JP2000053744A - Resin composition, adhesive, adhesive film, lead frame using the same and semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition capable of using for contact members of a semiconductor device, having heat resistance useful for fixing inner lead wire by including a copolymer obtained by reacting a tetracarboxylic acid dianhydride and diamine or the like and a specific polyether. SOLUTION: This resin composition is obtained by including the copolymer obtained by reacting (A) the tetracarboxylic acid dianhydride, (B) the diamine (e.g.; 1,2-diaminopropane or the like) or diisocyanate and (C) the polyether of formula R-Q1-O-(Q2-O-)p-Q3-R (Q1 to Q3 are each an 1-10C alkylene; R is OH or COOH; p is 0 to 100). The preferable amount of the component C in weight is 30 to 70% to the sum of component A, B and C. The component A including at least 50% of bisphenol A bistrimellitate dianhydride based on the gross of the component A is preferred.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition, an adhesive, an adhesive film which is used for an adhesive member of a semiconductor device and has heat resistance and is particularly suitable for fixing inner leads, a lead frame using the same, The present invention relates to a semiconductor device.

[0002]

2. Description of the Related Art Adhesive tapes used in semiconductor devices include lead fixing tapes, LOC tapes, die bond tapes, and the like. For example, the lead fixing tape fixes lead pins of a lead frame, and the lead frame itself or the semiconductor device. Used to improve overall productivity and reliability. Semiconductor devices, especially QFP (Quad Flat)
Conventionally, an adhesive tape in which a thermosetting resin adhesive is applied on a heat-resistant base film has been used as a lead fixing tape for holding down inner leads.

[0003]

However, since the conventional lead fixing tape uses a thermosetting resin for the adhesive layer as described above, the heat resistance is not sufficient, and a large amount of outgas is generated by heat during wire bonding. At that time, there were problems such as clogging the capillary and wire bond failure due to lead contamination. The present invention solves such a problem and provides an adhesive member that improves wire bondability at high temperatures, particularly a heat-resistant adhesive suitable for a lead fixing tape, a film adhesive, a lead frame and a semiconductor device using the same. To provide.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies on the relationship between various resins and their compositions, heat resistance and adhesiveness. The present inventors have found that a lead fixing tape can be obtained, and have completed the present invention. That is, the present invention is the following resin composition, adhesive, adhesive film, lead frame and semiconductor device using the same. (1) A resin composition containing a copolymer obtained by reacting (a) tetracarboxylic dianhydride, (b) diamine or diisocyanate, and (c) a polyether compound represented by the formula (1). R-Q1-O- [Q2-O-] p-Q3-R (1) (Q1, Q2 and Q3 are alkylene having 1 to 10 carbon atoms;
R is OH or COOH, and p is an integer of 0-100. (2) The resin composition according to the above (1), wherein the weight of (c) is 30 to 70% based on the total weight of (a) + (b) + (c). (3) Tetracarboxylic dianhydride (a) is bisphenol A bistrimellitate dianhydride, 2,2-bis [4
-(3,4-dicarboxy) phenyl] propane dianhydride and benzophenone tetracarboxylic dianhydride selected from the group consisting of at least 50 mol% of the total amount of tetracarboxylic dianhydrides. The resin composition according to any one of the above (1) and (2).

(4) An adhesive containing a copolymer obtained by reacting (a) tetracarboxylic dianhydride, (b) diamine or diisocyanate, and (c) a polyether compound represented by the formula (1). (5) The adhesive according to (4), wherein the weight of (c) is 30 to 70% based on the total weight of (a) + (b) + (c). (6) Tetracarboxylic dianhydride (a) is bisphenol A bistrimellitate dianhydride, 2,2-bis [4
-(3,4-dicarboxy) phenyl] propane dianhydride and benzophenone tetracarboxylic dianhydride selected from the group consisting of at least 50 mol% of the total amount of tetracarboxylic dianhydrides. The adhesive according to any one of the above (4) and (5). (7) A film-like adhesive comprising the adhesive layer of any of the above (4) to (6).

