JPH06346030A - Heat-resistant adhesive material - Google Patents

Abstract

PURPOSE:To obtain a heat-resistant adhesive material capable of bonding an adhesive at a low temperature, free from lowering of adhesiveness at high temperature, excellent in electric characteristics and chemical resistance, and further, remarkably improved in adhesion. CONSTITUTION:This heat-resistant adhesive material has a thermoplastic heat- resistant adhesive layer A on at least one side of a heat-resistant resin layer B and the thickness of the thermoplastic heat-resistant adhesive layer A is >=0.1mum and <=15mum and modulus (at 250 deg.C) of the thermoplastic heatresistant adhesive layer A is >=10<6>dyn/cm<2> and <10dyn/cm<2>.

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 heat resistant adhesive material used as a peripheral material for lead frames.

[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 required.

For example, a LOC (lead on chip) adhesive tape for fixing an IC chip on a lead frame with a double-sided adhesive tape, and a heat spreader for bonding an IC chip and a metal heat dissipation plate for heat dissipation of the IC chip. Such as adhesive tape.

Currently, this adhesive tape is generally used by a lead frame maker, after being taped on the lead frame, thermocompression-bonded to an IC chip by a semiconductor maker, and then the chip and the lead frame are subjected to ultrasonic waves. Wire bonding is performed at a temperature of about 180 ° C, and resin sealing is performed at a temperature of about 180 ° C to 200 ° C. After that, it is mounted by solder reflow at a temperature of around 250 ° C. Therefore, the adhesive tape is required to have not only electric characteristics but also sufficient room temperature adhesive strength immediately after taping, adhesive strength with an IC chip, wire bonding characteristics, and good overall characteristics such as solder heat resistance.

[0006]

At present, as this adhesive tape, a polyimide film coated with epoxy thermosetting adhesive on both sides is used. However, when this epoxy resin is used for an adhesive tape for LOC, for example, NIKKEI MICRODEVICES 1989 9
As described in the monthly issue, etc., the gas generated during curing contaminates the metal surface of the substrate, resulting in problems such as reduced adhesive strength and package cracks.

Further, the adhesive tape is required to have a characteristic that parts can be joined (laminated) at a low temperature. That is, when bonding (lamination) with a component such as Cu at a temperature exceeding 300 ° C., Cu is oxidized and properties such as adhesive strength are deteriorated. Therefore, bonding (lamination) between components at a low temperature of 300 ° C. or less What is needed is an adhesive that can.

Under these circumstances, recently, a method has been studied in which a thermoplastic adhesive is used to suppress the gas generated during curing and to enable low temperature lamination.

Conventionally, thermoplastic adhesives (so-called hot melt adhesives) have been widely used in various fields because they can be easily bonded by simply heating and pressurizing the adherends together and can be used immediately without curing. Is well known.
For example, the field of bookbinding, wrapping paper containers, woodworking / plywood, shoes / assemblers, etc. As these base polymers, various ones such as ethylene-vinyl acetate, polyamide, polyester, polycarbonate, polyvinyl acetal, etc. are used depending on the use and purpose.

However, since adhesive tapes for LOC, heat spreaders, etc. are required to have a characteristic that the adhesive strength does not decrease at high temperature during solder reflow or resin sealing, these thermoplastic adhesives (hot melt adhesive)
The adhesive material obtained by coating the polyimide resin film on the polyimide resin film cannot be used in the field of semiconductor mounting because of insufficient heat resistance. The reason for this is that when a normal thermoplastic adhesive exceeds the temperature at which parts are joined (laminated), the adhesive plasticizes and loses its adhesive strength. In other words, it was impossible to perform solder reflow or resin encapsulation at a temperature higher than the joining (lamination) temperature of parts.

In view of the above-mentioned drawbacks of the prior art, the present invention was devised by specifying an adhesive layer and a heat-resistant resin layer, and its purpose is to:
Despite the use of a thermoplastic resin, the parts can be joined (laminated) at low temperature, and the adhesive strength does not decrease at high temperature during solder reflow or resin encapsulation. It is an object of the present invention to provide a high-performance heat-resistant adhesive material having a very small amount of gas generated upon heating and excellent adhesiveness, chemical resistance and dimensional stability.

