JPH02272077A - Heat-resistant adhesive material - Google Patents

Abstract

PURPOSE:To provide the title material for films or tapes insulate or fix electrical and electronic parts, etc., made up of the first layer consisting of non- thermoplastic aromatic polyimide supporting film and the second layer consisting of a thermoplastic aromatic polyimide adhesive layer. CONSTITUTION:The objective material made up of (A) the first layer consisting of a non-thermoplastic aromatic polyimide supporting film with recurring unit of formula I (Ar is aromatic tetracarboxylic acid; R is symmetric aromatic p-substituted diamine; n is integer >=1) as the main constituent and (B) the second layer consisting of a thermoplastic aromatic polyimide adhesive layer with recurring unit of formula II (R is symmetric aromatic m-substituted diamine) as the main constituent.

Description

[Detailed Description of the Invention] [Field of Industrial Application] This invention relates to a heat-resistant adhesive material used for films or tapes for insulating or fixing electronic parts, electrical parts, etc. that require heat resistance. It is something.

[Conventional technology]

In recent years, large-scale computers have become larger in capacity and faster, and semiconductor devices, such as VLSI, are becoming increasingly smaller and more highly integrated. As a technique for mounting such semiconductor elements on a substrate, for example, a multi-chip substrate module in which a plurality of semiconductor elements are simultaneously mounted on a substrate has been proposed.

However, with the progress of computers, there is a trend towards higher density packaging, and in order to mount semiconductor elements with an increased number of input terminals on a small area substrate, it becomes necessary to perform high density wiring on the mounting board as well. A copper-polyimide multilayer wiring board was developed in line with the above requirements, but since the copper conductor is easily oxidized, the surface of the first layer where the copper wiring is exposed is also overcoated with liquid polyimide varnish (polyamic acid solution). There is a need to prevent the oxidation of However, forming a protective film using expensive liquid polyimide varnish up to the top layer of the wiring board means that the overcoat film formed on the top layer is not required to have insulation properties between the eyebrows. As described above, this is uneconomical and further complicates the manufacturing process of the substrate. Therefore, as a solution to the above problem, a process of applying the liquid polyimide varnish using a spin code method and baking it at approximately 350°C under a nitrogen stream to form a protective film, or a process that simplifies the process of the spin code method is proposed. As a coating method, a method of coating using a screen printing method using polyimide paste has been proposed. However, the above screen printing method also requires firing at a high temperature of 300 to 350'C under a nitrogen stream. Furthermore, a method that is cheaper and simplifies the manufacturing process is to attach a heat-resistant aromatic polyimide film to the copper wiring protection part of the top layer where the copper wiring is exposed. The reality is that an adhesive film with properties that can be used in this method has not yet been developed. In other words, in such multilayer wiring packages, it is an adhesive that can be used for applications that have heat resistance against the heat generated by the device itself, metallization in post-processes, and the high-temperature heat treatment process used to bond the top lid of the package container using low-melting-point glass. Film has not yet been developed.

On the other hand, ceramic packages using lead frames with tabs are adhesively sealed by heating the top and bottom lids of the ceramic container from 450"C to 500"C using low-melting glass. When a polyimide tape for fixing lead frames that has a layer of hardening acrylic adhesive, rubber/epoxy adhesive, rubber/phenol adhesive, etc. is used for fixing lead bins, the heat resistance of the polyimide tape is low, so it cannot be heated. Defects such as contamination of the element surface by the organic tar that sometimes occurs, generation of pinholes due to outgassing of the low-melting point glass sealing part due to the generated gas components, and thinning of the tape thickness, and furthermore, When exposed, the high-temperature adhesive strength for adhesively fixing the lead pins is significantly reduced, resulting in a number of problems including the inability to prevent thermal deformation of the glue-dobin, such as lead shift.

In order to solve these problems, it is necessary to improve the heat resistance of the components constituting the adhesive layer, and there is a strong desire to develop a tape containing such an adhesive layer.

The present invention was made in view of the above circumstances, and an object thereof is to provide a heat-resistant adhesive material having excellent heat resistance.

[Means for solving problems]

In order to achieve the above object, the heat-resistant adhesive material of the present invention has a two-layer structure, and the first layer has the following general formula (I).
The second layer is composed of a non-thermoplastic aromatic polyimide support film whose main component is a repeating unit represented by the following general formula (II), and the second layer is a thermoplastic aromatic polyimide support film whose main component is a repeating unit represented by the following general formula (II). The structure consists of a polyimide adhesive layer.

