JP2002012845A - Adhesive film and semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive film for die bond, having good adhesion in a hot condition, and high reliability in a condition of high temperature and high humidity, and further to provide a semiconductor device obtained by using the adhesive film. SOLUTION: This adhesive film contains a polyimide resin having a repeating unit represented by general formula (I) (wherein, R is a divalent organic group as a diamine residue). The semiconductor device is obtained by sticking semiconductor elements to each other or the semiconductor element to a supporting member by using the adhesive film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive film used as a bonding material for a semiconductor element such as an IC or LSI and a supporting member such as a lead frame or an insulating support substrate, that is, an adhesive film used as a die bonding material, and manufactured using the same. Semiconductor device to be used.

[0002]

2. Description of the Related Art Conventionally, an Au-Si eutectic alloy, solder, silver paste, or the like has been used for joining an IC or LSI to a lead frame. The Au-Si eutectic alloy has high heat resistance and high moisture resistance, but has a large elasticity, so that it is easily broken when applied to a large chip, and is expensive.
Although solder is inexpensive, it has poor heat resistance, and its elastic modulus is as high as Au-Si eutectic alloy, making it difficult to apply it to large chips.

On the other hand, silver paste is inexpensive, has high moisture resistance, has the lowest elastic modulus among the above three, and has heat resistance applicable to a thermocompression bonding wire bonder at 350 ° C. It is the mainstream of materials for bonding lead frames. However, as ICs and LSIs have become more highly integrated in recent years and the chips have become larger,
When the lead frame is bonded to the C or LSI with the silver paste, it is difficult to spread the silver paste over the entire surface of the chip and apply it.

[0004] Microelectronic Manufacturing and Testing (MICROELECTRONIC)
MANUFACTURING AND TESTING (October 1985) reported an adhesive film for die bonding in which a conductive filler was filled in a thermoplastic resin. In this method, the temperature is raised to around the melting point of the thermoplastic resin and pressure bonding is performed. The conductive adhesive film reported in the above magazine can lower the bonding temperature if a thermoplastic resin having a low melting point is selected and used, so that damage to the chip such as oxidation of the lead frame can be reduced. However, since the adhesive strength at the time of heat is low, it cannot withstand heat treatment after die bonding, for example, a wire bonding and a sealing step. If a thermoplastic resin having a high melting point is used so as to withstand such heat treatment, there is a problem that the bonding temperature becomes high and the lead frame is damaged by oxidation or the like.

[0005] In order to solve these problems, there is an adhesive film using a specific polyimide resin, and an adhesive film for die bonding containing a conductive filler or an inorganic filler (see JP-A-6-45639 and JP-A-7-45639). 228697
JP-A-11-92744 and others.

[0006] The adhesive film for die bonding can be bonded at a relatively low temperature and has a good adhesive strength when heated. Therefore, it can be suitably used not only for the 42 alloy lead frame but also for the copper lead frame and the insulating support base.
However, recent semiconductor mounting methods have reduced the number of sealing members for protecting semiconductor elements in order to achieve a smaller and thinner than conventional semiconductor mounting methods. Therefore, it is easily affected by temperature and humidity, and it is difficult to ensure reliability under high temperature and high humidity conditions.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide an adhesive film for die bonding having good adhesive strength at the time of heat and high reliability under high temperature and high humidity conditions, and a semiconductor device using the same.

[0008]

The present invention relates to a compound represented by the general formula (I):

Embedded image (Where R is a divalent organic group as a diamine residue)
The present invention relates to an adhesive film containing a polyimide resin having a repeating unit represented by the formula:

Further, the present invention provides that the polyimide resin represented by the above general formula (I) comprises 3% of all tetracarboxylic dianhydrides.
0 mol% or more of the formula (II)

Embedded image And to an adhesive film obtained by reacting a tetracarboxylic dianhydride containing a tetracarboxylic dianhydride with a diamine.

