JP3513829B2 - Adhesive film - Google Patents

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 moisture resistance, has the lowest elastic modulus of the above three, and has heat resistance applicable to thermo-compression bonding type wire bonder at 350 ° C. 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 have 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 (JP-A-6-145639). , JP-A-7-228697, etc.).

[0005]

The adhesive film reported by the above-mentioned microelectronic manufacturing and testing can lower the adhesive temperature when a thermoplastic resin having a low melting point is selected and used.
Although the damage to the chip such as the oxidation of the lead frame is small, it cannot withstand the heat treatment (for example, wire bonding, encapsulation process, etc.) after die bonding because the adhesive strength at the time of heat is low. 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.

Since 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 heat, it can be suitably used for 42 alloy lead frames for die bonding. However, the copper lead frame which has recently been used is susceptible to oxidation, and therefore, an adhesive film that can be bonded at a temperature lower than that of the above adhesive film is desired in order to avoid damage due to oxidation. In addition, since the insulating support substrate having low thermal conductivity has a large coefficient of thermal expansion, it tends to warp during heating and bonding, and also has high water absorption. Therefore, if the adhesive film absorbs the moisture, the reliability of the semiconductor package at the time of heating is deteriorated. Therefore, in this case, low hygroscopicity is desired in addition to low-temperature adhesiveness. INDUSTRIAL APPLICABILITY The present invention can be suitably used not only for 42 alloy lead frames for die bonding but also for copper lead frames, and also for insulating supporting substrates. Low stress / low temperature adhesiveness and low hygroscopicity. The purpose is to provide an adhesive film of.

[0007]

The present invention provides a compound of formula (I)

[Chemical 3] (In the formula, n = 10 is shown.) The tetracarboxylic acid dianhydride is 30 mol% of the total tetracarboxylic acid dianhydride.
A tetracarboxylic dianhydride containing the above, and formula (II)

[Chemical 4] (In the formula, Q ₁ and Q ₂ each independently represent an alkylene group having 1 to 5 carbon atoms or a phenylene group, and Q ₃ , Q ₄ , Q ₅
And Q ₆ are each independently an alkyl group having 1 to 5 carbon atoms,
It represents a phenyl group or a phenoxy group, and p represents an integer of 1 to 50. ) Is an adhesive film containing a polyimide resin obtained by reacting diamine containing 3 mol% or more of all diamines.
As the alkylene group having 1 to 5 carbon atoms of Q ₁ and Q _2, for example, methylene, ethylene, trimethylene, tetramethylene, there are pentamethylene or the like, Q _3,
Examples of the alkyl group having 1 to 5 carbon atoms among Q ₄ , Q ₅ and Q ₆ include methyl, ethyl, propyl, butyl,
There are pentyls, etc.

The adhesive film further comprises (B) a thermosetting resin: 0 to 200 parts by weight, and (C) a filler: 0 to 80, relative to 100 parts by weight of the polyimide resin (A).
An adhesive film can be prepared by containing 100 parts by weight.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION One of the raw materials for producing a polyimide resin for an adhesive film of the present invention, n in the formula (I) is 1
Examples of the tetracarboxylic dianhydride of 0, 1, 10-
(Decamethylene) bis (trimellitate dianhydride) there
It

The above tetracarboxylic dianhydride can be synthesized from trimellitic anhydride monochloride and the corresponding diol. The content of the tetracarboxylic dianhydride in the total tetracarboxylic dianhydride is 30 mol% or more, preferably 50 mol% or more, and more preferably 70 mol% or more. When it is less than 30 mol%, the temperature at the time of adhering the adhesive film becomes high, which is not preferable.

Examples of the tetracarboxylic dianhydride that can be used together with the tetracarboxylic dianhydride of the formula (I) include pyromellitic dianhydride and 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 (3,3
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 '- 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 integrators tetracarboxylic acid dianhydride, 1,
4,5,8- naphthalene integrators tetracarboxylic 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,
Thiofene-2,3,4,5-tetracarboxylic dianhydride, 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride, 3,4,3', 4'-biphenyltetracarboxylic dianhydride Anhydride, 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-phenylene bis (trimellitate anhydride),

Ethylene tetracarboxylic 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-cyclobutane tetracarboxylic dianhydride, bis (exo-bicyclo [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-carboxyphenyl)
Hexafluoropropane dianhydride, 2,2-bis [4-
(3,4-Dicarboxyphenoxy) phenyl] hexafluoropropane dianhydride, 4,4'-bis (3,4-
Dicarboxyphenoxy) diphenyl sulphates I de dianhydride, 1,4-bis (2-hydroxy hexafluoroisopropyl) benzene bis (trimellitic acid dianhydride),
1,3-bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimellitic dianhydride), 5-
(2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride, tetrahydrofuran-2,3,4,5-tetracarboxylic acid dianhydride, etc. You may use it in mixture of 2 or more types.

