JP2003292778A - Heat-resistant resin composition and adhesive film using same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a heat-resistant resin composition having good adhesion or fluidity and having excellent heat resistance and with slight residual volatiles, and an adhesive film using the same. <P>SOLUTION: The heat-resistant resin composition comprises 100 pts.wt. of a siloxane-modified polyamideimide resin and 1-150 pts.wt. of a thermosetting resin component. The siloxane-modified polyamideimide resin is obtained by reacting a mixture of a diamine having ≥3 aromatic rings with a siloxanediamine with trimellitic anhydride and then reacting a mixture containing the resultant diimidodicarboxylic acids with an aromatic diisocyanate. The thermosetting resin component is preferably an epoxy resin having ≥2 glycidyl groups. The adhesive film is obtained by coating the top surface of a supporting substrate with the heat-resistant resin composition as a varnish. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a heat resistant resin composition and an adhesive film using the same.

[0002]

2. Description of the Related Art Polyamide-imide resins are mainly used for electric wire coating materials (heat-resistant enamel wire) because they have excellent electrical properties, heat resistance, mechanical properties, and abrasion resistance. .

[0003]

Since the polyamide-imide resin is generally synthesized by using a solvent having a high boiling point, there are some problems in processing it into a film or sheet shape. For example, under a low temperature drying condition of 150 ° C. or lower, it is necessary to dry for a long time, and the residual volatile content of a generally obtained film or sheet is 10% by weight or more. Further, it was difficult to reduce the residual volatile content to 5% by weight or less when a sheet having a thickness of more than 100 μm was produced even under a high temperature drying condition of 150 ° C. or higher. Further, when a resin composition obtained by mixing a thermosetting resin component with a polyamideimide resin is formed into a sheet under high temperature drying conditions, the thermosetting reaction proceeds, and it is difficult to produce a so-called B-stage state sheet. One of the applications of the polyamide-imide resin is an interlayer adhesive film for wiring boards. This is in the form of a film or sheet formed by applying a resin composition containing a polyamide-imide resin and a thermosetting resin component on a suitable substrate, but in such a case, it remains in the film or sheet. If the volatile content is high, voids or bubbles may be generated in the film or sheet during the process including heat treatment such as pressing, thermocompression bonding, laminating, etc., or the curing process after heating, which may lead to deterioration of the insulation property. It is preferably 5% by weight or less, and more preferably 1% by weight or less. In addition, it is necessary to maintain the fluidity of the film or sheet in order to bring the film or sheet into close contact with the base material of the printed circuit board or to fill the irregularities of the copper foil thickness of the printed circuit such as the copper foil circuit. ,
It is necessary to dry the coating at a low temperature that does not cause a thermosetting reaction. Further, regardless of the thickness of the sheet, for example, 10
It is preferable that the residual volatile content of the sheet can be reduced even in the sheet having a film thickness of more than 0 μm. Further, it is preferable that the adhesion between the substrate and the film or sheet obtained from the resin composition is high. The present invention is a heat-resistant resin composition having a small residual volatile content so that the polyamide-imide resin can be applied as an interlayer adhesive film for wiring boards, good adhesiveness and fluidity, and excellent heat resistance, and an adhesive film using the same. The challenge was to provide

[0004]

The present invention is a heat resistant resin composition containing 100 parts by weight of a siloxane-modified polyamide-imide resin and 1 to 150 parts by weight of a thermosetting resin component. Further, the present invention provides the general formula (1 formula) and the general formula (2) obtained by reacting trimellitic anhydride with the mixture of a diamine having three or more aromatic rings and a siloxanediamine in the siloxane-modified polyamideimide resin. A siloxane-modified polyamideimide resin obtained by reacting a mixture containing a diimidedicarboxylic acid represented by the formula) with an aromatic diisocyanate represented by the general formula (3), wherein the thermosetting resin component is two or more glycidyl groups. A heat-resistant resin composition which is an epoxy resin having

[0005]

[Chemical 4]

[0006]

[Chemical 5]

[0007]

[Chemical 6]