Further, the present invention relates to (A) 100 parts by weight of a polyimide resin having a repeating unit represented by the general formula (I), (B) 200 parts by weight or less of a thermosetting resin, and (C) a filler. The present invention relates to the adhesive film containing 8000 parts by weight or less. In addition, the present invention relates to a semiconductor device in which semiconductor elements are bonded to each other or a semiconductor element and a support member using the adhesive film.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The polyimide resin having a repeating unit represented by the general formula (I) used in the present invention has the formula (I)
It can be obtained by reacting a tetracarboxylic dianhydride containing the tetracarboxylic dianhydride represented by I) with a diamine. The tetracarboxylic dianhydride represented by the formula (II) accounts for 30 mol% of all the tetracarboxylic dianhydrides.
It is preferably used in an amount of 50 mol% or more, more preferably 70 mol% or more.

The tetracarboxylic dianhydride usable together with the tetracarboxylic dianhydride of the formula (II) includes, for example, pyromellitic dianhydride, 3,3 ', 4,4'-diphenyltetracarboxylic dianhydride. Anhydrous, 2,2 ', 3
3'-diphenyltetracarboxylic dianhydride, 2,2-
Bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride Anhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, bis (2,3-
Dicarboxyphenyl) methane dianhydride, bis (3,4
-Dicarboxyphenyl) methane dianhydride, bis (3,
4-dicarboxyphenyl) sulfone dianhydride, 3,
4,9,10-perylenetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 3,4 3 ', 4'-benzophenonetetracarboxylic dianhydride, 2,3,2', 3-benzophenonetetracarboxylic dianhydride, 2,3,3 ', 4'-benzophenonetetracarboxylic dianhydride, , 2,5,6-
Naphthalenetetracarboxylic dianhydride, 2,3,6,7
-Naphthalenetetracarboxylic dianhydride, 1,2,4
5-naphthalenetetracarboxylic dianhydride, 1,4
5,8-naphthalenetetracarboxylic dianhydride, 2,6
-Dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,
5,8-tetracarboxylic dianhydride, 2,3,6,7-
Tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, phenanthrene-1,8,9,10-
Tetracarboxylic dianhydride, pyrazine-2,3,5,6
-Tetracarboxylic dianhydride, thiophene-2,3
4,5-tetracarboxylic dianhydride, 2,3,3 ',
4'-biphenyltetracarboxylic dianhydride, 3,4
3 ', 4'-biphenyltetracarboxylic dianhydride,
2,3,2 ', 3'-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) dimethylsilane dianhydride, bis (3,4-dicarboxyphenyl) methylphenylsilane dianhydride , Bis (3,4-dicarboxyphenyl) diphenylsilane dianhydride, 1,
4-bis (3,4-dicarboxyphenyldimethylsilyl) benzene dianhydride, 1,3-bis (3,4-dicarboxyphenyl) -1,1,3,3-tetramethyldicyclohexane dianhydride, p-phenylenebis (trimellitate anhydride), ethylenetetracarboxylic dianhydride,
1,2,3,4-butanetetracarboxylic dianhydride, decahydronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6 ,
7-hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, cyclopentane-1,2,3,4
-Tetracarboxylic dianhydride, pyrrolidine-2,3
4,5-tetracarboxylic dianhydride, 1,2,3,4-
Cyclobutanetetracarboxylic dianhydride, bis (exobicyclo [2,2,1] heptane-2,3-dicarboxylic dianhydride) sulfone, bicyclo- (2,2,2) -oct (7) -ene 2 , 3,5,6-tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,2-bis [4- (3,4-dicarboxy) Phenoxy) phenyl]
Hexafluoropropane dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydride, 1,4-bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimellitic acid dianhydride) Anhydride), 1,3-bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimellitic dianhydride), 5- (2,5-dioxotetrahydrofuryl)-
There are 3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride and the like, and two or more kinds may be used in combination.

