JP3505769B2 - Heat resistant adhesive material - Google Patents

Abstract

PURPOSE:To provide a heat-resistant adhesive material having high adhesive power and excellent heat-resistance, electrical characteristics, chemical resistance, etc., by laminating a heat-resistant adhesive composed of a polyimide resin at a specific thickness to a polyphenylene sulfide resin film. CONSTITUTION:This heat-resistant adhesive material is a laminate containing a heat-resistant adhesive on one or both surfaces of a polyphenylene sulfide resin film, wherein at least one of the adhesive layer is a polyimide resin layer having a thickness of 5.5-15mum. The polyimide resin film is preferably a thin film produced by reacting an aromatic tetracarboxylic acid such as 3,3',4,4'- benzophenonetetracarboxylic acid dianhydride with a diamine component containing 75-96mol% of a siloxane-based diamine of formula ((n) is >=1; R1 and R2 each is a lower alkylene or a phenylene; R3 to R6 each is phenyl, phenoxy, etc.) and imidating the obtained polyamic acid. The diamine component is preferably incorporated with 15-50mol% of 4,4'-diaminodiphenylsulfone to improve the adhesivity.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-resistant adhesive material, and more particularly to a high-quality heat-resistant adhesive material having high adhesive strength and excellent dimensional stability.

[0002]

2. Description of the Related Art As electronic devices are becoming smaller and higher in performance, smaller, thinner, lighter and higher density packages are required in the field of semiconductor mounting.

In this semiconductor mounting technology, development of a high-performance heat-resistant adhesive tape for joining parts to each other has been demanded.

For example, a LOC (lead on c) is used to fix an IC chip on a lead frame with a double-sided adhesive tape.
hip) adhesive tape, and for heat dissipation of IC chips I
For example, an adhesive tape for a heat spreader that bonds a C chip to a metal heat sink.

At present, this adhesive tape is used in which both sides of a polyimide film are coated with an epoxy thermosetting adhesive. If this epoxy resin is used as an adhesive tape for LOC, NIKKEI MICR
As described in the ODEVICES 1989 issue, etc., there is a problem that the gas generated during curing contaminates the metal surface of the substrate, causing a decrease in adhesive strength and the occurrence of package cracks.

When used for a heat spreader, when the tape is punched into a use shape using a mold, the polyimide film and the adhesive "cut".
Is bad, so filamentous scraps, so-called "burrs" occur,
There is a problem that it cannot be used unless a step for removing it, for example, an ion blower washing, is unnecessary.

Under these circumstances, there has recently been a demand for a heat-resistant adhesive tape which has a good punching property, generates no gas, and has a low water absorption rate, but it has not yet been put into practical use.

Conventionally, polyphenylene sulfide resin films have been used in various fields by taking advantage of the excellent characteristics such as heat resistance, flame retardancy, chemical resistance, and electrical characteristics of the resin. For example, FPCs (flexible printed circuit boards) for capacitors, which are laminated with a metal foil and an adhesive, insulating materials for motors and transformers, wire coating materials and the like are well known (Japanese Patent Publication No. 5-77323).

[0009]

As described above, the polyphenylene sulfide resin film has various characteristics and is known as a heat-resistant resin film having a low water absorption rate, but it is still a polyphenylene sulfide resin film. A heat-resistant adhesive tape in which a heat-resistant adhesive is laminated on both sides of a film has not been put into practical use.

The cause is that, as is well known, the surface of the polyphenylene sulfide resin film is chemically extremely stable and inactive, and there is a problem that the adhesive force between the laminated adhesive and the polyphenylene sulfide resin film is extremely weak. This is because, in particular, when a polyimide-based adhesive is applied and laminated, there is a problem that the applied adhesive film is easily peeled off. Although the adhesiveness is slightly improved by subjecting the surface of the polyphenylene sulfide resin film to corona discharge treatment, it has not reached a practical level and has not been put into practical use.

In order to solve these various drawbacks, the present inventors previously proposed Japanese Patent Application No. 5-241322. However, according to this technique, a phenomenon that air remains between the adhesive and the lead frame when the lead frame is pressure-bonded, that is, a so-called "air trap" occurs.

