JP2003226857A - Adhesive film and semiconductor device using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To prepare an adhesive film having low stress and low-temperature adhesiveness not only used for 42 alloy lead frames as a die bond for semiconductor elements, but also usable for copper lead frames and further usable for insulating support substrates. <P>SOLUTION: The adhesive film comprises a polyimide resin obtained by reacting a tetracarboxylic acid dianhydride containing a tetracarboxylic dianhydride represented by formula (I) in an amount of ≥30 mol% based on the total tetracarboxylic acid dianhydride with a diamine containing a diamine represented by formula (II) in an amount of ≥10 wt.% based on the total diamine. A semiconductor device is prepared by using the adhesive film. <P>COPYRIGHT: (C)2003,JPO

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 supporting substrate, that is, a die bonding material.

[0002]

2. Description of the Related Art Conventionally, an Au-Si eutectic alloy, solder, silver paste, or the like has been used to bond an IC or LSI to a lead frame. The Au-Si eutectic alloy has high heat resistance and moisture resistance, but has a large elastic modulus and is easily cracked when applied to a large chip, and is expensive.
Although solder is inexpensive, it has poor heat resistance and has a high elastic modulus similar to Au-Si eutectic alloy, making it difficult to apply to large chips. On the other hand, silver paste is inexpensive, has high humidity resistance, has the lowest elastic modulus among the above three, and has heat resistance applicable to a thermocompression bonding wire bonder at 350 ° C., so that it is currently used for ICs and LSIs and lead frames. Is the mainstream adhesive material. However, as ICs and LSIs have been highly integrated in recent years and the chips have become larger, I
When attempting to bond C or LSI to a lead frame with a silver paste, it is difficult to spread the silver paste over the entire surface of the chip and apply it. Microelectronic Manufacturing and Testing (MICROELECTRONIC M
ANUFACTURING AND TESTING (October 1985) reported an adhesive film for die bonding in which a conductive resin was filled in a thermoplastic resin. In this method, the temperature is raised to near the melting point of the thermoplastic resin and pressure bonding is performed. Further, the present inventors previously proposed an adhesive film using a specific polyimide resin, and an adhesive film for die bonding containing a conductive filler or an inorganic filler therein (Japanese Patent Laid-Open No. 6-145639, special feature). Kaihei 7-2286
97 gazette etc.).

[0003]

The adhesive film reported by the above-mentioned microelectronic manufacturing and testing can lower the bonding temperature by selecting and using a thermoplastic resin having a low melting point, which leads to oxidation of the lead frame. Etc., the damage to the chip is small, but the adhesive force at the time of heat is low, so that it cannot withstand the heat treatment after die bonding (for example, wire bonding, sealing step, etc.). When a thermoplastic resin having a high melting point that can withstand heat treatment is used, the adhesion temperature becomes high and the lead frame is easily damaged by oxidation or the like.

The adhesive film previously proposed by the present inventors can be bonded at a relatively low temperature and has a good adhesive strength at the time of heating. However, copper lead frames (which are susceptible to oxidation) that have begun to be used in recent years and insulating support substrates with low thermal conductivity (because of their large thermal expansion, they tend to warp during heat bonding)
There is a strong demand for an adhesive film that can be bonded at a lower temperature for bonding to the. The present invention is for use in die bonding.
An object of the present invention is to provide a low-stress, low-temperature adhesive adhesive film that can be suitably used not only for an alloy lead frame but also for a copper lead frame and also for an insulating support substrate.

[0005]

The present invention provides a compound of formula (I)

[Chemical 3] A tetracarboxylic dianhydride containing 30 mol% or more of all tetracarboxylic dianhydrides represented by the formula:

[Chemical 4] (However, Q ₁ , Q ₂ and Q ₃ represent alkylene having 1 to 10 carbon atoms and n represents an integer of 2 to 30) and reacted with a diamine containing 10% or more by weight of the total diamine. It is intended to provide an adhesive film containing a polyimide resin obtained by the above. Further, the present invention is an adhesive containing (B) thermosetting resin: 0 to 200 parts by weight and (C) filler: 0 to 8000 parts by weight, relative to 100 parts by weight of the polyimide resin (A). It provides a film. The present invention also provides a semiconductor device manufactured using the adhesive film.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The tetracarboxylic dianhydride of the formula (I), which is one of the raw materials for producing the polyimide resin used in the adhesive film of the present invention, may be used alone, but other tetracarboxylic acids may be used. You may use it with an acid dianhydride. Further, the amount of the tetracarboxylic dianhydride of the formula (I) contained is 30 mol% or more, preferably 50 mol% or more, more preferably 70 mol% or more based on the total tetracarboxylic dianhydride. . When it is less than 30 mol%, low stress resistance and moisture resistance tend to be lowered. In the present invention, the ratio of the tetracarboxylic dianhydride of the formula (I) may be 100 mol% with respect to the total tetracarboxylic dianhydride.