Other diamines as raw materials for producing the polyimide resin for the adhesive film of the present invention include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,1
Aliphatic diamines such as 2-diaminododecane, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,3'-diaminodiphenyl ether;
3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane,
4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenyldifluoromethane, 3,4'-diaminodiphenyldifluoromethane, 4,4'-diaminodiphenyldifluoromethane, 3,3'-diaminodiphenylsulfone, 3,4 '-Diaminodiphenyl sulfone,
4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfide, 3,4'-diamino diphenyl sulfide, 4,4'-diamino diphenyl sulfide, 3,3'-diamino diphenyl ketone , 3,
4'-diaminodiphenyl ketone, 4,4'-diaminodiphenyl ketone, 2,2-bis (3-aminophenyl) propane, 2,2 '-(3,4'-diaminodiphenyl) propane, 2,2-bis (4-aminophenyl)
Propane, 2,2-bis (3-aminophenyl) hexafluoropropane, 2,2- (3,4'-diaminodiphenyl) hexafluoropropane, 2,2-bis (4-
Aminophenyl) hexafluoropropane, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4
-Aminophenoxy) benzene, 3,3 '-(1,4-
Phenylenebis (1-methylethylidene)) bisaniline, 3,4 '-(1,4-phenylenebis (1-methylethylidene)) bisaniline, 4,4'-(1,4-phenylenebis (1-methylethylidene) ) Bisaniline, 2,2-bis (4- (3-aminophenoxy) phenyl) propane, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 2,2-bis (4- (3
-Aminophenoxy) phenyl) hexafluoropropane, 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane, bis (4- (3-aminophenoxy) phenyl) sulfide, bis (4- (4
-Aminophenoxy) phenyl) sulfide, bis (4
Aromatic diamines such as-(3-aminophenoxy) phenyl) sulfone and bis (4- (4-aminophenoxy) phenyl) sulfone, and diaminosiloxanes represented by the general formula (III)

Embedded image [In the formula (III), R ¹ and R ² represent a divalent hydrocarbon group, R ³ and R ⁴ represent a monovalent hydrocarbon group, and R ¹ and R ² , R ³ and R ⁴
May be the same or different, and s represents an integer of 1 or more].

Examples thereof include 1,1,3,3-tetramethyl-1,3-bis (4-aminophenyl) disiloxane and 1,1,3,3-tetraphenoxy-1,3-bis (4 -Aminoethyl) disiloxane, 1,1,3,3-
Tetraphenyl-1,3-bis (2-aminoethyl) disiloxane, 1,1,3,3-tetraphenyl-1,3
-Bis (3-aminopropyl) disiloxane, 1,1,
3,3-tetramethyl-1,3-bis (2-aminoethyl) disiloxane, 1,1,3,3-tetramethyl-
1,3-bis (3-aminopropyl) disiloxane,
1,1,3,3-tetramethyl-1,3-bis (3-aminobutyl) disiloxane, 1,3-dimethyl-1,3
-Dimethoxy-1,3-bis (4-aminobutyl) disiloxane, 1,1,3,3,5,5-hexamethyl-
1,5-bis (4-aminophenyl) trisiloxane,
1,1,5,5-tetraphenyl-3,3-dimethyl-
1,5-bis (3-aminopropyl) trisiloxane,
1,1,5,5-tetraphenyl-3,3-dimethoxy-1,5-bis (4-aminobutyl) trisiloxane,
1,1,5,5-tetraphenyl-3,3-dimethoxy-1,5-bis (5-aminopentyl) trisiloxane, 1,1,5,5-tetramethyl-3,3-dimethoxy-1, 5-bis (2-aminoethyl) trisiloxane, 1,1,5,5-tetramethyl-3,3-dimethoxy-1,5-bis (4-aminobutyl) trisiloxane, 1,1,5,5 -Tetramethyl-3,3-dimethoxy-1,5-bis (5-aminopentyl) trisiloxane, 1,1,3,3,5,5-hexamethyl-1,5-
Bis (3-aminopropyl) trisiloxane, 1,1,
3,3,5,5-hexaethyl-1,5-bis (3-aminopropyl) trisiloxane, 1,1,3,3,5
5-hexapropyl-1,5-bis (3-aminopropyl) trisiloxane and the like. These diamines may be used alone or in combination of two or more.

The condensation reaction between the tetracarboxylic dianhydride and the diamine is carried out in an organic solvent. In this case, the tetracarboxylic dianhydride and the diamine are preferably used in equimolar or almost equimolar, and the order of addition of each component is arbitrary. Examples of the organic solvent used include dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, hexamethylphosphorylamide, m-cresol, o-chlorophenol and the like.

The reaction temperature is preferably 80 ° C. or less,
0 ° C. is more preferred. As the reaction proceeds, the viscosity of the reaction solution gradually increases. In this case, polyamic acid, which is a precursor of polyimide, is generated.