In view of the drawbacks of the prior art, the present invention further improves the technology of Japanese Patent Application No. 5-241322.
The base film, which was created by specifying the adhesive and its thickness, the purpose is, while using a polyphenylene sulfide resin film, a polyimide-based adhesive film coated The adhesion of the polyphenylene sulfide resin film is strong, the amount of gas generated during heating is extremely small, and it has excellent low water absorption, adhesiveness, chemical resistance, punching property, that is, "cut", and no air trap. It is an object to provide a heat resistant adhesive material having characteristics.

[0013]

The object of the present invention is as follows.
A laminate having a heat resistant adhesive on at least one surface of a polyphenylene sulfide resin film, wherein at least one of the heat resistant adhesives has a thickness of 5.5 μm or more and 15 μm or more.
It is achieved by a heat-resistant adhesive material characterized by being a polyimide-based resin of m or less.

The polyphenylene sulfide resin film in the present invention is not particularly limited, and all known ones can be used, and commercially available ones may be used, but the film surface is subjected to low temperature plasma treatment or corona discharge treatment. Is preferred. By performing these treatments, the adhesion of the polyphenylene sulfide resin film can be significantly improved.

The low temperature plasma treatment can be carried out under reduced pressure, and the method thereof is not particularly limited, but for example, the internal electrode type electric discharge treatment apparatus having a counter electrode composed of a drum electrode and a plurality of rod electrodes is used. A substrate to be treated is set, and an atmosphere gas is adjusted to 0.01 to 10 Torr, preferably 0.02 to 1 Torr, and a high voltage of direct current or alternating current is applied between the electrodes to perform discharge to generate plasma of the gas. Then, the surface of the substrate may be exposed to the plasma for treatment. The conditions of the low-temperature plasma treatment differ depending on the processing equipment, the type of gas, the pressure, the frequency of the power source, etc., so the optimum conditions may be selected appropriately.

As the gas used for the low temperature plasma treatment,
Ar, N ₂ , He, CO ₂ , CO, air, water vapor, O ₂
These gases can be used alone or as a mixture, and are not particularly limited.

On the other hand, the corona discharge treatment has a smaller effect of improving the adhesiveness as compared with the low temperature plasma treatment. Therefore, it is necessary to select a heat resistant adhesive to be laminated.

The polyimide resin as a heat-resistant adhesive applied to at least one surface of the polyphenylene sulfide resin film is obtained by reacting an aromatic tetracarboxylic acid with a diamine component containing 70 mol% or more of a siloxane diamine. It is preferably a thin film obtained by imidizing the obtained polyamic acid.

The aromatic tetracarboxylic acid used in the present invention includes 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride and 2,2', 3,3'-benzophenone tetracarboxylic dianhydride. Things, 2, 2 ',
3,3'-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetra Carboxylic dianhydride, 2,2-bis (3,3
4-dicarboxyphenyl) propane dianhydride, 2,2
-Bis (2,3-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,1- Bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, 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-
Perylene tetracarboxylic dianhydride, 2,3,6,7-
Anthracene tetracarboxylic dianhydride, 1,2,7,
8-phenanthrenetetracarboxylic dianhydride, etc. may be mentioned. These may be used alone or in combination of two or more.

The diamine component used in the present invention contains at least 70 mol% or more of a siloxane-based diamine in the diamine component. It is more preferably 75 mol% or more and 96 mol% or less. When the diamine component is other than the siloxane-based diamine, "punching chips" are likely to occur during punching, and when the siloxane-based diamine is less than 70 mol% in the diamine component, the adherable temperature is 200.
If the temperature exceeds ℃ and exceeds 96 mol%, the heat resistance becomes insufficient, which is not preferable.

Examples of the siloxane-based diamine used in the present invention include those represented by the following general formula [I].