As the siloxane-based diamine of the formula (II), which is one of the other raw materials for producing the polyimide resin for the adhesive film of the present invention, when p is 1, 1,1,3,3-tetramethyl-1, 3-bis (4-aminophenyl) disiloxane, 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, 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
3,5,5-hexapropyl-1,5-bis (3-aminopropyl) trisiloxane, etc.,

When p is 3 to 50,

[Chemical 5]

[Chemical 6]

[Chemical 7] Etc., and these may be used in combination of two or more kinds. Expression (I
The siloxane-based diamine of I) is 3 for all diamines.
The diamine content is at least mol%, preferably at least 5 mol%, and more preferably at least 10 mol%. If it is less than 3 mol%, the properties of low stress, low temperature adhesiveness and low hygroscopicity cannot be exhibited.

Other diamines can be used in combination with the above formula (II). As the diamine that can be used in combination,
1,2-diaminoethane, 1,3-diaminopropane,
1,4-diaminobutane, 1,5-diaminopentane,
Fats such as 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane and 1,12-diaminododecane Group diamine, 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 '
- diaminodiphenyl difluoromethane, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulphates I de, 3,
4'-diaminodiphenyl sulphates I de, 4,4'-diaminodiphenyl sulphates I de,

3,3'-diaminodiphenyl 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) Sulf I, bis (4- ( Four
- aminophenoxy) phenyl) Sulf I, bis (4
Aromatic diamines such as-(3-aminophenoxy) phenyl) sulfone and bis (4- (4-aminophenoxy) phenyl) sulfone can be mentioned.

The condensation reaction of tetracarboxylic dianhydride and 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 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.

The reaction temperature is 80 ° C. or lower, preferably 0-5.
It is 0 ° C. 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.

The polyimide can be obtained by subjecting the above reaction product (polyamic acid) to dehydration and ring closure. Dehydration ring closure is 1
It can be performed using a method of heat treatment at 20 ° C to 250 ° C or a chemical method. In the case of the method of heat treatment at 120 ° C. to 250 ° 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 is a generic term for polyimide and its precursor. Polyimide precursors include not only polyamic acid but also polyamic acid partially imidized.

In the case of performing dehydration ring closure by a chemical method, acetic anhydride, propionic anhydride, acid anhydride of benzoic anhydride, carbodiimide compound such as dicyclohexylcarbodiimide, etc. are used as a ring-closing agent. 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. Further, in order to improve the adhesive force, a silane coupling agent, a titanium coupling agent, a nonionic surfactant, a fluorine surfactant, a silicone additive, etc. may be appropriately added to the polyimide resin.

The adhesive film of the present invention can be made into an adhesive film by incorporating the above-mentioned polyimide resin with a thermosetting resin and / or a filler. When a thermosetting resin is used, the thermosetting resin (B) is 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. Choose from

When a thermosetting resin containing an epoxy resin, a phenol resin and a curing accelerator is used as the thermosetting resin, the adhesive film is (1) a tetracarboxylic dianhydride of the formula (I) 30 mol% of dianhydride
A polyimide resin (A) obtained by reacting a tetracarboxylic dianhydride containing the above with a diamine containing 10 mol% or more of all diamines of the formula (II); 100 parts by weight, an epoxy resin; 200 parts by weight, phenol resin; 0 to 150 parts by weight, based on 100 parts by weight of epoxy resin, and a curing accelerator; 0 to 50 parts by weight, based on 100 parts by weight of epoxy resin, dissolved in an organic solvent, (2) It can be manufactured by coating on a base film and heating.

At least 2 thermosetting resins are contained in one molecule.
In the case of an imide compound having one thermosetting imide group, (1) the tetracarboxylic acid dianhydride of the formula (I) contains 30 mol% or more of all tetracarboxylic acid dianhydrides. And a polyimide resin (A) obtained by reacting a diamine of the formula (II) with 10% by mole or more of all diamines; 100 parts by weight, and at least two thermosetting imides in one molecule. An imide compound having a group; 0 to 200 parts by weight is dissolved in an organic solvent, (2) coated on a base film and heated.

When a 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 is characterized in 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 0 to 200 parts by weight, preferably 0 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 is deteriorated.

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. The amount of epoxy resin is
0 to 200 parts by weight for 100 parts by weight of polyimide resin,
It is preferably 0 to 100 parts by weight, and if it exceeds 200 parts by weight, the film formability becomes poor.