(8) When heated at 270 ° C. for 10 minutes, the weight loss of the adhesive layer is 1% or less (weight ratio) with respect to the weight of the adhesive layer before heating. Film adhesive. (9) At least one side of the heat-resistant film has the above (4)
An adhesive film on which an adhesive layer according to any one of (1) to (6) is formed.

(10) When heated at 270 ° C. for 10 minutes, the weight loss of the adhesive layer is not more than 1% (weight ratio) with respect to the weight of the adhesive layer before heating (9). Adhesive film.

(11) A lead frame to which the adhesive of (7) or (8) or the adhesive film of (9) or (10) is attached. (12) A semiconductor device including the lead frame, wherein at least an adhesive member is sealed with a sealing material.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a copolymer obtained by reacting (a) tetracarboxylic dianhydride, (b) diamine or diisocyanate, and (c) a polyether compound represented by the formula (1) Are the above (a), (b) and (c)
And other components such as a catalyst are appropriately added, and the mixture is reacted under the conditions for forming a polyetherimide copolymer.
Although the obtained reaction product can be used as it is, it is preferable to use a copolymer obtained by mixing a poor solvent such as alcohol and water and drying a precipitate obtained.

The tetracarboxylic dianhydride (a) that can be used in the present invention includes pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (BTDA), 3,3 ', 4,4'-
Biphenyltetracarboxylic dianhydride, 2,2-bisphthalic acid hexafluoroisopropylidene dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride,
Bis (3,4-dicarboxyphenyl) sulfone dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 2,2-bis [4-
(3,4-dicarboxyphenoxy) phenyl] propane anhydride,

[0011] Ethylene glycol bis trimellitate dianhydride, decamethylene glycol bis trimellitate dianhydride, bisphenol A bis trimellitate dianhydride (BABT), 2,2-bis [4- (3,4-dicarboxy) phenyl] propane Dianhydride (BPADA),
2,2-bis [4- (3,4-dicarboxyphenylbenzoyloxy) phenyl] hexafluoropropane dianhydride, 4,4 ′-[1,4-phenylenebis (1-methylethylidene)] bisphenylbistri Melitate dianhydride and the like can be used, and two or more kinds may be used in combination. As these tetracarboxylic dianhydrides, derivatives such as free acids (tetracarboxylic acids), diesters and dichlorides can also be used.

Among these, bisphenol A
Bistrimellitate dianhydride (BABT), 2,2-bis [4- (3,4-dicarboxy) phenyl] propane dianhydride (BPADA) or 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride And the amount thereof is preferably such that a tetracarboxylic dianhydride selected from BABT, BPADA and BTDA is 50 moles based on the total amount of the tetracarboxylic dianhydride based on the total amount of the tetracarboxylic dianhydride. % Is preferable.

Further, a tricarboxylic anhydride such as trimellitic anhydride may be used in addition to the tetracarboxylic dianhydride as long as the properties such as adhesive strength and heat resistance of the adhesive are not impaired.

As the diamine which can be used,
1,2-diaminopropane, 1,3-diaminopropane, 1,2-diamino-2-methylpropane, 1,4-
Diaminobutane, 1,6-diaminohexane, 1,7-
Diaminoheptane, 1,8-diaminooctane, 1,9
-Diaminononane, 1,10-diaminodecane, 1,1
Alkylenediamines such as 2-diaminododecane,

Isophoronediamine, phenylenediamine, tolylenediamine, xylylenediamine, naphthalenediamine, dicyclohexylmethanediamine, 4,
4'-diaminodiphenylmethane, 4,4'-diaminodiphenylether, 4,4'-diaminodiphenylsulfone, 4,4'-diaminobenzanilide, 3,3 '
-Diaminodiphenylsulfone, 3,3'-diaminobenzophenone, 3,3'-dimethyldiphenyl-4,
4'-diamine, 3,3 ', 5,5'-tetramethyl-
4,4'-diaminodiphenylmethane, 3,3 ', 5
5′-tetraisopropyl-4,4′-diaminodiphenylmethane, 1,4-bis (4-aminocumyl) benzene, 1,3-bis (4-aminocumyl) benzene, 1,
4-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 2,2-bis [4
-(4-aminophenoxy) phenyl] propane, 2,
2-bis [4- (3-aminophenoxy) phenyl] propane, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4 -Aminophenoxy) phenyl] ether, 2,2-bis [4- (4-aminophenoxy) phenyl] biphenyl,

A siloxane diamine represented by the following formula:

Embedded image [In the formula, R ¹ and R ² represent a divalent organic group, R ³ and R ⁴ represent a monovalent organic group, and m represents an integer of 1 to 100. And these may be used in combination of two or more.