[Chemical 2] (In the formula, n represents an integer of 1 or more. R ₁ and R ₂ are the same or different and each represents a lower alkylene group or a phenylene group, and R ₃ , R ₄ , R ₅ and R ₆ are They are the same or different and each represents a lower alkyl group, a phenyl group or a phenoxy group.) Specific examples of the siloxane-based diamine represented by the general formula [I] include 1,1,3,3-tetramethyl-1, 3-bis (4-aminophenyl) disiloxane, 1,1,3
3-tetraphenoxy-1,3-bis (4-aminoethyl) disiloxane, 1,1,3,3,5,5-hexamethyl-1,5-bis (4-aminophenyl) trisiloxane, 1,1 , 3,3-Tetraphenyl-1,3-bis (2-aminoethyl) disiloxane, 1,1,3,3-
Tetraphenyl-1,3-bis (3-aminopropyl)
Disiloxane, 1,1,5,5-tetraphenyl-3,
3-dimethyl-1,5-bis (3-aminopropyl) trisiloxane, 1,1,5,5-tetraphenyl-3,
3-dimethoxy-1,5-bis (4-aminobutyl) trisiloxane, 1,1,5,5-tetraphenyl-3,
3-dimethoxy-1,5-bis (5-aminopentyl)
Trisiloxane, 1,1,3,3-tetramethyl-1,
3-bis (2-aminoethyl) disiloxane, 1,1,
3,3-tetramethyl-1,3-bis (3-aminopropyl) disiloxane, 1,1,3,3-tetramethyl-
1,3-bis (4-aminobutyl) disiloxane, 1,
3-dimethyl-1,3-dimethoxy-1,3-bis (4
-Aminobutyl) disiloxane, 1,1,5,5-tetramethyl-3,3-dimethoxy-1,5-bis (2-aminoethyl) trisiloxane, 1,1,5,5-tetramethyl-3 , 3-dimethoxy-1,5-bis (4-aminobutyl) trisiloxane, 1,1,5,5-tetramethyl-3,3-dimethoxy-1,5-bis (5-aminopentyl) trisiloxane, 1,1,3,3,5,5-
Hexamethyl-1,5-bis (3-aminopropyl) trisiloxane, 1,1,3,3,5,5-hexaethyl-1,5-bis (3-aminopropyl) trisiloxane, 1,1,3,3 3,5,5-hexapropyl-1,5
-Bis (3-aminopropyl) trisiloxane, and the like. The siloxane-based diamines may be used alone or in admixture of two or more.

Diamine components other than siloxane-based diamines include 4,4'-diaminodiphenyl ether,
Known compounds such as 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, and paraphenylenediamine can be used. Among these, 4,4'-diaminodiphenyl ether is added to the diamine component in an amount of 15 to 50
When it is used by containing it by mol%, the adhesiveness with the polyphenylene sulfide resin film becomes specifically excellent. Therefore, when such a polyimide resin is used as a heat resistant adhesive, a sufficiently practical heat resistant adhesive material can be obtained simply by subjecting the polyphenylene sulfide resin film to corona discharge treatment (without low temperature plasma treatment). To be

The reaction between the aromatic tetracarboxylic acid and the diamine can be carried out according to a conventionally known method.
For example, a substantially stoichiometric amount of acid component and diamine component,
The reaction may be performed at a temperature of 0 to 80 ° C. in an organic solvent such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2pyrrolidone. These solvents may be used singly or as a mixture of two or more kinds, and as long as polyamic acid does not protrude, benzene, toluene, hexane, cyclohexane, tetrahydrofuran,
Methyl ethyl ketone or the like may be added.

The concentration of the polyamic acid varnish is not particularly limited, but is usually 5 to 60% by weight, preferably 10 to 40% by weight.

The heat-resistant adhesive material of the present invention has a heating temperature of 10
The amount of gas generated at 0 ° C to 280 ° C is 100
It is preferable to satisfy the condition of 0 ppm or less. If the amount of generated gas is 1000 ppm or less, there is no foaming when adhered to metal foil, heat resistant resin, etc., but preferably 150 p
pm or less, more preferably 100 ppm or less.

The heating temperature of the heat-resistant adhesive material is 100 to
The amount of gas generated at 280 ° C. is a DT / DTG-MS method “TG: Thermogravimetric Analysis” DTG: Derivative Thermogravimetric Analysis MS: Mass Spectormetry described below for the sample of the heat-resistant adhesive material. Analysis) ”.

The heat-resistant adhesive material of the present invention preferably has a bondable temperature of 210 ° C. or less, and 200 ° C.
The following is more preferable. Here, the bondable temperature means that after cutting the heat-resistant adhesive material into a width of 10 mm and a length of 100 mm, copper foil having the same size and a thickness of 0.2 mm is superposed and thermocompression-bonded, and cut into a width of 5 mm, and then tensilon. At a pulling speed of 50 mm / min and a 90 ° peel strength of 0.5 kg / cm or more. If the bonding temperature exceeds 210 ℃,
After adhering to the copper frame, the surface of the copper frame is oxidized, causing a problem of insufficient adhesion of the gold wire after wire bonding.
Further, when the bonding temperature is 200 ° C. or lower, the bonding process becomes close to the existing epoxy production conditions, the existing equipment can be used, and the cost is great.

