JP2003013033A - Adhesive resin composition and adhesive sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide both an adhesive resin composition having good preservation stability at normal temperature and capable of carrying out bonding with good heat resistance (adhesive strength) in a short time even at relatively low temperatures and an adhesive sheet using the adhesive resin composition. SOLUTION: This adhesive resin composition is characterized by comprising a polyimide resin soluble in solvents and a bisalkenyl-substituted nadimide.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an adhesive resin composition and an adhesive sheet. The adhesive resin composition and the adhesive sheet of the present invention are used, for example, for fixing electric and electronic parts such as semiconductor chips, substrates and lead frames.

[0002]

2. Description of the Related Art Heretofore, as an adhesive for fixing electric and electronic parts, a paste-like adhesive or a heat-resistant base material coated with an adhesive has been known. Examples of the adhesive used here include thermosetting resins such as epoxy resin type, acrylic resin type, and rubber-phenol resin type. However, since these adhesives require a high temperature and a long time for heating and curing, they are inferior in workability for bonding. Further, these adhesives usually have to be stored at a low temperature of 5 ° C. or lower, and have various drawbacks such as complicated handling.

On the other hand, a hot-melt type film adhesive using a thermoplastic polyimide resin can be heat-bonded to an adherend in a short time. Such a polyimide-based adhesive does not need to be heat-cured after bonding, and has no problem in storage stability at room temperature. However, since the polyimide-based adhesive has a high glass transition temperature, a high temperature is required for processing, and there is a high possibility that the adherend will be thermally damaged. On the other hand, when an adhesive having a low glass transition temperature is used, the low-temperature processability is excellent, but the heat resistance (adhesive strength) is low and the reliability is significantly reduced.

[0004]

DISCLOSURE OF THE INVENTION The present inventors have found that the adhesive resin composition has good storage stability at room temperature and can be bonded with good heat resistance (adhesive strength) in a short time even at a relatively low temperature. Another object is to provide an adhesive sheet using the adhesive resin composition.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that the above objects can be achieved by the adhesive resin composition and adhesive sheet shown below, It came to completion.

That is, the present invention relates to a solvent-soluble polyimide resin and the following general formula (1):

[Chemical 2] (Wherein, R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and R ³ represents a diamine residue). And an adhesive resin composition.

In the above adhesive resin composition of the present invention, a solvent-soluble type is used as the polyimide resin, which has a relatively low glass transition temperature and is 200 ° C. or less (for example, 50
Even at a relatively low temperature (about 150 ° C.), good adhesion can be achieved in a short time, and package cracks are less likely to occur. Further, the adhesive resin composition of the present invention contains bisalkenyl-substituted nadiimide as a curing agent, and thus has high heat resistance (adhesive strength) after curing. In addition, the storage stability of the polyimide-based adhesive resin composition is not impaired and is good due to the addition of the salkenyl-substituted nadiimide.

In the adhesive resin composition, it is preferable that 1 to 100 parts by weight of a bisalkenyl-substituted nadimide is mixed with 100 parts by weight of a polyimide resin.

The mixing ratio of the bisalkenyl-substituted nadiimide compound to the polyimide resin is not particularly limited and is appropriately determined in consideration of the processability and adhesiveness of the adhesive sheet, but the addition effect of the bisalkenyl-substituted nadiimide compound is effective. To achieve this, the amount of the polybisalkenyl-substituted nadiimide compound is 1 part by weight or more, preferably 5 parts by weight or more, more preferably 10 parts by weight or more, relative to 100 parts by weight of the polyimide resin. On the other hand, when the amount of the polybisalkenyl-substituted nadimide compound is increased, the strength of the adhesive sheet tends to be low. Therefore, the amount of the polybisalkenyl-substituted nadimide compound is 100 parts by weight based on 100 parts by weight of the polyimide resin. The amount is preferably 80 parts by weight or less, more preferably 60 parts by weight or less.

In order to shorten the curing time of the adhesive composition, the adhesive resin composition may further contain a bisalkenyl-substituted nadimide curing catalyst.

The amount of the curing catalyst blended is not particularly limited, but is 0.01 to 30 parts by weight based on 100 parts by weight of the total amount of the polyimide resin and the bisalkenyl-substituted nadiimide. The compounding amount of the curing catalyst is preferably 0.5 to 5 parts by weight.