The diisocyanates which can be used include the above-mentioned diamines such as "amino"
Can be replaced with "isocyanate".

The polyether compound which can be used in the present invention includes a compound represented by the following formula (1): RQ1-O- [Q2-O-] p-Q3-R (1) (where Q1, Q2 and Q3 are carbon atoms) Alkylene having the formulas 1 to 10, such alkylenes include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, methylene, propylene, butylene, hexylene and the like. And R is OH or CO
OH, and p is an integer of 0 to 100. ) Is a polyether having a hydroxy group at both ends or a polyether having a carboxylic acid at both ends.

As the polyether having a hydroxy group at both terminals, HO-[(CH ₂ ) ₄ -O] n-H Mw = 250 HO-[(CH ₂ ) ₄ -O] n-H Mw = 650 HO chromatography [(CH _{2) 4} over O] n over H Mw = 1000 HO chromatography [(CH _{2) 4} over O] n over H Mw = 1800 HO chromatography [(CH _{2) 4} over O] n over H Mw = 2900 HO-[(CH ₂ ) ₄ -O] n-H Mw = 4500. These polyethers may be used alone or in combination of two or more.

As the polyether having a carboxylic acid at both terminals, HOOC— (CH ₂ ) ₂ —O — [(CH ₂ ) ₄ —O] n— (CH) ₂ —COOH Mw = 350 HOOC— (CH ₂₎ ) _2-O over [(CH _{2) 4} over O] n over (CH) _2-COOH Mw = 1100 HOOC chromatography (CH _{2) 2} over O over [(CH _{2) 4} over O] n over (CH) ₂ —COOH Mw = 2100. These polyethers may be used alone or in combination of two or more.

The reaction product (polyetherimide copolymer) obtained by reacting the contents of (a) tetracarboxylic dianhydride; (b) a diamine or diisocyanate; and (c) a polyether compound; In the preparation, the used amount (weight) of the polyether (c) as a raw material is 30 to 70% based on the total weight of the resin raw material, that is, the total weight of the above (a) + (b) + (c). preferable. In this case, a material having good adhesive strength and heat resistance can be obtained. (A), (b), and (c) above, and other components (such as catalysts)
Reactant (polyetherimide copolymer)
Are mixed in an organic solvent. At this time, the amounts of the tetracarboxylic dianhydride (a) and the diamine or diisocyanate (b) used are the same as those of the polyether (c).
Is adjusted in consideration of the amount of the functional group.

In the present invention, when a polyether having carboxyl groups at both ends is used as the polyether, tetracarboxylic dianhydride and a polyether having both carboxyl groups at both ends (acid component), diamine or diisocyanate are used. (Amine component) is based on the use of equimolar amounts. The acceptable excess of any one is preferably within 50 mol%, more preferably within 20 mol%.

The organic solvent used in the reaction (polyetherimide copolymer formation reaction) includes aprotic polar solvents such as N-methyl-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, sulfolane, and the like.
Examples thereof include ether-based organic solvents such as tetrahydrofuran, dioxane, monoglyme, and diglyme. Also,
Raw material monomers and reactants (polyetherimide copolymer)
For dissolution of an organic solvent, an appropriate amount of an organic solvent such as benzene, toluene, xylene, methyl ethyl ketone, methyl cellosolve, and cellosolve acetate can be used.