Examples of the tetracarboxylic dianhydride which can be used together with the tetracarboxylic dianhydride of the formula (I) include pyromellitic dianhydride and 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride. Anhydrous, 2,2 ', 3
3'-biphenyltetracarboxylic dianhydride, 2,2-
Bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride Anhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 3, 4, 9, 10-
Perylene tetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, benzene-
1,2,3,4-tetracarboxylic dianhydride, 3,4
3 ', 4'-benzophenone tetracarboxylic dianhydride, 2,3,2', 3'-benzophenone tetracarboxylic dianhydride, 2,3,3 ', 4'-benzophenone tetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,4,5-naphthalene-tetracarboxylic dianhydride, 1 , 4,5,8-Naphthalene-tetracarboxylic dianhydride, 1,2- (ethylene) bis (trimellitate anhydride), 1,3- (trimethylene) bis (trimellitate anhydride), 1,4-
(Tetramethylene) bis (trimellitate anhydrous),
1,5- (Pentamethylene) bis (trimellitate anhydride), 1,6- (hexamethylene) bis (trimellitate anhydride), 1,7- (heptamethylene) bis (trimellitate anhydride), 1,8- ( Octamethylene) bis (trimellitate anhydride), 1,9- (nonamethylene)
Bis (trimeritate anhydride), 1,10- (decamethylene) bis (trimeritate anhydride), 1,12- (dodecamethylene) bis (trimeritate anhydride), 1,1
6- (hexadecamethylene) bis (trimeritate anhydride), 1,18- (octadecamethylene) bis (trimeritate anhydride), 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 acid dianhydride, Phenanthrene-1,8,9,10-tetracarboxylic acid dianhydride, Pyrazine-2,3,5,6-tetracarboxylic acid dianhydride, Thiofene -2,3,4,5-tetracarboxylic dianhydride, 2,3,3 ', 4'-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-phenylene bis (trimellitate anhydride), ethylene tetracarboxylic dianhydride, 1,2,3,4-butane tetracarboxylic 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 (exo-bicyclo [2.2.1] heptane-
2,3-dicarboxylic acid anhydride) sulfone, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, 2,2-bis (3,4-) Dicarboxyphenyl) hexafluoropropane dianhydride,
2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] hexafluoropropane dianhydride, 4,
4'-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 1,4-bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimellitic anhydride), 1,3-bis (2 -Hydroxyhexafluoroisopropyl) benzenebis (trimellitic anhydride), 5- (2,5-dioxotetrahydrofuryl)
-3-Methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride, tetrahydrofuran-2,3,4,5-
There are tetracarboxylic dianhydrides and the like, and two or more kinds may be mixed and used. When using a tetracarboxylic dianhydride other than the tetracarboxylic dianhydride represented by the formula (I), the amount thereof should be 0.1 to 30 mol% of the total tetracarboxylic dianhydride. Is preferable, and 0.1-5
It is more preferably 0 mol%, and even more preferably 0.1 to 30 mol%.

Diamine, which is another raw material for producing the polyimide resin used in the adhesive film of the present invention, has the formula (II)

[Chemical 5] Diamine (however, Q ₁ , Q ₂ and Q ₃ have 1 to 1 carbon atoms)
0 represents alkylene and n represents an integer of 2 to 30. )
Is 10% or more (eg 10
˜100%), preferably 20% or more, more preferably 30% or more. If it is less than 10%, the properties of low stress and low temperature adhesiveness cannot be exhibited.

The range of the weight average molecular weight of the diamine represented by the above formula (II) is preferably 100 or more, more preferably 200 or more,
It is particularly preferably 300 or more. The upper limit is 30
It is preferably set to 00.