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. The amount of the phenol resin is 0 to 150 parts by weight, preferably 0 to 120 parts by weight, based on 100 parts by weight of the epoxy resin. If it exceeds 150 parts by weight, the curability becomes insufficient.

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 0 to 50 parts by weight, preferably 0 to 20 parts by weight, based on 100 parts by weight of the epoxy resin.
If it exceeds 0 parts by weight, the storage stability becomes poor.

The organic solvent used in the production of the above-mentioned adhesive film is not limited as long as it can dissolve, knead or disperse the material uniformly. 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-bis-maleimidobenzene, meta-bis-maleimidobenzene, and para-bis-maleimidobenzene. In addition to maleimidobenzene, 1,4-bis (p-maleimidocumyl) benzene and 1,4-bis (m-maleimidocumyl) benzene, imide compounds represented by the following formulas (III) to (V), etc. There is.

[0035]

[Chemical 8] [In Formula (III), X is O, CH ₂ , CF ₂ , SO ₂ , S, C
O, 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. ]

[0036]

[Chemical 9] [In the formula (IV), 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. ]

[0037]

[Chemical 10] [In Formula (V), m shows an integer of 0-4. ]

The amount of the imide compound used in the present invention is
The amount is 0 to 200 parts by weight, preferably 0 to 100 parts by weight, based on 100 parts by weight of the polyimide resin. If it exceeds 200 parts by weight, the film formability is deteriorated.

[0039] As the imide compound of formula (III), for example, 4, 4 '- bismaleimide diphenyl ether,
4, 4 '- bismaleimide diphenylmethane, 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-maleimide phenyl) propane, 4, 4' - bismaleimide diphenyl trifluoromethane, 1,1,1,
3,3,3-hexafluoro-2,2-bis (4-maleimidophenyl) propane and the like.

Examples of the imide compound of the formula (IV) 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, etc.

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 inorganic materials such as silica, alumina, titania, glass, iron oxide and ceramics. The substance filler is added for the purpose of imparting low thermal expansion and low moisture absorption to the adhesive.
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 0 to 8000 parts by weight, preferably 0 to 400 parts by weight based on 100 parts by weight of the polyimide resin.
It is in the range of 0 parts by weight. If it is more than 8000 parts by weight, the adhesiveness will be reduced.

Mixing and kneading in the case of using a filler can be carried out by appropriately combining an ordinary stirrer, a ladle machine, a three-roller, a ball mill and other dispersing machines.

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.
It heats at the temperature of 0.1 to 30 minutes, and performs it. After that, the adhesive film is usually peeled off from the base film at room temperature and used.

The obtained adhesive film is a semiconductor element such as IC or LSI, a lead frame such as a 42 alloy lead frame or a copper lead frame, a plastic film such as polyimide, epoxy resin or polyimide resin, or a substrate such as glass nonwoven fabric. It can be used for joining a support member made of a material such as polyimide, epoxy resin, or polyimide resin impregnated and cured, or ceramics such as alumina. 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-
It is 300 ° C. and 0.1 to 300 seconds.

[0047]

EXAMPLES The present invention will be described below with reference to examples. Synthesis example 500m equipped with thermometer, stirrer and calcium chloride tube
Diamine represented by the following formula in a 4-necked flask

[Chemical 11] 45.0 g (0.05 mol) and 2,2-bis (4-
(4-Aminophenoxy) phenyl) propane 20.5
g (0.05 mol) was weighed, 150 g of N-methyl-2-pyrrolidone was added, and the mixture was stirred. After dissolution of the diamine, 52.2 g (0.1 mol) of decamethylene bis trimellitate dianhydride was added in small portions while cooling the flask in an ice bath. 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 acetic anhydride 25.5 g (0.2
5 mol) and 19.8 g (0.25 mol) of pyridine were added, and the mixture was stirred at room temperature for 2 hours. Pour the reaction into water,
The precipitated polymer was collected by filtration and dried to obtain a polyimide resin (A).

Examples 1 to 3 As shown in the formulation table (Table 1), No. 1-3 varnishes were prepared. In Table 1, various symbols have the following meanings. YDCN-702: Tohto Kasei, Cresol novolac type epoxy
(Epoxy equivalent 220) N-865: Dainippon Ink, bisphenol novolac type epoxy (epoxy equivalent 208) H-1: Meiwa Kasei, phenol novolac (OH equivalent 106) VH-4170: Dainippon Ink, bisphenol A novolac
(OH equivalent 118) TPPK: Tokyo Kasei, tetraphenylphosphonium tetraphenylborate 2P4MHZ: Shikoku Kasei, Cureazole 2P4MHZ TCG-1: Tokuriki Kagaku, silver powder DMAC: Dimethylacetamide DMF: Dimethylformamide

[0049]

[Table 1]

Formulated No. 1 to 30 varnishes each
It is applied on a polypropylene film (base film) to a thickness of -50 μm, and then at 80 ° C. for 10 minutes, followed by 150
After heating at 30 ° C. for 30 minutes, the base film was peeled off at room temperature to obtain an adhesive film.