In the present invention, the thermosetting resin component is
It is preferable to contain an epoxy resin having two or more glycidyl groups and a curing accelerator or curing agent therefor, and the siloxane-modified polyamideimide resin is a diamine (A) and a siloxanediamine (B) having three or more aromatic rings. Mixture (A / B = 99.9 / 0.1-0.1 /
99.9 (molar ratio)) and trimellitic anhydride (A +
The molar ratio of B) to trimellitic anhydride is 1 /
A mixture containing a diimidedicarboxylic acid represented by the general formula (1 formula) or the general formula (2 formula) obtained by reacting at 2.05 to 1 / 2.20 and an aromatic diisocyanate represented by the general formula (3 formula) And the molar ratio of the total moles of (A + B) to the aromatic diisocyanate is 1 / 1.05 to 1 / 1.50.
It is preferable that the siloxane-modified polyamideimide is obtained by reacting with a siloxane-modified polyamideimide resin. Further, the siloxane-modified polyamideimide resin is 2,2-bis [4- {4- (5-hydroxycarbonyl-1) as an aromatic diimidedicarboxylic acid. , 3-dione-isoindolino) phenoxy} phenyl] propane (C) and bis (5-hydroxycarbonyl-1,3-dione-isoindolino) propylpolydimethylsiloxane (D) in a molar mixture (C / D = 9).
9.9 / 0.1 to 0.1 / 99.9 (molar ratio)) and aromatic diisocyanate (C + D) total moles and diisocyandiisocyanate molar ratio 1 / 1.05 to 1 / 1.5
A siloxane-modified polyamideimide obtained by reacting with 0 is preferable. Furthermore, the present invention is an adhesive film obtained by applying the above heat-resistant resin composition to a varnish and applying the varnish on a supporting substrate. The heat resistant resin composition of the present invention,
A resin composition comprising 100 parts by weight of a siloxane-modified polyamide-imide resin and 1 to 150 parts by weight of a thermosetting resin component, wherein the varnish solvent has a fast volatilization rate and the residual volatile content is 5% by weight or less even in a thick film. It is possible to obtain an adhesive film having good adhesion to a substrate. In the present invention, simply described as an adhesive film means both an adhesive film and an adhesive sheet.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION A siloxane-modified polyamide-imide resin is obtained by reacting a mixture of a diamine having three or more aromatic rings and a siloxanediamine with trimellitic anhydride, the general formula (1) and the general formula (2). A mixture containing a diimidedicarboxylic acid represented by the formula) and the general formula (3)
It is preferable to use a siloxane-modified polyamideimide resin obtained by reacting an aromatic diisocyanate represented by

When trimellitic anhydride is reacted with a mixture of a diamine having 3 or more aromatic rings and a siloxane diamine, the mixture of the aromatic diimide dicarboxylic acid and the siloxane diimide dicarboxylic acid obtained as a reaction product is also soluble. High, it becomes possible to react with diisocyanate in a solution state in the next step, and the synthesis efficiency is improved. At this time, 2.05 to 2.20 moles of trimellitic anhydride are reacted with respect to the total moles of aromatic diamine and siloxane diamine, and the subsequent diisocyanate is 1.05 to 1.50 moles of the total moles of diamine. It is possible to synthesize a high-molecular-weight siloxane-modified polyamideimide resin without adding a catalyst or the like by preferably reacting in an amount of 1.20 to 1.30 times the molar amount. A mixture of the above-mentioned (A) diamine having three or more aromatic rings and (B) siloxanediamine (A / B = 99.9 / 0.1).
To 0.1 / 99.9 molar ratio) and trimellitic anhydride are reacted at a total molar number of (A + B) and trimellitic anhydride molar ratio of 1 / 2.05 to 1 / 2.20. A mixture of the diimidedicarboxylic acids represented by the general formulas (1) and (2) and the aromatic diisocyanate represented by the general formula (3) with respect to the total moles of diamine (A + B) in a molar ratio of 1 It is preferably a siloxane-modified polyamideimide resin obtained by reacting /1.05 to 1 / 1.50. And, for example, as an aromatic diamine (C)
2,2-bis [4-, obtained by reacting a mixture of 2,2-bis [4- (4-aminophenoxy) phenyl] propane with (D) diaminopolydimethylsiloxane as siloxane diamine and trimellitic anhydride {4-
(5-Hydroxycarbonyl-1,3-dione-isoindolino) phenoxy} phenyl] propane and bis (5
-Hydroxycarbonyl-1,3-dione-isoindolino) propyl polydimethylsiloxane mixture (C /
D = 99.9 / 0.1 to 0.1 / 99.9 molar ratio) and 4,4′-diphenylmethane diisocyanate as an aromatic diisocyanate (C + D) molar ratio 1/1.
It is preferably a siloxane-modified polyamide-imide resin obtained by reaction at 05 to 1 / 1.50. Further, as a method for producing the siloxane-modified polyamide-imide resin used in the present invention, a mixture of (A) diamine and (B) siloxane diamine having three or more aromatic rings (A / B = 9).
9.9 / 0.1 to 0.1 / 99.9 molar ratio) and trimellitic anhydride to the total number of moles of (A + B) and trimellitic anhydride molar ratio 1 / 2.05 to 1/2 .20 in the presence of an aprotic polar solvent at 50-90 ° C,
Furthermore, aromatic hydrocarbon which can be azeotroped with water is added in an amount of 0.1 to 0.5 by weight of the aprotic polar solvent, and 120 to 18
A reaction is performed at 0 ° C. to produce a mixture containing an aromatic diimide dicarboxylic acid and a siloxane diimide dicarboxylic acid, and this is reacted with an aromatic diisocyanate to produce a siloxane-modified polyamideimide resin. It is also possible to produce a siloxane-modified polyamideimide resin by producing an aromatic diimide dicarboxylic acid, then removing the aromatic hydrocarbon from the solution, and reacting it with an aromatic diisocyanate. The produced siloxane-modified polyamide-imide resin can be dissolved in the aprotic polar solvent to form a solvent varnish.