Specific examples of the diamine of the above formula (II) include H ₂ N- (CH ₃ ) ₃ -O- (CH ₂ ) _4- O- (CH ₂ ) _3- NH ₂ H ₂ N- (CH _{3) 3 -O- (CH 2)} 2 -O- (CH 2) 2 -O- (CH 2) 3 -NH 2 H 2 N- (CH 3) 3 -O- (CH 2) 2 -O- _{(CH 2) 2 -O- (CH} 2) 2 -O-
_{(CH 2) 3 -NH 2 H} 2 N- (CH 3) 3 - [O- (CH 2) 4] n-O- (CH 2) 3 -NH 2 Mw =
_{350 H 2 N- (CH 3)} 3 - [O- (CH 2) 4] n-O- (CH 2) 3 -NH 2 Mw =
_{750 H 2 N- (CH 3)} 3 - [O- (CH 2) 4] n-O- (CH 2) 3 -NH 2 Mw =
_{1100 H 2 N- (CH 3)} 3 - [O- (CH 2) 4] n-O- (CH 2) 3 -NH 2 Mw =
_{2100 H 2 N-CH (CH} 3) - (CH 2) - [O-CH (CH 3) - (CH 2)] n-O- (C
_{H 2) -CH (CH 3)} -NH 2 Mw = 230 H 2 N-CH (CH 3) - (CH 2) - [O-CH (CH 3) - (CH 2)] n-O- (C
_{H 2) -CH (CH 3)} -NH 2 Mw = 400 H 2 N-CH (CH 3) - (CH 2) - [O-CH (CH 3) - (CH 2)] n-O- (C
H ₂₎ there is _{-CH (CH 3) -NH 2 Mw} = 2000 , etc., may be used as a mixture of two or more.

Other diamines can be used in combination with the above formula (II). As the diamine that can be used in combination,
Ethylenediamine, 1,3-diaminopropane, 1,4
-Diaminobutane, 1,5-diaminopentane, 1,6
-Diaminohexane, 1,7-diaminoheptane, 1,
8-diaminooctane, 1,9-diaminononane, 1,
Aliphatic diamines such as 10-diaminodecane and 1,12-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'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,
4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl ketone, 3,4'-diaminodiphenyl ketone, 4,4'-diaminodiphenyl ketone, 2,2
-Bis (3-aminophenyl) propane, 2- (3-aminophenyl) -2- (4'-aminophenyl) propane, 2,2-bis (4-aminophenyl) propane,
2,2-bis (3-aminophenyl) hexafluoropropane, 2- (3-aminophenyl) -2- (4'-aminophenyl) hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoro Propane 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
-Phenylene bis (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- (3-aminophenoxy) phenyl) sulfone,
Aromatic diamines such as bis (4- (4-aminophenoxy) phenyl) sulfone, diaminosiloxane represented by the general formula (III)

[Chemical 6] (In the formula, Q ₄ and Q ₅ each independently represent an alkylene group having 1 to 5 carbon atoms or a phenylene group, and Q ₆ , Q ₇ , Q
₈ and Q ₉ each independently represent an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a phenyl group or a phenoxy group, and p represents an integer of 1 to 50. ) And the like.

As the siloxane-based diamine, when p is 1, 1,1,3,3-tetramethyl-1,3-bis (4-aminophenyl) disiloxane, 1,1,3,3
-Tetraphenoxy-1,3-bis (2-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 (4-aminobutyl) disiloxane, 1,3-dimethyl-1,3-dimethoxy-1,
3-bis (4-aminobutyl) disiloxane, etc.,
When p is 2, 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, when p is 3 to 50,

[Chemical 7]

[Chemical 8]

[Chemical 9] Etc., and these may be used in combination of two or more kinds.

When using these diamines other than the diamines of formula (II), the amount is 0.1% of the total diamine weight.
˜90% is preferable, 0.1 to 80% is more preferable, and 0.1 to 70% is more preferable. The condensation reaction of tetracarboxylic dianhydride and diamine is performed in an organic solvent. In this case, the tetracarboxylic dianhydride and the diamine are preferably used in equimolar or almost equimolar amounts, and the addition order of each component is arbitrary. Examples of the organic solvent used include dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, hexamethylphosphorylamide, m-cresol, and o-chlorophenol. Reaction temperature is 8
The temperature is preferably 0 ° C. or lower, more preferably 0 to 5
It is 0 ° C. The reaction time is preferably 0.5 to 100 hours, more preferably 1 to 48 hours. As the reaction proceeds, the viscosity of the reaction solution gradually increases. In this case, polyamic acid that is a precursor of polyimide is generated.