When an organic solvent is added to the obtained reaction product (polyetherimide copolymer) to form a liquid resin composition such as varnish, N-methyl-pyrrolidone, N, N -Dimethylacetamide, N, N
-Aprotic polar solvents such as dimethylformamide; ether-based organic solvents such as tetrahydrofuran, dioxane, monoglyme and diglyme; benzene, toluene, xylene, methyl ethyl ketone, cyclohexanone, methyl cellosolve, cellosolve acetate, and mixed solvents thereof.

The liquid resin composition (varnish) may be directly applied to an adherend such as a semiconductor element or a lead frame to be used as an adhesive member, or may be used in advance as a film (or sheet). It may be applied to an adherend and then thermocompression-bonded.

The adhesive in the form of a film (or a sheet) is prepared by appropriately diluting the resin composition of the present invention with the above-mentioned organic solvent, and then, on a flat plate such as a glass plate or a stainless plate, or a film such as polyester. After casting and coating with a constant thickness on the upper part, usually, it is first heated at about 80 to 150 ° C. for several minutes to several hours, and subsequently heated at about 200 to 300 ° C. for several minutes to several hours. Obtained by peeling from the film.

After the resin composition of the present invention is applied or spread or impregnated on a substrate such as a film or sheet, it is heated and dried to form a multi-layer adhesive film or composite sheet. it can. As the substrate used,
Cloth such as film, glass cloth, carbon fiber cloth, and polyaramid cloth; and metal foil such as copper foil, aluminum foil, and stainless steel foil.

The adhesive film of the present invention, in which an adhesive layer is formed on at least one side of the heat-resistant film, is obtained by appropriately diluting the resin composition of the present invention with the above-mentioned organic solvent and then forming a heat-resistant base film. The film can be produced by coating the film on one side or both sides and subjecting it to a heat treatment in the same manner as described above. When applied to both surfaces of the heat resistant film, the type of adhesive may be the same or different. The method for applying the adhesive to the heat-resistant film is not particularly limited. The coating may be performed by any method such as a doctor blade, a knife coater, and a die coater. Further, the film may be applied through a film in a varnish of an adhesive, but it is not preferable because the thickness is difficult to control.

Examples of the heat-resistant film used herein include films of engineering plastics such as polyimide, polyamide, polysulfone, polyphenylene sulfide, polyether ether ketone, and polyarylate. Glass transition temperature (T
As g), one having a Tg higher than that of the adhesive is used, preferably 200 ° C. or more, more preferably 250 ° C. or more. A heat-resistant film having a water absorption of 3% by weight or less, preferably 2% by weight or less is used. Therefore, a polyimide film is preferably used as the heat-resistant film in terms of Tg, water absorption, and coefficient of thermal expansion. In particular, a polyimide film having physical properties such that Tg is 250 ° C. or more, water absorption is 2% by weight or less, and thermal expansion coefficient is 3 × 10 −5 / ° C. or less is preferable.

The heat-resistant film is desirably subjected to a surface treatment in order to increase the adhesive strength with the adhesive. As the surface treatment method, any treatment such as alkali treatment, chemical treatment such as silane coupling treatment, physical treatment such as sand blast, plasma treatment, corona treatment, etc. can be used, but depending on the type of adhesive. The most suitable treatment may be used, but preferably a chemical treatment or a plasma treatment.

When the adhesive film of the present invention is used as a lead fixing tape, an adhesive film having an adhesive layer formed on one surface of a heat-resistant film is usually used, but the adhesive layer surface may be bonded with a protective film. .

When the film-like adhesive or the adhesive film of the present invention is used for a lead fixing tape, a LOC tape, or the like, when the adhesive is heated at 270 ° C. for 10 minutes, the weight of the adhesive layer decreases. It is preferably 1% (weight ratio) or less based on the weight of the previous adhesive layer. Also, 20
Adhesive film (adhesive tape) stuck at 0 ° C or less is 2
Preferably, it does not move at 50 ° C.