Examples of the diamine having three or more aromatic rings used in the present invention include 2,2-bis [4- (4-aminophenoxy) phenyl] propane (hereinafter abbreviated as BAPP) and bis [4- (3. -Aminophenoxy) phenyl]
Sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, bis [4-
(4-Aminophenoxy) phenyl] methane, 4,4 ′
-Bis (4-aminophenoxy) biphenyl, bis [4
-(4-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ketone,
1,3-bis (4-aminophenoxy) benzene, 1,
4-bis (4-aminophenoxy) benzene and the like can be exemplified, and they can be used alone or in combination. BAPP is particularly preferable to other diamines in terms of balance of properties of polyamide-imide and cost.

As the siloxane diamine used in the present invention, those represented by the general formula (4) are used.

[0013]

[Chemical 7]

Examples of such siloxane diamines include those represented by the general formula (5). Among these, amino-modified silicone oil X-22-161AS (amine equivalent 45
0), X-22-161A (amine equivalent 840), X-
22-161B (amine equivalent 1500), the product name of Shin-Etsu Chemical Co., Ltd., BY16-853 (amine equivalent 650), BY16-853B (amine equivalent 2200)
The product names such as those manufactured by Toray Dow Corning Silicone Co., Ltd. are mentioned as commercially available products.

[0015]

[Chemical 8]

As the aromatic diisocyanate used in the present invention, 4,4'-diphenylmethane diisocyanate (hereinafter abbreviated as MDI), 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, 2,4-tolylene dimer and the like can be exemplified. These can be used alone or in combination.

As the thermosetting resin component used in the present invention,
Epoxy resin, phenol resin, polyester resin, polyimide resin, bismaleimide triazine resin and the like can be used. Epoxy resin is more preferable in terms of adhesiveness and handleability. The epoxy resin of thermosetting resin component is 2
It is preferable to use an epoxy resin having one or more glycidyl groups and a curing accelerator thereof, or an epoxy resin having two or more glycidyl groups and a curing accelerator and a curing agent thereof. The more glycidyl groups are, the better, and it is more preferable that the number is 3 or more. The blending amount varies depending on the number of glycidyl groups, and the blending amount may be smaller as the glycidyl group is larger. Further, it is more preferable to use a curing agent for epoxy resin in combination.

The curing agent or curing accelerator for the epoxy resin is not limited as long as it reacts with the epoxy resin or accelerates curing, and examples thereof include amines, imidazoles, polyfunctional phenols, acid anhydrides. Goods can be used. As the amines, dicyandiamide, diaminodiphenylmethane, guanylurea and the like can be used, as the imidazoles, alkyl group-substituted imidazole, benzimidazole and the like can be used, and as the polyfunctional phenols, hydroquinone, resorcinol, bisphenol A and halogens thereof can be used. A compound, a novolak resin, a resole resin, or the like, which is a condensate with an aldehyde, can be used. As the acid anhydride, phthalic anhydride, benzophenonetetracarboxylic acid, or the like can be used. Of these, imidazoles are preferably used as the curing accelerator.