The polyimide can be obtained by dehydrating and ring-closing the above reaction product (polyamic acid). Dehydration ring closure is 1
The heat treatment can be performed at 20 ° C. to 250 ° C. or a chemical method. In the case of a method of performing heat treatment at 120 ° C. to 250 ° C., the heat treatment is preferably performed while removing water generated in the dehydration reaction outside the system. At this time, water may be azeotropically removed using benzene, toluene, xylene, or the like. In the present invention, the polyimide resin is a general term for polyimide and its precursor. Polyimide precursors include, in addition to polyamic acid, polyamic acid partially imidized.

In the case of ring closure by dehydration by a chemical method, acetic anhydride, propionic anhydride, acid anhydride of benzoic anhydride, carbodiimide compounds such as dicyclohexylcarbodiimide and the like are used as a ring closing agent. At this time, if necessary, a ring-closing catalyst such as pyridine, isoquinoline, trimethylamine, aminopyridine, imidazole and the like may be used. The ring-closing agent or the ring-closing catalyst is preferably used in an amount of 1 to 8 mol per 1 mol of tetracarboxylic dianhydride. In order to improve the adhesive strength, a silane coupling agent, a titanium-based coupling agent, a nonionic surfactant, a fluorine-based surfactant, a silicone-based additive, or the like may be appropriately added to the polyimide resin.

The adhesive film of the present invention can also be formed by adding a thermosetting resin and / or a filler to the polyimide resin. When using a thermosetting resin, the thermosetting resin (B) is an epoxy resin,
It is preferable to select from a resin containing a phenolic resin and a curing accelerator, or an imide compound having at least two thermosetting imide groups in one molecule.

When a thermosetting resin containing an epoxy resin, a phenol resin and a curing accelerator is used as the thermosetting resin, the adhesive film may be made of (1) a polyimide resin having a repeating unit represented by the general formula (I) ( A) It is preferable to use 0 to 200 parts by weight of the epoxy resin with respect to 100 parts by weight of the epoxy resin.
It is preferable to use 0 to 150 parts by weight with respect to 0 parts by weight, and it is preferable to use 0 to 50 parts by weight of the curing accelerator with respect to 100 parts by weight of the epoxy resin. These can be dissolved in an organic solvent, (2) applied to a base film, and heated to produce a film.

The thermosetting resin has at least two in one molecule.
In the case of an imide compound having two thermosetting imide groups, (1) at least two imide compounds per molecule per 100 parts by weight of a polyimide resin (A) having a repeating unit represented by the general formula (I) It is preferable to use an imide compound having a thermosetting imide group of 0 to 200 parts by weight,
It is more preferable to use 150 parts by weight, and these can be dissolved in an organic solvent, (2) applied onto a base film, and heated to produce a film.

When a filler is contained, examples of the filler (C) include conductive fillers such as silver powder, gold powder, and copper powder, and inorganic fillers such as silica, alumina, titania, glass, iron oxide, and ceramic. Filler-containing adhesive film, after dissolving the polyimide resin in the organic solvent, add the filler, add other components as needed,
The paste-like mixture obtained by mixing and kneading can be uniformly applied on a base film and heated to produce the paste-like mixture.

The adhesive film containing the thermosetting resin has a feature that the shear adhesive strength when heated is high. However, since the peel adhesive strength when heated is reduced, an adhesive film containing or not containing a thermosetting resin can be used depending on the purpose of use. Here, the thermosetting resin is a resin that forms a three-dimensional network structure by heating and cures.

When a thermosetting resin is contained, the amount of the thermosetting resin is preferably from 0 to 200 parts by weight, more preferably from 0 to 150 parts by weight, based on 100 parts by weight of the polyimide resin (A). And more preferably 1 to 100 parts by weight. If it exceeds 200 parts by weight, the film-forming properties tend to be poor.

When an epoxy resin, a phenol resin and a resin containing a curing accelerator are selected as the thermosetting resin, the epoxy resin to be used has at least two in the molecule.
A glycidyl ether type epoxy resin of phenol is preferred from the viewpoint of curability and properties of a cured product containing epoxy groups. Examples of such a resin include bisphenol A, bisphenol AD, bisphenol S, bisphenol F or a condensate of halogenated bisphenol A and epichlorohydrin, glycidyl ether of phenol novolak resin, glycidyl ether of cresol novolak resin, and glycidyl ether of bisphenol A novolak resin. And the like.

The amount of epoxy resin is 10
0 to 200 parts by weight, preferably 0 to 10 parts by weight,
0 parts by weight is more preferable, and 1 to 90 parts by weight is further preferable. If it exceeds 200 parts by weight, the film-forming properties tend to be poor.