Polyimide can be obtained by dehydration ring closure of the above reaction product (polyamic acid). Dehydration ring closure is 1
It can be performed using a method of performing heat treatment at 20 ° C. to 250 ° C. for 30 to 300 minutes or a chemical method. 120 ℃ ~ 25
In the case of the method of heat treatment at 0 ° C., it is preferable to perform it while removing water generated by the dehydration reaction outside the system. At this time, water may be removed azeotropically by using benzene, toluene, xylene or the like. In the present invention, the polyimide resin means a partially imidized polyimide and / or polyamic acid. When performing a dehydration ring closure by a chemical method,
As the ring-closing agent, acetic anhydride, propionic anhydride, acid anhydride of benzoic anhydride, carbodiimide compound such as dicyclohexylcarbodiimide, etc. are used. At this time, a ring-closing catalyst such as pyridine, isoquinoline, trimethylamine, aminopyridine, or imidazole may be used if necessary. The ring-closing agent or ring-closing catalyst is preferably used in the range of 1 to 8 mol per 1 mol of tetracarboxylic dianhydride. The polyimide resin used in the present invention has a weight average molecular weight measured by gel permeation chromatography (GPC) of preferably 10,000 to 200,000, more preferably 20,000 to 100,000. . Also, 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, etc. may be added to the polyimide resin as appropriate.

The adhesive film of the present invention can be prepared by adding a thermosetting resin and / or a filler to the above polyimide resin. For example, (A) polyimide resin: 100 parts by weight, (B) thermosetting resin: 0 to 200 parts by weight and (C) filler: 0 to 800
Include 0 parts by weight. When using a thermosetting resin,
The thermosetting resin (B) is preferably selected from an epoxy resin, a resin containing a phenol resin and a curing accelerator, or an imide compound having at least two thermosetting imide groups in one molecule.

When the thermosetting resin containing an epoxy resin, a phenol resin and a curing accelerator is used as the thermosetting resin, the adhesive film may be, for example, (1) a tetracarboxylic dianhydride of the formula (I) A polyimide resin (A) obtained by reacting a tetracarboxylic dianhydride containing 30 mol% or more of tetracarboxylic dianhydride with a diamine containing 10% or more of the total weight of diamines of formula (II); 100 parts by weight, epoxy resin: 1 to 200 parts by weight, phenol resin: 1 to 600 parts by weight per 100 parts by weight of epoxy resin, curing accelerator: 0 to 50 parts by weight per 100 parts by weight of epoxy resin dissolved in an organic solvent. Then, if necessary, the filler (C) is further dispersed, and the product (2) is coated on the base film and heated to produce the composition. The adhesive film in the case of using an imide compound having at least two thermosetting imide groups in one molecule as the thermosetting resin is, for example, (1) a tetracarboxylic dianhydride of the formula (I) 30 mol% of carboxylic dianhydride
Polyimide resin (A) obtained by reacting a tetracarboxylic dianhydride containing the above with a diamine containing 10% or more by weight of the diamine of the formula (II); 100 parts by weight, and at least 2 in one molecule. An imide compound having one thermosetting imide group; 1 to 200 parts by weight of the imide compound is dissolved in an organic solvent, and (C) filler is further dispersed if necessary,
(2) It is manufactured by coating on a base film and heating.

When the filler is contained, examples of the filler (C) include conductive fillers such as silver powder, gold powder and copper powder, and inorganic substance fillers such as silica, alumina, titania, glass, iron oxide and ceramics. The adhesive film containing a filler is prepared by dissolving a polyimide resin in an organic solvent, adding a filler, and optionally other components, and mixing and kneading. The paste-like mixture thus obtained is evenly applied onto a base film and heated to produce. The adhesive film containing the thermosetting resin has a characteristic that the shear adhesive force when heated is high. However, since the peel adhesive strength at the time of heating is reduced, it is advisable to use an adhesive film containing or not containing a thermosetting resin depending on the purpose of use. Here, the thermosetting resin is a resin that is cured by forming a three-dimensional network structure by heating.

When the thermosetting resin is contained, the amount of the thermosetting resin is 1 to 200 parts by weight, preferably 1 to 100 parts by weight, based on 100 parts by weight of the polyimide resin (A). If it exceeds 200 parts by weight, the film formability tends to deteriorate. When a resin containing an epoxy resin, a phenol resin and a curing accelerator is selected as the thermosetting resin, the epoxy resin used is at least 2 in the molecule.
A glycidyl ether type epoxy resin of phenol, which contains a single epoxy group, is preferable from the viewpoint of curability and cured product characteristics. Examples of such resins include condensates of bisphenol A, bisphenol AD, bisphenol S, bisphenol F or halogenated bisphenol A and epichlorohydrin, glycidyl ether of phenol novolac resin, glycidyl ether of cresol novolac resin, glycidyl ether of bisphenol A novolac resin. Etc. When using an epoxy resin, the amount thereof is preferably 1 to 200 parts by weight, more preferably 1 to 100 parts by weight, based on 100 parts by weight of the polyimide resin.
When the amount is more than 200 parts by weight, the film forming property tends to deteriorate. Further, the epoxy equivalent is 100 to 500.
Epoxy resin is preferred.

