocompression bonding is performed. However, the wettability with respect to the adherend may be reduced and the adhesive force may be reduced.

The polyimide resin composition solution 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. In addition to the above components, various additives such as a leveling agent for providing surface smoothness, a leveling agent, and a defoaming agent can be added to the polyimide resin composition solution of the present invention as required. Further, in order to control the evaporation rate of the solvent in the polyimide resin solution, an aromatic hydrocarbon solvent can be used within the range where it is uniformly dissolved.

In the present invention, the polyimide resin composition solution is used as an adhesive, and the polyimide resin solution obtained above is used as a film-like adhesive by using, for example, a roll or a metal sheet, Alternatively, a release sheet such as a polyester sheet is cast or coated by a flow coater, a roll coater or the like to form a resin layer film, which is dried by heating and then peeled to obtain a polyimide resin film. You can The heat treatment at this time is usually 50 to 150 ° C., more preferably 50 to 150 ° C.
It is carried out at 120 ° C., and it is possible to produce a film adhesive without the curing component such as an epoxy resin being crosslinked. The heat treatment time is usually about 0.1 to 1 hour, and it is possible to completely remove the solvent at a low temperature in a short time, and suppress the foaming due to the residual solvent when the film adhesive is thermocompression bonded. You can

[0029]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. The abbreviations in Examples and Comparative Examples are as follows. PI: Polyimide NMP: N-Methyl-2-pyrrolidone Ep-A: Cresol novolac type epoxy resin (Nippon Kayaku Co., Ltd., trade name EOCN-1020-80, epoxy equivalent 200) Ep-B: Hydrogenated bisphenol A Type epoxy resin (Toto Kasei Co., Ltd., trade name ST5080, epoxy equivalent 63
0) Si-A: N-phenyl-γ-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM57)
3)

(Synthesis of PI-A) In an Erlenmeyer flask, 438.50 g of anisole was placed, and 1,3-bis (3
-Aminophenoxy) benzene 43.85 g (0.15
Mol) and α, ω-bis (3-aminopropyl) polydimethylsiloxane (average molecular weight 837) (k = 9 in formula (1)) 125.55 g (0.15 mol),
It heated at 70 degreeC and stirred until it melt | dissolved (A liquid).

Next, 120.55 g of anisole and 228.35 g of toluene were placed in a three-necked flask equipped with a dry nitrogen gas introduction tube, a condenser, a thermometer, a dropping funnel, and a stirrer, and nitrogen gas was flowed. Next, the acid component 4,4'-
93.07 g (0.30 mol) of oxydiphthalic dianhydride was charged, a Dean-Stark tube filled with toluene was attached to the flask, and the system was heated in an oil bath until reflux occurred. Next, the solution A was put into a dropping funnel and dropped into the flask over 1 hour. Water generated during that time was removed from the system using a Dean-Stark tube. After heating for 3 hours, it was cooled to obtain a desired polyimide resin solution. The obtained polyimide resin was Mw = 76100 when measured in terms of polystyrene using a GPC measuring device manufactured by Tosoh Corporation.

(Synthesis of PI-B) An Erlenmeyer flask was charged with 574.72 g of anisole, and 2,2-bis [4] was added.
-(4-Aminophenoxy) phenyl] propane 57.
47 g (0.14 mol) and α, ω-bis (3-aminopropyl) polydimethylsiloxane (average molecular weight 837)
(K = 9 in formula (1)) 117.18 g (0.14
Mol) was added, and the mixture was heated to 70 ° C. and stirred until it was dissolved (Liquid A).

Next, 115.68 g of anisole and 94.15 g of toluene were placed in a three-necked flask equipped with a dry nitrogen gas introduction tube, a condenser, a thermometer, a dropping funnel, and a stirrer, and nitrogen gas was flowed. Next, 86.86 g (0.28 mol) of 4,4'-oxydiphthalic dianhydride, which is an acid component, was charged, a Dean-Stark tube filled with toluene was attached to the flask, and the system was set in an oil bath. Heat until reflux occurs. Next, the solution A was put into a dropping funnel and dropped into the flask over 1 hour. Water generated during that time was removed from the system using a Dean-Stark tube. After heating for 3 hours, it was cooled to obtain a desired polyimide resin solution. The obtained polyimide resin is GP manufactured by Tosoh Corporation.
When measured in terms of polystyrene using a C measurement device, Mw was 40100.

When the amount of residual solvent in the obtained polyimide resin film was measured by the purge & trap-GC / MS method, the residual amount of anisole as a solvent was 5 ppm.

(Synthesis of PI-C) An Erlenmeyer flask was charged with 438.50 g of anisole, and 1,3-bis (3
-Aminophenoxy) benzene 43.85 g (0.15
Mol) and α, ω-bis (3-aminopropyl) polydimethylsiloxane (average molecular weight 837) (k = 9 in formula (1)) 125.55 g (0.15 mol),
It heated at 70 degreeC and stirred until it melt | dissolved (A liquid).