The resin composition or the adhesive of the present invention may contain fillers such as ceramic powder, glass powder, silver powder, copper powder, resin particles and rubber particles, and coupling agents.
As the coupling agent, a coupling agent such as vinyl silane, epoxy silane, amino silane, mercapto silane, titanate, aluminum chelate, and zircoaluminate can be used, but a silane coupling agent is preferable. Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane Γ-glycidoxypropylmethyldiethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β
-(Aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane,
N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, etc., a silane coupling agent having an organic reactive group at the terminal, of which an epoxysilane coupling agent having an epoxy group is preferable. Used. Here, the organic reactive group is a functional group such as an epoxy group, a vinyl group, an amino group, and a mercapto group. The addition of the silane coupling agent
In order to improve the reflow crack resistance and the adhesive strength of the semiconductor package to be manufactured, the content is preferably 1 to 15 parts by weight, more preferably 2 to 10 parts by weight, based on 100 parts by weight of the total amount of the resin. it can.

The adhesive or the adhesive film of the present invention is used as a lead fixing tape for a lead frame,
Used as an adhesive for semiconductor packages such as LOC package, conventional package, COL package, package with heat spreader, etc.
It can also be used to bond lead frames and heat spreaders. Depending on the application of the adhesive or the adhesive film, a solvent may be left in the film-like adhesive or the adhesive film for the purpose of lowering the bonding temperature at the time of bonding. In this case, the amount of the remaining solvent is set to a level not exceeding 10% by weight.

A semiconductor device when used as a lead fixing tape for a lead frame is manufactured, for example, as follows. An adhesive film piece or a film-like adhesive piece (adhesive member) of the present invention having a predetermined size is applied to the inner lead portion of the lead frame at 150 to 300 ° C and 0.01 to 1 ° C.
After thermocompression bonding at 0 Mpa for 0.1 to 10 seconds, a die bonding material (silver paste, die bonding film, or the like) is mounted on a die pad portion of a lead frame, and a semiconductor element is mounted on the die bonding material and pressure-bonded. The lead frame and the semiconductor element are joined with a gold wire or the like, and sealed with a sealing material such as an epoxy resin to obtain a semiconductor device (FIG. 1).

FIG. 2 shows an example of a semiconductor device using the adhesive film of the present invention (adhesive layers on both sides of a base film) as a LOC tape. FIG. 3 shows an example of a semiconductor device used for bonding a lead frame of a die package and a semiconductor element. The adhesive or the adhesive film (adhesive member) of the present invention is used for bonding a lead frame of a package with a heat spreader to a heat spreader. FIG. 4 shows examples of the semiconductor devices used.

[0037]

