JPH11228914A - Adhesive film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an adhesive film showing good adhesion at low temperatures by mixing a thermosetting resin and a filler with a polyimide resin obtained by reaction of a tetracarboxylic acid anhydride on a diamine. SOLUTION: A tetracarboxylic acid dianhydride which contains not less than 30 mol.% of a tetracarboxylic acid dianhydride represented by formula I [n is 1-6; X is independently connected or a 1-10C alkyl group; Y is a compound represented by formula II (R is H or an 1-10C alkyl] as exemplified by 1,4-cylcohexanediol-bis(trimellitate dianhydride) is made to react on a diamine (for example; 1,2-diaminoethane) at temperatures not more than 80 deg.C to produce a polyamide acid which is then dehydrated and ring-closed to produce a polyimide resin. An adhesive film is obtained by mixing 1-200 pts.wt. of a thermosetting resin (for example; an epoxy resin, a phenol resin and a hardening accelerator) and 0-8,000 pts.wt. of a filler (for example; conductive filler such as silver powder, an inorganic filler such as silica, etc.), with 100 pts.wt. of the obtained polyimide resin.

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, 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 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. Is the mainstream of adhesive materials. 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.

[0003] 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 around the melting point of the thermoplastic resin and pressure bonding is performed.

[0004]

The adhesive film reported in the above-mentioned microelectronic manufacturing and testing can reduce the bonding temperature by using a thermoplastic resin having a low melting point.
Although damage to the chip, such as oxidation of the lead frame, is small, the adhesive strength at the time of heat is low, so that it cannot withstand heat treatment (for example, wire bonding, a sealing step, etc.) after die bonding. When a thermoplastic resin having a high melting point that can withstand heat treatment is used, the bonding temperature increases, and the lead frame is easily damaged by oxidation or the like.

The present invention provides a low-temperature adhesive film which can be used not only for 42-alloy lead frames for die bonding but also for copper lead frames and also for insulating supporting substrates. It is intended to be.

[0006]

According to the present invention, (A) the following formula (I)

Embedded image [In the formula, n represents an integer of 1 to 6, X represents a direct bond or an alkyl group having 1 to 10 carbon atoms, and Y represents a divalent group shown below.

Embedded image (However, each of the four Rs is independently hydrogen or carbon atom 1
To 10 alkyl groups). The polyimide resin obtained by reacting a tetracarboxylic dianhydride represented by the following formula with a diamine and a tetracarboxylic dianhydride containing 30 mol% or more of the total tetracarboxylic dianhydride: 100 parts by weight (B) thermosetting resin: 1 to 200 parts by weight,
And (C) a filler: an adhesive film containing 0 to 8000 parts by weight.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The tetracarboxylic dianhydride of the formula (I) used in the present invention includes 1,4-cyclohexanediol bis (trimellitate dianhydride) 1,3-cyclohexanediol bis (trimellitate dianhydride) 1,2-cyclohexanediol bis (trimellitate dianhydride) 1,1-bicyclohexyl-4,4′-diol bis (trimellitate dianhydride) (2,2-bis (4-hydroxycyclohexyl) propane) bis (trimellitate) Dianhydride) and the like, and two or more of these may be used in combination.

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

The tetracarboxylic dianhydride usable together with the tetracarboxylic dianhydride of the formula (I) 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-naphthalene-tetracarboxylic dianhydride, 1,4
5,8-naphthalene-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,
Thiophene-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-phenylenebis (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-cyclobutanetetracarboxylic 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-dicarboxyphenyl) hexafluoropropane dianhydride Object, 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 dianhydride),
1,3-bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimellitic dianhydride), 5-
(2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride and the like. You may mix and use more than one type.

The diamines usable in 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, 1,12-diaminododecane, 4,9
Dioxadodecane-1,12-diamine, 4,7,1
Aliphatic diamines such as 0-trioxatridecane-1,13-diamine, etc., 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'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfide, 3,4'-diaminodiphenylsulfide, ,
4'-diaminodiphenyl sulfide,

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) sulfide, bis (4- (4
-Aminophenoxy) phenyl) sulfide, bis (4
And aromatic diamines such as-(3-aminophenoxy) phenyl) sulfone and bis (4- (4-aminophenoxy) phenyl) sulfone.

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, cyclohexanone, dimethylsulfoxide, hexamethylphosphorylamide, m-cresol, o-chlorophenol and the like.

The reaction temperature is 80 ° C. or less, preferably 0 to 5
0 ° C. 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 subjecting the above reactant (polyamic acid) to dehydration ring closure. 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.