The phenol resin used has at least two phenolic hydroxyl groups in the molecule. Examples of such a resin include phenol novolac resin, cresol novolac resin, bisphenol A novolac resin and poly-p-vinyl. Examples thereof include phenol and phenol aralkyl resin. When a phenol resin is used, the amount thereof is preferably 1 to 600 parts by weight, more preferably 1 to 15 parts by weight, based on 100 parts by weight of the epoxy resin.
The amount is 0 parts by weight, more preferably 1 to 120 parts by weight. 6
If it exceeds 00 parts by weight, curability tends to be insufficient. Further, a phenol resin having an OH equivalent of 50 to 600 is preferable.

The curing accelerator is not particularly limited as long as it is used to cure the epoxy resin. Examples of such compounds include imidazoles, dicyandiamide derivatives, dicarboxylic acid dihydrazides, 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 0 to 50 parts by weight, more preferably 0.1, based on 100 parts by weight of the epoxy resin.
-50 parts by weight, more preferably 0.1-20 parts by weight,
If it exceeds 50 parts by weight, the storage stability becomes poor. The organic solvent used in the production of the adhesive film is not limited as long as it can uniformly dissolve, knead or disperse the material, for example, dimethylformamide, dimethylacetamide,
N-methylpyrrolidone, dimethyl sulfoxide, diethylene glycol dimethyl ether, toluene, benzene, xylene, methyl ethyl ketone, tetrahydrofuran, ethyl cellosolve, ethyl cellosolve acetate,
Butyl cellosolve, dioxane and the like.

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-bis-maleimidobenzene, meta-bis-maleimidobenzene, and para-bis-maleimidobenzene. In addition to maleimidobenzene, 1,4-bis (p-maleimidocumyl) benzene, 1,4-bis (m-maleimidocumyl) benzene, imide compounds represented by the following formulas (IV) to (VI), etc. There is.

[Chemical 10] [In the formula (IV), X is O, CH ₂ , CF ₂ , SO ₂ , S,
CO, C (CH ₃ ) ₂ or C (CF ₃ ) ₂ is shown, and R ¹ , R
² , R ³ and R ⁴ each independently represent hydrogen, a lower alkyl group, a lower alkoxy group, fluorine, chlorine or bromine,
D represents a dicarboxylic acid residue having an ethylenically unsaturated double bond. ]

[Chemical 11] [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 is shown, 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. ]

[Chemical 12] [In Formula (VI), m shows the integer of 0-4. When the imide compound is used in the present invention, the amount thereof is preferably 1 to 200 parts by weight, more preferably 1 to 100 parts by weight with respect to 100 parts by weight of the polyimide resin. 200
If it exceeds the weight part, the film formability tends to deteriorate.

Examples of the imide compound of the formula (IV) include 4,4'-bismaleimide diphenyl ether,
4,4'-bismaleimidodiphenylmethane, 4,4 '
-Bismaleimide-3,3'-dimethyl-diphenylmethane, 4,4'-bismaleimide diphenyl sulfone,
4,4'-bismaleimide diphenyl sulfide, 4,
4'-bismaleimide diphenyl ketone, 2,2-bis (4-maleimidophenyl) propane, 4,4'-bismaleimide diphenyl fluoromethane, 1,1,1,
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, 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 and the like.