[Effect]

That is, in order to obtain an adhesive material such as a film having an adhesive layer with excellent heat resistance, the present inventors have conducted extensive research focusing on the constituent components of the support film and adhesive layer that constitute the adhesive material. . As a result, a non-thermoplastic aromatic polyimide support film containing repeating units represented by the formula (n) as a main component was used as a component constituting the molded body, and a non-thermoplastic aromatic polyimide support film mainly composed of repeating units represented by the formula (n) was used as a component constituting the adhesive layer. ) The inventors discovered that by combining these adhesives, a heat-resistant adhesive material with excellent heat resistance can be obtained, and this invention has been achieved. .

It should be noted that the term "main component" here includes the case where the entire component consists only of the main component.

The heat-resistant adhesive material of the present invention comprises a non-thermoplastic aromatic polyimide support film represented by the above-mentioned formula (■) and a thermoplastic aromatic polyimide adhesive represented by the above-mentioned general formula (I[). It can be obtained using

The non-thermoplastic aromatic polyimide support film represented by formula (1) above is obtained by reacting an aromatic tetracarboxylic dianhydride with a symmetrical aromatic para-substituted diamine.

As the aromatic tetracarboxylic dianhydride, one represented by the following general formula (V) is used.

Specifically, pyromellitic dianhydride, 3.3', 4.
4'-benzophenone tetracarboxylic dianhydride, 2,
3.3',4'-benzophenonetetracarboxylic dianhydride, 3.3',4.4'biphenyltetracarboxylic dianhydride, 2,3°3',4'-biphenyltetracarboxylic dianhydride 2,2-bis(3,4-dicarboxyphenyl)propanihydride, 2,2-bis(2,3
-dicarboxyphenyl)brovanni anhydride, 2゜2-
Bis(3,4-dicarboxyphenyl)hexafluoropropanide anhydride, 2,2-bis(23-dicarboxyphenyl)hexafluoropropanide anhydride, bis(3
, 4-dicarboxyphenyl)ether dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride,
Bis, (3,4-dicarboxyphenyl)sulfidic anhydride, 1.1-bis(2,3-dicarboxyphenyl)ethanihydride, bis(2,3-dicarboxyphenyl)methanidianhydride, 2,3 , 6.7-naphthalenetetracarboxylic dianhydride, 1,4゜5.8-naphthalenetetracarboxylic dianhydride, 1.2,5.6-naphthalenetetracarboxylic dianhydride, 1.2,3 .4-Benzenetetracarboxylic dianhydride, 3,4,9.10-perylenetetracarboxylic dianhydride, 2,3,6.7-anthracenetetracarboxylic dianhydride, 1,2,7゜8 -phenanthrenetetracarboxylic dianhydride, bis(3,4
-dicarboxyphenyl)tetramethyldisiloxane dianhydride, bis(2,3-dicarboxyphenyl)tetramethyldisiloxane dianhydride, bis(3,4-dicarboxyphenoxy)dimethylsiloxane dianhydride, bis(2-dicarboxyphenyl)tetramethyldisiloxane dianhydride, ，
Examples include 3-dicarboxyphenoxy) dimethylsilane anhydride. These can be used alone or in combination.

As the symmetrical aromatic rose-substituted diamine, one represented by the following general formula (VI) is used.

IhN-R-Nl(,...(Vl) Specifically, p-fuynylenediamine, 4,4'-diaminodiphenyl ether, 4,4-diaminodiphenylsulfone, 4.4' diaminodiphenylsulfide,
4.4'-diaminobenzophenone, 4,4'diaminodiphenylmethane, 2゜2-bis(4-aminophenyl)propane, 2゜2-bis(4-aminophenyl)tetrafluoropropane, 1.4-bis (4-aminophenoxy)benzene, 4.4'-bis(4-aminophenyl)diphenyl ether, 4.4'-bis(4-aminophenyl)diphenyl sulfone, 4.4'-bis(4-
aminophenyl) diphenyl sulfide, 4,4'-bis(4-aminophenyl) diphenylmethane, 4,4'
-bis(4-aminophenoxy)diphenyl ether,
4.4'-bis(4-aminophenoxy)diphenylsulfone, 4.4'-bis(4-aminophenoxy)diphenylsulfide, 4.4'-bis(4-aminophenoxy)diphenylmethane, 2.2-bis[ 4-(4-aminophenoxy)phenyl]propane, 2,2-bis(
Examples include 4-(4-aminophenoxy)phenyl]hexafluoropropane and 1,3-bis(γ-aminopropyl)tetramethyldisiloxane. These can be used alone or in combination.