Further, 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, and the like may be appropriately added to the polyimide resin.

The adhesive film of the present invention is obtained by adding a thermosetting resin to the above-mentioned polyimide resin or by adding a thermosetting resin and a filler to the above-mentioned polyimide resin. The thermosetting resin is a resin that forms a three-dimensional network structure by heating and cures. The thermosetting resin (B) is selected from an epoxy resin, a phenol resin and a resin containing a curing accelerator (catalyst), or an imide compound having at least two thermosetting imide groups in one molecule.

In the case where a thermosetting resin containing an epoxy resin, a phenol resin and a curing accelerator is used as the thermosetting resin, (1) the tetracarboxylic dianhydride of the formula (I) is composed of all tetracarboxylic dianhydrides. 30 mol% of acid dianhydride
100 parts by weight of a polyimide resin (A) obtained by reacting the tetracarboxylic dianhydride containing the above with a diamine; 1 to 200 parts by weight of an epoxy resin; and 100 parts by weight of a phenol resin; To 150 parts by weight and a curing accelerator (catalyst); 0.01 to 50 parts by weight with respect to 100 parts by weight of the epoxy resin, dissolved in an organic solvent, (2) applied on a base film, and heated. Can be manufactured.

The thermosetting resin has at least two in one molecule.
In the case of an imide compound having two thermosetting imide groups, (1) a tetracarboxylic dianhydride in which the tetracarboxylic dianhydride of the formula (I) contains at least 30 mol% of all tetracarboxylic dianhydrides; Polyimide resin (A) obtained by reacting a product with a diamine; 100 parts by weight, and an imide compound having at least two thermosetting imide groups in one molecule; 1 to 200 parts by weight in an organic solvent. It is manufactured by dissolving, (2) coating on a base film and heating.

When a filler is contained, the filler (C) may be a conductive filler such as silver powder, gold powder, or copper powder, or an inorganic filler such as silica, alumina, titania, glass, iron oxide, ceramic, or boron nitride. is there.

The filler-containing adhesive film is prepared by dissolving a polyimide resin in an organic solvent, adding a filler, adding other components as necessary, and mixing and kneading. The obtained paste-like mixture is uniformly applied on a base film and heated to produce the paste-like mixture.

The amount of the thermosetting resin is 1 to 200 parts by weight, preferably 1 to 100 parts by weight, per 100 parts by weight of the polyimide resin (A). If the amount is less than 1 part by weight, the adhesiveness will be poor, and if it exceeds 200 parts by weight, the film forming property will 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
1 to 200 parts by weight based on 100 parts by weight of the polyimide resin,
It is preferably from 5 to 100 parts by weight, and if it is less than 1 part by weight, the adhesiveness is poor, and if it exceeds 200 parts by weight, the film formability is 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 2 to 150 parts by weight, preferably 50 to 120 parts by weight based on 100 parts by weight of the epoxy resin. If the amount is less than 2 parts by weight or exceeds 150 parts by weight, the curability becomes insufficient.

The curing accelerator (catalyst) is not particularly limited as long as it is used for curing the epoxy resin. Such as, for example, imidazoles,
Dicyandiamide derivative, dicarboxylic dihydrazide,
Triphenylphosphine, tetraphenylphosphonium tetraphenylborate, 2-ethyl-4-methylimidazole-tetraphenylborate, 1,8-diazabicyclo (5,4,0) undecene-7-tetraphenylborate and the like are used. These may be used in combination of two or more. The amount of the curing accelerator is 0.01 to 50 parts by weight, preferably 0.1 to 2 parts by weight, per 100 parts by weight of the epoxy resin.
0 parts by weight. If the amount is less than 0.01 part by weight, the curability becomes insufficient, and if it exceeds 50 parts by weight, the storage stability deteriorates.

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, dimethylsulfoxide, Diethylene glycol dimethyl ether, toluene, benzene, xylene, methyl ethyl ketone, tetrahydrofuran, ethyl cellosolve, ethyl cellosolve acetate, butyl cellosolve, dioxane,
And cyclohexanone.

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, imide compounds represented by the following formulas (II) to (IV), and the like There is.