The present invention also relates to an adhesive sheet formed of the above adhesive resin composition. The present invention also relates to an adhesive sheet characterized by having an adhesive layer formed of the adhesive resin composition on at least one surface of a support.

Further, the present invention relates to a method of manufacturing an electronic component, characterized in that an electronic component member is assembled using the adhesive sheet, and an electronic component assembled by the manufacturing method.

The adhesive sheet using the adhesive resin composition of the present invention has excellent storage stability and can be stored at room temperature for a long period of time. In addition, low temperature adhesion is possible and workability is improved. Since it has excellent heat resistance (adhesive strength) and excellent adhesiveness to metals, it is used for fixing treatment of electric and electronic parts such as microelectronic materials and semiconductor mounting materials, and has an extremely high industrial utility value.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below.

The polyimide resin which is the main component of the adhesive resin composition of the present invention is an imidized product obtained by a dehydration condensation reaction of a tetracarboxylic dianhydride and a diamine component by a conventionally known method, and is used as a solvent. It is soluble.

As the tetracarboxylic dianhydride,
3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic acid Acid dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride and the like can be mentioned, and one of these is These may be used alone or in admixture of two or more.

The diamine component is 4,4'-diaminodiphenyl sulfide, 2,2-bis [4- (p-aminophenoxy) phenyl] propane, 2,2-bis [3- (p-aminophenoxy) phenyl. ]propane,
2,2-bis [4- (p-aminophenylthioether) phenyl] propane, 2,2-bis [3- (p-aminophenylthioether) phenyl] propane, 4,
4'-bis (p-aminophenoxy) diphenyl sulfone, 3,3'-bis (p-aminophenoxy) diphenyl sulfone, 3,4'-bis (p-aminophenoxy)
Diphenyl sulfone, 4,4'-bis (p-aminophenoxy) diphenyl ether, 3,3'-bis (p-aminophenoxy) diphenyl ether, 3,4'-bis (p-aminophenoxy) diphenyl ether, 4,
4'-bis (p-aminophenoxy) diphenyl sulfide, 3,3'-bis (p-aminophenoxy) diphenyl sulfide, 3,4'-bis (p-aminophenoxy) diphenyl sulfide, 4,4'-bis ( p-aminophenyl thioether) diphenyl sulfone, 3,
3'-bis (p-aminophenyl thioether) diphenyl sulfone, 3,4'-bis (p-aminophenyl thioether) diphenyl sulfone, 4,4'-bis (p
-Aminophenyl thioether) diphenyl ether,
3,3'-bis (p-aminophenyl thioether) diphenyl ether, 3,4'-bis (p-aminophenyl thioether) diphenyl ether, 4,4'-bis (p-aminophenyl thioether) diphenyl sulfide, 3,3 ' -Bis (p-aminophenyl thioether) diphenyl sulfide, 3,4'-bis (p-aminophenyl thioether) diphenyl sulfide, 4,
4'-bis (p-aminophenoxy) diphenyl, 3,
3'-bis (p-aminophenoxy) diphenyl, 3,
4'-bis (p-aminophenoxy) diphenyl, 4,
4'-bis (p-aminophenoxy) benzophenone,
3,3'-bis (p-aminophenoxy) benzophenone, 3,4'-bis (p-aminophenoxy) benzophenone, 4,4'-bis (p-aminophenylthioether) diphenyl, 3,3'-bis ( p-aminophenyl thioether) diphenyl, 3,4'-bis (p-aminophenyl thioether) diphenyl, 4,4'-bis (p-aminophenyl thioether) benzophenone, 3,3'-bis (p-aminophenyl thioether) ) Benzophenone, 3,4'-bis (p-aminophenylthioether) benzophenone, 1,4-bis (p
-Aminophenylthioether) benzene, 1,3-bis (p-aminophenylthioether) benzene, 4,
4 '-(p-phenylenediisopropylidene) dianiline, 4,4'-(m-phenylenediisopropylidene)
Examples thereof include dianiline and 2,2-bis [4- (p-aminophenoxy) phenyl] hexafluoropropane. One of these may be used alone or two or more thereof may be used in combination.

The polyimide resin may be used in combination with other tetracarboxylic dianhydride and diamine components as long as they are soluble in the solvent. Examples of other tetracarboxylic dianhydrides that can be used in combination include aromatic tetracarboxylic acid such as pyromellitic dianhydride and naphthalenetetracarboxylic dianhydride. Other diamines that can be used in combination include 4,4'-diaminodiphenyl ether and 3,4 '.
-Diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-
Diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4 '
-Diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,
Examples include 4'-diaminodiphenyl, 3,4'-diaminodiphenyl, 3,3'-diaminodiphenyl, m-phenylenediamine, p-phenylenediamine and the like.