The non-thermoplastic aromatic polyimide support film used in this invention is produced using the above raw materials, for example, in the following manner. That is, an aromatic tetracarboxylic dianhydride and a symmetric aromatic para-substituted diamine are mixed in approximately equimolar amounts in an organic solvent for 60 minutes with cooling as necessary, according to a known method (US Pat. No. 4,065,345). Low-temperature solution polymerization is performed in which polymerization is carried out at temperatures below °C to create a transparent and viscous polyamic acid polymer solution, which is cast onto a glass plate or stainless steel mirror surface and dried at 100 to 180 °C. Then, it is produced by dehydrating and ring-closing at 180 to 300°C and peeling off from the casting base material. Furthermore, the non-thermoplastic aromatic polyamide supported molded product obtained as described above was heated to 300 to 400°C using a pin tenter or the like.
It is also possible to carry out a stretching process.

As the organic solvent, N-methyl-2-pyrrolidone,
N,N-dimethylformaldehyde, NN-dimethylacetaldehyde, 1,3-dimethyl-2-imidacillin, N,N-diethylacetamide, dimethyl sulfoxide, hequinamethylphosphoramide, tetramethylurea,
Examples include N-methylcaprolactam. These organic solvents may be used alone or in combination.

When manufacturing a non-thermoplastic aromatic polyimide support film as described above, it is preferable that the intrinsic viscosity of the polyamic acid polymer solution is set in the range of 0.8 to 6 dl/g. The above-mentioned intrinsic viscosity is a value measured in N-methyl-2-pyrrolidone at a concentration of 0.5 g/all (30''C) and calculated in the following 2.

Particularly suitable non-thermoplastic aromatic polyimide support films obtained in the above method are those represented by the following general formulas (I[I) and (IV), such as Kapton manufactured by DuPont, Examples include Avical manufactured by Kanegafuchi Chemical Co., Ltd., Ubilex R type and Ubilex S type manufactured by Ube Industries, Ltd., and U-Film U and U-Film manufactured by Nitto Denko Corporation.

The thickness of the non-thermoplastic aromatic polyimide support film is not particularly limited, and is, for example, 12.5 all
(1/2m1ffi), 25 am (ln
iffi) 40t1m, 50 (2mij2)
, 75μm (3mil, 125μva (5
mil) etc. In addition, in order to improve the adhesive strength with the thermoplastic aromatic polyimide adhesive layer, the adhesive layer forming surface of the non-thermoplastic aromatic polyimide support film was subjected to flame treatment, corona treatment, and 0! Plasma treatment, sputtering treatment, metal Na treatment, etc. can be performed.

Further, the thermoplastic aromatic polyimide adhesive that forms the thermoplastic aromatic polyimide adhesive layer on the surface of the non-thermoplastic aromatic polyimide support film contains an aromatic tetracarboxylic dianhydride and a symmetric aromatic meta-substituted diamine. It can be obtained using

Examples of the aromatic tetracarboxylic dianhydride include those similar to the raw materials for the non-thermoplastic aromatic polyimide support film.

Examples of the symmetric aromatic meta-substituted diamine include those represented by the following general formula (■).

HtN-C "X-kuy-NH!"・(■) Specifically, 3.3'-diaminophenyl ether, 3.3'
-diaminodiphenyl sulfide, 33'-diaminodiphenylsulfone, 3,3-diaminodiphenylmethane, 2,2-bis(3-aminophenyl)propane, 2,
2-bis(3-aminophenyl)tetrafluoropropane, 1.3-bis(3-aminophenyl)propane1.
3-bis(3-aminophenyl)hexafluoropropane, 3.3'-benzophenone, 1°3-bis(3-aminophenyl)benzene, l.