[0030]

Embedded image [In the formula (II), X is O, CH ₂ , CF ₂ , SO ₂ , S, C
O, C (CH ₃ ) 2 or C (CF ₃ ) ₂ , R ₁ ,
R ₂ , R ₃ and R ₄ are each independently hydrogen, having 1 to 1 carbon atoms.
0 represents an alkyl group, an alkoxy group having 1 to 10 carbon atoms, fluorine, chlorine or bromine, and D represents a dicarboxylic acid residue having an ethylenically unsaturated double bond. ]

[0031]

Embedded image [In the formula (III), Y is O, CH ₂ , CF ₂ , SO ₂ , S, C
O, C (CH ₃ ) 2 or C (CF ₃ ) ₂ , R ₅ , R ₆ , R ₇
And R ₈ each independently represent hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, fluorine, chlorine or bromine, and D represents a dicarboxylic acid residue having an ethylenically unsaturated double bond. Is shown. ]

[0032]

Embedded image [In the formula (IV), m represents an integer of 0 to 4. ]

The amount of the imide compound used in the present invention is
The amount is 1 to 200 parts by weight, preferably 1 to 100 parts by weight, based on 100 parts by weight of the polyimide resin. If the amount is less than 1 part by weight, the adhesiveness will be poor, and if it exceeds 200 parts by weight, the film forming property will be poor.

The imide compound of the formula (II) includes, for example, 4,4-bismaleimide diphenyl ether,
4-bismaleimidediphenylmethane, 4,4-bismaleimide-3,3′-dimethyl-diphenylmethane,
4,4-bismaleimidodiphenyl sulfone, 4,4-
Bismaleimide diphenyl sulfide, 4,4-bismaleimide diphenyl ketone, 2,2'-bis (4-maleimidophenyl) propane, 4,4-bismaleimide diphenylfluoromethane, 1,1,1,3,3,3- And hexafluoro-2,2-bis (4-maleimidophenyl) propane.

Examples of the imide compound of the formula (III) 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 silica, alumina, titania, glass, iron oxide, ceramic, and boron nitride are used. It is added for the purpose of imparting a low thermal expansion property and a low moisture absorption rate to an inorganic material filler adhesive such as. 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 from 0 to 8000 parts by weight, preferably from 0 to 400 parts by weight, per 100 parts by weight of the polyimide resin.
The range is 0 parts by weight. If the amount is more than 8000 parts by weight, the adhesiveness decreases.

Mixing and kneading when a filler is used can be carried out by appropriately combining ordinary dispersing machines 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 used solvent 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. That is, the adhesive film of the present invention is sandwiched between the above-described semiconductor element and the supporting member, and the two are bonded by heating and pressing. The heating temperature is usually 100 to
300 ° C. for 0.1 to 300 seconds.

[0042]

The present invention will be described below with reference to examples. Synthesis Example 1 500 m equipped with a thermometer, a stirrer, and a calcium chloride tube
l in a four-necked flask, 41 g (0.1 mol) of 2,2-bis (4- (4-aminophenoxy) phenyl) propane
And 150 g of dimethylacetamide and stirred.
After dissolution of the diamine, while cooling the flask in an ice bath,
1,4-cyclohexanediol bis (trimellitate dianhydride)

[0043]

Embedded image 46.2 g (0.1 mol) were added in small portions. After reacting at room temperature for 3 hours, 30 g of xylene was added, and the mixture was heated at 150 ° C. while blowing nitrogen 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 (A).

Synthesis Example 2 500 m equipped with a thermometer, a stirrer and a calcium chloride tube
l, four-necked flask, 32.94 g of 4,4'-methylene-bis (2,6-diisopropylaniline)
(0.09 g), 1,3-bis (3-aminopropyl)
2.48 g (0.01 mol) of tetramethyldisiloxane
And 150 g of N-methyl-2-pyrrolidone were taken and stirred. After dissolution of the diamine, the flask was cooled in an ice bath while (2,2-bis (4-hydroxycyclohexyl) propane) bis (trimellitate dianhydride) was added.

[0045]

Embedded image 58.8 g (0.1 mol) were 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. Then, 25.5 g (0.25 mol) of acetic anhydride and 19.8 g (0.25 mol) of pyridine were added, and the mixture was added at room temperature for 2 hours. Stirred. The reaction solution was poured into water, and the precipitated polymer was collected by filtration and dried to obtain a polyimide resin (B).

Synthesis Example 3 500 m equipped with a thermometer, a stirrer and a calcium chloride tube
In a 1-liter four-necked flask, 41 g (0.1 mol) of 2,2-bis (4- (4-aminophenoxy) phenyl) propane and 150 g of dimethylacetamide were placed and stirred. After dissolution of the diamine, the flask was cooled in an ice bath while 1,1-bicyclohexyl-4,4′-diol bis (trimellitate dianhydride) was added.