The solvent-soluble polyimide resin is a polyimide resin obtained by combining the above-mentioned tetracarboxylic dianhydride component and diamine component with each other at room temperature.
A resin that can be dissolved at a resin concentration of 1% by weight or more, preferably 5% by weight or more. Examples of the solvent include N, N-dimethylformamide, N, N-dimethylacetamide,
Amide solvents such as N, N-diethylacetamide and N-methyl-2-pyrrolidone, sulfur-containing solvents such as dimethyl sulfoxide and dimethyl sulfone, phenolic solvents such as phenol, cresol and xylenol, acetone, tetrahydrofuran, pyridine and tetramethyl. Urea 1,
Examples include 3-dioxane, 1,4-dioxane, dichloromethane and the like.

Such a polyimide resin is available as a commercial product in the form of a varnish dissolved in a solvent. For example, Rikacoat PN-20 from Shin Nippon Rika Co., Ltd. <is from Ricacoat EN-20, BI Engineering Co., Ltd. It is available under the trade name Cupiron.

The bisalkenyl-substituted nadiimide represented by the general formula (1) used as a curing agent in the adhesive resin composition of the present invention is described in JP-A-59-80662.
Japanese Patent Laid-Open No. 60-178862 and Japanese Patent Laid-Open No. 61-88662.
Any of the known bisalkenyl-substituted nadiimides described in JP-A-18761 and JP-A-63-170358 can be used. The bisalkenyl-substituted nadimide can generally be prepared by reacting the corresponding alkenyl-substituted nadic acid anhydride with a diamine.

As such a bisalkenyl-substituted nadiimide, the diamine is an aliphatic diamine, N, N '.
-Ethylene-bis (allylbicyclo [2,2,1] hept-5-ene-2,3-dicarboximide), N,
N'-trimethylene-bis (allylbicyclo [2,2,2
1] Hept-5-ene-2,3-dicarboximide), N, N'-hexamethylene-bis (allylbicyclo [2,2,1] hept-5-ene-2,3-dicarboxyl) Imido), N, N′-dodecamethylene-bis (allylbicyclo [2,2,1] hept-5-ene-2,3-
Bisalkenyl-substituted nadiimides such as dicarboximide).

As another bisalkenyl-substituted nadiimide, the diamine is an aromatic diamine, N, N '.
-P-phenylene-bis (allylbicycloro [2,2,2
1] Hept-5-ene-2,3-dicarboximide), N, N'-m-phenylene-bis (allylbicyclo [2,2,1] hept-5-ene-2,3-di) Carboximide), bis {4- (allylbicyclo [2,2,2
1] hept-5-ene-2,3-dicarboximide)
Examples include phenyl} methane, bis {4- (allylbicyclolo [2,2,1] hept-5-ene-2,3-dicarboximido) phenyl} ether, and the like. Also,
The diamine is a phenylene alkylene diamine, N,
N'-p-xylylene-bis (allylbicyclo [2,2
2,1] Hept-5-ene-2,3-dicarboximide), N, N'-m-phenylene-bis (allylbicyclo [2,2,1] hept-5-ene-2,3- Dicarboximide) and the like. These bisalkenyl-substituted nadiimides can be used alone or in combination.

Examples of the curing catalyst include organic peroxides, onium salts, cation catalysts, organic group-containing metal compounds and the like, and at least one selected from these may be blended and used.

As the organic peroxide, for example, di-t
-Butyl peroxide, di-t-amyl peroxide,
t-butyl cumyl peroxide, diacetyl peroxide, dipropionyl peroxide, diiso-butyryl peroxide, benzoyl peroxide, peroxysuccinic acid, t-butyl hydroperoxide, cyclohexyl hydroperoxide, cumene hydroperoxide,
t-butylperoxybenzoate, t-butylperoxypivalate, 1,1-di-t-butylperoxycyclohexane, di- (t-butylperoxy) isophthalate, t-butylperoxymale And tert-butyl peroxyisopropyl carbonate, 2-di-t-butyl peroxybutane and the like.

Examples of onium salts include ammonium compounds, phosphonium compounds, arsonium compounds, stibonium compounds, oxonium compounds, sulfonium compounds, selenonium compounds, stannonium compounds, and iodonium compounds.