As a method for obtaining the heat-resistant adhesive material of the present invention satisfying the above-mentioned various characteristics, for example, the following method can be mentioned.

That is, a solvent solution containing 10 to 40% by weight of the above polyamic acid varnish is discharged from a film forming slit and uniformly applied onto a polyphenylene sulfide resin film which has been subjected to a low temperature plasma treatment or a corona discharge treatment. Examples of the coating method include a roll coater, a knife coater, a hermetic coater, a comma coater and a doctor blade float coater. Then, the solvent of the solution applied to the heat-resistant resin film as described above is usually or continuously heated at a temperature of about 60 ° C. or higher and about 200 ° C. for 10 to 60 minutes, and then further imidized. Heat treatment. As the heat treatment for imidization, it is preferable to perform heat treatment at 200 to 280 ° C. for about 1 to 15 minutes.

In this way, an imidized thin film of polyamic acid of 5.5 μm or more and 15 μm or less is formed on the polyphenylene sulfide resin film. The film thickness is 5.
If the thickness is less than 5 μm, a phenomenon in which air is left between the adhesive and the lead frame when pressure-bonded to the lead frame, that is, a so-called “air trap” easily occurs, which is not preferable. On the other hand, if the film thickness exceeds 15 μm, the wire bondability tends to be poor, which is not preferable. The film thickness of the adhesive may be preferably selected depending on the wire bonding conditions. Then, a polyester film having a thickness of 15 to 60 μm, if necessary, for prevention of contamination and scratches,
It is preferable that a protective film such as polypropylene is laminated on the imidized thin film.

As a part of the use example of the product of the present invention, it is laminated with a metal, for example, a flexible printed circuit board laminated with a copper foil, a carrier tape for TAB and an adhesive tape for fixing a lead frame, an adhesive tape for a heat spreader, LO.
There are various materials such as lead frame peripheral materials such as C adhesive tape.

When used as a specific example in a double-sided adhesive tape for a heat spreader, after punching the product of the present invention into the intended shape, the protective film on the polyimide resin is peeled off to remove the adsorbed moisture and then overlapped with the lead frame. It may be combined by thermocompression bonding at a temperature of 150 ° C. or higher and 210 ° C., and further adhesively fixed to a heat spreader. In order to improve the adhesive strength, it is preferable to further perform heat curing. The pressure, temperature, and heating curing conditions may be appropriately selected depending on the resin composition, film thickness, and the like. Also,
The method of thermocompression bonding may be preferably selected depending on the manufacturing process such as heat pressing and heating rolls.

[0033]

EXAMPLES The present invention will now be described in detail based on examples, but the present invention is not limited to these. In the following description, the amount of gas generated during foaming and heating and the adhesive force are evaluated and measured by the following methods, respectively.

[Foaming] After removing the copper foil by etching, the surface of the adhesive was observed with an optical microscope.

[Amount of evolved gas] About 100 mg of a sample having an imidized thin film was weighed with a precision scientific balance, and then TG / DT
It was measured by the G-MS method.

The TG / DTG-MS method is a method in which a TG device has an M
This is a method in which the S device is directly connected and the change in the concentration of the gas generated from the sample during heating is tracked as a function of temperature simultaneously with the change in weight. The measuring machine and measuring conditions are as follows.

Measuring instrument: TG (macro balance) -MS simultaneous measurement device manufactured by Shimadzu Corporation Data processing; Data processing system "THADAP-TGMS" manufactured by Toray Research Center; Measurement accuracy; 10 ppm measurement mode; Sample in platinum container 50 in advance
After vacuum-drying at 6 ℃ for 6 hours, set it on the TG device, and then run dry helium at 50 ml / min for 12 hours or more, then
The temperature rise was started at 0 ° C./min, the TG-MS curve up to 300 ° C. was measured, and the total amount of evolved gas from 100 ° C. to 280 ° C. was obtained.