[0047]

Embedded image 49.14 g (0.09 mol) and 3,3 ′, 4,4 ′
-3.22 g of benzophenonetetracarboxylic dianhydride
(0.01 mol) was added in small portions. After reacting at room temperature for 3 hours, 30 g of xylene was added, and the mixture was heated at 150 ° C. while blowing nitrogen 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 (C).

[0048]

Table 1 Table 1 Formulation table (unit: parts by weight) --------------------------------------------- Material No. 1 2 3 4 5 6 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− polyimide A BCA None A 100 parts 100 parts 100 parts 100 parts-100 parts Epoxy N-865 N-865 YDCN-702 ESCN-195 YDCN-702 None Resin 10 100 100 50 50 100-Phenol VH-4170 VH-4170 H-1 H-1 H-1 None Resin 5.6 70 48 24 10-Cured TPPK TPPK 2P4MHZ 2MA-0K TPPK None Accelerator 0.5 10 1 0.5 0.4-Filler TCG-1 No alumina Silica No silica 100 190-80 45 − Solvent DMF DMF DMAc DMAc NMP DMF 100 1000 500 400 200 100 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− −−−−−−

Examples 1 to 4 As shown in the composition table of Table 1, Varnishes of Nos. 1 to 6 (Examples Nos. 1 to 4 of the present invention and Comparative Examples Nos. 5 and 6) were prepared. Various symbols in Table 1 have the following meanings. YDCH-702: Toto Kasei, Cresol novolak epoxy
(Epoxy equivalent 220) N-865: Dainippon Ink, bisphenol novolak epoxy (Epoxy equivalent 208) ESCN-195: Nippon Kayaku, Cresol novolak epoxy (Epoxy equivalent 200) H-1: Meiwa Kasei, Phenol novolak ( OH equivalent 106) VH-4170: Dainippon Ink, Bisphenol A Novolak
(OH equivalent 118) TCG-1: Tokuriki Chemical, silver powder DMAC: dimethylacetamide NMP: N-methylpyrrolidone DMF: dimethylformamide

The mixed No. 1 to 6 varnishes each 30
５０50 μm thick on a polypropylene film (base film), at 80 ° C. for 10 minutes, then 150
After heating at 30 ° C. for 30 minutes, the base film was peeled off at room temperature to obtain an adhesive film.

Test Example 1 The peel adhesive force at each bonding temperature of the adhesive films obtained in Examples 1 to 6 (Examples Nos. 1 to 4 of the present invention and Comparative Examples Nos. 5 and 6) was measured (Table 2). The peel adhesive strength was measured by cutting the adhesive film into a size of 8 mm × 8 mm, sandwiching the cut between an 8 mm × 8 mm silicon chip and a copper lead frame, and applying a load of 1000 g to the chip.
After pressure bonding at 0 ° C or 250 ° C for 3 seconds, 250 ° C,
The peel strength at the time of heating for 20 seconds was measured.

[0052]

Table 2 Table 2 Peel adhesion of adhesive film --------------------------------------------------------------------------- Peel adhesion Force (kgf / chip)------------------------------------------------------------------------------------- −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 200 ° C. 1.5 1.6 1.7 1.7 1.6 −0.2 250 ° C 1.7 1.9 1.9 1.9 −0.4 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− −−−− * The film was brittle and did not form a film.

[0053]

The adhesive film of the present invention has excellent low-temperature adhesiveness. It can be used not only for 42 alloy lead frames for die bonding but also for copper lead frames and also for insulating supporting substrates.

──────────────────────────────────────────────────続 き Continuing on the front page (51) Int.Cl. ⁶ Identification code FI C09J 201: 00) (72) Inventor Yuji Hasegawa 48 Wadai, Tsukuba-shi, Ibaraki Pref. Takashi Masuko 48 Wadai, Tsukuba City, Ibaraki Prefecture Within Tsukuba Development Laboratory, Hitachi Chemical Co., Ltd.

Claims (1)

[Claims] (A) The following formula (I): [In the formula, n represents an integer of 1 to 6, X represents a direct bond or an alkyl group having 1 to 10 carbon atoms, and Y represents a divalent group shown below. (However, each of the four Rs is independently hydrogen or carbon atom 1
To 10 alkyl groups). The polyimide resin obtained by reacting a tetracarboxylic dianhydride represented by the following formula with a diamine and a tetracarboxylic dianhydride containing 30 mol% or more of the total tetracarboxylic dianhydride: 100 parts by weight (B) thermosetting resin: 1 to 200 parts by weight,
And (C) a filler: an adhesive film containing 0 to 8000 parts by weight.