Specific examples of the ammonium compound include benzyltriethylammonium chloride, benzyltriethylammonium bromide. Phenyltrimethylammonium bromide, tetra-n-butylammonium chloride, tetra-n-butylammonium perchlorate, tetraethylammonium tetrafluoroborate, m-trifluoromethylphenyltrimethylammonium bromide, tetra-n-butylammonium trifluoromethanesulfonate, etc .; phosphonium Examples of the compound include methyltriphenylphosphonium iodide, methyltriphenylphosphonium bromide, benziltriphenylphosphonium chloride, tetraphenylphosphonium bromide, 3-bromopropyltriphenylphosphonium bromide, and the like; arsonium compounds include benzyldiphenyl Arsonium chloride, tetraphenylarsonium bromide, tetra-n-butyl Arsonium chloride, etc .; Styvonium compound, benzyltriphenylstibonium chloride, tetraphenylstibonium bromide, etc .; Oxonium compound, triphenyloxonium chloride, triphenyloxonium bromide, etc .; Sulfonium compound, triphenylsulfonium Tetrafluoroborate, triphenylsulfonium hexafluoroarsenate, tri (p-methoxyphenyl) sulfonium hexafluorophosphate, tri (p-tolyl) sulfonium tetrafluoroborate, dimethylphenacylsulfonium hexafluorophosphate, dimethylphenacylsulfonium tetrafluoroborate Etc .; as the selenonium compound, triphenylselenonium tetrafluoroborate , Triphenylselenonium hexafluoroarsenate, triphenylselenonium hexafluoroantimonate, p- (t-butylphenyl) diphenylselenonium hexafluoroarsenate, etc .; Stannonium compounds include triphenylstannonium chloride, triphenyl Stannonium bromide, tri-n-butylstannonium bromide, benzyldiphenylstannonium chloride, etc .; as iodonium compounds, diphenyliodonium chloride, diphenyliodonium bromide, diphenyliodonium perchlorate, diphenyliodonium tetrafluoroborate, iodonium hexa Fluoroarsenate, iodonium hexafluorophosphate,
Iodonium hexafluoroantimonate, (p-methoxyphenyl) phenyliodonium tetrafluoroborate, di (2-nitrophenyl) iodonium hexafluoroarsenate, di (p-tolyl) iodonium hexafluorophosphate, di (p-chlorophenyl) iodonium hexa Examples thereof include fluoroarsenate.

As the cation catalyst, for example, sulfuric acid,
Dimethyl sulfate, diethyl sulfate, pyridine sulfate, phosphoric acid, phosphorous acid, phenylphosphonic acid, phenylphosphinic acid, triethyl phosphate, dimethyl phosphate, phenyl phosphite, methanesulfonic acid, trifluoromethanesulfonic acid, m-xylene -4-sulfonic acid, p-xylene-
2-sulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, p-toluenesulfonic acid / triphenylamine complex, p-toluenesulfonic acid nitrobenzenesulfonic acid / pyridine complex, naphthalenesulfonic acid, methyl benzenesulfonic acid, p-toluene Ethyl sulfonate, etc.
An acid or a Bronsted acid which releases an acid, or an ester thereof, an amine complex; boron trichloride, boron trifluoride,
Boron trifluoride / ether complex, iron trichloride, tin tetrachloride, titanium tetrachloride, aluminum chloride, aluminum chloride / pyridine complex, aluminum bromide, zinc chloride, antimony pentachloride, etc., a halide showing Lewis acidity or its base. And the like.

As the organic group-containing metal compound, magnesium, zinc, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zirconium, molybdenum, ruthenium, rhodium, lanthanum, cerium,
Hafnium, transition elements such as tantalum or tungsten, preferably magnesium, zinc, vanadium, manganese, acetylacetone salts such as iron or cerium, carboxylates, metallocenes, alcoholates, chelate compounds or organometallic compounds, more preferably magnesium, zinc. Acetoneacetone salts or carboxylates of vanadium, manganese, iron or cerium.

The adhesive resin composition of the present invention is prepared by blending the above-mentioned solvent-soluble polyimide resin, bisalkenyl-substituted nadimide, and a curing catalyst, preferably within the above range. A fine inorganic filler may be blended within a range that does not impair the heat resistance. Further, various additives such as a leveling agent, a leveling agent, and a defoaming agent may be added as necessary to impart surface smoothness.