The required amount of these curing agents or curing accelerators is, in the case of amines, the equivalent of active hydrogen of the amine,
It is preferable that the epoxy equivalents of the epoxy resin are almost equal. In the case of dicyandiamide, the equivalent ratio to active hydrogen is not simply obtained, and empirically, 1 to 10 parts by weight is necessary for 100 parts by weight of the epoxy resin. In the case of polyfunctional phenols and acid anhydrides, 0.6 to 1.2 equivalents are required for 1 equivalent of epoxy groups of the epoxy resin. If the amount of these curing agents or curing accelerators is small, the uncured epoxy resin remains and the Tg (glass transition temperature) becomes low, and if the amount is too large, the unreacted curing agent and curing accelerator remain and the insulating property Is reduced.

The heat-resistant resin composition of the present invention, when used in a wiring board, is used for improving the plating adhesion of the inner wall of the through hole and for manufacturing the wiring board by the additive method.
A catalyst for electroless plating can also be added. In the present invention, these compositions are mixed in an organic solvent to obtain a heat resistant resin composition. As such an organic solvent, any solvent may be used as long as it has solubility, and dimethylacetamide, dimethylformamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, γ-butyrolactone, sulfolane, cyclohexanone, etc. Can be used. This heat-resistant resin composition is applied onto a supporting base material such as a PET (polyethylene terephthalate) film that has been subjected to a release treatment to produce an adhesive film, or one side or both sides of a metal foil of the supporting base material is applied to form a metal. The adhesive film with a foil can be used, and after application, it can be used by heating and drying to a cured state according to the purpose. When a metal foil is used as the supporting base material, the metal foil can be used for a wiring circuit or the like. A film can also be obtained by removing the metal foil by etching. The compounding ratio of this heat resistant resin composition can be determined by the amount of siloxane in the siloxane-modified polyamideimide resin and the epoxy equivalent of the epoxy resin. The solvent volatilization rate of the heat-resistant resin composition varnish, that is, the drying rate increases as the amount of siloxane in the composition increases. If a siloxane-modified polyamide-imide resin with a large amount of siloxane is used, a varnish with a high drying rate can be obtained even if a larger amount of a thermosetting resin component such as an epoxy resin is added, and as a result, under more mild drying conditions. An adhesive film with less residual volatile content can be obtained. Further, the epoxy group of the epoxy resin reacts with the amide group of the siloxane-modified polyamideimide resin. Therefore, when the epoxy resin alone or the epoxy resin and its curing accelerator or curing agent are used as the thermosetting resin component, the ratio of the amide equivalent of the siloxane-modified polyamideimide resin and the epoxy equivalent of the epoxy resin is 1 or less. Preferably. When the compounding amount of the epoxy resin is large, the unreacted epoxy resin remains in the film even after curing, and Tg does not rise. The adhesive film can be cured by heating. When the epoxy resin alone is used as the thermosetting resin component, the temperature is usually 180 ° C or higher, preferably 200 ° C or higher, and an addition reaction occurs between the glycidyl group of the epoxy resin and the amide group of the siloxane-modified polyamideimide resin. A three-dimensional crosslinked resin is obtained. When a basic catalyst such as imidazole is used as the curing accelerator, the curing temperature can be cured at a low temperature of about 160 ° C, and an insertion reaction occurs between the glycidyl group of the epoxy resin and the amide group of the siloxane-modified polyamideimide resin. A three-dimensional crosslinked resin is obtained. The present invention will be specifically described below with reference to examples.