Evaluation Test The adhesive films obtained in Examples 1 to 3 were measured for peel adhesion and hygroscopicity, and the adhesive films obtained in Examples 1 to 3 were used to form silicon chips on lead frames. The warp of the chip when bonded was measured (Table 2).

[Table 2] Table 2 Peel adhesion and hygroscopicity of adhesive film and chip warpage ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ ━━━ contact wear full I le-time item No.1 No.2 No.3 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ ━━━━━ Peel adhesion Kgf / chip Kgf / chip Kgf / chip ・ Adhesion temperature: 180 ° C 1.8 1.7 2.0 ・ Adhesion temperature: 250 ° C 2.0 2.5 2.3 Moisture absorption < 0.02% <0.02% <0.02% Chip warp 3 μm 4 μm 3 μm ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ ━━━━

The peel adhesion, hygroscopicity and chip warpage are measured as follows. <Measurement method of peel adhesion> Adhesive film is 8mm × 8m
It is cut into a size of m, sandwiched between an 8 mm x 8 mm silicon chip and a copper lead frame, a load of 1000 g is applied, and pressure bonding is performed at 180 ° C or 250 ° C for 5 seconds, then 250 ° C, 20 seconds. The peel strength during heating was measured.

<Measurement Method of Hygroscopicity> Adhesive film 180
After curing at 0 ° C for 1 hour, it is cut into a size of 50 mm x 50 mm, heated at 120 ° C for 1 hour under reduced pressure, cooled, and then the weight (X ₁ ) is measured. Then, this film is immersed in ion-exchanged water at room temperature for 24 hours, taken out, and water droplets on the surface are carefully wiped off with a filter paper, and then the weight (X ₂ ) is measured again. The hygroscopicity (moisture absorption rate) is calculated by the following formula. Moisture absorption rate (%) = (X ₂ −X ₁ ) / X ₁ × 100

<Chip Warpage Measuring Method> 1 piece of adhesive film
Cut into a size of 3 mm × 13 mm, sandwich this between a copper lead frame and a silicon chip of 13 mm × 13 mm, apply a load of 1000 g, and 250 ° C.
After press-bonding for 5 seconds, the temperature was returned to room temperature, and this was linearly scanned with a surface roughness meter for 11 mm, and the maximum height (μm) from the baseline was determined to be the chip warp.

[0055]

The adhesive film of the present invention has low stress, low temperature adhesiveness, and low hygroscopicity. Therefore, it can be suitably used for a copper lead frame for die bonding, and can also be suitably used for an insulating support substrate. It can also be used with 42 alloy leadframes.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toshihiko Kato 48 Wadai, Tsukuba City, Ibaraki Prefecture Hitachi Chemical Co., Ltd. Tsukuba Development Laboratory (72) Inventor Yasuhisa Odagawa 48 Wadai, Tsukuba City, Ibaraki Hitachi Chemical Co., Ltd. (56) Reference JP-A-8-27431 (JP, A) JP-A-8-34968 (JP, A) JP-A-5-331444 (JP, A) JP-A-6-145639 ( JP, A) JP 7-228697 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C09J 4/00-201/10

Claims (2)

(57) [Claims] 1. Formula (I): (In the formula, n = 10 is shown.) The tetracarboxylic acid dianhydride is 30 mol% of the total tetracarboxylic acid dianhydride.
A tetracarboxylic dianhydride containing the above, and a compound of formula (II): (In the formula, Q ₁ and Q ₂ each independently represent an alkylene group having 1 to 5 carbon atoms or a phenylene group, and Q ₃ , Q ₄ , Q ₅
And Q ₆ are each independently an alkyl group having 1 to 5 carbon atoms,
It represents a phenyl group or a phenoxy group, and p represents an integer of 1 to 50. An adhesive film containing a polyimide resin obtained by reacting a diamine containing 3 mol% or more of all diamines with a siloxane-based diamine represented by the formula (1). 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 siloxane-based diamine of the formula (II). Is a polyimide resin obtained by reacting a diamine containing 3 mol% or more of all diamines: 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.