3-bis(3-aminophenoxy)benzene, 22-bis(4-(3-aminophenoxy)phenyl)propane, 2.2-bis(4-(3-aminophenoxy)phenylcotetrafluoropropane, 1,3 -Bis(3-aminophenoxy)benzene, 4,4'-bis(3-aminophenoxy)biphenyl, bis(4-(3-aminophenoxy)phenyl)ketone, bis(4-(3-aminophenoxy)phenyl) Sulfide, bis(4-(3-aminophenoxy)phenyl)sulfone, bis(4-(3-aminophenoxy)phenyl)
-aminophenoxy)phenyl]ether, 4.4'-
Bis(3-aminosulfonyl)ether, 4,4'-bis(3-aminophenylsulfonyl)diphenyl ether, 4,4'bis(3-aminethiophenoxy)diphenylsulfone, 1,4-bis(4-(3- Examples include aminophenoxy)benzoyl]benzene, etc. These may be used alone or in combination.

In addition, 0 to 50 mol% of the symmetrical meta-substituted diamine may be used alone or in combination with two or more symmetrical aromatic para-substituted diamines represented by the formula (Vl). The proportion of the aromatic substituted diamine used must be within a range that allows the resulting thermoplastic aromatic polyimide adhesive to exhibit thermoplasticity.

The thermoplastic aromatic polyamic acid solution that becomes the thermoplastic aromatic polyimide adhesive used in the present invention is prepared using the above raw materials, for example, in the following manner. That is,
Aromatic tetracarboxylic dianhydride and symmetrical aromatic meta-substituted diamine are heated at 60°C in approximately equimolar organic solvent until the intrinsic viscosity reaches 0.3 to 3.0 dfl/g with cooling as necessary. A transparent and viscous polyamic acid solution of a thermoplastic aromatic polyimide precursor can be prepared by performing the following low-temperature solution polymerization reaction.

The thermoplastic aromatic polyimide adhesive thus obtained preferably has a glass transition temperature of 280°C or lower, particularly preferably 200°C or lower. Having a glass transition temperature as low as described above is extremely effective in the adhesive of the present invention, in which the adhesive function of the adhesive layer is expressed in the rubber region. For example, 3, 3' developed by the US aerospace side (NASA)
, 4,4'-benzophenone tetracarboxylic dianhydride (hereinafter abbreviated as rBTDA) and 3,3'-diaminobenzophenone (U.S. Patent No. 4)
065345, US Pat. No. 4,094,862). Also, as another example, BTDA
and 1,3-bis(3-aminophenoxy)benzene.

Further, the thermoplastic aromatic polyimide adhesive may contain the non-thermoplastic polyimide precursor solution in an amount of 0 to 50% by weight. That is, if the mixing ratio of the non-thermoplastic aromatic polyimide precursor solution exceeds 50% by weight, the resulting adhesive layer will have poor adhesion in the rubber region above the glass transition temperature.

The heat-resistant adhesive material of the present invention can be obtained, for example, as follows. That is, the thermoplastic aromatic polyimide precursor solution that forms the thermoplastic aromatic polyimide adhesive layer is poured onto one side of the non-thermoplastic aromatic polyimide support film using a roll coater, knife coater, flow coater, applicator, etc. Spread and apply at 120-200°C
Obtained by drying. After the heat-resistant adhesive material thus obtained is adhered to an object to be adhered, imidization is completed by heating it to 200 to 350°C. In this case, the organic solvent in the thermoplastic aromatic polyimide adhesive layer formed by the above method is 0 to 3
It may remain in a proportion of 0% by weight. In addition, instead of completing the imidization by heating after contacting the object to be bonded as described above, it is possible to
The imidization may be completed in advance by post-heating at 0 to 350°C.

The thermoplastic aromatic polyimide adhesive layer is non-adhesive at room temperature and has good handling properties, and the method for adhering the polyimide adhesive layer to the object to be adhered is to raise the glass transition temperature to 10° using a hot plate. C to 15
Set the temperature above 0°C, and apply 2 to 50 kg/c.
This is done by thermocompression bonding at a pressure of +fl.

Further, in order to prevent foreign matter from adhering to the polyimide adhesive layer, a polyester film, a polypropylene film, a fluororesin film, or the like may be used as a protective film on the surface of the polyimide adhesive layer.

A heat-resistant adhesive tape using the heat-resistant adhesive material thus obtained can be obtained, for example, by winding the heat-resistant adhesive material around a resin tube or paper tube, and cutting the tube into slits in the long sleeve direction.

The heat-resistant adhesive material of this invention obtained in this way is
As shown in the drawings, a thermoplastic aromatic polyimide adhesive layer 2 is formed on a non-thermoplastic aromatic polyimide support film 1 . Therefore, it has excellent heat resistance.

[Effects of the Invention] As described above, the heat-resistant adhesive material of the present invention can be applied to a non-thermoplastic aromatic polyimide molded article represented by the above-mentioned formula (1), and a heat-resistant adhesive material represented by the above-mentioned formula (II). Since it is constructed with a plastic aromatic polyimide adhesive layer, it has excellent heat resistance. Therefore, it is ideal for applications that require heat resistance, such as adhesive films for insulating and fixing electronic components.

Next, examples will be described together with comparative examples.

[Example 1] In a container equipped with a stirrer 9, a cooling tube, a thermometer, and a nitrogen inlet tube, 21.2 g of 3,3'-diaminobenzophenone (0
, 1 mol) and N,N-dimethylacetamide 302.6
I put g. And BTDA32.2 under nitrogen flow
g (0.1 mol) was gradually added and stirred for 6 hours while maintaining the temperature below 60°C in a water bath, resulting in an intrinsic viscosity of 0.
A light brown transparent viscous polyamic acid solution of 85 d/g was prepared. Next, the above polyamic acid solution was applied to a thickness of 50 μm (
1 on Kapton film (manufactured by DuPont)
The mixture was dried at 50''C for 2 hours and applied using an applicator to a thickness of 25 μm to obtain an aromatic polyimide structure which is the desired heat-resistant adhesive material.

Thermal decomposition initiation temperature after heating the obtained aromatic polyimide structure at 300'C for 1 hour (10°C/under nitrogen flow)
The temperature was raised at n+in and measured by TGA (manufactured by Rigaku Denki Co., Ltd.) was 520°C. Next, this was cut into 10 pieces in width, preheated on a 200°C hot plate, and placed on a 42 alloy plate with a thickness of 0.2011 IIm, weighing 6 kg.
/C4 pressure for 1 second, then 250
Heated at °C for 6 hours. Thereafter, it was cooled to room temperature, and the adhesive strength of 90@vinyl at that time was 2.2 kgf/cm.

[Example 2] Under a nitrogen stream, 29.2 g (0.1 mol) of 1,3-bis(3-aminophenoxy)benzene and 32.2 g BTDA (
(0.1 mol) was subjected to a polymerization reaction at 60°C or lower. Other than that, a pale brown transparent viscous polyamic acid solution C (hereinafter referred to as "varnish A") having an intrinsic viscosity of 1.8 dl/g was prepared in the same manner as in Example 1. This varnish A was dried at 150°C for 4 hours on Upilex 25SS (manufactured by Ube Industries, Ltd.) with a thickness of 25 μm, and then applied with an applicator to a thickness of 15 μm. A polyimide structure was obtained.

The thermal decomposition initiation temperature after heating the obtained aromatic polyimide structure at 350°C for 1 hour was 485°C. Next, in the same manner as in Example 1, 90° with 4270i
When the adhesive force of the pill was measured, it was 1.9 kgf/c
It was va.

(Example 3) 279.9 g of N-methyl-2-pyrrolidone was mixed with 20.9 g of 4,4-diaminodiphenyl ether in an organic solvent under a nitrogen stream.
0 g (0.1 mol) and 29.4 g (0.1 mol) of 3.3', 4.4-biphenyltetracarboxylic dianhydride were polymerized at 60°C or lower. Other than that, Example 1
A pale brown transparent viscous polyamic acid solution (hereinafter referred to as "varnish B") having an intrinsic viscosity of 3.5 dfl/g was prepared in the same manner as above. Next, 90 parts by weight of varnish A and 10 parts by weight of varnish B were thoroughly mixed, and this mixed solution was dried at 150'C for 1 hour on Avical 50AH (manufactured by Kanegafuchi Kagaku Co., Ltd.) with a thickness of 50 μm. It was coated with a roll coater to a thickness of 22 μm to obtain an aromatic polyimide structure which is the desired heat-resistant adhesive material. The amount of remaining solvent at this time is 1
It was 5% by weight.

The thermal decomposition onset temperature after heating the obtained aromatic polyimide structure at 250°C for 6 hours was 485°C. Next, in the same manner as in Example 1, a 90"
'When we measured the adhesive strength of the vinyl, it was 1.7 kgf/C.
! It was l.

[Comparative Example 1] Avical 50AH with a thickness of 50 μm using only varnish B
(manufactured by Kanegafuchi Kagaku Co., Ltd.) was dried at 150'C for 1 hour and then coated with a roll coater to a thickness of 22 μI to obtain an aromatic polyimide structure which is a heat-resistant adhesive material. The amount of residual solvent at this time was 14% by weight.

The thermal decomposition onset temperature after heating the obtained aromatic polyimide structure at 250°C for 6 hours was 530°C. Next, this was thermocompression bonded onto a 4270 machine in the same manner as in Example 1, but no adhesion occurred. Furthermore, even after thermocompression bonding for 60 seconds, the 90° beer contact force is 0.01 kgf 7
cm, which was a significantly low value.

[Comparative Example 2] 236.9 g of N-methyl-2-pyrrolidone and 20.9 g of 4.4-diaminodiphenyl ether in an organic solvent under a nitrogen stream.
0g (0.1 mol) and pyromellitic dianhydride 21.8
g (0.1 mol) was subjected to a polymerization reaction at 60°C or lower.

Other than that, the procedure was the same as in Example 1, and the intrinsic viscosity was 3.3 dl/
A light brown transparent viscous polyamic acid solution of 1.g was prepared. Next, this polyamic acid solution was applied to Kapton 2 with a thickness of 50 μm.
00)1 (manufactured by DuPont) using an applicator to give a thickness of 20 μm after drying at 180° C. for 1 hour to obtain an aromatic polyimide structure as a heat-resistant adhesive material.

The thermal decomposition onset temperature after heating the obtained aromatic polyimide structure at 350°C for 1 hour was 560°C. Next, this was thermocompressed onto a 4270-I board in the same manner as in Example 1, but no adhesion occurred.

[Comparative Example 3] 40 parts by weight of varnish A and 860 parts by weight of varnish were thoroughly mixed, and this mixed solution was dried on Avical 50AH (manufactured by Kanegafuchi Chemical Co., Ltd.) with a thickness of 50 μm at 150°C for 1 hour, and the thickness was as follows. Coating was performed using a roll coater so that the thickness was 22 μm. The amount of residual solvent at this time was 15% by weight.

After heating the obtained aromatic polyimide structure at 250'C for 6 hours, the thermal decomposition onset temperature was 490'C.

Next, in the same manner as in Example 1, the adhesion force of 90@vinyl with a 4270 plate was measured, and it was found to be 0.1 kg f.
/cffl, which was extremely low.

The glass transition temperature of the thermoplastic aromatic polyimide adhesive layer of Example 1 product and Example 2 product is 255, respectively.
”C and 193°C.

As described above, the examples have higher thermal decomposition initiation temperatures and higher adhesive strength than the comparative examples. From this, it can be seen that the above example products are effective for use in fields where heat resistance is required.

[Brief explanation of drawings]

The drawing is a longitudinal sectional view showing an embodiment of the present invention. 1...Non-thermoplastic aromatic polyimide molded body 2...
Thermoplastic Aromatic Polyimide Adhesive Layer Patent Applicant Nitto Denko Corporation Representative Patent Attorney Yukihiko Nishifuji

Claims (1)

[Claims] (1) It has a two-layer structure, and the first layer has the following general formula (
The second layer consists of a non-thermoplastic aromatic polyimide support film whose main component is a repeating unit represented by I).
A heat-resistant adhesive material comprising a thermoplastic aromatic polyimide adhesive layer containing a repeating unit represented by the following general formula (II) as a main component. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) In the above formula (I), Ar is an aromatic tetracarboxylic acid residue, R is a symmetric aromatic para-substituted diamine residue, and n is 1 is an integer greater than or equal to ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(II) [In the above formula (II), Ar is an aromatic tetracarboxylic acid residue, R is a symmetric aromatic meta-substituted diamine residue, and n is It is an integer greater than or equal to 1. (2) The heat-resistant adhesive material according to claim (1), wherein the thermoplastic aromatic polyimide adhesive layer has a glass transition temperature of 280° C. or lower. (3) Claim (1) or (2), wherein the non-thermoplastic aromatic polyimide support film is mainly composed of repeating units represented by the following general formulas (III) and (IV).
Heat resistant adhesive material as described. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(IV) [In the above formulas (III) and (IV), n is a positive integer. be. ]