A radical polymerization agent may be used to accelerate the curing of these imide compounds. Examples of the radical polymerization agent include acetylcyclohexyl sulfonyl peroxide, isobutyryl peroxide, benzoyl peroxide, octanoyl peroxide, acetyl peroxide, dicumyl peroxide, cumene hydroperoxide, and azobisisobutyronitrile. At this time, the amount of the radical polymerization agent used is preferably 0.01 to 1.0 parts by weight with respect to 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 silica, alumina, boron nitride, titania, glass, iron oxide, ceramics are added. It is added for the purpose of imparting a low thermal expansion property and a low moisture absorption rate to an inorganic substance filler adhesive such as. Two or more kinds of these conductive fillers or inorganic substance fillers may be mixed and used. Moreover, you may mix and use a conductive filler and an inorganic substance filler in the range which does not impair physical properties. The amount of the filler is preferably 0 to 8000 parts by weight, more preferably 0 to 4000 parts by weight, still more preferably 0 to 1000 parts by weight, based on 100 parts by weight of the polyimide resin. If it is more than 8000 parts by weight, the adhesiveness tends to decrease. When the filler is blended, the lower limit is 100% of the polyimide resin.
It is preferably 1 part by weight and more preferably 3 parts by weight with respect to parts by weight. Mixing and kneading when using a filler can be carried out using a normal stirrer, raider, triple roll,
It can be carried out by appropriately combining a dispersing machine such as a ball mill.

After uniformly coating the varnish or paste mixture thus obtained on the base film, the solvent used is sufficiently vaporized, that is, about 60 to 200 ° C.
The adhesive film is produced by heating at the temperature of 0.1 to 30 minutes. After that, the adhesive film is usually peeled off from the base film at room temperature and used. As the base film, for example, polypropylene film, polyethylene terephthalate film, polytetrafluoroethylene film, polyimide film or the like is used. The thickness of the adhesive film is not particularly limited, but is usually 1 to 2
The thickness is preferably 00 μm, more preferably 1 to 100 μm.

Further, the adhesive film of the present invention may have a multi-layer structure, if necessary. FIG. 1 shows an example thereof. In FIG. 1, 1 is an adhesive film of the present invention having a three-layer structure, in which an adhesive layer composed of the above components is provided on both sides of a base film 3. As a method for producing such a film, for example, in the above production method, a varnish or a pasty mixture is applied to a base film, and after drying,
Similarly, a method of applying a varnish or a pasty mixture to the back surface thereof and drying it may be mentioned. The same material as the base film is used as the base film. The thickness of the adhesive layer is usually preferably 1 to 200 μm, more preferably 1 to 100 μm. The thickness of the base film is not particularly limited and is determined according to the application and the total thickness required.

The obtained adhesive film is a semiconductor element such as an IC or 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. It can be used for joining a support member such as an insulating support substrate made of ceramics such as alumina or the like, which is obtained by impregnating and hardening plastics such as polyimide, epoxy resin or polyimide resin. That is, the adhesive film of the present invention is sandwiched between the semiconductor element and the supporting member as described above, and they are thermocompression bonded to bond them. The heating temperature is usually 100 to 300 ° C. and 0.1 to 300 seconds, and the pressure is usually 0.01 to 1 per semiconductor element.
The load is 0 kgf.

The semiconductor device of the present invention is not particularly limited in its structure as long as it is manufactured by using the adhesive film of the present invention. For example, the semiconductor element, the supporting member for the semiconductor element, the semiconductor element as described above. There is a semiconductor device containing the adhesive film of the present invention in which an adhesive film and a supporting member are joined together. FIG. 2 shows a semiconductor device having a general structure. In FIG. 2, the semiconductor element 4 is adhered to the semiconductor element supporting member 5 via the adhesive film 1 of the present invention, and the connection terminal (not shown) of the semiconductor element 4 is connected to the external connection terminal (not shown) via the wire 6. ), And is sealed by the sealing material 7. In recent years, semiconductor devices having various structures have been proposed, and the application of the adhesive film of the present invention is not limited to this structure as long as most of the area of the semiconductor element is in contact with the adhesive film.

FIG. 3 shows an example of a semiconductor device having a structure in which semiconductor elements are bonded together. In FIG. 3, the semiconductor element 4 of the first stage is bonded to the semiconductor element supporting member 5 via the adhesive film 1 of the present invention, and the semiconductor element 4 of the first stage is further bonded via the adhesive film 1 ′ of the present invention. The semiconductor element 4'of the step is adhered. The connection terminals (not shown) of the first-stage semiconductor element 4 and the second-stage semiconductor element 4'are electrically connected to the external connection terminals (not shown) via the wires 6, and the sealing material (see FIG. It is sealed by (not shown). Thus, the adhesive film of the present invention can be suitably used for a semiconductor device having a structure in which a plurality of semiconductor elements are stacked.