[Adhesive strength] * Adhesive tape for heat spreader and LOC Shear stress; After making the sample shown in FIG. 1 and placing it in a heating furnace at 190 ° C. for 3 minutes, the shear stress was applied with a tensilon at a pulling speed of 50 mm. It was measured in minutes. Practically 1.0 kg /
Adhesive force of cm ² or more is required.

[Punching property] After punching the adhesive tape with a die into the shape shown in FIG. 2, the edges were observed with a microscope (NIKON Co., Ltd. SMZ-10; magnification 13.2 to 80 times) to obtain "burrs". I checked for foreign matter.

[Water absorption rate] A 60 mm × 60 mm sample is prepared. Dry in an oven at 200 ° C. for 10 minutes and measure the weight with a precision balance (W ₀ ). 85 ° C x 85% RH
It is left to stand for 24 hours, and the weight is measured (W ₁ ). From these, the water absorption rate (σ) is calculated by the following formula.

Σ (%) = (W ₁ −W ₀ ) / W ₀ × 100 Example 1 N, N− in a 300 ml four-necked flask equipped with a thermometer, a stirrer, a reflux condenser and a dry N ₂ inlet. Dimethylacetamide (115 g) was added, and bis (3-aminopropyl) tetramethyldisiloxane was added 11.68 under a nitrogen stream.
After dissolving g (75 mol%) and 4,4'-diaminodiphenyl ether 3.13 g (25 mol%), 20.19 g (100 mol%) of 3,3 ', 4,4'-benzophenone tetracarboxylic acid dianhydride was dissolved. In addition,
Stirring was continued at 10 ° C for 1 hour. Then, the mixture was stirred at 50 ° C. for 3 hours and reacted to obtain a polyamic acid varnish.

The varnish was applied to a 50 μm polyphenylene sulfide resin film (“Torelina” (manufactured by Toray Industries, Inc.)) which had been subjected to a low temperature plasma treatment in an Ar atmosphere in advance so that the film thickness after drying was 7 μm. Dry for 10 minutes at 130 ℃, 10 minutes at 130 ℃, 160 ℃
And dried for 15 minutes. 230 ° C for imidization of the coated product
It heat-treated for 5 minutes. The generated gas amount of the film was measured and found to be 60 ppm or less.

The above-prepared film was slit into a width of 10 mm, laminated with 42 alloy used as a metal foil for a lead frame, and heated at a bar temperature of 200 ° C. to obtain a pressure of 4 kg / cm ² with a heat seal tester. ,
Bonding was performed with a pressure bonding time of 10 seconds. No bubbling was observed in the laminated product, the shear stress was 10 kg / cm ² , and the water absorption was 0.2%. The adhesive tape for LOC and the adhesive tape for heat spreader sufficiently satisfied the practical level. The punching property was also good, and there were no abnormalities such as occurrence of "burrs", "cracking" of the adhesive, and air traps.

Example 2 115 g of N, N-dimethylacetamide was placed in a reactor similar to that of Example 1, and 14.32 g (90 mo) of bis (3-aminopropyl) tetramethyldisiloxane was added under a nitrogen stream.
1%) and 0.69 g (10%) of paraphenylenediamine
mol%), and then dissolved in 3,3 ', 4,4' benzophenone tetracarboxylic acid dianhydride 18.56 g (10
0 mol%) and 1.40 g of pyromellitic dianhydride were added, and stirring was continued at 10 ° C. for 1 hour. Then 3 at 50 ℃
The mixture was stirred and reacted for a time to obtain a polyamic acid varnish.

The varnish was applied to a low-temperature plasma-treated 75 μm polyphenylene sulfide resin film (“Torelina” (manufactured by Toray Industries, Inc.)) in the same manner as in Example 1 so that the film thickness after drying was 10 μm. It was dried at 80 ° C. for 10 minutes, further dried at 120 ° C. for 10 minutes, and further dried at 150 ° C. for 15 minutes. The coated product was heat-treated at 230 ° C. for 5 minutes for imidization. The generated gas amount of the film was measured and found to be 60 ppm or less.

The film produced above had good punching properties, and there were no abnormalities such as occurrence of "burrs", "cracking" of the adhesive and air traps.