The phenol resin used has at least two phenolic hydroxyl groups in the molecule. Examples of such a resin include a phenol novolak resin, a cresol novolak resin, a bisphenol A novolak resin, and a poly-p-vinyl resin. Phenol, phenol aralkyl resin and the like can be mentioned. The amount of the phenol resin is preferably from 0 to 150 parts by weight, more preferably from 0 to 120 parts by weight, even more preferably from 10 to 100 parts by weight, based on 100 parts by weight of the epoxy resin. If it exceeds 150 parts by weight, the curability tends to be insufficient.

The curing accelerator is not particularly limited as long as it is used for curing the epoxy resin. Such compounds include, for example, imidazoles, dicyandiamide derivatives, dicarboxylic dihydrazide, triphenylphosphine, tetraphenylphosphonium tetraphenylborate, 2-ethyl-4-methylimidazole-
Tetraphenyl borate, 1,8-diazabicyclo (5.4.0) undecene-7-tetraphenyl borate and the like are used. These may be used in combination of two or more.

The amount of the curing accelerator is preferably from 0 to 50 parts by weight, more preferably from 0 to 20 parts by weight, even more preferably from 0.1 to 10 parts by weight, based on 100 parts by weight of the epoxy resin. Here, if it exceeds 50 parts by weight, storage stability tends to deteriorate.

The organic solvent used in the production of the adhesive film is not particularly limited as long as it can uniformly dissolve, knead or disperse the material. For example, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, Examples include diethylene glycol dimethyl ether, toluene, benzene, xylene, methyl ethyl ketone, tetrahydrofuran, ethyl cellosolve, ethyl cellosolve acetate, butyl cellosolve, and dioxane.

When an imide compound having at least two thermosetting imide groups in one molecule is used as the thermosetting resin, examples of the compound include ortho-bismaleimide benzene, metabismaleimide benzene, parabis Maleimide benzene, 1,4-bis (p-maleimidocumyl) benzene, 1,4-bis (m-maleimidocumyl) benzene, and imide compounds represented by the following formulas (IV) to (VII) There is.

[0032]

Embedded image [In the formula (IV), X is O, CH ₂ , CF ₂ , SO ₂ , S, C
O, C (CH ₃ ) ₂ or C (CF ₃ ) ₂ , and R ⁵ , R ⁶ , R ⁷
And R ⁸ each independently represent hydrogen, a lower alkyl group, a lower alkoxy group, fluorine, chlorine or bromine, and D represents a dicarboxylic acid residue having an ethylenically unsaturated double bond.

[0033]

Embedded image [In the formula (V), Y is O, CH ₂ , CF ₂ , SO ₂ , S, C
O, C (CH ₃ ) ₂ or C (CF ₃ ) ₂ , R ⁹ , R ¹⁰ , R
¹¹ and R ¹² each independently represent hydrogen, a lower alkyl group, a lower alkoxy group, fluorine, chlorine or bromine, and D represents a dicarboxylic acid residue having an ethylenically unsaturated double bond.

[0034]

Embedded image [In the formula (VI), m represents an integer of 0 to 4, and D represents a dicarboxylic acid residue having an ethylenically unsaturated double bond.]

[0035]

Embedded image [In the formula (VI), R ¹³ and R ¹⁴ are divalent hydrocarbon groups, R ¹⁵
And R ¹⁶ represent a monovalent hydrocarbon group, and R ¹³ and R ¹⁴ , R ¹⁵
And R ¹⁶ may be the same or different, D represents a dicarboxylic acid residue having an ethylenically unsaturated double bond, and n represents an integer of 1 or more.

In each structural formula, examples of the dicarboxylic acid residue having an ethylenically unsaturated double bond represented by D include a maleic acid residue and a citraconic acid residue.

The amount of the imide compound used in the present invention is
0 to 200 parts by weight, preferably 0 to 150 parts by weight, more preferably 1 to 1 part by weight based on 100 parts by weight of the polyimide resin.
00 parts by weight is more preferred. If it exceeds 200 parts by weight, the film-forming properties tend to be poor.