[0012]

The object of the present invention is as follows.
A heat-resistant adhesive material having a thermoplastic heat-resistant adhesive layer A on at least one surface of a heat-resistant resin layer B, wherein the thickness of the thermoplastic heat-resistant adhesive layer A is 0.1 μm or more and 15 μm or less, and This is achieved by a heat-resistant adhesive material characterized in that the elastic modulus of the thermoplastic heat-resistant adhesive layer A at 200 ° C. is 10 ⁶ dyn / cm ² or more and 10 ⁹ dyn / cm ² or less.

That is, conventionally, the adhesive layer formed on at least one surface of the heat-resistant resin layer had a large thickness of about 20 μm.
The object of the present invention is achieved by using a material that has a specific elastic modulus and is as thin as m or more and 15 μm or less.

The thermoplastic heat-resistant adhesive layer A in the heat-resistant adhesive material of the present invention has an elastic modulus at 200 ° C. of 10 ⁶ dyn /
It is important that it is not less than cm ^{2 and not} more than 10 ⁹ dyn / cm ² . More preferably, it is 5 × 10 ⁷ dyn / cm ² or more and 5 × 10 ⁸ dyn / cm ² or less. When the elastic modulus at 200 ℃ exceeds 10 ⁹ dyn / cm ² , when using a heat resistant adhesive material as double-sided adhesive tape for LOC, for example, the temperature at which it can be laminated with the lead frame exceeds 300 ℃. Therefore, for example, when laminated with a copper-based metal for a heat spreader, the metal is oxidized and the adhesive strength is reduced. Further, if it is less than 10 ⁷ dyn / cm ² , the adhesive strength is largely reduced during solder reflow.

The thermoplastic heat-resistant adhesive layer A is coated on at least one surface of the heat-resistant resin layer B, and it is important that its thickness is 0.1 μm or more and 15 μm or less.
More preferably 0.5 μm or more and 12 μm or less,
When performing wire bonding using ultrasonic waves together, it is preferable that the adhesive strength be as thin as possible within a range satisfying a practical level. If it exceeds 15 μm, the heating efficiency by ultrasonic waves during wire bonding decreases. 0.1
If it is less than μm, the adhesive force cannot be secured.

The glass transition point of the thermoplastic heat-resistant adhesive layer A is preferably 50 ° C. or higher and 200 ° C. or lower. When the glass transition point is lower than 50 ° C., the temperature at which bonding (lamination) is possible is low, but the adhesive strength is largely reduced during solder reflow or at the resin sealing temperature, which is not preferable. Further, when the temperature exceeds 200 ° C, the temperature at which bonding (lamination) is possible becomes 300 ° C or more, which is not preferable.

Examples of the material of the thermoplastic heat-resistant adhesive layer A include a polyimide resin, a polyamide resin, a polyamideimide resin, and a polyethersulfone resin, but from the viewpoint of heat resistance, the polyimide resin is used. Is preferred. Furthermore, it is preferable that the polyimide resin is a thin film obtained by imidizing a polyamic acid composed of a diamine component containing 5 mol% or more of a siloxane-based diamine and an aromatic tetracarboxylic acid.

Aromatic tetracarboxylic acids include 3,3
′, 4,4′-Benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyl tetracarboxylic dianhydride , Pyromellitic dianhydride, 3,3
′, 4,4′-biphenyltetracarboxylic dianhydride,
2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 2,2-bis (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-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2, 7,8-phenanthrene tetracarboxylic acid dianhydride or the like is used. These may be used alone or in combination of two or more.

The diamine component is preferably a diamine component containing 5 mol% or more of a siloxane-based diamine as described above. More preferably 10 mol% or more and 96 mol% or less, and further preferably 50 mol% or more 94.
It is not more than mol%.

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

[0021]

[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 Each of which is the same or different and represents a lower alkyl group, a phenyl group or a phenoxy group), specific examples of those 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-1,5bis (4-aminobutyl) trisiloxane,
1,1,5,5-tetraphenyl-3,3-dimethoxy-1,5bis (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,
1,3,3,5,5-hexapropyl-1,5-bis (3-aminopropyl) trisiloxane and the like can be mentioned.

These siloxane-based diamines may be used alone or in admixture of two or more. Further, as the diamine component other than the siloxane-based diamine, a conventionally known diamine component can be used in combination.