The present invention will be described below in detail with reference to examples. Example 1 1,000 m equipped with a stirrer, a thermometer, and a nitrogen gas inlet tube
polyethers having a hydroxy group at both ends l four-necked flask (HO chromatography [(CH _{2) 4} over O] n over H Mw = 65
0), and 69.5 g (0.100 mol) of bisphenol A bistrimellitate dianhydride (BABT).
g (0.034 mol) and 400 g of sulfolane were added, and the temperature was raised to 200 ° C. while stirring under a nitrogen atmosphere. 33.5 g (0.134) of diphenylmethane diisocyanate
Mol), the mixture was reacted at 200 ° C. for 2 hours, and then cooled to room temperature. The obtained reaction product (copolymer reaction solution) was poured into methanol, and the generated precipitate was separated. This was pulverized with a mixer, washed with water, and dried to obtain a polyetherimide powder having a polyether content of 55% by weight. The obtained polyether powder was converted from polyetherimide powder by gel permeation chromatography (hereinafter abbreviated as GPC;
The weight average molecular weight was 220,000 in terms of polystyrene when measured using MF, a liquid speed of 1 ml / min, and detection using a UV detector. 3.0 g of this polyetherimide powder and 0.30 g of γ-glycidoxypropyltrimethoxysilane (CPL amount: 10% by weight) were weighed, and the concentration of the polyetherimide powder was 25% by weight. N, N-dimethylformamide was added and dissolved to obtain a varnish. This varnish is applied on a polyester film so that the finished adhesive layer thickness is 25 μm, and is first heated at 100 ° C. for 30 minutes, and then the adhesive layer is peeled off from the polyester film.
Stop at the metal frame and heat it further at 250 ° C for 10 minutes.
A 5 μm single layer film adhesive was prepared. In addition, using a differential thermobalance (heating rate: 10 ° C./min, in air)
The% weight loss temperature (hereinafter abbreviated as Td) was 320 ° C. The weight loss when heated at 270 ° C. for 10 minutes was 0.7% by weight. Separately, the varnish was coated on one side of a 50 μm thick heat-resistant polyimide film (UPILEX S, manufactured by Ube Industries, Ltd.) so that the finished adhesive layer thickness was 25 μm, and heat-treated in the same manner as described above. Thus, an adhesive tape with a base film was obtained. 10 mm × 2
It was cut into a size of 0 mm, and this was cut into a copper alloy as a lead frame material so that the adhesive layer was in contact therewith, at a temperature of 180 ° C.
After pressure-bonding under the conditions of pressure: 3 MPa and time: 3 seconds, the 90-degree peel strength (measuring temperature: 25 ° C., tensile speed: 50 mm / min) was measured according to JIS C6481, and it was 600 N / m. there were. The peeling strength when the bonding temperature was 70 ° C. and 150 ° C. was 150 N / m and 600 N / m, respectively.
The adhesive tape with the base film is attached to the comb pattern portion of the two-layer flexible wiring board on which the 60 μm / 60 μm (line / space) comb pattern is formed.
When the resistance was measured under the conditions of 5 ° C., 85% RH, and 5 V applied, the resistance was 1 × 10 ¹³ (ohm) or more even after 400 hours. Further, the adhesive tape with the base film adhered at 180 ° C. was placed on a hot plate at 250 ° C. and pressed with a pair of tweezers from obliquely above, and the tape did not move. Further, the semiconductor device (package) shown in FIG. 1 was manufactured using the above-mentioned adhesive tape with a base film. 85 ℃, 85
After absorbing moisture for 48 hours at% RH, infrared ray reflow was performed, but no package crack occurred.

Example 2 1,000 m equipped with a stirrer, thermometer and nitrogen gas inlet tube
polyethers having a hydroxy group at both ends l four-necked flask (HO chromatography [(CH _{2) 4} over O] n over H Mw = 65
0) to 65.0 g (0.100 mol), 3,3 ′, 4
4'-benzophenonetetracarboxylic dianhydride (BT
15.4 g (0.048 mol) of DA) and 400 g of sulfolane were added, and the mixture was heated to 200 ° C. while stirring under a nitrogen atmosphere. 37. diphenylmethane diisocyanate
After adding 0 g (0.148 mol), the mixture was reacted at 200 ° C. for 2 hours, and then cooled to room temperature. The obtained reaction product (copolymer reaction solution) was poured into methanol, and the generated precipitate was separated. This was pulverized with a mixer, washed with water, and dried to obtain a polyetherimide powder having a polyether content of 55% by weight. When the obtained polyether powder was measured for the polyetherimide powder using GPC, the weight average molecular weight was 190,000 in terms of polystyrene. 3.0 g of this polyetherimide powder and 0.30 g of γ-glycidoxypropyltrimethoxysilane (CPL amount: 10% by weight) were weighed, and the concentration of the polyetherimide powder was 25% by weight. N, N-dimethylformamide was added and dissolved to obtain a varnish. Next, a single-layer film-like adhesive was produced in the same manner as in Example 1. The Td of the obtained film adhesive was 320 ° C. The weight loss when heated at 270 ° C. for 10 minutes was 0.5% by weight. Next, an adhesive tape with a base film was prepared in the same manner as in Example 1, and the same test as in Example 1 was performed. The 90 degree peel strength when the adhesive tape with the base film is pressed against the copper alloy is 500 N /
m, and the peel strength when the bonding temperature was 70 ° C. and 150 ° C. was 50 N / m and 400 N / m, respectively. The adhesive tape with the base film is adhered to the comb pattern portion of the two-layer flexible wiring board on which the 60 μm / 60 μm (line / space) comb pattern is formed, and the conditions are 156 ° C., 85% RH, and 5 V applied. The resistance was measured at 1 × 1 × 10 ¹³ (oh
m). The adhesive tape with the base film adhered at 180 ° C. was placed on a hot plate at 250 ° C. and pressed with a pair of tweezers from an obliquely upper side, and the tape did not move.