The adhesive resin composition of the present invention can be prepared by dissolving the polyimide resin soluble in the solvent and the alkenyl-substituted nadiimide compound in a common solvent and using it as a varnish. Molded into
It can be an adhesive sheet. Sheet thickness is 1 to 200
Although it is generally 0 μm, it is not limited to this and can be appropriately determined according to the purpose of adhesion. Further, the shape and size of the adhesive sheet can be appropriately determined according to the adherend such as the lead frame or the semiconductor chip.

In forming the adhesive sheet, conductivity is imparted, heat transfer is improved, elastic modulus is adjusted, and dimensional stability is improved.
Especially for the purpose of increasing the elastic modulus, for example, aluminum,
Metals or alloys such as copper, silver, gold, nickel, chromium, lead, tin, zinc, palladium, solder, alumina, silica,
If necessary, one kind or two or more kinds of various inorganic powders composed of magnesia, ceramics such as silicon nitride, and other carbons may be blended.

The drying temperature of the film after varnish coating is 10
The temperature is 0 to 300 ° C, preferably 120 to 200 ° C, and most preferably 130 to 180 ° C. If the drying temperature is lower than 100 ° C, the solvent may remain in the film. Further, at a high temperature exceeding 300 ° C., heat curing of the film may proceed.

Further, these films may be formed on a support. In order to produce a laminated adhesive sheet having such a constitution, a solution of the adhesive resin composition of the present invention may be applied onto a support, and a film formed in advance is laminated by pressing or the like. You may.

As the support, a metal foil, an insulating film, or a material whose surface is subjected to a release treatment with silicone, fluorine or the like can be used. As the metal foil, any of aluminum, copper, silver, gold, nickel, indium, chromium, lead, tin, zinc, palladium, iron, etc. is preferably used, and may be used alone or an alloy of a plurality of metals. May be. As the insulating film, various films may be used as long as they have heat resistance and chemical resistance such as polyimide, polyester and polyethylene terephthalate. The metal foil and the insulating film may be used alone, or a two-layer structure of both, that is, a two-layer base material such as metal foil / insulating film may be used. Examples of the two-layer base material include a copper / polyimide two-layer base material.

As the above-mentioned support, in order to impart easy peeling property, an acrylic pressure-sensitive adhesive to which an additive exhibiting easy peeling property by heating or ultraviolet irradiation is added can be used. As such a support, Riva Alpha (manufactured by Nitto Denko Co., Ltd.), which is a heat foaming peeling type, and ELEP holder (manufactured by Nitto Denko Co., Ltd.), which has a peeling function by ultraviolet curing, are commercially available. it can.

The adhesive sheet of the present invention is thermoset even by the heat treatment at a relatively low temperature and exhibits a strong adhesive force. The adhesive sheet has a long tape life and can be stored even at room temperature. The heat treatment can be performed by an appropriate method such as a heater, ultrasonic waves, or ultraviolet rays. Therefore, the adhesive sheet of the present invention can be preferably used for the adhesion treatment of various materials, and particularly the adhesion treatment of electric / electronic components represented by semiconductor chips and lead frames, which require highly reliable adhesion treatment. Preferred for surface protection.

[0039]

EXAMPLES The present invention will be described in more detail below with reference to examples and comparative examples. The properties of the obtained adhesive resin composition and adhesive sheet were measured as follows.

(Heat Resistance: Adhesive Strength) The adhesive sheets prepared in each of the examples and comparative examples were cut into strips having a width of 10 mm, and pressed under the following conditions; temperature: 150 ° C., pressure:
It was thermocompression bonded to the SUS304 plate at 3.92 MPa, time: 10 seconds. The thermocompression-bonded sample was left in a hot air oven at 250 ° C. for 2 hours and left at room temperature for 30 minutes, and then the adhesive force between the adhesive sheet and the SUS304 plate was measured by 90 ° peel (speed 50 mm / min).

Example 1 N, N'- was added to 100 parts by weight of solid content of polyimide varnish (New Japan Rika Co., Ltd., Ricacoat EN-20).
Hexamethylene-bis (allylbicyclo [2,2,1]
Hept-5-ene-2,3-dicarboximide) {Maruzen Petrochemical Co., Ltd., BANI-H, hereinafter BANI-
Abbreviated as H} 10 parts by weight was added and mixed uniformly to prepare a solution of the adhesive resin composition. This solution was applied to a polyethylene terephthalate film having a thickness of 75 μm,
30 μm in thickness by drying for 30 minutes with hot air at ℃
The adhesive layer of was formed to obtain the adhesive sheet of the present invention. Next, when the adhesiveness was evaluated using this adhesive sheet, the adhesive force was 13 N / cm. Also, when this adhesive sheet was left at room temperature for one month and the adhesive strength was measured in the same manner, no decrease in adhesiveness was observed.