[0031]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. Synthesis Example 1 A 500 ml four-necked flask equipped with a thermometer, a stirrer and a silica gel tube was charged with etherdiamine 400 (BASF).
Manufactured by the company, in the formula (II), Q ₁ = CH (CH ₃ )-(C
_{H 2), Q 2 = CH} (CH 3) - (CH 2), Q 3 =
_{(CH 2) -CH (CH 3} ), n = 4.6) 16.0g
(0.04 mol), 1,12-diaminododecane 12.
0 g (0.06 mol) and 150 g of N-methyl-2-pyrrolidone were taken and stirred. Then, while cooling the flask in an ice bath, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride 52.
1 g (0.1 mol) was added in small portions. After reacting at room temperature for 5 hours, 100 g of xylene was added, and heated at 180 ° C. for 3 hours while blowing N ₂ gas to remove xylene azeotropically with water to obtain a polyimide varnish (A). The weight average molecular weight of the polyimide was 56,000.

Synthesis Example 2 Etherdiamine 2000 (BAS) was placed in a 500 ml four-necked flask equipped with a thermometer, a stirrer and a silica gel tube.
Made by F company, in formula (II), Q ₁ = CH (CH ₃ )-(C
_{H 2), Q 2 = CH} (CH 3) - (CH 2), Q 3 =
_{(CH 2) -CH (CH 3} ), n = 32.1) 20.0
g (0.01 mol), 1,12-diaminododecane 1
8.0 g (0.09 mol) and 150 g of N-methyl-2-pyrrolidone were taken and stirred. Then, while cooling the flask in an ice bath, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride 5
2.1 g (0.1 mol) was added in small portions. After the completion of the addition, the mixture was reacted in an ice bath for 3 hours and further at room temperature for 4 hours, then 100 g of xylene was added and heated at 180 ° C. for 3 hours while blowing N ₂ gas to remove xylene azeotropically with water to remove polyimide varnish. (B) was obtained. The weight average molecular weight of the polyimide was 66,000.

Synthesis Example 3 500 ml square equipped with thermometer, stirrer and silica gel tube
In a two-necked flask, 2,2-bis (4- (4-aminophen)
41 g (0.1 mol) of (oxy) phenyl) propane and
And 150 g of N-methyl-2-pyrrolidone and stirred.
It was After dissolving the diamine, cool the flask in an ice bath.
Et al., 2,2-bis [4- (3,4-dicarboxypheno
52.1 g (0.1) of (xy) phenyl] propane dianhydride
Mol) was added in small portions. Let it react for 3 hours at room temperature
Then, add 100 g of xylene and add N ₂Blow gas
And heat at 180 ℃ for 3 hours to remove azeotropically with water.
Then, the polyimide varnish (C) was obtained. Polyimide weight
The average molecular weight was 72,000.

Examples 1 to 8 and Comparative Examples 9 to 11 As shown in the formulations of Tables 1, 2 and 3, Nos. 1-1
1 (Example Nos. 1 to 8 of the present invention, Comparative Examples No. 9 to 1)
The varnish of 1) was prepared. In Table 1, Table 2 and Table 3, various symbols have the following meanings. YDCN-702: Sumitomo Chemical Co., Ltd., cresol novolac epoxy resin (epoxy equivalent 220) N-865: Dainippon Ink and Chemicals Co., bisphenol A novolac epoxy resin (epoxy equivalent 20)
8) ESCN-195: Nippon Kayaku Co., Ltd., cresol novolac type epoxy resin (epoxy equivalent 200) H-1: Meiwa Kasei Co., phenol novolac resin (OH equivalent 106) VH-4170: Dainippon Ink Chemical Industry Co., Ltd., bisphenol A novolac (OH equivalent 118) TCG-1: Tokuriki Chemical Co., Ltd., silver powder TPPK: Kitako Chemical Co., Ltd., epoxy resin curing accelerator 2P4MHZ: Shikoku Kasei Co., Ltd., Imidazole-based epoxy resin curing accelerator 2MA-OK: Shikoku Kasei Co., Ltd., imidazole-based epoxy resin curing accelerator BMDADPM: 4,4'-bismaleimidediaminodiphenylmethane, Tokyo Kasei Co., thermosetting imide compound BMPPP : 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane, manufactured by KI Kasei Co., Ltd.,
Thermosetting imide compound BPO: Benzoyl peroxide, NOF Corporation
Made, thermal polymerization initiator

[0035]

[Table 1]

[0036]

[Table 2]

[0037]

[Table 3] No. 1 to 11 varnishes, 30 to 50 μm each
On a polypropylene film (base film) to a thickness of, and heat at 80 ° C for 10 minutes, then at 150 ° C for 30 minutes, and then peel off the base film at room temperature to remove the adhesive film (25 μm thick). Obtained.