Next, 348.90 g of anisole was placed in a three-necked flask equipped with a dry nitrogen gas introduction tube, a condenser, a thermometer, a dropping funnel, and a stirrer, and nitrogen gas was flowed. Next, 93.07 g (0.30 mol) of 4,4'-oxydiphthalic acid dianhydride, which is an acid component, was added, a Dean-Stark tube was attached to the flask, and the system was refluxed in an oil bath. Heated up. Next, the solution A was put into a dropping funnel and dropped into the flask over 1 hour. Water generated during that time was removed from the system using a Dean-Stark tube. After heating for 3 hours, it was cooled to obtain a desired polyimide resin solution. The obtained polyimide resin was Mw = 55400 when measured in terms of polystyrene using a GPC measuring device manufactured by Tosoh Corporation.

(Synthesis of PI-D) JP-A-7-20702
According to Example 1 described in JP-A No. 4-311, 13.2 g (0.03 mol) of 2,2-bis (3,4-dicarboxyphenyl) perfluoropropane dianhydride and 3,3′-as acid anhydride components. 4,4′-biphenyltetracarboxylic dianhydride (0.07 mol), and 66 g of γ-butyrolactone and 84 g of anisole were charged as a solvent, and 1,1′-3,3′-tetramethyl was used as a diamine component. −
1,3-bis (3-aminopropyl) disiloxane 7.
5 g (0.03 mol), 2,2-bis [4- (4-aminophenoxy) phenyl] propane 28.7 g (0.0
Γ-butyrolactone solution 96.2 in which
g was gradually added while heating so that the temperature of the reaction system was 50 to 60 ° C. In the above-mentioned preparation, the solvent was finally 60% by weight of γ-butyrolactone and 4% of anisole.
It was prepared to be 0% by weight. After completion of dropping, the mixture was further stirred at room temperature for 10 hours, and then the flask was equipped with a reflux condenser with a water receiver, and then the reaction system was heated to 150 ° C.
The reaction was carried out for a period of time to carry out dehydration ring closure to obtain a desired solution of a transparent and transparent polyimide resin. The obtained polyimide resin was Mw = 44000 when measured in terms of polystyrene using a GPC measuring device manufactured by Tosoh Corporation.

(Synthesis of PI-E) Dry nitrogen gas inlet tube,
NMP in a three-necked flask equipped with a condenser, thermometer, and stirrer.
454.35 g was put and nitrogen gas was flown. Next, 58.47 g (0.200 mol) of 1,3-bis (3-aminophenoxy) benzene as an amine component and α, ω-bis (3-aminopropyl) polydimethylsiloxane (average molecular weight 837) (formula ( In 1) k = 9) 251.1
0 g (0.300 mol) was added and stirred until uniform. After uniformly dissolving, while keeping the system at 20 ° C. in an ice-water bath, 155.11 g (0.500 mol) of 4,4′-oxydiphthalic acid dianhydride, which is an acid component, was kept in powder form.
The mixture was added over a period of 1 minute, and stirring was continued for 2 hours to obtain a polyamic acid solution. During this time, the flask was kept at 20 ° C. Then, the nitrogen gas introduction 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 ice water bath was replaced with an oil bath to heat the system and remove the generated water outside the system. After heating for 3 hours and cooling, a polyimide solution E (PI-E) was obtained.

Examples 1 to 6 and Comparative Examples 1 to 3 The polyimide solutions obtained above were mixed with the respective components in the formulations shown in Table 1, and mixed with the formulations shown in Examples 1 to 6 and Table 2. The adhesive solutions of Comparative Examples 1 to 3 were prepared.

[0040]

[Table 1]

[0041]

[Table 2]

[Preparation of Film Adhesive] (Preparation Method A) A commercially available release film (polyester film) was coated with the solution of the above polyimide resin by a roll coater to a thickness of 25 μm, and the temperature was 50 ° C. In 2
Min, 90 ° C. for 2 minutes and 120 ° C. for 2 minutes to obtain a polyimide resin film with a release film.

(Preparation Method B) A commercially available release film (polyester film) was coated with the solution of the above-mentioned polyimide resin by a roll coater so as to have a thickness of 25 μm,
Drying was performed at 80 ° C. for 2 minutes, 120 ° C. for 2 minutes, and 180 ° C. for 2 minutes to obtain a polyimide resin film with a release film.