Example 2 A solution of an adhesive resin composition was prepared and an adhesive sheet was prepared in the same manner as in Example 1 except that the amount of BANI-H used was changed to 60 parts by weight. did. When the adhesiveness was evaluated using this adhesive sheet, the adhesive force was 10 N / cm. Also, when this adhesive sheet was left at room temperature for one month and the adhesive strength was measured in the same manner, no decrease in adhesiveness was observed.

Example 3 In Example 1, instead of BANI-H, bis {4-
(Allylbicyclo [2,2,1] hept-5-ene-2
, 3-Dicarboximido) phenyl} methane (manufactured by Maruzen Petrochemical Co., Ltd., BANI-M) was used in the same manner as in Example 1 except that 20 parts by weight of the adhesive resin composition was prepared and bonded. A sheet was prepared. When the adhesiveness was evaluated using this adhesive sheet, the adhesive force was 12 N / cm.
Met. Also, when this adhesive sheet was left at room temperature for one month and the adhesive strength was measured in the same manner, no decrease in adhesiveness was observed.

Example 4 An adhesive resin was prepared in the same manner as in Example 1 except that 1 part by weight of p-toluenesulfonic acid was further added in preparing the solution of the adhesive resin composition. A solution of the composition was prepared and an adhesive sheet was prepared. Next, when the adhesiveness was evaluated using this adhesive sheet, the adhesive force was 11 N / cm. However, in (heat resistance: adhesive strength), the sample was cured at 200 ° C. in a hot air oven at 250 ° C. Also, when this adhesive sheet was left at room temperature for one month and the adhesive strength was measured in the same manner, no decrease in adhesiveness was observed.

Comparative Example 1 In Example 1, instead of BANI-H, an epoxy resin (Epicoat 828, Japan Epoxy Resin Co., Ltd.) was used.
A solution of an adhesive resin composition was prepared in the same manner as in Example 1 except that the above) was used, and an adhesive sheet was manufactured. When the adhesiveness of this adhesive sheet was evaluated, the adhesive force was 12 N / cm. Further, when the adhesive strength was measured in the same manner after leaving this adhesive sheet at room temperature for one month, the adhesive strength was lowered to 3 N / cm, and it was confirmed that the storage stability was low.

Comparative Example 2 A solution of an adhesive resin composition was prepared in the same manner as in Example 1 except that BANI-H was not added, and an adhesive sheet was prepared. When the adhesiveness of this adhesive sheet was evaluated, the adhesive force was 3 N / cm,
It was observed that the adhesion was low.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4J004 AA11 AA17 AB05 BA02 CA01                       CA08 CC02 CC03 FA05 FA08                 4J026 AB34 BA40 DB06 DB24 DB32                       GA07 GA08                 4J040 EH031 HC22 JA09 JB02                       KA14 KA23 LA06 LA08 NA20                       PA23

Claims (8)

[Claims] 1. A solvent-soluble polyimide resin and the following general formula (1): (Wherein, R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and R ³ represents a diamine residue). Adhesive resin composition. 2. With respect to 100 parts by weight of the polyimide resin,
The adhesive resin composition according to claim 1, wherein 1 to 100 parts by weight of the bisalkenyl-substituted nadimide is mixed. 3. The adhesive resin composition according to claim 1, further comprising a bisalkenyl-substituted nadimide curing catalyst. 4. The adhesive resin according to claim 3, wherein the compounding amount of the curing catalyst is 0.01 to 30 parts by weight based on 100 parts by weight of the total amount of the polyimide resin and the bisalkenyl-substituted nadimide. Composition. 5. An adhesive sheet formed from the adhesive resin composition according to claim 1. 6. The support according to claim 1, which is provided on at least one surface of the support.
An adhesive sheet having an adhesive layer formed from the adhesive resin composition according to any one of to 4. 7. A method of manufacturing an electronic component, which comprises assembling an electronic component member using the adhesive sheet according to claim 5. 8. An electronic component assembled by the manufacturing method according to claim 7.