Example 3 1,000 m equipped with a stirrer, thermometer and nitrogen gas inlet tube
polyethers having a hydroxy group at both ends l four-necked flask (HO chromatography [(CH _{2) 4} over O] n over H Mw = 65
6) (0.100 mol), 18.7 g (0.036 mol) of 2,2-bis [4- (3,4-dicarboxy) phenyl] propane dianhydride (BPADA) and 400 g of sulfolane. The temperature was raised to 200 ° C. while stirring in a nitrogen atmosphere. After adding 34.0 g (0.136 mol) of diphenylmethane diisocyanate, the mixture was reacted at 200 ° C. for 2 hours, and then cooled to room temperature. The obtained reaction product (copolymer reaction solution) was poured into methanol, and the generated precipitate was separated. This is crushed with a mixer, washed with water, and dried to obtain a polyether content of 55% by weight.
Was obtained. When the obtained polyether powder was measured for the polyetherimide powder using GPC, the weight average molecular weight was 17 in terms of polystyrene.
It was 0000. 3.0 g of this polyetherimide powder and 0.15 g (amount of CPL: 5% by weight) of γ-glycidoxypropyltrimethoxysilane were weighed,
N, N-dimethylformamide was added and dissolved therein so that the concentration of the polyetherimide powder became 25% by weight, to prepare a varnish. Next, a single-layer film-like adhesive was produced in the same manner as in Example 1. The Td of the obtained film adhesive was 320 ° C. Also, at 270 ° C, 10
The weight loss upon heating for one minute was 0.7% by weight. Next, an adhesive tape with a base film was prepared in the same manner as in Example 1, and the same test as in Example 1 was performed. When the adhesive tape with the base film is pressed against a copper alloy, the 90-degree peel strength is 600 N / m, and the adhesive temperature is 70 ° C. and 1 ° C.
The peel strength at 50 ° C. was 50 N /
m and 500 N / m. The above-mentioned adhesive tape with a base film is attached to the comb-shaped pattern portion of the two-layer flexible wiring board on which a 60 μm / 60 μm (line / space) comb-shaped pattern is formed, 156 ° C., 85% RH, 5V
When the resistance value was measured under the conditions of application, it was 1 × 1 × 10 ¹³ (ohm) or more even after 400 hours. The adhesive tape with the base film adhered at 180 ° C. was placed on a hot plate at 250 ° C. and pressed with a pair of tweezers from an obliquely upper side, and the tape did not move.

Comparative Example 1 A film-like adhesive was produced by using an acrylic nitrile-butadiene rubber and a thermosetting resin mainly composed of a phenol resin as an adhesive. Hereinafter, an adhesive tape with a base film was prepared and tested in the same manner as in Example 1. 2
2.3% by weight when heated at 70 ° C for 10 minutes
Met. The 90-degree peel strength when the obtained adhesive tape with a base film was pressed against a copper alloy was 800.
N / m, the peel strength when the bonding temperature was 70 ° C. and 150 ° C. was 50 N / m and 750 N / m, respectively.
Met. The adhesive tape with the base film is adhered to the comb pattern portion of the two-layer flexible wiring board on which the 60 μm / 60 μm (line / space) comb pattern is formed, and the conditions are 156 ° C., 85% RH, and 5 V applied. The resistance was measured at 1 × 10 ¹³ (ohm) after 200 hours.
It was below.

[0041]

The resin composition according to any one of claims 1 to 3,
To 8 and the raw materials for the adhesive films of claims 9 and 10. The adhesive according to claims 4 to 6 has excellent heat resistance and is used for bonding electronic components. The adhesives according to claims 7 and 8 and the adhesive films according to claims 9 and 10 have excellent heat resistance and low outgassing, and are suitable as adhesive tapes for electronic components such as LOC tapes and lead fixing tapes. The semiconductor device according to claim 12 manufactured using the lead frame according to claim 11 has high reliability.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view showing an example of a semiconductor device using an adhesive film of the present invention as a lead fixing tape.