The imide compound of the formula (IV) includes, for example, 4,4-bismaleimide diphenyl ether,
4-bismaleimidediphenylmethane, 4,4-bismaleimide-3,3'-dimethyldiphenylmethane, 4,
4-bismaleimide diphenyl sulfone, 4,4-bismaleimide diphenyl sulfide, 4,4-bismaleimide diphenyl ketone, 2,2'-bis (4-maleimidophenyl) propane, 4,4-bismaleimide diphenylfluoromethane, , 1,1,3,3,3-hexafluoro-2,2-bis (4-maleimidophenyl) propane and the like.

Examples of the imide compound of the formula (V) include bis [4- (4-maleimidophenoxy) phenyl] ether, bis [4- (4-maleimidophenoxy) phenyl] methane and bis [4- (4- Maleimidophenoxy) phenyl] fluoromethane, bis [4- (4
-Maleimidophenoxy) phenyl] sulfone, bis [4- (3-maleimidophenoxy) phenyl] sulfone, bis [4- (4-maleimidophenoxy) phenyl] sulfide, bis [4- (4-maleimidophenoxy) phenyl] ketone, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, 1,1,1,
3,3,3-hexafluoro-2,2-bis [4- (4
-Maleimidophenoxy) phenyl] propane.

In order to accelerate the curing of these imide compounds, a radical polymerization agent may be used. Examples of the radical polymerization agent include acetylcyclohexylsulfonyl peroxide, isobutyryl peroxide, benzoyl peroxide, octanoyl peroxide, acetyl peroxide, dicumyl peroxide, cumene hydroperoxide, azobisisobutyronitrile, and the like. At this time, the amount of the radical polymerization agent used is preferably about 0.01 to 1.0 part by weight based on 100 parts by weight of the imide compound.

Among the fillers, conductive fillers such as silver powder, gold powder, and copper powder are added for the purpose of imparting conductivity or thixotropy to the adhesive, and inorganic fillers such as silica, alumina, titania, glass, iron oxide, and ceramics are added. The substance filler is added for the purpose of imparting a low thermal expansion property and a low moisture absorption rate to the adhesive.
These conductive fillers or inorganic fillers may be used as a mixture of two or more. Further, a conductive filler and an inorganic filler may be mixed and used as long as physical properties are not impaired.

The amount of the filler is preferably 0 to 8000 parts by weight based on 100 parts by weight of the polyimide resin,
A range of 0 parts by weight is more preferable, and a range of 10 to 2000 parts by weight is further preferable. If the amount is more than 8000 parts by weight, the adhesiveness tends to decrease. Mixing and kneading in the case of using a filler can be carried out by appropriately combining ordinary dispersers such as a stirrer, a grinder, a three-roll mill and a ball mill.

After uniformly applying the varnish or paste mixture thus obtained on a base film, the conditions under which the solvent used is sufficiently volatilized, that is, approximately 60 to 200 ° C.
At a temperature of 0.1 to 30 minutes. Thereafter, the adhesive film is usually used by peeling off the base film at room temperature.

The obtained adhesive film is composed of a semiconductor element such as an IC or an LSI, a lead frame such as a 42 alloy lead frame or a copper lead frame, a plastic film such as a polyimide, an epoxy resin or a polyimide resin, or a substrate such as a glass nonwoven fabric. Impregnated and cured with a plastic such as polyimide, epoxy resin, polyimide resin, or a support member such as ceramics such as alumina. Further, depending on the type of the package, the semiconductor elements can be used for the joint.

The bonding conditions are as follows: the adhesive film of the present invention is sandwiched between the semiconductor element and the support member or between the semiconductor elements as described above, and the two are bonded by heating and pressing.
The heating temperature is usually 100 to 300 ° C., 0.1 to 300
Seconds.

[0046]

The present invention will be described below with reference to examples.

Synthesis Example 1 500 ml equipped with a thermometer, a stirrer and a calcium chloride tube
In a four-necked flask, 41 g (0.1 mol) of 2,2-bis (4-aminophenoxyphenyl) propane and 150 g of dimethylacetamide were taken and stirred. After dissolution of the diamine, the flask was cooled in an ice bath,
52 g (0.1 mol) of-(4,4'-isopropylidene diphenoxy) bis (phthalic dianhydride) were added in small portions. After reacting at room temperature for 3 hours, xylene 30
g, and heated at 150 ° C. while blowing N ₂ gas to azeotropically remove xylene with water. The reaction solution was poured into water, and the precipitated polymer was collected by filtration and dried to obtain a polyimide resin (A1).