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 and may be appropriately selected depending on the coating apparatus, the coating thickness, and the like.

The heat resistant resin layer B preferably has an elastic modulus at 250 ° C. in the range of 10 ⁸ dyn / cm ² or more and 10 ¹⁰ dyn / cm ² or less. If the elastic modulus at 250 ° C is less than 10 ⁸ dyn / cm ² , the heat resistance is insufficient. For example, when used as an adhesive tape for LOC, the process of wire bonding the IC chip and the lead frame while applying ultrasonic waves. In this case, the resin softens and causes defective bonding, which is not preferable. When it exceeds 10 ¹⁰ dyn / cm ² , the gap between the thermoplastic heat-resistant adhesive layer A and the adherend is several μm
If there is a foreign substance such as a silicon wafer powder of about 15 μm that cannot be removed by washing, there is no buffering effect of “wrapping” the foreign substance, which is apt to cause a problem of adhesion failure, which is not preferable.

As examples of the heat resistant resin layer B, polyphenylene sulfide resin, polyether ether ketone resin, polyimide resin, polyaramid resin, polyamideimide resin, polyetherimide resin, polyparabanic acid resin, polysulfone resin. , And thermosetting or thermoplastic resins such as epoxy resin, but polyphenylene sulfide resin, polyimide resin, polyaramid resin, etc. are preferable from the viewpoint of water absorption, dimensional stability, heat resistance, adhesiveness, etc. . Inorganic and organic fillers may be added to these resins as needed.

Further, the heat-resistant resin layer B may be used alone or as a laminate of the above resins, if necessary.

Further, these resins are preferably subjected to surface treatment such as known adhesion improvement such as corona discharge, low temperature plasma and resin coating.

For example, as a method of low-temperature plasma treatment performed under reduced pressure, a substrate to be treated is set in an internal electrode type discharge treatment device having a counter electrode composed of a drum-shaped electrode and a plurality of rod-shaped electrodes, and the treatment is carried out. 0.01 to 10 gas
r, preferably 0.02 to 1 Torr, and a high voltage of direct current or alternating current is applied between the electrodes to cause discharge, plasma of the gas is generated, and the base material surface is exposed to the plasma for treatment. Good. 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.

The heat-resistant adhesive material of the present invention is
It is used by laminating on one side or both sides of a heat resistant resin film. Examples of the heat resistant resin film include polyphenylene sulfide resin, polyether ether ketone resin, polyimide resin, polyaramid resin, polyamideimide resin, polyetherimide resin, polyparabanic acid resin, polysulfone resin, and fluorine. A known film such as a system resin can be used. As a matter of course, like the heat-resistant resin layer B described above, these resins are preferably subjected to surface treatment such as corona discharge, low temperature plasma, resin coating, and other well-known adhesion improvement.

The heat-resistant adhesive material of the present invention has a heating temperature of 10
It is preferable that the amount of gas generated at 0 to 300 ° C. satisfies the condition of 500 ppm or less. More preferably 2
It is 50 ppm or less, more preferably 100 ppm or less. The smaller the amount of generated gas, the smaller the amount of foaming when bonded to a metal foil, a heat resistant resin or the like.

The heating temperature of the heat-resistant adhesive material is 100 to
The amount of gas generated at 300 ° C. is a DT / DTG-MS method TG: Thermogravimetoric Analysis described later for the sample of the heat-resistant adhesive material.
(Thermogravimetric analysis) DTG: Derivative Thermogravimetoric Analysis
(Differential Thermogravimetric Analysis) MS: Mass Spectorometory
(Mass spectrometry) ”.

Next, as a specific example of the heat-resistant adhesive material of the present invention, a method for producing an example based on a biaxially oriented poly-p-polyphenylene sulfide resin film will be described below.

That is, a solvent solution containing the above polyamic acid varnish in an amount of 5 to 40% by weight is applied onto a polyphenylene sulfide resin film which has been subjected to a low temperature plasma treatment so that the film thickness after drying becomes 0.1 μm or more and 15 μm or less. Examples of the coating method include a roll coater, a knife coater, a hermetic coater, a comma coater and a doctor blade float coater.