[0021]

EXAMPLES (Synthesis Examples 1 to 3) Diamine having 3 or more aromatic rings in a 1 liter separable flask equipped with a 25 ml water content quantitative receiver with a cock connected to a reflux condenser, a thermometer, and a stirrer. And BAPP (2,2-bis [4-
(4-Aminophenoxy) phenyl] propane), a reactive silicone oil as siloxane diamine X-22-
161AS (trade name manufactured by Shin-Etsu Chemical Co., Ltd., amine equivalent 416), TMA (trimellitic anhydride), and NMP (N-methylpyrrolidone) as an aprotic polar solvent were charged at a mixing ratio shown in Table 1, and 80 ° C. Stirred for 30 minutes. Then, after adding 100 ml of toluene as an aromatic hydrocarbon which can be azeotroped with water, the temperature is raised to about 160 ° C. for 2 hours.
It was refluxed for an hour. Make sure that about 7.2 ml or more of water has accumulated in the moisture quantitative receiver and that no water outflow can be seen. While removing the effluent accumulated in the moisture quantitative receiver, keep the temperature up to approximately 190 ° C. The temperature was raised to remove the toluene. Then, the solution was returned to room temperature, 60.1 g (0.24 mol) of MDI (4,4′-diphenylmethane diisocyanate) was added as an aromatic diisocyanate, and the mixture was reacted at 190 ° C. for 2 hours. After the reaction was completed, an NMP solution of a siloxane-modified polyamideimide resin was obtained.

[0022]

[Table 1]

(Examples 1 to 10) E as the siloxane-modified polyamide-imide resin of Synthesis Examples 1 to 3 and epoxy resin
Table 2 for SCN195 (trade name of Sumitomo Chemical Co., Ltd.)
In addition, the compounding amount shown in 1) was further added, and 2-ethyl-4-methylimidazole was added in an amount of 1.0% by weight with respect to the epoxy resin, and the mixture was stirred for about 1 hour until the resin became uniform, and then 24 hours for defoaming. Then, the mixture was allowed to stand at room temperature to obtain a resin composition. The resin composition was applied onto a release PET film, which is a supporting substrate, so that the film thickness after drying was 50 μm, and the temperature was 120 ° C.
It was dried for 30 minutes to obtain a B-stage adhesive film. Then, the adhesive film was peeled off from the supporting substrate, fixed on a frame made of polytetrafluoroethylene resin, and heat-treated at 180 ° C. for 60 minutes to obtain a cured adhesive film. The properties of the cured adhesive film were measured and the results are shown in Table 2. Also, from the weight change of the adhesive film before and after the heat treatment, B
The residual volatiles in the stage film were measured and the results are shown in Table 2.
It is also shown.

Comparative Example 1 In the formulation of Example 6, a siloxane-free polyamideimide resin was used in place of the siloxane-modified polyamideimide resin. Other than that, a B-stage adhesive film was prepared under the same drying conditions as in Examples 1 to 10 and the residual volatile content was measured.
The value was as high as 5% by weight.

The resin compositions of Examples 6 and 10 and Comparative Example 1 were coated with the varnishes so as to obtain a film having a thickness of 120 μm, and the residual volatile content with the drying time was measured. The measurement result is shown in FIG. In the varnish of Comparative Example 1, the residual volatile content was almost unchanged at 8% by weight, but in the varnishes of Examples 6 and 10, the residual volatile content was 3% by weight or less.

Example 11 The compounding ratio (weight) of the siloxane-modified polyamideimide resin of Synthesis Example 2 and ESCN-195 was set to 60/40. Varnish of Example 6 and Comparative Example 2
An adhesive film is produced using the varnish of the resin composition of
Further, the adhesive film was cured at 290 ° C. for 1 hour, and the Tg of the cured film was measured. The measurement result is shown in FIG. From FIG. 2, it is 260 degreeC in Example 6.
However, in Comparative Example 2, the maximum value of tan δ was observed at 170 ° C. corresponding to the unreacted epoxy resin.

[0027]

[Table 2]

The measured values shown in Examples and Comparative Examples are
It is measured by the following measuring method. (1) Glass transition point (Tg) and storage elastic modulus It was measured under the following conditions using a dynamic viscoelasticity measuring device DVE-V4 type (manufactured by Rheology Co., Ltd.).・ Jig: Tension ・ Distance between chucks: 20 mm ・ Measurement temperature: 50 to 350 ° C. ・ Raising rate: 5 ° C./min ・ Measurement frequency: 10 Hz ・ Sample size; 5 mm width × 30 mm length Tg is the maximum value of tan δ Using. (2) Copper foil adhesive strength Electrolytic roughening copper foil TSC-35 (trade name of Furukawa Circuit Foil Co., Ltd.) has a film thickness of 5 after drying the varnish on the roughened surface.
It was applied so as to have a thickness of 0 μm, dried at 150 ° C. for 30 minutes, and then heat-treated at 180 ° C. for 1 hour to obtain a sample.
The resin surface was ground with sandpaper # 600 and adhered to the resin plate with an epoxy adhesive (Araldite Standard), the copper foil was peeled off with a width of 10 mm at the varnish dry film interface, and the copper foil adhesion was measured according to JIS C6481.

As described above, the heat-resistant resin composition of the present invention has a good solvent drying property, and a B-stage adhesive film having a small residual volatile content can be obtained under mild conditions. The cured product has a high Tg of 190 ° C. or higher, and has a high adhesive force to the copper foil.

[0030]

As described above, according to the present invention, it is possible to provide a heat-resistant resin composition excellent in heat resistance and solvent drying property, and an adhesive film using the same.

[Brief description of drawings]

FIG. 1 is a drawing showing a relationship between a drying time and a residual volatile content in a 120 μm film produced from the varnishes of Examples 6, 10 and Comparative Example 1.

FIG. 2 is a drawing showing Tg of cured films obtained from the varnishes of Example 6 and Comparative Example 2.

─────────────────────────────────────────────────── ─── Continued Front Page (51) Int.Cl. ⁷ Identification Code FI Theme Coat (Reference) C09J 183/04 C09J 183/04 201/00 201/00 F Term (Reference) 4J002 CC04X CD00X CM02X CM04W CP17W 4J004 AA11 AA12 AA13 AA15 CA06 CA08 CC02 FA05 FA08 4J040 EC002 EH031 EK111 JA09 JB02 MB03 NA19

Claims (6)

[Claims] 1. A siloxane-modified polyamide-imide resin 1
A heat-resistant resin composition comprising 00 parts by weight and 1 to 150 parts by weight of a thermosetting resin component. 2. A general formula (1) or a general formula (2) obtained by reacting trimellitic anhydride with a mixture of a diamine having 3 or more aromatic rings and a siloxane diamine in a siloxane-modified polyamide-imide resin. A siloxane-modified polyamideimide resin obtained by reacting a mixture containing a diimide dicarboxylic acid shown with an aromatic diisocyanate shown by the general formula (3), wherein the thermosetting resin component is an epoxy having two or more glycidyl groups. It is a resin, The heat resistant resin composition of Claim 1 characterized by the above-mentioned. [Chemical 1] [Chemical 2] [Chemical 3] 3. The thermosetting resin component contains an epoxy resin having two or more glycidyl groups and a curing accelerator or curing agent therefor.
The heat resistant resin composition as described in 1. 4. A mixture of a diamine (A) having 3 or more aromatic rings and a siloxane diamine (B), wherein the siloxane-modified polyamide-imide resin (A / B = 99.9 /).
0.1 to 99.9 (molar ratio)) and trimellitic anhydride (A + B) in a total molar ratio of trimellitic anhydride of 1 / 2.05 to 1 / 2.20. A mixture containing the diimidedicarboxylic acid represented by the general formula (1) and the general formula (2) obtained by the reaction and the aromatic diisocyanate represented by the general formula (3) are added to the total moles of (A + B) and the aroma. The molar ratio of group diisocyanate is 1 / 1.05
The heat-resistant resin composition according to any one of claims 1 to 3, which is a siloxane-modified polyamideimide obtained by reacting at 1 / 1.50. 5. A siloxane-modified polyamide-imide resin is used as an aromatic diimide dicarboxylic acid as 2,2-bis [4- {4- (5-hydroxycarbonyl-1,3-dione-isoindolino) phenoxy} phenyl] propane (C ) And bis (5-hydroxycarbonyl-1,3-)
Dione-isoindolino) propyl polydimethylsiloxane (D) molar mixture (C / D = 99.9 / 0.1
0.1 / 99.9 (molar ratio)) and aromatic diisocyanate at a total molar ratio of (C + D) and a molar ratio of diisocyanate of 1 / 1.05 to 1 / 1.50, obtained by reacting siloxane-modified polyamideimide It is a resin, The heat resistant resin composition in any one of Claim 1 thru | or 4 characterized by the above-mentioned. 6. An adhesive film obtained by applying the heat-resistant resin composition according to claim 1 as a varnish on a supporting substrate.