Test Example 1 No. The peel adhesive strength of each of the adhesive films obtained in Examples 1 to 11 (Example Nos. 1 to 8 of the present invention and Comparative Examples Nos. 9 to 11) at each adhesive temperature was measured (Table 4). In addition, the peel adhesive force is obtained by cutting the adhesive film into a size of 5 mm × 5 mm, sandwiching it between a 5 mm × 5 mm silicon chip and a copper lead frame, and applying a load of 200 g to 1
After crimping at 80 ℃ or 250 ℃ for 3 seconds, 250
The peel strength at 20 ° C. for 20 seconds was measured.

[0039]

[Table 4]

Test Example 2 No. 1 to 11 (Examples Nos. 1 to 8 of the present invention and Comparative Examples Nos. 9 to 11) were used to measure chip warpage (Table 4). For chip warp, the adhesive film was cut into a size of 13 mm × 13 mm, sandwiched between a silicon chip of 13 mm × 13 mm and a copper lead frame, and a load of 1000 g was applied to the chip at 250 ° C. After crimping for 2 seconds, chip warpage was measured. Note that the chip warp was a measured value of the maximum height (μm) from the baseline when the surface was scanned with a surface roughness meter for 11 mm in a straight line.

[0041]

[Table 5]

[0042]

Since the adhesive film of the present invention has low stress and low temperature adhesiveness, it can be suitably used not only for the 42 alloy lead frame for die bonding but also for the copper lead frame, and further it can be used as an insulating support substrate. Can also be suitably used.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing an adhesive film of one embodiment of the present invention.

FIG. 2 is a cross-sectional view illustrating a semiconductor device of one embodiment of the present invention.

FIG. 3 is a cross-sectional view illustrating a semiconductor device of one embodiment of the present invention.

[Explanation of symbols]

1 Adhesive film 1'adhesive film 2 Adhesive layer 3 Base film 4 Semiconductor element 4'semiconductor element 5 Semiconductor element support members 6 wires 7 Sealant

Continued front page    F-term (reference) 4J004 AA02 AA03 AA11 AA18 BA02                       FA05                 4J040 EB031 EB032 EC001 EC002                       EH031 EH032 HA066 HA136                       HA306 HA346 HA366 JA09                       JB02 KA32 KA42 LA06 LA09                       MA02 NA20                 4J043 PA02 PA04 PC11 PC14 QB15                       QB26 RA35 SA06 SA43 SA44                       SA47 SA72 SB01 SB02 TA12                       TA22 TA43 TA44 TA61 TA66                       TA67 TA70 TA71 TA74 TA78                       TB01 TB02 UA022 UA032                       UA052 UA082 UA121 UA122                       UA131 UA132 UA141 UA142                       UA151 UA152 UA252 UA262                       UA332 UA382 UA622 UA632                       UA652 UA662 UA672 UA712                       UA761 UA771 UA781 UB011                       UB012 UB021 UB022 UB051                       UB061 UB062 UB121 UB122                       UB131 UB151 UB152 UB172                       UB281 UB282 UB301 UB302                       UB312 UB321 UB351 UB401                       UB402 VA011 VA012 VA021                       VA022 VA031 VA032 VA041                       VA051 VA061 VA062 VA071                       VA081 VA092 VA102 WA05                       WA09 WA16 XA16 XA17 XA19                       YA06 YA08 ZA02 ZB11                 5F047 BA33 BB03

Claims (3)

[Claims] 1. Formula (I): A tetracarboxylic dianhydride containing 30 mol% or more of all tetracarboxylic dianhydrides represented by the formula (II): (However, Q ₁ , Q ₂ and Q ₃ represent alkylene having 1 to 10 carbon atoms and n represents an integer of 2 to 30) and reacted with a diamine containing 10% or more by weight of the total diamine. An adhesive film containing the resulting polyimide resin. 2. A tetracarboxylic dianhydride containing (A) a tetracarboxylic dianhydride of the formula (I) in an amount of 30 mol% or more of all tetracarboxylic dianhydrides, and a diamine represented by the formula (II). Polyimide resin obtained by reacting diamine containing 30% or more of the total weight of diamine: 100 parts by weight
On the other hand, an adhesive film containing (B) a thermosetting resin: 0 to 200 parts by weight and (C) a filler: 0 to 8000 parts by weight. 3. A semiconductor device manufactured by using the adhesive film according to claim 1.