Synthesis Example 2 500 ml equipped with thermometer, stirrer and calcium chloride tube
Was charged with 43.2 g (0.1 mol) of bis (4- (3-aminophenoxy) phenyl) sulfone and 150 g of N-methyl-2-pyrrolidone and stirred. After dissolution of the diamine, 4,4 '-(4,4'
52 g (0.1 mol) of -isopropylidene diphenoxy) bis (phthalic dianhydride) were added. The reaction was carried out at 5 ° C. or lower for 5 hours, 20.4 g (0.2 mol) of acetic anhydride and 15.8 g (0.2 mol) of pyridine were added, and the mixture was stirred for 1 hour at room temperature. The reaction solution was poured into water, and the precipitated polymer was collected by filtration and dried to obtain a polyimide resin (A2).

Synthesis Example 3 In a 500 ml four-necked flask equipped with a thermometer, a stirrer, and a calcium chloride tube, 32.8 g (0.08 mol) of 2,2-bis (4-aminophenoxyphenyl) propane was added.
5.08 g (0.02 mol) of 3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane and 100 g of dimethylacetamide were taken and stirred. After dissolution of the diamine, the flask was cooled in an ice bath,
41.6 g (0.08 mol) of 4 '-(4,4'-isopropylidene diphenoxy) bis (phthalic dianhydride) and 6.44 g of benzophenonetetracarboxylic dianhydride
(0.02 mol) was added in small portions. After completion of the addition, the mixture was reacted in an ice bath for 3 hours and further at room temperature for 4 hours, and then 25.5 g (0.25 mol) of acetic anhydride and 19.8 g of pyridine were used.
(0.25 mol) and stirred for 2 hours at room temperature. The reaction solution was poured into water, and the precipitated polymer was collected by filtration and dried to obtain a polyimide resin (A3).

Synthesis Example 4 500 ml equipped with a thermometer, a stirrer and a calcium chloride tube
In a four-necked flask, 41 g (0.1 mol) of 2,2-bis (4-aminophenoxyphenyl) propane and 150 g of dimethylacetamide were taken and stirred. After dissolution of the diamine, the flask was cooled in an ice bath,
-(4,4'-isopropylidenediphenyl) -bis (trimellitate dianhydride) 59.2 g (0.1 mol)
Was added in small portions. After reacted for 3 hours at room temperature, xylene 30g was added, while blowing N ₂ gas 150
C. and azeotropically removed xylene with water. The reaction solution was poured into water, and the precipitated polymer was collected by filtration and dried to obtain a polyimide resin (A4).

Examples 1 to 3 and Comparative Example 1 As shown in the composition table (Table 1), Nos. 1 to 4 varnishes were prepared. In Table 1, various symbols have the following meanings.

YDCN-702: a cresol novolak type epoxy resin manufactured by Toto Kasei Co., Ltd. (epoxy equivalent: 22)
0) N-865: Bisphenol novolak type epoxy resin (epoxy equivalent 208) manufactured by Dainippon Ink and Chemicals, Inc. H-1: Phenol novolak resin (OH equivalent 106) manufactured by Meiwa Kasei Co., Ltd. VH-4170: Large Bisphenol A novolak resin (OH equivalent: 118) manufactured by Nippon Ink Chemical Industry Co., Ltd. TPPK: manufactured by Tokyo Chemical Industry Co., Ltd., tetraphenylphosphonium tetraphenylborate 2P4MHZ: manufactured by Shikoku Chemicals Co., Ltd., Curesol 2P4M
HZ TCG-1: silver powder manufactured by Tokuriki Chemical Co., Ltd. DMAC: dimethylacetamide DMF: dimethylformamide

[0053]

[Table 1]

Each of the prepared varnishes No. 1 to No. 4
Coat on a polypropylene film (base film) to a thickness of 50 μm, at 80 ° C. for 10 minutes, then at 150 ° C.
For 30 minutes, and then peeled off the base film at room temperature to obtain an adhesive film.

[Evaluation Test] The adhesive films obtained in Examples 1 to 3 and Comparative Example 1 were evaluated for reliability under high-temperature and high-humidity conditions and measured for peel adhesion (Table 2).