Next, the solvent of the solution applied to the heat resistant resin film as described above is usually continuously or intermittently heated at a temperature of about 60 ° C. to about 190 ° C. for 10 to 60 minutes, and then necessary. Depending on the case, heat treatment for imidization is performed. 18 as the heat treatment for imidization
It is preferable to perform heat treatment in the range of 0 to 300 ° C. for about 0.5 to 15 minutes.

The elastic modulus of the thermoplastic heat-resistant adhesive layer A of the heat-resistant adhesive material thus produced, the glass transition point,
The elastic modulus of the heat resistant resin layer B can be measured by scraping off the adhesive layer, the resin layer and the like and analyzing them.

As a part of the use examples of the heat resistant adhesive material according to the present invention, lamination of heat resistant resin films, lamination with metal, for example, flexible printed circuit board laminated with copper foil, carrier tape for TAB and lead frame fixing There are various materials such as lead frame peripheral materials such as adhesive tape for use, adhesive tape for LOC and adhesive tape for heat spreader.

As a specific example, when used in a double-sided adhesive tape for LOC, after slitting the product of the present invention to the intended width, after removing the protective film on the thermoplastic heat-resistant adhesive to remove the adsorbed moisture, Overlay with lead frame 1
Heat compression bonding at a temperature of 50 ° C to 300 ° C, and further I
The C chip may be adhesively fixed. In order to improve the adhesive strength, it is preferable to further perform heat curing. Pressure bonding temperature, pressure and heat curing conditions are resin composition, film thickness,
It may be appropriately selected depending on the situation. Further, the method of thermocompression bonding may be preferably selected depending on the manufacturing process such as heat press or heating roll.

[0040]

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 elastic modulus, the amount of gas generated during heating, the adhesive force, the film thickness, and the wire bonding property are evaluated and measured by the following methods, respectively.

[Elastic Modulus] Two samples (4 mm × 40 mm) were used.
It was measured at 3 ° C. and 50% RH after adjusting for 24 hours or more.

The measuring machine and measuring conditions are as follows.

Measuring instrument; RHEO VIBRON D
DV-II-EA [manufactured by ORIENTEC Co., Ltd.] Measurement temperature: room temperature to 280 ° C (measurement temperature interval; 2 ° C) Drive frequency: 110 Hz [Generated gas amount] Approximately 100 samples having an imidized thin film
After weighing mg with a precision scientific balance, it was measured by the DT / DTG-MS method.

The DT / 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 measuring device manufactured by Shimadzu Corporation Data processing: Data processing system manufactured by Toray Research Center "THADAP-TGMS" 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 400 ° C was measured, and the total amount of evolved gas from 150 ° C to 300 ° C was obtained.

[Adhesive Strength] According to JIS C-6481, a sample having a width of 2 mm was peeled at 90 ° and measured with a tensilon at a pulling speed of 50 mm / min. Practically 0.8
Adhesive force of kg / cm or more is required.

[Film Thickness] The thicknesses of the base film, the heat resistant resin layer and the thermoplastic heat resistant adhesive layer were measured by the following apparatus.

Measuring instrument: Surface roughness profile measuring instrument "SURFCOM 1500A" manufactured by Tokyo Seimitsu Co., Ltd. (Measurement accuracy; nm to μm) [Wire bonding property] Gold on the lead frame (42 alloy) after the second bonding The state of line collapse was observed with an optical microscope.

Testing machine: NTC BONDER WA-1472
Bonding conditions manufactured by KAIJI ELECTRIC CO., LTD. Substrate heating temperature: 250 ° C Ultrasonic frequency: 60kHz (5W) Gold wire diameter: 30μm Varnish synthesis [Varnish A] Thermometer, stirrer, reflux condenser and dry N ₂ inlet In a 300 ml four-necked flask equipped with the above, 146 g of N, N-dimethylacetamide was placed in a reactor, and 14.0 g (90 mol%) of bis (3-aminopropyl) tetramethyldisiloxane and 0.68 g of p-phenylenediamine under a nitrogen stream. After dissolving (10 mol%), 20.3 g (100 mol%) of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride was added,
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 A.

The varnish A was coated on a copper foil (35 μm) mirror surface with a bar coater so that the film thickness after drying was about 20 μm, dried at 80 ° C. for 10 minutes, and further dried at 150 ° C. for 10 minutes. Heat treatment was performed at 250 ° C. for 30 minutes. After that, the copper foil was removed by etching, washed with water, and the amount of generated gas in the dried film was measured and found to be 60 ppm or less.
The elastic modulus at 200 ° C. was 2 × 10 ⁸ dyn / cm ² . The glass transition point was 92 ° C.