In addition, a resin-coated surface of the above produced film,
Overlap with a copper plate with a thickness of 0.25 mm and set the upper and lower bar temperatures to 2
Pressure 4kg / with a heat roll tester heated to 00 ℃
cm ^2, was laminated by bonding time of 10 seconds, laminated and ones without foaming, shear stress at 190 ° C. 1
The water absorption rate was 1.5 kg / cm ² , and the water absorption rate was 0.3%, which was sufficiently satisfactory as an adhesive tape for LOC and an adhesive tape for heat spreader.

Comparative Example 1 The polyamic acid varnish obtained in Example 1 was treated with low temperature plasma in the same manner as in Example 1 to obtain a 50 μm polyphenylene sulfide resin film (“Torelina” (Toray Industries, Inc.).
(Manufactured)) so that the film thickness after drying would be 3 μm (drying and heat treatment conditions are the same as in Example 1).

The coated film was cut into the same size as a heat spreader (thickness 0.15 mm, 19 mm × 19 mm) and then laminated, and the pressure was 4 kg / cm ² and the pressure bonding time was 10 with a heat seal tester heated to a bar temperature of 180 ° C.
Bonding in seconds, and then the bonded product with a lead frame for QFP (copper, 0.15 mm thickness, 208 pins) and a heat seal tester with a bar temperature of 200 ° C. at a pressure of 4 kg / c.
^They were bonded together at m ² and a compression time of 15 seconds. The sample had an "air trap" and was at a level that was not practical.

[0050]

EFFECTS OF THE INVENTION Since the present invention is configured as described above, the adhesive force between the coated polyimide-based adhesive film and the polyphenylene sulfide resin film is strong even though the polyphenylene sulfide resin film is used. It can be easily bonded to metals, heat resistant resins, etc. Furthermore, the amount of gas generated during heating is extremely small,
Moreover, it has excellent low water absorption, adhesiveness, electrical characteristics, and chemical resistance, and also has good punching property, that is, "cutting" and no air trap.

[Brief description of drawings]

FIG. 1 Shear stress (adhesive force) of the heat-resistant adhesive material of the present invention
It is a figure showing the sample for measuring.

FIG. 2 is a diagram showing an example of a punching shape of the heat resistant adhesive material of the present invention.

Front page continuation (58) Fields surveyed (Int.Cl. ⁷ , DB name) C09J 7/02 H01L 21/312 H01L 21/52

Claims (9)

(57) [Claims] 1. A laminate having a heat resistant adhesive on at least one side of a polyphenylene sulfide resin film, wherein at least one of the heat resistant adhesives has a thickness of 5.5 μm.
A heat-resistant adhesive material, characterized in that it is a polyimide-based resin of m or more and 15 μm or less. 2. The heat-resistant adhesive material according to claim 1, which has a bondable temperature of 210 ° C. or lower. 3. A polyimide resin comprising a thin film formed by imidizing a polyamic acid obtained by reacting an aromatic tetracarboxylic acid with a diamine component containing 70 mol% or more of a siloxane diamine. Item 1. A heat resistant adhesive material according to item 1. 4. A siloxane-based diamine having the following general formula [I]:
The heat-resistant adhesive material according to claim 3, which is represented by: [Chemical 1] (In the formula, n represents an integer of 1 or more. R ₁ and R ₂ are the same or different and each represents a lower alkylene group or a phenylene group, and R ₃ , R ₄ , R ₅ and R ₆ are They are the same or different and each represents a lower alkyl group, a phenyl group or a phenoxy group.) 5. The heat-resistant adhesive material according to claim 1, wherein the amount of gas generated at a heating temperature of 100 ° C. or higher and 280 ° C. or lower is 1000 ppm or less. 6. The heat-resistant adhesive material according to claim 1, wherein the surface of the polyphenylene sulfide resin film is subjected to low-temperature plasma treatment or corona discharge treatment. 7. The heat resistant adhesive material according to claim 1, which is a peripheral material of a lead frame. 8. The heat-resistant adhesive material according to claim 7, which is an adhesive tape for fixing a lead frame, an adhesive tape for a heat spreader or an adhesive tape for a lead-on-chip. 9. A polyimide adhesive composition is applied to at least one surface of a polyphenylene sulfide resin film, dried, and then heat-treated at 200 to 270 ° C. so that the thickness of the polyimide adhesive is 5.5 μm or more and 15 μm or less. A method for producing a heat-resistant adhesive material, comprising: