JPH11246840A - Adhesive for electronic part and adhesive tape - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject adhesive capable of bonding and hardening at a comparatively low temperature, having sufficient heat resistance, reliability and the like, and useful as adhesion of a lead pin or the like of a semiconductor device by dissolving a specific polyimide and a compound having a plurality of maleimide groups in an organic solvent. SOLUTION: This adhesive is obtained by dissolving (A) at least one polyimide selected from (i) a polyimide containing a structural unit of formula I (Ar is a divalent group of formula II or the like; Ra is a divalent group having 2-6 benzene rings; X<1> is NH or the like; Y is O or the like), (ii) a polyimide having a structural unit of formula III (Rb is a 2-20C alkylene or the like; X<2> is NH or the like) and (iii) a polyimide containing the structural units of formulas I and III in an arbitrary proportion, and (B) a compound having two or more maleimide groups (e.g. a compound of formula IV) in a proportion of 10-900 pts.wt. component B based on 100 pts.wt. component A in an organic solvent such as tetrahydrofuran.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electronic component used for bonding between members around a lead frame constituting a semiconductor device, for example, a lead pin, a substrate for mounting a semiconductor chip, a heat sink, and a semiconductor chip itself. The present invention relates to an adhesive and an adhesive tape.

[0002]

2. Description of the Related Art Conventionally, an adhesive tape used in a resin-encapsulated semiconductor device includes a lead frame fixing tape,
There is an AB tape and the like. For example, in the case of an adhesive tape for fixing a lead frame, it is used for fixing the lead pins of the lead frame and for improving the production yield and productivity of the lead frame itself and the entire semiconductor assembly process. I have.

[0003] In general, a resin-encapsulated semiconductor device is manufactured by a lead frame maker after an adhesive tape is taped on lead pins of a lead frame, brought into the semiconductor maker, mounted with an IC, and sealed with a resin. It is manufactured by. For this reason, the adhesive tape for fixing lead frames has not only improved electrical reliability at the semiconductor level and workability during taping, but also sufficient adhesive strength at room temperature immediately after taping and sufficient heat resistance to withstand heating in the semiconductor device assembly process. Is required. At present, as an adhesive tape for such applications, for example, on a support such as a polyimide film, polyacrylonitrile, polyacrylic acid ester or acrylonitrile-butadiene copolymer alone or other resin such as a synthetic rubber resin. In this case, an adhesive modified with the above or an adhesive mixed with another resin is applied to form a B-stage state.

As a resin-encapsulated semiconductor device (semiconductor package) to which an adhesive tape for fixing a lead frame is applied, for example, a device having a structure shown in FIGS. In FIG. 1, the lead pin 3 and the plane 2
The semiconductor chip 1 is mounted on the plane 2 by the adhesive layer 6 and the semiconductor chip 1 and the lead pins 3
And a structure sealed with a resin 5 together with the bonding wire 4 therebetween. In FIG. 2, the lead pins 3 of the lead frame are fixed to the semiconductor chip 1 and the adhesive layer 6, and have a structure in which the lead pins 3 are sealed together with the bonding wires 4 by the resin 5. Further, in FIG. 3, the semiconductor chip 1 is mounted on the die pad 7, the electrodes 8 are fixed by the adhesive layer 6, and the space between the semiconductor chip 1 and the electrodes 8 and between the electrode 8 and the lead pins are provided. 3 are connected by bonding wires 4 and are sealed with a resin 5.

[0005]

In the resin-sealed semiconductor device having the structure shown in FIGS. 1 to 3, an adhesive tape coated with a conventional nylon-based or acrylic-based resin adhesive was used for the adhesive layer. In this case, there are problems such as insufficient heat resistance and the like, and when a synthetic rubber-based adhesive is used, there is a problem that the generated gas contaminates the lead frame and lowers the reliability of the package. Was. In addition, when a conventional polyimide resin adhesive or the like is used, since relatively strict setting conditions are required for taping temperature, pressure, curing of the polyimide resin, and the like, there is a high possibility that a metal material such as a lead frame is damaged. Therefore, development of an adhesive that can be bonded and cured at a low temperature and has high heat resistance and reliability has been desired. Therefore, an object of the present invention is to provide an adhesive for electronic components that can be adhered and cured at a relatively low temperature and has sufficient heat resistance and reliability, and an adhesive tape for electronic components using the same. .

[0006]

The first liquid adhesive for electronic parts of the present invention is a polyimide containing (I) (a) a structural unit represented by the following general formula (1) in an organic solvent. ,
(B) A polyimide containing a structural unit represented by the following general formula (2) and (c) a structural unit represented by the following general formula (1) and a structural unit represented by the general formula (2) are optionally selected. At least one polyimide selected from the polyimides contained in a proportion of (II) and a compound containing two or more maleimide groups (II), and the component (II) is added to 100 parts by weight of the component (I). It is characterized by being 10 to 900 parts by weight.

[0007]

Embedded image [In the formula, Ar represents a divalent group represented by the following general formula (3) or the following general formula (4). Ra represents a divalent group having 2 to 6 benzene rings, and Rb represents 2 to 20 carbon atoms.
Alkylene group, —CH ₂ CH ₂ (OCH ₂ CH ₂ ) _n
- (n is an integer from 1 to 8.) Ether chain or -R 'represented by _{- [Si (CH 3) 2} O] m Si (C
_{H 3) 2 -R '- (} R' is an alkyl group or -CH ₂ OC ₆ H ₄ having 1 to 10 carbon atoms - dimethylsiloxane group indicates, m is represented by an integer from 1 to 20). Is shown.
X ¹ represents NH, NR (R represents an alkyl group having 1 to 4 carbon atoms) or S. X ² is NH, NR (R represents an alkyl group having 1 to 4 carbon atoms),

Embedded image Or S is shown. ]

[0008]

Embedded image (Wherein, Y is -O -, - CO -, - S -, - SO 2 - or _{-C (CH 3) 2 - .R} 1 ~R 4 showing a each represent an alkyl group having 1 to 4 carbon atoms Or an alkoxy group having 1 to 4 carbon atoms.)

The second adhesive for electronic parts of the present invention comprises (I) (a) a polyimide containing a structural unit represented by the general formula (1) in an organic solvent; And (c) a polyimide containing a structural unit represented by the general formula (1) and a structural unit represented by the general formula (2) at an arbitrary ratio. And at least one polyimide, (II) a compound containing two or more maleimide groups, and (III) a diamine compound represented by the following general formula (5) or an amino group at both terminals represented by the following general formula (6) Weight average molecular weight 200-
7,000 diaminopolysiloxane compounds are dissolved, and 100 parts by weight of component (I) is added to component (I).
The total amount of I) and component (III) is 10 to 900 parts by weight.

H ₂ N—R ⁵ —NH ₂ (5) (wherein, R ⁵ represents a divalent aliphatic group, aromatic group or alicyclic group having 1 to 12 carbon atoms.)

Embedded image (In the formula, R ⁶ represents a divalent aliphatic group, aromatic group or alicyclic group having 1 to 3 carbon atoms, and k is an integer of 0 to 7.)

The first adhesive tape for electronic parts of the present invention comprises:
The heat-resistant film is characterized in that an adhesive layer formed using the above-mentioned adhesive is laminated on at least one surface of the heat-resistant film. Further, the second adhesive tape for electronic parts of the present invention comprises:
It is characterized in that an adhesive layer formed by using an adhesive of the above-mentioned component is laminated on one surface of a peelable film.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. First, the adhesive for electronic components according to the present invention will be described. For the first adhesive for electronic components, a polyimide selected from (a) to (c) as the component (I) and a compound containing a maleimide group as the component (II) are used. Among the polyimides used as component (I),
The polyimide of (a) contains bismaleimide represented by the following general formula (8) as a basic structural unit.

Embedded image In the general formula (8), Ar is a divalent group represented by the following general formula (3) or the following general formula (4).

[0013]

Embedded image In the general formula (3), Y represents -O-, -CO-, -S
—, —SO ₂ — or —C (CH ₃ ) ₂ —.

Embedded image In the general formula (4), R ^{1 to} R ⁴ are an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, respectively.

Specific examples of the bismaleimide represented by the above general formula (8) include the following. A
As the bismaleimide in which r is represented by the general formula (3),
4,4'-bis (3-maleimidophenoxy) diphenyl ether, 4,4'-bis (3-maleimidophenoxy) benzophenone, bis [4- (3-maleimidophenoxy) phenyl] sulfide, 4,4'-bis (3 −
Maleimidophenoxy) diphenylsulfone, 2,2-
Bis (p-maleimidophenoxyphenyl) propane,
2,2-bis (m-maleimidophenoxyphenyl) propane and the like.

The bismaleimide in which Ar is represented by the general formula (4) includes bis (4-maleimido-3,5-
Dimethylphenyl) methane, bis (4-maleimide-
3,5-diethylphenyl) methane, bis (4-maleimido-3,5-dipropylphenyl) methane, bis (4
-Maleimido-3,5-diisopropylphenyl) methane, bis (4-maleimido-3,5-dibutylphenyl) methane, bis (4-maleimido-3-methyl-5)
Ethylphenyl) methane, bis (4-maleimido-3-
Methyl-5-methylphenyl) methane, bis (4-maleimido-3,5-dimethoxyphenyl) methane, bis (4-maleimido-3,5-diethoxyphenyl) methane, bis (4-maleimido-3,5- Dipropoxyphenyl) methane, bis (4-maleimido-3,5-diisopropoxyphenyl) methane, bis (4-maleimido-
3,5-dibutoxyphenyl) methane, bis (4-maleimido-3-methoxy-5-ethoxyphenyl) methane and the like.

In the polyimide (a), the compound represented by the following general formula (9), which constitutes another basic structural unit of the polyimide, includes a diamine having an amino group at both terminals and There are two types of dithiols whose terminals are mercapto groups. HX ¹ -Ra-X ¹ H (9) In the general formula (9), Ra is a divalent group having 2 to 6 benzene rings, X ¹ is NH, NR (R is
-4) or S.

Among the polyimides obtained using this compound, those which improve the solubility in solvents include R
a represents two or more benzene rings, particularly -O-, -S-,-
CH ₂ —, —C (＝ O) —, —CO—NH—, —CO—
_{O -, - SO 2 -,} - C (CH 3) 2 - or -C (C
Those linked linearly by F ₃ ) ₂ -or the like and at the meta or para position are preferred. The hydrogen of each of these benzene rings may be appropriately substituted with a substituent. Both ends of the compound, as the diamine compound is an amino group, in the case of the primary amines X ¹ is NH, X ¹
Is a secondary amine in which R is NR (R is an alkyl group having 1 to 4 carbon atoms).

Specific examples in which the compound represented by the general formula (9) is a primary diamine include 3,4'-oxydianiline, 4,4'-oxydianiline, and 4,4'-diaminodiphenylmethane 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4 '
-Diamino-3,3'-dimethyldiphenylmethane,
4,4'-diamino-3,3'-diethyldiphenylmethane, bis (4-amino-2,5-dimethylphenyl)
Methane, bis (4-amino-2,5-dimethylphenyl) methane, bis (4-amino-2-ethyl-5-methylphenyl) methane, 4,4'-diamino-3,3'-
Dimethoxydiphenylmethane, 4,4'-diamino-
3,3'-diethoxydiphenylmethane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane,
4,4'-diaminobenzanilide, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylsulfone, 3,3 '
-Diaminodiphenyl sulfone, 4,4 '-(isopropylidene) dianiline, 3,3'-(isopropylidene) dianiline, 4,4'-diaminobenzophenone,
1,3-bis [2- (4-aminophenyl) isopropyl] benzene, 1,4-bis [2- (4-aminophenyl) isopropyl] benzene, bis [2- (4-aminophenyl) propyl] benzene, 1,4-bis (aminophenoxy) benzene, 3,3'-dimethyl-4,4 '
-Diaminobiphenyl, 3,3'-dimethoxy-4,
4'-diaminobiphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, 3,4'-diaminodiphenylether, bis (aminophenoxy) diphenylether, bis (aminophenoxyphenyl) propane,
Bis [4- (4-aminophenoxy) phenyl] sulfone, bis (aminophenoxyphenyl) ketone, 2,2
-Bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, bis (aminophenoxyphenyl) biphenyl, bis (aminophenoxyphenyl) diphenyl ether, 4,4'-bis [3- (4-amino-α, α '-Dimethylbenzyl) phenoxy] diphenylsulfone, 4,4'-bis [3- (4-amino-α,
α′-dimethylbenzyl) phenoxy] benzophenone, 4,4′-bis [4- (4-amino-α, α′-dimethylbenzyl) phenoxy] diphenylsulfone,
4,4'-bis [4- (4-amino-α, α'-dimethylbenzyl) phenoxy] benzophenone, 9,9-bis (4-aminophenyl) fluorene, 9,9-bis (4-aminophenoxy) Fluorene and the like can be mentioned, and these can be used as a mixture.

Further, as a specific example in which the compound represented by the general formula (9) is a secondary diamine, 4,4'-di (N
-Methylamino) diphenylmethane, 3,4'-di (N
-Methylamino) diphenylmethane, 4,4'-di (N
-Methylamino) diphenyl ether, 3,4'-di (N-methylamino) diphenyl ether, 4,4'-
Examples thereof include di (N-methylamino) benzanilide, 4,4'-di (N-methylamino) benzophenone, and 3,3'-di (N-methylamino) benzophenone.

Further, specific examples of the dithiol in which the functional group X ¹ of the compound represented by the general formula (9) is a mercapto group include 3,4′-dimercaptodiphenyl ether,
Besides 4,4'-dimercaptodiphenyl ether, etc.,
Among the primary diamines exemplified above, those obtained by replacing "amino" with "mercapto" or those obtained by replacing "amine" with "thiol" can be given.
The polyimide (a) can be produced by reacting the bismaleimide represented by the general formula (8) with the compound represented by the general formula (9) in the presence of active hydrogen.

In the polyimide of (b) used as the component (I), the compound represented by the following general formula (10) constituting another basic structural unit has amino groups at both ends. There are two types: diamines or dithiols, both ends of which are mercapto groups. HX ² —Rb—X ² H (10) In the general formula (10), Rb is an alkylene group having 2 to 20 carbon atoms, —CH ₂ CH ₂ (OCH ₂ CH ₂ ) _n — (n
Is an integer of 1 to 8. Ether chains or -R 'represented _{by) - [Si (CH 3)} 2 O] m Si (CH 3) 2 -
R '-(R' is an alkyl group having 1 to 10 carbon atoms or -C
H ₂ OC ₆ H ₄ —, wherein m is an integer of 1 to 20. ). Also,
X ² is NH, NR (R represents an alkyl group having 1 to 4 carbon atoms),

Embedded image Or S.

The diamine compound having an amino group at both ends includes a primary amine in which X ² is NH and a diamine compound in which X ² is N
In some cases, the secondary amine is R (R is an alkyl group having 1 to 4 carbon atoms). In the compound represented by the general formula (10), as the primary diamine, ethylenediamine,
Propylene diamine, 1,4-diaminobutane, hexamethylenediamine, octamethylenediamine, decamethylenediamine, hexadecamethylenediamine, dodecamethylenediamine, di (aminoethyl) ether, 1,8
-Diamino-3,6-dioxaoctane, 1,10-diaminodecane, 1,11-diamino-3,6,9-trioxaundecane, 1,3-bis (3-aminopropyl) -1,1,1 3,3-tetramethyldisiloxane,
1,3-bis (10-aminodecyl) -1,1,3,3
-Tetramethyldisiloxane, 1,3-bis (3-aminophenoxymethyl) -1,1,3,3-tetramethyldisiloxane and α, ω-bis (3-aminopropyl) poly represented by the following structural formula Dimethylsiloxane and the like can be mentioned, and these can be used as a mixture. H ₂ NCH ₂ CH ₂ CH ₂ [Si (CH ₃ ) ₂ O] _n S
i (CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ NH ₂ (where n is 3 or 7)

Among the compounds represented by the general formula (10),
As the secondary diamine in which the functional group X ² is represented by NR,
N, N'-dimethylethylenediamine, N, N'-dimethylpropylenediamine, N, N'-dimethyl-1,4
Diaminobutane, N, N'-dimethylhexamethylenediamine, N, N'-dimethyloctamethylenediamine, N, N'-dimethyldecamethylenediamine,
N'-dimethylhexadecamethylenediamine, N, N '
-Dimethyldodecamethylenediamine and the like. Examples of the secondary amine having a cyclic functional group X ² include 1,3-di (4-piperidyl) propane and 1,4-di (4-piperidyl) propane.
Examples thereof include di (4-piperidyl) butane, 1,6-di (4-piperidyl) hexane, 1,8-di (4-piperidyl) octane, and 1,10-di (4-piperidyl) decane.

Further, as the dithiol in which the functional group X ² is a mercapto group, those obtained by replacing “amino” with “mercapto” in the primary diamine and secondary diamine exemplified above, or “amine” Those substituted for "thiol" can be mentioned. The polyimide of (b) can be produced by reacting the bismaleimide represented by the general formula (8) with the compound represented by the general formula (10) in the presence of active hydrogen.

The polyimide (c) used as the component (I) contains the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) at an arbitrary ratio. By increasing the ratio of the structural unit represented by the general formula (2), the glass transition temperature of the obtained polyimide can be lowered. The polyimide of (c) is obtained by reacting the bismaleimide represented by the general formula (8), the compound represented by the general formula (9) and the compound represented by the general formula (10) in the presence of active hydrogen. It can be manufactured by the following.

Next, a method for producing the polyimide of the component (I) will be described. The polyimide of component (I) can be prepared by combining the above-mentioned bismaleimide compound with diamine, dithiol or a mixture thereof in an organic solvent, if necessary, with a tertiary amine catalyst such as tributylamine or triethylamine (reactant). In the presence of 20 parts by weight or less)
10 to 200 ° C, preferably 1 to 130 ° C
It is manufactured by heating for 48 hours. In particular, as a diamine or dithiol to react with bismaleimide,
When an aliphatic compound represented by the general formula (10) is used, the aliphatic diamine or the like usually has a high reactivity with maleimide, and thus is used at a relatively low temperature of 0 to 50 ° C. It is preferred to react.

As the organic solvent used in the above reaction, a protic phenolic solvent such as phenol, cresol, xylenol, p-chlorophenol or N-methyl-2-pyrrolidone, N, N-dimethylacetamide,
N, N-dimethylformamide, dimethylsulfoxide, sulfolane, hexamethylphosphoric triamide,
In aprotic polar solvents such as 3-dimethyl-2-imidazolidone, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, hexanoic acid, benzoic acid, p-toluenesulfonic acid,
An acid such as camphorsulfonic acid is added to an aprotic solvent 10
Examples thereof include those in which 1 to 100 parts by weight are added to 0 parts by weight. If these compounds having active hydrogen do not exist in the reaction system, the reaction of bismaleimide cannot be controlled, and only insoluble polyimide will be obtained. Further, in this reaction system, benzene, toluene, xylene, methyl ethyl ketone, acetone, tetrahydrofuran, dioxane, monoglyme, diglyme, methyl cellosolve, cellosolve acetate, methanol, ethanol, isopropanol, chloride Methylene, chloroform, trichlene, nitrobenzene and the like may be mixed and used. Also, by reacting bismaleimide and diamine or dithiol in equimolar amounts, a polyimide having a high degree of polymerization can be produced, but if necessary, any one of the polyimides can be prepared using an excess amount of 10 mol% or less. It is also possible to manufacture.

On the other hand, as the compound containing a maleimide group used as the component (II), any compound having any structure can be used. From the viewpoints of electrical reliability and solubility in a solvent, the following formula (7) -1) to (7-5) are preferred.

Embedded image

In the first adhesive for electronic parts, the mixing ratio of the component (I) and the component (II) is 100
Component (II) is used in an amount of 10 to 900 parts by weight, preferably 20 to 800 parts by weight, more preferably 50 to 5 parts by weight based on parts by weight.
Set to the range of 00 parts by weight. If the component (II) is less than 10 parts by weight, when the adhesive layer is cured to the B stage,
The hot melting temperature of the adhesive layer is increased, which is not suitable for a desired use. On the other hand, if it exceeds 900 parts by weight,
When the adhesive layer is cured to the B stage, the adhesive layer itself becomes brittle and the workability deteriorates, or the adhesion to the heat-resistant film as a support decreases.

The above-mentioned components (I) and (II) are mixed in an organic solvent in which both are dissolved. Examples of the organic solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, sulfolane, hexamethylphosphoric triamide, 1,3-dimethyl-2-amide.
Imidazolidone, hexane, benzene, toluene, xylene, methyl ethyl ketone, acetone, diethyl ether, tetrahydrofuran, dioxane, monoglyme,
Diglyme, methyl cellosolve, cellosolve acetate, methanol, ethanol, propanol, isopropanol, methyl acetate, ethyl acetate, acetonitrile,
Examples thereof include methylene chloride, chloroform, carbon tetrachloride, chlorobenzene, dichlorobenzene, dichloroethane, and trichloroethane. Of these, the type and amount in which both components are dissolved are appropriately selected and used.

Next, in addition to the components (I) and (II) used in the first electronic component adhesive, the second adhesive for electronic components further includes a component (III): It contains a diamine compound represented by the following general formula (5) or a diaminopolysiloxane compound represented by the following general formula (6) and having amino groups at both ends and having a weight average molecular weight of 200 to 7,000. H ₂ N—R ⁵ —NH ₂ (5) In the general formula (5), R ⁵ is a divalent aliphatic group, aromatic group or alicyclic group having 1 to 12 carbon atoms.

Examples of the diamine compound represented by the general formula (5) used as the component (III) include the following. 3,3'-diaminobiphenyl, 3,4'-diaminobiphenyl, 4,4'-diaminobiphenyl, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-
Diaminodiphenylmethane, 2,2- (3,3'-diaminodiphenyl) propane, 2,2- (3,4'-diaminodiphenyl) propane, 2,2- (4,4'-diaminodiphenyl) propane, 2- (3,3'-diaminodiphenyl) hexafluoropropane, 2,2-
(3,4'-diaminodiphenyl) hexafluoropropane, 2,2- (4,4'-diaminodiphenyl) hexafluoropropane, 3,3'-oxydianiline,
3,4'-oxydianiline, 4,4'-oxydianiline, 3,3'-diaminodiphenyl sulfide, 3,
4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 1,3-
Bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3
-Aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 3,3'-bis (3-aminophenoxy) diphenyl ether, 3,3'-bis (4-aminophenoxy) diphenyl ether, 3,
4'-bis (3-aminophenoxy) diphenyl ether, 3,4'-bis (4-aminophenoxy) diphenyl ether, 4,4'-bis (3-aminophenoxy)
Diphenyl ether, 4,4'-bis (4-aminophenoxy) diphenyl ether, 1,4-bis [1- (4
-Aminophenyl) -1-methylethyl-bis (3-aminophenoxy)] biphenyl, 3,3'-bis (4-
Aminophenoxy) biphenyl, 3,4'-bis (3-
Aminophenoxy) biphenyl, 3,4'-bis (4-
Aminophenoxy) biphenyl, 4,4'-bis (3-
Aminophenoxy) biphenyl, 4,4'-bis (4-
Aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-
Aminophenoxy) phenyl] sulfone, 2,2-bis [3- (3-aminophenoxy) phenyl] propane,
2,2-bis [3- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-
Aminophenoxy) phenyl] propane, 2,2-bis [3- (3-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [3- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2 -Bis [4- (3-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 9,9-
Bis (3-aminophenyl) fluorene, 9,9-bis (4-aminophenyl) fluorene and the like.

As the polysiloxane compound having an amino group at both ends represented by the general formula (6) and having a weight average molecular weight of 200 to 7,000, for example, bis (3-aminopropyl) tetra Examples thereof include methyldisiloxane, aminopropyl-terminated dimethylsiloxane tetramer or octamer, bis (3-aminophenoxymethyl) tetramethyldisiloxane, and the like, and these may be used as an appropriate mixture.

With respect to the mixing ratio of the above components, the component (I)
The total amount of component (II) and component (III) is set to 10 to 900 parts by weight, preferably 20 to 800 parts by weight, particularly preferably 50 to 500 parts by weight, per 100 parts by weight. When the total amount of the component (II) and the component (III) is less than 10 parts by weight, when the adhesive layer is cured to the B stage, the hot melting temperature of the adhesive layer becomes high, which is not suitable for a desired use. Become. On the other hand, if the amount exceeds 900 parts by weight, when the adhesive layer is cured to the B stage, the adhesive layer itself becomes brittle and the workability deteriorates, or the adhesion to the heat-resistant film as a support decreases. I do.

Further, the component (I) is replaced by the component (II) and the component
When compounding (III), the amino group equivalent of component (III) is added to 0.01 mole equivalent of maleimide group of component (II) in the total amount of component (II) and component (III). ~ 2.0 molar equivalents, preferably 0.05 ~
1.5, particularly preferably in the range of 0.1 to 1.0. When the amino group equivalent is less than 0.01, the solubility of the component (II) decreases, and it becomes difficult to prepare an adhesive. And the preparation of the adhesive becomes impossible. The mixing of the components (I), (II) and (III) is carried out in a solvent in which they are dissolved. As the solvent, the same solvent as that exemplified in the first electronic component adhesive is used.

A reaction accelerator is added to the first and second electronic component adhesives of the present invention, if necessary, in order to accelerate the curing reaction. As the reaction accelerator used,
Diazabicyclooctane, methyl ethyl ketone peroxide, cyclohexane peroxide, 3,3,5-
Trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, methyl acetoacetate peroxide, acetylacetone peroxide,
1,1-bis (t-butylperoxy) -3,3,5-
Trimethylhexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (t-butylperoxy) octane, n-butyl-4,4-bis (t-butylperoxy) valate, 2 , 2-Bis (t-butylperoxy) butane, t-butyl hydroperoxide, cumene hydroperoxide, di-isopropylbenzene hydroperoxide, p-menthane hydroperoxide, 2,5-dimethylhexane-2,5
-Dihydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, di-cumyl peroxide, α, α'-bis (t -Butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne , Acetyl peroxide, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, benzoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, succinic acid peroxide, 2,4-dichloro Benzoyl peroxide, m-toluoylpa -Oxide, di-isopropylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, di-n-propylperoxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, di-myristylperoxy Dicarbonate, di-2-ethoxyethylperoxydicarbonate, di-methoxyisopropylperoxydicarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, di-allylperoxydicarbonate, t-butyl Peroxyacetate,
t-butylperoxyisobutyrate, t-butylperoxypivalate, t-butylperoxyneodecanate, cumylperoxyneodecanate, t-butylperoxy-2-ethylhexanate, t-butylperoxy -3,5,5-trimethylhexanate, t-butylperoxylaurate, t-butylperoxybenzoate, di-t-butylperoxyisophthalate, 2,
5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxymaleic acid, t-butylperoxyisopropyl carbonate, cumylperoxyoctate, t-hexylperoxyneodecanate, t-hexyl Organic peroxides such as peroxypivalate, t-butylperoxyneohexanate, acetylcyclohexylsulfonyl peroxide, t-butylperoxyallylcarbonate, 1,2-dimethylimidazole, 1-methyl-2-ethylimidazole, 2
-Methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1- Benzyl-2-phenylimidazole trimellitate, 1-benzyl-2-ethylimidazole, 1-benzyl-2-ethyl-5-methylimidazole, 2-ethylimidazole, 2-isopropylimidazole, 2-phenyl-4- Benzylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-isopropylimidazole, 1-cyanoethyl 2-phenylimidazole, 1
-Cyanoethyl-2-methylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl (1 ')]-ethyl-s-triazine ,
2,4-diamino-6- [2′-ethyl-4-methylimidazolyl (1 ′)]-ethyl-s-triazine, 2,
4-diamino-6- [2'-undecylimidazolyl (1 ')]-ethyl-s-triazine, 2-methylimidazolium isocyanuric acid adduct, 2-phenylimidazolium isocyanuric acid adduct, 2,4 -Diamino-6- [2'-methylimidazolyl (1 ')]-ethyl-s-triazine-isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-
Phenyl-4-benzyl-5-hydroxymethylimidazole, 4,4'-methylene-bis (2-ethyl-5-
Methylimidazole), 1-aminoethyl-2-methylimidazole, 1-cyanoethyl-2-phenyl-4,
5-di (cyanoethoxymethyl) imidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazole / benzotriazole adduct, 1-aminoethyl-2-ethylimidazole,
1- (cyanoethylaminoethyl) -2-methylimidazole, N, N '-[2-methylimidazolyl (1)-
Ethyl] -adipoyldiamide, N, N'-bis [2-
Methylimidazolyl (1) -ethyl] urea, N- [2-
Methylimidazolyl (1) -ethyl] urea, N, N'-
[2-Methylimidazolyl (1) -ethyl] dodecandioyldiamide, N, N '-[2-methylimidazolyl (1) -ethyl] eicosandioilediamide, 1-benzyl-2-phenylimidazole hydrochloride And the like, and triphenylphosphine.

The first and second adhesives for electronic parts of the present invention may contain a filler having a particle size of 1 μm or less in order to stabilize taping characteristics when applied to an adhesive tape. The content of the filler is 4 to 40% by weight of the total solids, and is preferably set in the range of 9 to 24% by weight. When the content is less than 4% by weight, the effect of stabilizing the taping characteristics is reduced. On the other hand, when the content is more than 40% by weight, the adhesive strength of the adhesive tape is reduced, and the processability of laminating or the like is deteriorated. Examples of the filler used in the present invention include silica, quartz powder, alumina, calcium carbonate, magnesium oxide, diamond powder, mica, fluororesin, and zircon powder.

If necessary, the above-mentioned adhesive for electronic parts is isolated after completion of the reaction, washed with an organic solvent, water or a mixed solvent thereof, and dissolved again in the above-mentioned organic solvent before use. be able to. Organic solvents used for cleaning the adhesive include acetone, methyl ethyl ketone,
Hexane, benzene, toluene, xylene, methanol, ethanol, propanol, diethyl ether, tetrahydrofuran, methyl acetate, ethyl acetate, acetonitrile, methylene chloride, chloroform, carbon tetrachloride, chlorobenzene, dichlorobenzene, dichloroethane, trichloroethane and the like.

Next, the adhesive tape for electronic parts of the present invention using the above liquid adhesive will be described. In order to produce the adhesive tape for electronic parts of the present invention, the above-mentioned first or second adhesive for electronic parts is applied to, for example, one or both sides of a heat-resistant film or applied to one side of a peelable film. After that, it may be dried. At that time, the thickness of the formed coating layer is preferably in the range of 5 to 100 μm, particularly preferably in the range of 10 to 50 μm. As the heat-resistant film used for the adhesive tape, for example, polyimide,
Examples thereof include a film of a heat-resistant resin such as polyphenylene sulfide, polyether, polyparabanic acid, and polyethylene terephthalate, and a composite heat-resistant film such as an epoxy resin-glass cloth and an epoxy resin-polyimide-glass cloth. A polyimide resin film is particularly preferable. The thickness of the heat-resistant film is set in the range of 7.5 to 130 μm, preferably 12.5 to 75 μm. If the thickness is smaller than this, the elasticity of the adhesive tape becomes insufficient, and if the thickness is larger than that, it becomes difficult to punch out the adhesive tape. Therefore, the above range is preferable.

The releasable film functions as a temporary support, and has a thickness of 1 to 200 μm, preferably 10 to 100 μm. Examples of the peelable film that can be used include a polypropylene film, a fluororesin-based film, a polyethylene film, a polyethylene terephthalate film or paper, and the like, in which the surface thereof is optionally treated with a silicone resin to impart releasability. Can be These peelable films have a 90 ° peel strength of 0.01 to 7.0 g / cm.
It is desirable to have a range of When the peel strength is smaller than the above range, there is a problem that the peelable film is easily peeled off when the adhesive tape is transported, and when the peel strength is larger than the above range, the peelable film is not sufficiently peeled from the adhesive layer. Workability decreases.

Further, on one or both sides of the heat-resistant film,
After forming the adhesive layer by applying the adhesive, a releasable protective film may be further provided on the adhesive layer. As the protective film, the same as the above-mentioned peelable film can be used.

[0042]

EXAMPLES (Production Example of Adhesive for Electronic Parts) Example 1 28.53 g (50%) of 2,2-bis (p-maleimidophenoxyphenyl) propane was placed in a flask equipped with a stirrer.
Mmol) and 7.21 g of octamethylenediamine (50
Mmol) and 250 ml of m-cresol were introduced at room temperature and stirring was continued for 6 hours. Next, a precipitate formed by injecting the obtained polyimide varnish into methanol is separated, and then subjected to a step of pulverizing, washing, and drying to obtain a polyimide having a structural unit represented by the general formula (2). 0 g (95% yield) was obtained. Next, 50 parts by weight of the obtained polyimide, 47 parts by weight of a compound represented by the formula (7-1) (MB8000, manufactured by Mitsubishi Yuka Co., Ltd.)
1,3-bis (3-aminopropyl) -1,1,3,3
-A liquid adhesive having a solid content of 40% by weight, in which 3 parts by weight of tetramethyldisiloxane and 1 part by weight of an organic peroxide (Perbutyl P, manufactured by NOF Corporation) are added, mixed and sufficiently dissolved in tetrahydrofuran. I got

Example 2 28.53 g (50 mmol) of 2,2-bis (p-maleimidophenoxyphenyl) propane, 7.21 g (50 mmol) of N, N'-dimethylhexamethylenediamine and 250 ml of m-cresol were used. Example 1
33.0 g (yield: 92%) of a polyimide comprising the structural unit represented by the general formula (2) was obtained in the same manner as in the above. next,
The same procedure as in Example 1 was carried out except that the polyimide used in Example 1 was replaced with the polyimide obtained above, and the solid content ratio was 4%.
A 0% by weight liquid adhesive was obtained.

Example 3 28.53 g (50 mmol) of 2,2-bis (p-maleimidophenoxyphenyl) propane, 9.32 g (50 mmol) of 1,3-bis (4-piperidyl) propane and 250 ml of m-cresol Example 1
35.0 g (yield: 92%) of a polyimide comprising the structural unit represented by the general formula (2) was obtained in the same manner as in the above. next,
The same procedure as in Example 1 was carried out except that the polyimide used in Example 1 was replaced with the polyimide obtained above, and the solid content ratio was 4%.
A 0% by weight liquid adhesive was obtained.

Example 4 Using 28.53 g (50 mmol) of 2,2-bis (p-maleimidophenoxyphenyl) propane, 8.62 g (50 mmol) of 1,10-diaminodecane and 250 ml of m-cresol In the same manner as in Example 1, polyimide 35.0 comprising a structural unit represented by the general formula (2)
g (94% yield). Next, a liquid adhesive having a solid content of 40% by weight was obtained in the same manner as in Example 1, except that the polyimide used in Example 1 was replaced with the polyimide obtained above.

Example 5 28.53 g (50 mmol) of 2,2-bis (p-maleimidophenoxyphenyl) propane and 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldiene Using 12.43 g (50 mmol) of siloxane and 250 ml of m-cresol, 40.0 g (yield 98%) of a polyimide having a structural unit represented by the general formula (2) was obtained in the same manner as in Example 1. Obtained. Next, a liquid adhesive having a solid content of 40% by weight was obtained in the same manner as in Example 1, except that the polyimide used in Example 1 was replaced with the polyimide obtained above.

Example 6 28.53 g (50 mmol) of 2,2-bis (p-maleimidophenoxyphenyl) propane, 9.11 g (50 mmol) of 1,8-dimercapto-3,5-dioxaoctane and m- Using 250 ml of cresol and 1 ml of triethylamine as a catalyst, 37.0 g (yield 98%) of a polyimide having a structural unit represented by the general formula (2) was obtained in the same manner as in Example 1. Next, a liquid adhesive having a solid content of 40% by weight was obtained in the same manner as in Example 1, except that the polyimide used in Example 1 was replaced with the polyimide obtained above.

Example 7 28.53 g (50 mmol) of 2,2-bis (p-maleimidophenoxyphenyl) propane, 7.51 g (50 mmol) of 1,6-dimercaptohexane, 250 ml of m-cresol and triethylamine as a catalyst 1 ml
And 35.6 g of a polyimide having a structural unit represented by the general formula (2) in the same manner as in Example 1 (yield: 9).
9%). Next, a liquid adhesive having a solid content of 40% by weight was obtained in the same manner as in Example 1, except that the polyimide used in Example 1 was replaced with the polyimide obtained above.

Example 8 Using 22.12 g (50 mmol) of bis (4-maleimido-3-ethyl-5-methylphenyl) methane, 7.21 g (50 mmol) of octamethylenediamine and 250 ml of m-cresol, Polyimide 2 comprising a structural unit represented by the general formula (2) in the same manner as in Example 1.
8.0 g (95% yield) was obtained. Next, a liquid adhesive having a solid content of 40% by weight was obtained in the same manner as in Example 1, except that the polyimide used in Example 1 was replaced with the polyimide obtained above.

Example 9 22.12 g (50 mmol) of bis (4-maleimido-3-ethyl-5-methylphenyl) methane and N, N'-
Using 5.02 g (50 mmol) of dimethylhexamethylenediamine and 250 ml of m-cresol, 25.0 g of a polyimide having a structural unit represented by the general formula (2) in the same manner as in Example 1 (yield: 85). %). Next, a liquid adhesive having a solid content of 40% by weight was obtained in the same manner as in Example 1, except that the polyimide used in Example 1 was replaced with the polyimide obtained above.

Example 10 bis (4-maleimido-3-ethyl-5-methylphenyl) methane (22.12 g, 50 mmol), 1,3-di (4-piperidyl) propane (9.32 g, 50 mmol) and m Example 1 using 250 ml of cresol
30.0 g (yield: 95%) of a polyimide composed of the structural unit represented by the general formula (2) was obtained in the same manner as described above. next,
The same procedure as in Example 1 was carried out except that the polyimide used in Example 1 was replaced with the polyimide obtained above, and the solid content ratio was 4%.
A 0% by weight liquid adhesive was obtained.

Example 11 22.12 g (50 mmol) of bis (4-maleimido-3-ethyl-5-methylphenyl) methane and 1,10-
Using 8.62 g (50 mmol) of diaminodecane and 250 ml of m-cresol, a polyimide 2 having a structural unit represented by the general formula (2) in the same manner as in Example 1
8.0 g (91% yield) was obtained. Next, a liquid adhesive having a solid content of 40% by weight was obtained in the same manner as in Example 1, except that the polyimide used in Example 1 was replaced with the polyimide obtained above.

Example 12 22.12 g (50 mmol) of bis (4-maleimido-3-ethyl-5-methylphenyl) methane and 1,3-bis (3-aminopropyl) -1,1,3,3- 12.43 g (50 mmol) of tetramethyldisiloxane and m-
32.0 g (yield: 93%) of a polyimide composed of the structural unit represented by the general formula (2) was obtained in the same manner as in Example 1 using 250 ml of cresol. Next, a liquid adhesive having a solid content of 40% by weight was obtained in the same manner as in Example 1, except that the polyimide used in Example 1 was replaced with the polyimide obtained above.

Example 13 22.12 g (50 mmol) of bis (4-maleimido-3-ethyl-5-methylphenyl) methane and 9.11 g of 1,8-dimercapto-3,5-dioxaoctane (5
0 mmol), 250 ml of m-cresol, and 1 ml of triethylamine as a catalyst, in the same manner as in Example 1 to obtain 30.0 g (yield: 96%) of a polyimide having a structural unit represented by the general formula (2). Obtained. Next, Example 1
The same procedure as in Example 1 was carried out except that the polyimide used in Example 1 was replaced with the polyimide obtained above, and the solid content was 40% by weight.
Of a liquid adhesive was obtained.

Example 14 22.12 g (50 mmol) of bis (4-maleimido-3-ethyl-5-methylphenyl) methane, 7.51 g (50 mmol) of 1,6-dimercaptohexane and m-
Cresol 250 ml and triethylamine 1 as catalyst
and the general formula (2) in the same manner as in Example 1 using
As a result, 28.0 g (yield 94%) of a polyimide having the structural unit represented by was obtained. Next, a liquid adhesive having a solid content of 40% by weight was obtained in the same manner as in Example 1, except that the polyimide used in Example 1 was replaced with the polyimide obtained above.

Example 15 In a flask equipped with a stirrer, 28.53 g (50%) of 2,2-bis (p-maleimidophenoxyphenyl) propane was added.
Mmol) and 3,4'-diaminodiphenyl ether 1
0.01 g (50 mmol) and m-cresol 250 m
and stirring was continued at a reaction temperature of 100 ° C. for 6 hours. Next, the obtained polyimide varnish is poured into methanol, the generated precipitate is separated, and then subjected to a step of pulverizing, washing and drying, thereby obtaining 38.0 g of a polyimide having a structural unit represented by the general formula (1). (99% yield)
I got Next, 50 parts by weight of the obtained polyimide, the formula (7)
-1) (MB8000, manufactured by Mitsubishi Yuka Co., Ltd.) 47 parts by weight, 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane 3 parts by weight and organic peroxide 1 part by weight of a product (Perbutyl P, manufactured by NOF CORPORATION) was added to tetrahydrofuran, mixed and sufficiently dissolved to obtain a liquid adhesive having a solid content of 40% by weight.

Example 16 28.53 g (50 mmol) of 2,2-bis (p-maleimidophenoxyphenyl) propane, 9.91 g (50 mmol) of 4,4'-diaminodiphenylmethane and m
-Using 250 ml of cresol, 38.0 g (yield: 99%) of a polyimide consisting of the structural unit represented by the general formula (1) was obtained in the same manner as in Example 15. Next, the same procedure as in Example 15 was carried out except that the polyimide used in Example 15 was replaced with the polyimide obtained above, and the solid content was 40%.
By weight, a liquid adhesive was obtained.

Example 17 28.53 g (50 mmol) of 2,2-bis (p-maleimidophenoxyphenyl) propane and bis (4-amino-2-ethyl-5-methylphenyl) methane 14.1
Using 2 g (50 mmol) and 250 ml of m-cresol, 42.0 g of a polyimide having a structural unit represented by the general formula (1) in the same manner as in Example 15 (yield: 98)
%). Next, a liquid adhesive having a solid content of 40% by weight was obtained in the same manner as in Example 15 except that the polyimide used in Example 15 was replaced with the polyimide obtained above.

Example 18 28.53 g (50 mmol) of 2,2-bis (p-maleimidophenoxyphenyl) propane and 12.7 g of bis (4-amino-2,5-dimethylphenyl) methane
0 mmol) and 250 ml of m-cresol.
In the same manner as in Example 15, 41.0 g (yield: 99%) of a polyimide comprising the structural unit represented by the general formula (1) was obtained. Next, a liquid adhesive having a solid content of 40% by weight was obtained in the same manner as in Example 15 except that the polyimide used in Example 15 was replaced with the polyimide obtained above.

Example 19 28.53 g (50 mmol) of 2,2-bis (p-maleimidophenoxyphenyl) propane and 15.5 g of bis (4-amino-2,5-diethylphenyl) methane (5
0 mmol) and 250 ml of m-cresol.
In the same manner as in Example 15, 44.0 g (yield: 100%) of a polyimide comprising the structural unit represented by the general formula (1) was obtained. Next, a liquid adhesive having a solid content of 40% by weight was obtained in the same manner as in Example 15 except that the polyimide used in Example 15 was replaced with the polyimide obtained above.

Example 20 28.53 g (50 mmol) of 2,2-bis (p-maleimidophenoxyphenyl) propane and 12.42 g (50 mmol) of 4,4'-diaminodiphenyl sulfone
In the same manner as in Example 15, 34.0 g (yield: 83%) of a polyimide having a structural unit represented by the general formula (1) was obtained using and m-cresol (250 ml). Next, a liquid adhesive having a solid content of 40% by weight was obtained in the same manner as in Example 15 except that the polyimide used in Example 15 was replaced with the polyimide obtained above.

Example 21 28.53 g (50 mmol) of 2,2-bis (p-maleimidophenoxyphenyl) propane, 11.37 g (50 mmol) of 4,4'-diaminobenzanilide and m
-Using 250 ml of cresol, 39.5 g (yield: 99%) of a polyimide having the structural unit represented by the general formula (1) was obtained in the same manner as in Example 15. Next, the same procedure as in Example 15 was carried out except that the polyimide used in Example 15 was replaced with the polyimide obtained above, and the solid content was 40%.
By weight, a liquid adhesive was obtained.

Example 22 28.53 g (50 mmol) of 2,2-bis (p-maleimidophenoxyphenyl) propane and 2,2-bis [4- (4-aminophenoxy) phenyl] propane 2
0.53 g (50 mmol) and m-cresol 250
of the structural unit represented by the general formula (1) 48.0 in the same manner as in Example 15 with the use of 48.0 ml.
g (98% yield). Next, a liquid adhesive having a solid content of 40% by weight was obtained in the same manner as in Example 15 except that the polyimide used in Example 15 was replaced with the polyimide obtained above.

Example 23 28.53 g (50 mmol) of 2,2-bis (p-maleimidophenoxyphenyl) propane and 17.23 g (50 mmol) of 1,3-bis [2- (4-aminophenyl) isopropyl] benzene ) And m-cresol 250
and 45.0 polyimide comprising the structural unit represented by the general formula (1) in the same manner as in Example 15 using
g (98% yield). Next, a liquid adhesive having a solid content of 40% by weight was obtained in the same manner as in Example 15 except that the polyimide used in Example 15 was replaced with the polyimide obtained above.

Example 24 28.53 g (50 mmol) of 2,2-bis (p-maleimidophenoxyphenyl) propane and 17.23 g (50 mmol) of 1,4-bis [2- (4-aminophenyl) isopropyl] benzene ) And m-cresol 250
and 45.0 polyimide comprising the structural unit represented by the general formula (1) in the same manner as in Example 15 using
g (98% yield). Next, a liquid adhesive having a solid content of 40% by weight was obtained in the same manner as in Example 15 except that the polyimide used in Example 15 was replaced with the polyimide obtained above.

Example 25 28.53 g (50 mmol) of 2,2-bis (p-maleimidophenoxyphenyl) propane and 18.42 g of 5,4'-bis (4-aminophenoxy) biphenyl (5
0 mmol) and 250 ml of m-cresol.
In the same manner as in Example 15, 46.0 g (98% yield) of a polyimide comprising the structural unit represented by the general formula (1) was obtained. Next, a liquid adhesive having a solid content of 40% by weight was obtained in the same manner as in Example 15 except that the polyimide used in Example 15 was replaced with the polyimide obtained above.

Example 26 28.53 g (50 mmol) of 2,2-bis (p-maleimidophenoxyphenyl) propane and 14.62 g (50 mmol) of 1,4-bis (4-aminophenoxy) benzene
(Mmol) and 250 ml of m-cresol in the same manner as in Example 15 to obtain 43.0 g (yield: 99%) of a polyimide having a structural unit represented by the general formula (1). Next, a liquid adhesive having a solid content of 40% by weight was obtained in the same manner as in Example 15 except that the polyimide used in Example 15 was replaced with the polyimide obtained above.

Example 27 28.53 g (50 mmol) of 2,2-bis (p-maleimidophenoxyphenyl) propane and 8.71 g (50 mmol) of 9,9-bis (4-aminophenoxy) fluorene
(Mmol) and 250 ml of m-cresol, and 37.0 g (yield: 99%) of a polyimide having a structural unit represented by the general formula (1) was obtained in the same manner as in Example 15. Next, a liquid adhesive having a solid content of 40% by weight was obtained in the same manner as in Example 15 except that the polyimide used in Example 15 was replaced with the polyimide obtained above.

Example 28 28.53 g (50 mmol) of 2,2-bis (p-maleimidophenoxyphenyl) propane and 12.22 g of 3,3'-dimethoxy-4,4'-diaminobiphenyl
(50 mmol) and 250 ml of m-cresol in the same manner as in Example 15, 38.0 g of a polyimide having a structural unit represented by the general formula (1) (93% yield)
I got Next, a liquid adhesive having a solid content of 40% by weight was obtained in the same manner as in Example 15 except that the polyimide used in Example 15 was replaced with the polyimide obtained above.