[Varnish B] 146 g of N, N-dimethylacetamide was placed in a 300 ml four-necked flask equipped with a thermometer, a stirrer, a reflux condenser, and a dry N ₂ inlet, and bis (3-aminopropyl) tetra was added under a nitrogen stream. 3.73 g (30 mol%) of methyldisiloxane and 4,4
′ -Diaminodiphenyl ether 10.30 g (70 m
ol%), and then 16.11 g (10%) of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride.
0 mol%) was added and 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 B.

The varnish B was coated on a copper foil (35 μm) mirror surface with a bar coater so that the film thickness after drying was about 20 μm, followed by drying at 80 ° C. for 10 minutes, and further at 150 ° C. for 10 minutes. Heat treatment was performed at 250 ° C. for 30 minutes. After that, the copper foil was removed by etching, washed with water, and the amount of generated gas in the dried film was measured and found to be 60 ppm or less.
The elastic modulus at 250 ° C. was 2 × 10 ⁹ dyn / cm ² .

Example 1 Varnish B was applied to a polyimide resin film of 50 μm (“UPILEX” 50S (manufactured by Ube Industries, Ltd.)) which had been subjected to low-temperature plasma treatment in an Ar atmosphere in advance, and the film thickness after drying was 2.
The coating was applied to 0 μm, dried at 80 ° C. for 10 minutes, further dried at 130 ° C. for 10 minutes, and further dried at 160 ° C. for 15 minutes. The above-mentioned varnish A was coated on the coated product so that the film thickness after drying was 3 μm, dried at 80 ° C. for 10 minutes, further dried at 150 ° C. for 10 minutes, and further 25 for imidization.
Heat treatment was performed at 0 ° C. for 30 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 30 mm, superposed with 42 alloy used as a metal foil for lead frames, and pressed at a surface temperature of 220 ° C. under a pressure of 7 kg / cm ² , and a heating time of 5 seconds. Pasted together. No foaming was observed in the laminated product, and the adhesive strength was 1.6 kg / cm. The crushability of the gold wire after wire bonding was also good. The adhesive tape for LOC, the adhesive tape for heat spreader, and the adhesive tape for fixing the lead frame sufficiently satisfied the practical level.

Example 2 Varnish A was subjected to low temperature plasma treatment in the same manner as in Example 1 70
μm polyphenylene sulfide resin film (“Torelina” manufactured by Toray Industries, Inc., elastic modulus at 250 ° C .; 3 × 10 ⁹ dy
n / cm ² ) so that the film thickness after drying is 1 μm.
It was dried at 0 ° C. for 10 minutes, further dried at 120 ° C. for 10 minutes, further dried at 150 ° C. for 15 minutes, and further heat-treated at 210 ° C. for 5 minutes. The generated gas amount of the film was measured and found to be 60 ppm or less.

The resin-coated surface of the above-prepared film and 200
A pressure of 30 kg / cm is obtained by superimposing 42 μm lead frame alloy and heating the surface temperature to 250 ° C.
² , pasted together with a heating time of 5 seconds. Adhesion is 1.7kg
A bonded product having a strong adhesive strength was obtained. The crushability of the gold wire after wire bonding was also good. L
Adhesive tape for OC, adhesive tape for heat spreader,
As an adhesive tape for fixing a lead frame, it was sufficiently satisfactory for practical use.

Example 3 Varnish A was treated with low temperature plasma in the same manner as in Example 1 70
μm polyphenylene sulfide resin film (“Torelina” manufactured by Toray Industries, Inc., elastic modulus at 250 ° C .; 3 × 10 ⁹ dyn /
cm ² ), so that the film thickness after drying is 10 μm, dried at 80 ° C. for 10 minutes, further dried at 120 ° C. for 10 minutes, further dried at 150 ° C. for 15 minutes, and further heated at 220 ° C. for 5 minutes.
Heat treatment was performed for a minute. The amount of generated gas in the film was measured and found to be 100 ppm or less.