FIG. 2 is a schematic cross-sectional view showing an example of a semiconductor device using the adhesive film of the present invention as a LOC tape.

FIG. 3 shows the adhesive or adhesive film (adhesive member) of the present invention.
FIG. 3 is a schematic cross-sectional view showing an example of a semiconductor device used for bonding a semiconductor element to a lead frame of a conventional package.

FIG. 4 is an adhesive or adhesive film (adhesive member) of the present invention.
FIG. 2 is a schematic cross-sectional view showing an example of a semiconductor device used for bonding a lead frame of a package with a heat spreader to a heat spreader.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Adhesive member of this invention 2 ... Semiconductor element 3 ... Lead frame 4 ... Wire 5 ... Sealant 6 ... Die bond material 7 ... Heat spreader

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09J 179/08 C09J 179/08 ZB H01L 21/52 H01L 21/52 E (72) Inventor Noriyuki Saito 48 Wadai, Tsukuba-shi, Ibaraki F-term in Tsukuba Development Laboratory, Hitachi Chemical Co., Ltd. (Reference) HA02 HA07 HB03 HB06 HB11 HB16 HC03 HC12 HC13 HC17 HC22 HC46 HC52 HC61 HC64 HC65 HC67 HC69 HC70 HC71 HC73 JA02 JA14 QC03 QC08 RA05 RA08 RA14 4J040 EF051 EF052 EF081 EF082 EF131 EF132 JA09 LA06 NA20 5F037

Claims (12)

[Claims] (1) a tetracarboxylic dianhydride;
(B) A resin composition containing a copolymer obtained by reacting a diamine or diisocyanate with (c) a polyether compound represented by the formula (1). R-Q1-O- [Q2-O-] p-Q3-R (1) (Q1, Q2 and Q3 are alkylene having 1 to 10 carbon atoms,
R is OH or COOH, and p is an integer of 0-100. ) 2. The weight of (c) is (a) + (b) +
2. The composition according to claim 1, wherein the content is 30 to 70% of the total weight of (c).
The resin composition as described in the above. 3. The tetracarboxylic dianhydride (a) is bisphenol A bistrimellitate dianhydride, 2,2-bis [4- (3,4-dicarboxy) phenyl] propane dianhydride and benzophenone tetracarboxylic dianhydride. The resin composition according to claim 1, wherein the resin composition contains at least 50 mol% of a tetracarboxylic dianhydride selected from anhydrides based on the total amount of the tetracarboxylic dianhydride. (A) a tetracarboxylic dianhydride;
(B) An adhesive containing a copolymer obtained by reacting a diamine or diisocyanate with (c) a polyether compound represented by the formula (1). 5. The weight of (c) is (a) + (b) +
The amount is 30 to 70% based on the total weight of (c).
The adhesive as described. 6. The tetracarboxylic dianhydride (a) is bisphenol A bistrimellitate dianhydride, 2,2-bis [4- (3,4-dicarboxy) phenyl] propane dianhydride and benzophenone tetracarboxylic dianhydride. The adhesive according to claim 4, wherein the adhesive contains at least 50 mol% of a tetracarboxylic dianhydride selected from anhydrides based on the total amount of the tetracarboxylic dianhydride. 7. A film-like adhesive comprising the adhesive layer according to any one of claims 4 to 6. 8. The film according to claim 7, wherein the weight loss of the adhesive layer when heated at 270 ° C. for 10 minutes is not more than 1% (weight ratio) with respect to the weight of the adhesive layer before heating. Glue. 9. An adhesive film having a heat-resistant film on at least one surface of which an adhesive layer according to any one of claims 4 to 6 is formed. 10. When heated at 270 ° C. for 10 minutes,
The adhesive film according to claim 9, wherein the weight loss of the adhesive layer is 1% or less (weight ratio) with respect to the weight of the adhesive layer before heating. 11. A lead frame to which the adhesive according to claim 7 or 8 or the adhesive film according to claim 9 or 10 is attached. 12. A lead frame according to claim 11, further comprising:
A semiconductor device in which at least an adhesive member is sealed with a sealing material.