Example 29 28.53 g (50 mmol) of 2,2-bis (p-maleimidophenoxyphenyl) propane and 10.62 g of 5,3'-dimethyl-4,4'-diaminobiphenyl (5.
0 mmol) and 250 ml of m-cresol.
In the same manner as in Example 15, 33.0 g (yield 84%) of a polyimide comprising the structural unit represented by the general formula (1) was obtained. Next, a liquid adhesive having a solid content of 40% by weight was obtained in the same manner as in Example 15 except that the polyimide used in Example 15 was replaced with the polyimide obtained above.

Example 30 28.53 g (50 mmol) of 2,2-bis (p-maleimidophenoxyphenyl) propane and bis [4- (4
-Aminophenoxy) phenyl] sulfone 21.63 g
(50 mmol) and 250 ml of m-cresol, in the same manner as in Example 15, 49.0 g of a polyimide comprising a structural unit represented by the general formula (1) (97% yield).
I got Next, a liquid adhesive having a solid content of 40% by weight was obtained in the same manner as in Example 15 except that the polyimide used in Example 15 was replaced with the polyimide obtained above.

Example 31 28.53 g (50 mmol) of 2,2-bis (p-maleimidophenoxyphenyl) propane and 25.93 g of 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane ( Using 50 ml of m-cresol and 250 ml of m-cresol, 52.0 g (yield: 95%) of a polyimide having a structural unit represented by the general formula (1) was obtained in the same manner as in Example 15. Next, the same procedure as in Example 15 was carried out except that the polyimide used in Example 15 was replaced with the polyimide obtained above, and the solid content was 40% by weight.
Of a liquid adhesive was obtained.

Example 32 27.83 g (50 mmol) of 4,4'-bis (m-maleimidophenoxy) benzophenone and 2,2-bis [4- (4-aminophenoxy) phenyl] propane 2
0.53 g (50 mmol) and m-cresol 250 m
l and the general formula (1) in the same manner as in Example 15.
As a result, 47.0 g (yield 97%) of a polyimide having the structural unit represented by was obtained. Next, Example 1 was repeated except that the polyimide used in Example 15 was replaced with the polyimide obtained above.
The same operation as in Example 5 was performed to obtain a liquid adhesive having a solid content of 40% by weight.

Example 33 Bis [4- (3-maleimidophenoxy) phenyl] sulfide 28.03 g (50 mmol) and 2,2-bis [4- (4-aminophenoxy) phenyl] propane 2
0.53 g (50 mmol) and m-cresol 250 m
l and the general formula (1) in the same manner as in Example 15.
As a result, 47.5 g (yield 98%) of a polyimide having the structural unit represented by the following formula was obtained. Next, Example 1 was repeated except that the polyimide used in Example 15 was replaced with the polyimide obtained above.
The same operation as in Example 5 was performed to obtain a liquid adhesive having a solid content of 40% by weight.

Example 34 In a flask equipped with a stirrer, 28.53 g (50%) of 2,2-bis (m-maleimidophenoxyphenyl) propane was added.
Mmol) and 1,3-bis (3-aminopropyl)-
6.21 g of 1,1,3,3-tetramethyldisiloxane
(25 mmol) was introduced into 250 ml of m-cresol and reacted at room temperature for 4 hours.
g (25 mmol) was added and reacted at 100 ° C. for 4 hours. The obtained polyimide varnish is poured into methanol, and the resulting precipitate is separated, crushed, washed, and dried. 42.0 g (yield 93%) of a polyimide containing the structural unit to be obtained was obtained. Next, 50 parts by weight of the obtained polyimide, 47 parts by weight of a compound represented by the formula (7-1) (MB8000, manufactured by Mitsubishi Yuka Co., Ltd.)
1,3-bis (3-aminopropyl) -1,1,3,3
-A liquid adhesive having a solid content of 40% by weight, in which 3 parts by weight of tetramethyldisiloxane and 1 part by weight of an organic peroxide (Perbutyl P, manufactured by NOF Corporation) are added, mixed and sufficiently dissolved in tetrahydrofuran. I got

Example 35 28.53 g (50 mmol) of 2,2-bis (m-maleimidophenoxyphenyl) propane and 4.56 g (25 mmol) of 1,8-dimercapto-3,5-dioxaoctane were added to m -Cresol was introduced into 250 ml, and reacted at room temperature for 4 hours. Then, 10.26 g (25 mmol) of 2,2-bis (p-aminophenoxyphenyl) propane was further added, and the mixture was reacted at 100 ° C. for 4 hours. The obtained polyimide varnish is poured into methanol, and the resulting precipitate is separated, crushed, washed and dried, and then subjected to the structural units represented by the general formula (1) and the structural units represented by the general formula (2). 41.0 g of polyimide containing structural units
(95% yield). Next, the obtained polyimide 50
Parts by weight of a compound represented by the formula (7-1) (MB800
0, manufactured by Mitsubishi Yuka Co., Ltd.) 47 parts by weight, 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane 3 parts by weight, and an organic peroxide (Perbutyl P, Japan 1 part by weight of Yushi Co., Ltd.) was added to tetrahydrofuran, mixed and sufficiently dissolved to obtain a liquid adhesive having a solid content of 40% by weight.

Example 36 28.53 g (50 mmol) of 2,2-bis (m-maleimidophenoxyphenyl) propane and 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldiene 6.21 g (25 mmol) of siloxane was introduced into 250 ml of m-cresol and reacted at room temperature for 4 hours, and then 4,4'-diaminodiphenylmethane 4.9 was added.
6 g (25 mmol) was added and reacted at 100 ° C. for 4 hours. The obtained polyimide varnish is poured into methanol, and the resulting precipitate is separated, crushed, washed and dried, and then subjected to the structural units represented by the general formula (1) and the structural units represented by the general formula (2). 37.0 g (93% yield) of a polyimide containing the structural unit to be obtained. Next, 50 parts by weight of the obtained polyimide, 47 parts by weight of a compound represented by the formula (7-1) (MB8000, manufactured by Mitsubishi Yuka Co., Ltd.)
1,3-bis (3-aminopropyl) -1,1,3,3
-A liquid adhesive having a solid content of 40% by weight, in which 3 parts by weight of tetramethyldisiloxane and 1 part by weight of an organic peroxide (Perbutyl P, manufactured by NOF CORPORATION) are added, mixed and sufficiently dissolved in tetrahydrofuran. I got

Example 37 28.53 g (50 mmol) of 2,2-bis (m-maleimidophenoxyphenyl) propane and 4.56 g (25 mmol) of 1,8-dimercapto-3,5-dioxaoctane were added to m -Cresol was introduced into 250 ml and allowed to react at room temperature for 4 hours. Then, 4.96 g (25 mmol) of 4,4'-diaminodiphenylmethane was further added thereto to give 10
The reaction was performed at 0 ° C. for 4 hours. The obtained polyimide varnish is poured into methanol, and the generated precipitate is separated, pulverized,
Through the steps of washing and drying, 36.0 g (95% yield) of a polyimide containing the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) was obtained. Next, 50 parts by weight of the obtained polyimide, the formula (7-
47 parts by weight of the compound represented by 1) (MB8000, manufactured by Mitsubishi Yuka Co., Ltd.), 3 parts by weight of 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane and an organic peroxide 1 part by weight of an oxide (Perbutyl P, manufactured by NOF Corporation) was added to tetrahydrofuran, mixed and sufficiently dissolved to obtain a liquid adhesive having a solid content of 40% by weight.

Example 38 70 parts by weight of the polyimide obtained in Example 22 were prepared according to the formula (7-
30 parts by weight of the compound represented by 1) (MB8000, manufactured by Mitsubishi Yuka Co., Ltd.) and 1 part by weight of an organic peroxide (Perbutyl P, manufactured by NOF CORPORATION) are added to tetrahydrofuran, mixed and dissolved sufficiently. Thus, a liquid adhesive having a solid content of 40% by weight was obtained. Example 39 In Example 38, 70 parts by weight of the polyimide was added to 50 parts by weight, and 30 parts by weight of the compound represented by the formula (7-1) was added to 50 parts by weight.
A liquid adhesive was obtained in the same manner as in Example 38 except that the amount was changed to parts by weight.

Example 40 In Example 38, 70 parts by weight of polyimide was added to 30 parts by weight, and 30 parts by weight of the compound represented by the formula (7-1) was added to 70 parts by weight.
A liquid adhesive was obtained in the same manner as in Example 38 except that the amount was changed to parts by weight. Example 41 In Example 38, 70 parts by weight of the polyimide was added to 10 parts by weight, and 30 parts by weight of the compound represented by the formula (7-1) was added to 90 parts by weight.
A liquid adhesive was obtained in the same manner as in Example 38 except that the amount was changed to parts by weight.

Example 42 The procedure of Example 38 was repeated, except that the compound represented by the formula (7-1) was replaced by a compound represented by the formula (7-2) (MB3000H, manufactured by Mitsubishi Yuka Co., Ltd.). A liquid adhesive was obtained in the same manner as in Example 38. Example 43 Example 38 was repeated except that the compound represented by the formula (7-1) was replaced by a compound represented by the formula (7-3) (MB7000, manufactured by Mitsubishi Yuka Co., Ltd.). The same operation was performed to obtain a liquid adhesive.

Example 44 The procedure of Example 38 was repeated, except that the compound represented by the formula (7-1) was replaced by the compound represented by the formula (7-4). Agent was obtained. Example 45 A liquid adhesive was obtained in the same manner as in Example 38, except that the compound represented by the formula (7-1) was changed to a compound represented by the formula (7-5). Was.

Example 46 30 parts by weight of the polyimide obtained in Example 22 were prepared according to the formula (7-
61 parts by weight of the compound represented by 1) (MB8000, manufactured by Mitsubishi Yuka Co., Ltd.), 9 parts by weight of 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane and an organic peroxide One part by weight of an oxide (Perbutyl P, manufactured by NOF Corporation) was added to tetrahydrofuran, mixed and sufficiently dissolved to obtain a liquid adhesive having a solid content of 40% by weight.

Example 47 In Example 46, the compound 6 of the formula (7-1)
Except that 1 part by weight was changed to 63 parts by weight and 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane 9 parts by weight was changed to 7 parts by weight. A liquid adhesive was obtained in the same manner as in Example 46. Example 48 In Example 46, the compound 6 represented by the formula (7-1):
Except that 1 part by weight was changed to 66 parts by weight and 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane was changed to 9 parts by weight to 4 parts by weight. A liquid adhesive was obtained in the same manner as in Example 46.

Example 49 In Example 46, the compound 6 of the formula (7-1)
Except that 1 part by weight was changed to 68 parts by weight, and 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane was changed to 9 parts by weight to 2 parts by weight. A liquid adhesive was obtained in the same manner as in Example 46. Example 50 In Example 46, 30 parts by weight of polyimide was added to 70 parts by weight, and 61 parts by weight of the compound represented by the formula (7-1) was added to 28 parts by weight.
In parts by weight, 1,3-bis (3-aminopropyl)
A liquid adhesive was obtained in the same manner as in Example 46, except that 9 parts by weight of -1,1,3,3-tetramethyldisiloxane was changed to 2 parts by weight.

Example 51 In Example 46, 30 parts by weight of the polyimide resin was added to 10 parts by weight.
61 parts by weight of the compound represented by the formula (7-1) to 85 parts by weight, and 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane 9 A liquid adhesive was obtained in the same manner as in Example 46 except that the weight part was changed to 5 parts by weight.

Example 52 In Example 46, the compound 6 of the formula (7-1)
1 part by weight to 62 parts by weight, and 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane 9 parts by weight to α, ω-bis (3-aminopropyl)
A liquid adhesive was obtained in the same manner as in Example 46, except that 8 parts by weight of polydimethylsiloxane (n = 3) was used.

Example 53 In Example 46, the compound 6 of the formula (7-1)
1 part by weight to 58 parts by weight and 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane 9 parts by weight to α, ω-bis (3-aminopropyl)
A liquid adhesive was obtained in the same manner as in Example 46, except that polydimethylsiloxane (n = 7) was replaced by 12 parts by weight.

Example 54 In Example 46, the compound 6 of the formula (7-1)
1 part by weight to 64 parts by weight, and 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane 9 parts by weight to 1,3-bis (3-aminophenoxymethyl) ) A liquid adhesive was obtained in the same manner as in Example 46, except that 6 parts by weight of 1,1,3,3-tetramethyldisiloxane was used.

Example 55 In Example 46, the compound 6 of the formula (7-1)
Except that 1 part by weight was replaced by 69 parts by weight and 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane by 9 parts by weight was replaced by 1 part by weight of ethylenediamine. A liquid adhesive was obtained in the same manner as in Example 46.

Example 56 In Example 46, the compound 6 of the formula (7-1)
Except that 1 part by weight was changed to 68 parts by weight and 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane 9 parts by weight was changed to hexamethylenediamine 2 parts by weight. Was operated in the same manner as in Example 46 to obtain a liquid adhesive.

Example 57 In Example 46, the compound 6 of the formula (7-1)
1 part by weight was changed to 67 parts by weight, and 9 parts by weight of 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane was changed to 3 parts by weight of 1,8-diaminooctane. A liquid adhesive was obtained in the same manner as in Example 46 except for the above.

Example 58 In Example 46, the compound 6 of the formula (7-1)
1 part by weight was changed to 66 parts by weight, and 9 parts by weight of 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane was changed to 4 parts by weight of 3,4-diaminodiphenyl ether. A liquid adhesive was obtained in the same manner as in Example 46 except for the above.

Example 59 In Example 46, the compound 6 of the formula (7-1)
1 part by weight to 63 parts by weight, and 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane 9 parts by weight to 2,2-bis [4- (4- A liquid adhesive was obtained in the same manner as in Example 46, except that 7 parts by weight of [aminophenoxy) phenyl] propane was used.

Example 60 Liquid adhesion was carried out in the same manner as in Example 46, except that the compound represented by the formula (7-1) was replaced by the compound represented by the formula (7-2). Agent was obtained.

Example 61 Liquid adhesion was carried out in the same manner as in Example 46, except that the compound represented by the formula (7-1) was replaced by the compound represented by the formula (7-3). Agent was obtained. Example 62 A liquid adhesive was obtained in the same manner as in Example 46, except that the compound represented by the formula (7-1) was changed to a compound represented by the formula (7-4). Was. Example 63 A liquid adhesive was obtained in the same manner as in Example 46, except that the compound represented by the formula (7-1) was changed to a compound represented by the formula (7-5). Was.

Example 64 In Example 46, except that the polyimide obtained in Example 22 was replaced with the polyimide obtained in Example 1,
A liquid adhesive was obtained in the same manner as in Example 46. Example 65 A liquid adhesive was obtained in the same manner as in Example 46, except that the polyimide obtained in Example 22 was replaced with the polyimide obtained in Example 15.

Comparative Example 1 A nylon epoxy adhesive (Toresin FS-410, manufactured by Teikoku Chemical Industry Co., Ltd.) (solid content: 20%, solvent: isopropyl alcohol: methyl ethyl ketone = 2: 1) was prepared. Comparative Example 2 A 20% by weight solution of N-methyl-2-pyrrolidone of a polyimide varnish (Lark TPI, manufactured by Mitsui Toatsu Chemicals, Inc.) was prepared.

Comparative Example 3 A weight average molecular weight of 70,0 represented by the following general formula (11)
No. 00, butadiene-acrylonitrile copolymer containing piperazinylethylaminocarbonyl group having an acrylonitrile content of 25% by weight and an amino group equivalent of 4,000 (a = 5
5, b = 1.8, c = 1) 50 parts by weight, the formula (7-
47 parts by weight of the compound represented by 1) (MB8000, manufactured by Mitsubishi Yuka Co., Ltd.), 3 parts by weight of 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane and an organic peroxide An oxide (Perbutyl P, manufactured by NOF Corporation) was added to tetrahydrofuran, mixed and sufficiently dissolved to obtain a liquid adhesive having a solid content of 40% by weight.

Embedded image

Comparative Example 4 In a flask equipped with a stirrer, 28.53 g (50%) of 2,2-bis (p-maleimidophenoxyphenyl) propane was added.
Mmol) and 7.21 g of octamethylenediamine (50
Mmol) and 250 ml of m-cresol were introduced at room temperature and stirring was continued for 6 hours. Next, a precipitate formed by injecting the obtained polyimide varnish into methanol is separated, and then subjected to a step of pulverizing, washing, and drying to obtain a polyimide having a structural unit represented by the general formula (2). 0 g (95% yield) was obtained. Next, 50 parts by weight of the obtained polyimide and 50 parts by weight of a bisphenol A type resole phenol resin were added to tetrahydrofuran, mixed and sufficiently dissolved to obtain a liquid adhesive having a solid content of 40% by weight.

(Production Example of Adhesive Tape for Electronic Parts) Adhesive Tapes 1 to 65 The liquid adhesive obtained in Examples 1 to 65 was applied to a thickness of 50 μm so that the thickness of the dried adhesive layer was 20 μm. And then dried at 150 ° C. for 5 minutes in a hot air circulating drier to form an adhesive tape 1
~ 65 were produced.

Comparative Adhesive Tape 1 The adhesive of Comparative Example 1 was dried with an adhesive layer having a thickness of 20 μm.
m was applied to both sides of the polyimide film, and dried in a hot-air circulation type dryer at 150 ° C. for 15 minutes to prepare Comparative Adhesive Tape 1. Comparative adhesive tape 2 The adhesive of Comparative Example 2 was dried with an adhesive layer having a thickness of 20 μm.
m, and dried in a hot-air circulation type dryer at 150 ° C. for 120 minutes and then at 250 ° C. for 60 minutes to obtain a comparative adhesive tape 2
Was prepared.

Comparative Adhesive Tape 3 The adhesive of Comparative Example 3 was dried with an adhesive layer having a thickness of 20 μm.
m was applied to both sides of the polyimide film and dried at 150 ° C. for 5 minutes in a hot air circulating drier to prepare a comparative adhesive tape 3. Comparative adhesive tape 4 The adhesive of Comparative Example 4 was dried with an adhesive layer having a thickness of 20 μm.
m was applied to both sides of the polyimide film and dried in a hot-air circulation type dryer at 150 ° C. for 5 minutes to prepare a comparative adhesive tape 4.

(Assembly of Lead Frame) A lead frame used for the semiconductor package shown in FIG. 1 was assembled under the working conditions shown in Table 1 by the following procedure. (A) Punching of adhesive tape The adhesive tape was punched into a ring shape using a mold. (B) Temporary Adhesion of Adhesive Tape A plane was placed on a hot plate, and the tape punched in a ring shape was pressed against the plane with a metal rod and temporarily adhered under the conditions shown in Table 1. (C) Assembling the lead frame Align the plane to which the adhesive tape was temporarily adhered in the above process with the lead frame body, and heat and press on a hot plate heated to 120 ° C. The sheets were laminated under the conditions described in 1. (D) Curing of Adhesive Tape With respect to the lead frames using the adhesive tapes 1 to 65 and the adhesives of Comparative Examples 1, 3, and 4, the adhesive layer was formed under a condition shown in Table 1 in a hot air circulating oven purged with nitrogen. Cured. The reason why the bonding conditions and the curing conditions are different at the time of assembling the lead frame is that the characteristics of the respective adhesive tapes are different. Here, the optimum bonding conditions were selected for each adhesive tape, and the adhesive was cured based on the optimum conditions.

[0105]

[Table 1]

(Assembly of Semiconductor Package) Thereafter, a semiconductor package was assembled by the following procedure using the manufactured lead frame. (A) Die bonding A semiconductor chip was bonded to a plane portion using a silver paste for die bonding, and cured at 150 ° C. for 2 hours. (B) Wire bonding A wire bonder is used to wire the wire pad on the semiconductor chip and the silver-plated portion at the end of the inner lead wire using a gold wire. (C) Molding Transfer molding with an epoxy-based molding agent. (D) Finishing process The package is finished through processes such as homing, die cutting, and plating of the outer lead portion.

(Evaluation Results of Adhesive Tape and Semiconductor Package) (a) Temperature at which taping is possible An evaluation was made as to whether or not the adhesive tape was easily and quickly adhered to an adherend, that is, to a plane or a lead pin. Specifically, the temperature range where each adhesive tape could be adhered to the lead frame was measured by a taping machine. As a result, the adhesive tapes 1 to 65 (hereinafter referred to as “the adhesive tape of the present invention”) and the comparative adhesive tapes 1, 3, and 4
In the case of using, the adhesive could be bonded in a temperature range of 100 to 240 ° C. However, bonding using the comparative adhesive tape 2 required a high temperature of 350 ° C. or more. (B) Oxidation of the lead frame By visually determining the discoloration of the lead frame surface,
During the curing of the adhesive, it was evaluated whether or not oxidation of the lead frame surface occurred. As a result, the adhesive tape of the present invention and the comparative adhesive tapes 1, 3, and 4 were not oxidized because they were taped at a low temperature, whereas the adhesive tape of Comparative Example 2 had a high adhesive temperature and a long time. , And discoloration was observed, and the lead frame was oxidized.

(C) Adhesive strength After affixing an adhesive tape on a copper plate at 150 ° C. (taping), a 90 ° peel strength at room temperature of a tape having a width of 10 mm was measured. As a result, the adhesive tape of the present invention had a weight of 400 to 500 g / 10 mm. On the other hand, that of the comparative adhesive tape 1 is 20 to 40 g / 1.
0 mm, 100 to 500 g /
10 mm, 300 to 47 for the adhesive tapes 3 and 4
0 g / 10 mm, and the fluctuation width was large between the comparative adhesive tapes.

(D) Voids When the adhesive was cured, whether or not voids generated in the adhesive were at a practically problematic level was evaluated by visual judgment using a microscope. As a result, no voids were observed in the adhesive tape of the present invention and the comparative adhesive tapes 2 to 4, whereas the comparative adhesive tape 1
In the case of, a void was observed.

(E) Workability Handling property (curl, running property) at the time of use such as taping of an adhesive tape when assembling a lead frame, and tackiness of the adhesive surface of the adhesive tape were also evaluated. As a result, the adhesive tape of the present invention, the comparative adhesive tape 3
And 4 all have good handling properties, and
While no tack was produced on the surface, the comparative adhesive tape 1 produced a surface tack, and the comparative adhesive tape 2 was curled, causing a problem in handling properties.

(F) Wire Bondability At the time of assembling the package, the wire bondability of the gold wire onto the lead frame during wire bonding was confirmed. As a result, in the test using the adhesive tape of the present invention and the comparative adhesive tapes 2 and 3, the bonding failure was zero in the test of 832 pins. On the other hand, in the case of using the comparative adhesive tape 1, bonding failure of 123 pins among 832 products was confirmed, and the bonding of the gold wire could not be performed to a sufficient strength. In addition, the comparative adhesive tape 4
In the case of using No. 1, bonding failure of 51 pins among 832 products was confirmed.

(G) Evaluation of Semiconductor Package The package obtained as described above was
T Test (Pressure Cooker Base)
d Test). Operating conditions for this test were applied to 5 volts, 121 ° C., 2 atm, 100%
The test was performed at RH and an electrical reliability test was performed. As a result, the adhesive tape of the present invention and the comparative adhesive tape 2
No. 4 did not cause a short circuit even after 1000 hours. On the other hand, in the case of using the comparative adhesive tape 1, short-circuit occurred in 223 hours.

(H) Evaluation of amount of gas generated during heating TGA (thermogravimetric / differential thermal analyzer) (TG / DTA32)
0, manufactured by Seiko Electronic Industry Co., Ltd.)
The sample was kept at 250 ° C. for 1 hour in a nitrogen atmosphere, and the weight loss rate was measured. As a result, the weight loss rate of the adhesive tape of the present invention was 0.2% by weight or less, whereas that of Comparative adhesive tape 1 was 7% by weight.
Is 0.2% by weight or less, Comparative Adhesive Tape 3 is 0.8% by weight, and Comparative Adhesive Tape 4 is 3.
It was 5% by weight.

As is clear from the above results, any of the adhesive tapes produced by using the adhesive of the present invention can produce a good semiconductor package. On the other hand, the comparative adhesive tapes all lead to oxidation of the lead frame, that the bonding conditions are not suitable for assembling the lead frame, the inability to wire bond gold wires, and the amount of gas generated during heating. However, it is not suitable for use in the production of electronic components.

[0115]

Since the adhesive for electronic parts of the present invention has the above-mentioned structure, it can be adhered and cured at a relatively low temperature, and has sufficient heat resistance and high reliability. The adhesive tape for electronic parts of the present invention manufactured by using, for example, a tape for fixing a lead frame, a tape for TAB, etc., between members around a lead frame constituting a semiconductor device, for example, a lead pin, a substrate for mounting a semiconductor chip. It can be suitably used for bonding a heat sink, a semiconductor chip itself and the like.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of an example of a resin-sealed semiconductor device to which an adhesive tape of the present invention is applied.

FIG. 2 is a cross-sectional view of another example of the resin-sealed semiconductor device to which the adhesive tape of the present invention is applied.

FIG. 3 is a cross-sectional view of another example of the resin-sealed semiconductor device to which the adhesive tape of the present invention is applied.

[Explanation of symbols]

1 semiconductor chip, 2 plane, 3 lead pin, 4
... bonding wire, 5 ... resin, 6 ... adhesive layer, 7 ...
Die pad, 8 ... electrode.

Claims (8)

[Claims] 1. A polyimide containing (I) (a) a structural unit represented by the following general formula (1) in an organic solvent:
(B) A polyimide containing a structural unit represented by the following general formula (2) and (c) a structural unit represented by the following general formula (1) and a structural unit represented by the general formula (2) are optionally selected. At least one polyimide selected from the polyimides contained in a proportion of (II) and a compound containing two or more maleimide groups (II), and the component (II) is added to 100 parts by weight of the component (I). An adhesive for electronic components, which is 10 to 900 parts by weight. Embedded image [In the formula, Ar represents a divalent group represented by the following general formula (3) or the following general formula (4). Ra represents a divalent group having 2 to 6 benzene rings, and Rb represents 2 to 20 carbon atoms.
Alkylene group, —CH ₂ CH ₂ (OCH ₂ CH ₂ ) _n
- (n is an integer from 1 to 8.) Ether chain or -R 'represented by _{- [Si (CH 3) 2} O] m Si (C
_{H 3) 2 -R '- (} R' is an alkyl group or -CH ₂ OC ₆ H ₄ having 1 to 10 carbon atoms - dimethylsiloxane group indicates, m is represented by an integer from 1 to 20). Is shown.
X ¹ represents NH, NR (R represents an alkyl group having 1 to 4 carbon atoms) or S. X ² is NH, NR (R represents an alkyl group having 1 to 4 carbon atoms), and Or S is shown. ] (Wherein, Y is -O -, - CO -, - S -, - SO 2 - or _{-C (CH 3) 2 - .R} 1 ~R 4 showing a each represent an alkyl group having 1 to 4 carbon atoms Or an alkoxy group having 1 to 4 carbon atoms.) 2. A polyimide containing (I) (a) a structural unit represented by the general formula (1) in an organic solvent,
(B) An arbitrary ratio of the polyimide containing the structural unit represented by the general formula (2) and (c) the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) At least one polyimide selected from polyimides containing, (II) a compound containing two or more maleimide groups, and
(III) dissolving a diamine compound represented by the following general formula (5) or a diaminopolysiloxane compound having an amino group at both terminals and having a weight average molecular weight of 200 to 7,000 represented by the following general formula (6), And component (I) 100
The total amount of component (II) and component (III) is 1 part by weight.
0 to 900 parts by weight of an adhesive for electronic parts. H ₂ N—R ⁵ —NH ₂ (5) (wherein, R ⁵ represents a divalent aliphatic group, aromatic group or alicyclic group having 1 to 12 carbon atoms). (In the formula, R ⁶ represents a divalent aliphatic group, aromatic group or alicyclic group having 1 to 3 carbon atoms, and k is an integer of 0 to 7.) 3. The component (II) and the component (III), based on 1 mole equivalent of the maleimide group of the component (II), in the total amount of the component (II) and the component (III)
3. The adhesive for electronic parts according to claim 2, wherein the amino group equivalent of (III) is 0.01 to 2.0. 4. The compound having two or more maleimide groups of the component (II) is selected from compounds represented by the following formulas (7-1) to (7-5). The adhesive for electronic components according to claim 1. Embedded image (In the formula, p is an integer of 0 to 7.) 5. The electronic component adhesive according to claim 1, wherein a filler having a particle size of 1 μm or less is contained in an amount of 4 to 40% by weight of the total solid. 6. An electronic component characterized by laminating an adhesive layer formed by the adhesive for electronic components according to claim 1 on at least one surface of a heat-resistant film. Adhesive tape. 7. The adhesive tape for electronic parts according to claim 6, wherein the heat-resistant film is a polyimide film. 8. An electronic component characterized in that an adhesive layer formed by the adhesive for electronic components according to claim 1 is laminated on at least one surface of a peelable film. Adhesive tape.