The resin-coated surface of the above-prepared film and 200
The pressure was 7 kg / cm ² with a heating press that was superposed on a 42 μm lead frame alloy and heated to a surface temperature of 220 ° C.
The pieces were pasted together with a heating time of 5 seconds. Adhesive force is 1.5kg / c
m, and a bonded product having a strong adhesive force was obtained. The crushability of the gold wire after wire bonding was also good. LO
As an adhesive tape for C, an adhesive tape for heat spreader, and an adhesive tape for fixing a lead frame, they were sufficiently satisfactory for practical use.

Comparative Example 1 Varnish A was treated with low temperature plasma in the same manner as in Example 1 70
μm polyphenylene sulfide resin film (“Torelina” manufactured by Toray Industries, Inc., elastic modulus at 250 ° C .; 3 × 10 ⁹ dy
n / cm ² ) so that the film thickness after drying is 20 μm, and is dried at 80 ° C. for 10 minutes, further at 120 ° C. for 10 minutes, further at 150 ° C. for 15 minutes, and at 210 ° C. 5
Heat treatment was performed for minutes. The generated gas amount of the film was measured and found to be 60 ppm or less.

The resin-coated surface of the above-prepared film and 200
A pressure of 30 kg / cm is obtained by superimposing 42 μm lead frame alloy and heating the surface temperature to 250 ° C.
² , pasted together with a heating time of 5 seconds. Adhesion is 1.7kg
Although a bonded product having a strong adhesive strength was obtained, the crushing of the gold wire after wire bonding was poor and the LOC
It was a level that could not be used as an adhesive tape for use, an adhesive tape for a heat spreader, or an adhesive tape for fixing a lead frame.

[0061]

Since the present invention is constructed as described above,
It can adhere to metals, heat resistant resins, etc. at temperatures of 300 ° C or less, and it does not lose its adhesive strength at high temperatures, does not cause foaming after lamination, and has excellent adhesiveness, heat resistance, electrical properties, and chemical resistance. An excellent heat resistant adhesive material can be reliably obtained.

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Claims (12)

[Claims] 1. A heat-resistant adhesive material having a thermoplastic heat-resistant adhesive layer A on at least one surface of a heat-resistant resin layer B, wherein the thermoplastic heat-resistant adhesive layer A has a thickness of 0.1 μm or more and 15 μm or less. And the thermoplastic heat-resistant adhesive layer A has an elastic modulus at 200 ° C. of 10 ⁶ dyn / cm ² or more and 10 ⁹ dyn /
A heat-resistant adhesive material characterized by having a size of cm ² or less. 2. The heat-resistant adhesive material according to claim 1, wherein the glass transition point of the thermoplastic heat-resistant adhesive layer A is 50 ° C. or higher and 200 ° C. or lower. 3. The heat resistant adhesive material according to claim 1, wherein the thermoplastic heat resistant adhesive layer A is a polyimide resin. 4. The polyimide resin comprises a thin film formed by imidizing a polyamic acid obtained by reacting a diamine component containing 5 mol% or more of a siloxane-based diamine with an aromatic tetracarboxylic acid. The heat-resistant adhesive material according to item 3. 5. The heat resistant adhesive material according to claim 4, wherein the diamine component contains 50 mol% or more of a siloxane-based diamine. 6. The heat-resistant adhesive material according to claim 4, wherein the siloxane-based diamine is represented by the following general formula [I]. [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.) 7. The heat-resistant adhesive material according to claim 1, wherein the heat-resistant resin layer B has an elastic modulus at 250 ° C. of 10 ⁸ dyn / cm ² or more and 10 ¹⁰ dyn / cm ² or less. 8. The heat resistant adhesive material according to claim 1, wherein the heat resistant resin layer B is a polyphenylene sulfide resin, a polyimide resin or a polyaramid resin. 9. 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 300 ° C. or lower is 500 ppm or less. 10. A heat resistant adhesive material comprising the heat resistant adhesive material according to claim 1 laminated on one side or both sides of a heat resistant resin film. 11. The heat resistant adhesive material according to claim 1, wherein the heat resistant adhesive material is a lead frame peripheral material. 12. The heat-resistant adhesive material according to claim 11, which is an adhesive tape for fixing a lead frame, an adhesive tape for a lead-on-chip or an adhesive tape for a heat spreader.