[0056]

[Table 2]

The method for evaluating the reliability under the conditions of high temperature and high humidity and the method for measuring the peel adhesive force are as follows. (Reliability under high temperature and high humidity conditions) Adhesive film 8mm x 1
The sheet was cut into a size of 0 mm, sandwiched between two frame-shaped frames each having a hole of 5 mm × 8 mm, and pressed under a load of 1000 g at 180 ° C. or 250 ° C. for 5 seconds. The test piece was placed in a pressure cooker maintained at 121 ° C. and 2 atm, and the hue of the film was determined every 100 hours.
The change in thickness was observed.

(Measurement of adhesive strength) Adhesive film was 8 mm x 8 mm
After being cut into 8 mm x 8 mm silicon chips and a copper lead frame, a 1000 g load was applied thereto, and the mixture was pressed at 180 ° C or 250 ° C for 5 seconds.
The peel strength at the time of heating at 250 ° C. for 20 seconds was measured.

[0059]

The adhesive film of the present invention has excellent reliability under high temperature and high humidity, and has high adhesive strength. Therefore, it can be suitably used for a next-generation semiconductor mounting technology using a 42 alloy lead frame, a copper lead frame, and an insulating support substrate for die bonding. A semiconductor device manufactured using this adhesive film has excellent reliability under high temperature and high humidity.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C08L 79/08 C08L 79/08 Z 5F047 83/07 83/07 C09J 7/00 C09J 7/00 H01L 21/52 H01L 21 / 52 E (72) Inventor Shinji Takeda 48 Wadai, Tsukuba-shi, Ibaraki F-term in Hitachi Chemical Co., Ltd. Research Institute 4F071 AA41 AA42 AA60 AA67 AB01 AB18 AB26 AB28 AB29 AC12 AE15 AE17 AH12 BA02 BB02 BC01 4J002 AA022 CC033 CC073 CD042 CD052 CD062 CD112 CD122 CM041 CM043 CP093 CP123 CP171 DA078 DE098 DE118 DE148 DJ018 DL008 DM008 EK000 EQ026 ET000 ET006 EU027 EU096 EU116 EW136 EW176 EY016 ECFD ECFDFD FD143 FD146 GJ01A05A05A05A05A05A05A05A05A05A05A05A05A05A05 EF041 EF042 EH031 EH032 GA30 HA066 HA136 HA306 HA346 HA366 JA09 JB02 KA32 KA39 LA06 LA07 LA08 MA02 MA05 MA09 MA10 NA20 PA30 PA33 4J043 PA02 PA04 PA08 PA19 PC015 PC115 PC135 PC145 PC195 QB31 RA34 SA06 SA42 SA54 SA81 SA85 SB A14 TA22 TA42 TA61 TA74 TA78 TB01 TB02 UA012 UA022 UA032 UA042 UA052 UA121 UA122 UA131 UA132 UA141 UA142 UA152 UA252 UA262 UA332 UA382 UA622 UA761 UA762 UB011 UB012 UB021 UB022 UB051 UB061 UB062 UB121 UB122 UB132 UB151 UB152 UB281 UB282 UB301 UB302 UB312 UB351 VA011 VA021 VA022 VA032 VA051 VA061 VA062 VA091 VA092 VA102 WA09 XA16 XA17 YA06 YA08 ZA02 ZA05 ZA12 ZB01 ZB11 ZB47 5F047 AA10 AA11 AA14 BA23 BA33 BB03

Claims (4)

[Claims] 1. A compound of the general formula (I) (Where R is a divalent organic group as a diamine residue)
An adhesive film containing a polyimide resin having a repeating unit represented by the formula: 2. The polyimide resin represented by the general formula (I) contains at least 30 mol% of the total tetracarboxylic dianhydride in the formula (II). The adhesive film according to claim 1, which is obtained by reacting a tetracarboxylic dianhydride containing a tetracarboxylic dianhydride represented by the following formula with a diamine. (A) 100 parts by weight of a polyimide resin having a repeating unit represented by the general formula (I),
3. The adhesive film according to claim 1, comprising (B) 200 parts by weight or less of a thermosetting resin and (C) 8000 parts by weight or less of a filler. 4. A semiconductor device comprising semiconductor elements bonded to each other or a semiconductor element and a supporting member using the adhesive film according to claim 1.