Next, the adhesive strength test and the appearance test of the obtained film adhesive were conducted and shown in Table 1. 1. Adhesion test Punching a film adhesive into a size of 5 mm ² , sandwiching it between a 4 × 4 mm silicon chip and a 42 alloy lead frame, applying a load of 500 g, and 200 ° C.
After press-bonding for 1 second, the shear adhesive strength of the product which was heat-treated at 180 ° C. for 1 hour was measured. 2. Appearance test Appearance test by sandwiching between a 4x4 mm glass chip and 42 alloy lead frame, applying a load of 500 g and crimping at 200 ° C for 1 second, and visually observing film foaming from the glass chip side. I went.

The residual solvent amount of the film was measured by the purge & trap-GC / MS method. [Purge & Trap-Gas Chromatograph / Mass Spectrometry (GC / MS) Method] Approximately 50 mg of the sample was put in a sample tube of the purge & trap, and volatile components were expelled with a helium gas at a flow rate of 50 mL / min while 250 ° C. × 15 min. The sample is heated under heating conditions. The volatile matter generated at this time is trapped at −80 ° C., and after the sample heating is completed, the trapped components are rapidly heated and introduced into the GC / MS meter. For the quantitative determination of each generated gas component, a diluted solution of n-decane in toluene was used under the same heating conditions as the sample, and Purge & Trap-G was used.
The converted quantitative value for each standard sample is calculated as a weight fraction with respect to the sample weight by performing C / MS method measurement and comparing the peak area values of the generated gas components.

[0046]

[Table 3]

[0047]

[Table 4]

[0048]

EFFECTS OF THE INVENTION According to the present invention, a polyimide resin composition solution containing a curing component such as an epoxy resin in a solvent having a low boiling point can be obtained, and furthermore, a solvent having a high boiling point such as γ-butyrolactone is not contained. It is possible to produce a film adhesive by heat treatment at low temperature for a short time, and it is possible to obtain a polyimide resin film in which a curing component such as an epoxy resin does not crosslink and an amount of residual solvent is extremely small. Therefore, it is possible to provide a film-like adhesive that can have heat resistance without impairing the adhesiveness and is optimal for electronic materials and the like that require high reliability and heat resistance.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09J 163/00 C09J 179/08 Z 179/08 183/10 183/10 C08K 5/54 F term (reference) 4J002 CD02X CD05X CD06X CM04W ED057 EJ027 EX026 EX036 EX076 EX086 FD146 FD207 GJ01 HA05 4J004 AA11 BA02 FA05 FA08 4J040 EC061 EC071 EH031 UA111 RB111 PA02 LA01 QA22 PA01 LA22 LA01 LA03 LA01 LA02 LA03 LA02 LA04 LA03 LA08 LA03 UB012 UB131 UB141 UB152 UB281 UB301 UB351 VA021 VA022 VA031 VA032 VA062 VA072 WA09 ZB01 ZB02 ZB11

Claims (5)

[Claims] 1. An aromatic tetracarboxylic dianhydride, a diaminopolysiloxane represented by the general formula (1), and an aromatic diamine or an aliphatic diamine are added to the general formula (2).
To a polyimide resin solution (A) having a repeating unit represented by the general formula (3) and a repeating unit represented by the general formula (4) obtained by polymerization using phenyl ether represented by A polyimide resin composition solution containing an epoxy compound (B) having at least two epoxy groups in one molecule and a silane coupling agent (C). [Chemical 1] [Chemical 2] [Chemical 3] [Chemical 4] In the formula, R ₁ and R ₂ are C ₁ to C 4 divalent aliphatic groups or aromatic groups, R ₃ , R ₄ , R ₅ and R ₆ are monovalent aliphatic groups or aromatic groups, R7 is a hydrogen atom or a carbon atom number 1 to
Is a monovalent hydrocarbon group of 6 and R8 has 1 to 6 carbon atoms.
, A monovalent hydrocarbon group, R ₉ and R ₁₀ are tetravalent aliphatic groups or aromatic groups, R ₁₁ is a divalent aliphatic or aromatic group, and k is an integer of 1 to 100. The ratio of m and n is 5 to 95 mol% and n is 5 to 100 mol% in total of each component.
It is 95 mol%. 2. The polyimide resin composition solution according to claim 1, wherein the reaction solvent contains, as an azeotropic solvent, a nonpolar solvent compatible with phenyl ether in an amount of 50% by weight or less based on the whole reaction solvent. 3. A phenyl ether represented by the formula (2) is:
The polyimide resin composition solution according to claim 1, which is anisole. 4. The component (B) is 0.01 to 200 parts by weight and the component (C) is 0.0 based on 100 parts by weight of the component (A).
The polyimide resin composition solution according to claim 1, 2 or 3, which is contained in a ratio of 1 to 50 parts by weight. 5. A polyimide resin composition solution according to any one of claims 1 to 4 is cast on one or both sides of a support, and then dried by heating at 150 ° C. or lower. A film adhesive.