JPH07228697A - Adhesive film - Google Patents

Abstract

PURPOSE:To obtain an adhesive film containing a polyimide resin synthesized by reacting tetracarboxylic acid dianhydride with a diamine, capable of performing a heat treatment in adhesion at low temperatures in the same manner as silver paste and useful as an adhesive material for adhesion between IC or LSI and a lead frame. CONSTITUTION:This film contains a polyimide resin synthesized by reacting tetracarboxylic acid dianhydrides containing >=70mol% the tetracarboxylic acid dianhydrides of the formula [(n) is 2 to 20] with a diamine (e.g. 1,2- diaminoethane or p-phenylenediamine).

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 an IC or LSI and a lead frame, 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.

[0004]

In the adhesive film reported in the above-mentioned magazine, if a thermoplastic resin having a low melting point is selected and used, the adhesive temperature can be lowered, and damage to the chip such as oxidation of the lead frame is prevented. It needs less. However, since the adhesive strength at the time of heat is low, it cannot withstand heat treatment after die bonding, such as wire bonding and sealing process. If a thermoplastic resin having a high melting point is used so as to withstand such heat treatment, the bonding temperature becomes high, and there is a problem of damage such as oxidation of the lead frame. An object of the present invention is to provide an adhesive film for a die bond which can be heat-treated at the time of die bonding at a relatively low temperature as in the conventional silver paste and has a high adhesive force at the time of heat.

[0005]

Means for Solving the Problems The adhesive film of the present invention has the formula (I)

[Chemical 2] (However, the integer of n = 2-20 is shown.) Tetracarboxylic dianhydride whose content of the tetracarboxylic dianhydride is 70 mol% or more with respect to the total tetracarboxylic dianhydride. An adhesive film containing a polyimide resin, which is obtained by reacting a product with a diamine.

The adhesive film of the present invention is manufactured as follows. (1) A polyimide resin obtained by reacting a diamine with a tetracarboxylic dianhydride having a content of the tetracarboxylic dianhydride of the formula (I) of 70 mol% or more of the total tetracarboxylic dianhydride ( A); 100 parts by weight is dissolved in an organic solvent, and (2) coated on a base film and heated.

The tetracarboxylic dianhydride of the formula (I) used as a raw material for the above polyimide resin is
When n is 2 to 5, 1,2- (ethylene) bis (trimeritate dianhydride), 1,3- (trimethylene) bis (trimeritate dianhydride), 1,4- (tetramethylene) bis (trimeritate dianhydride) Anhydrous), 1,5- (pentamethylene) bis (trimellitate dianhydride), n is 6
When it is -20, 1,6- (hexamethylene) bis (trimellitate dianhydride), 1,7- (heptamethylene) bis (trimellitate dianhydride), 1,8- (octamethylene) bis (trimellitate dianhydride) ), 1,9- (nonamethylene) bis (trimellitate dianhydride), 1,1
0- (decamethylene) bis (trimeritate dianhydride), 1,12- (dodecamethylene) bis (trimeritate dianhydride), 1,16- (hexadecamethylene) bistrimeritate dianhydride, 1,18- ( Octadecamethylene) bis (trimellitate dianhydride), etc.,
You may use these 2 or more types together.

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

Tetracarboxylic dianhydrides that can be used with the tetracarboxylic dianhydride of formula (I) include, for example, 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'-benzophenone tetracarboxylic acid dianhydride, 2,3,2', 3-benzophenone tetracarboxylic acid dianhydride, 2,3,3 ', 4'-benzophenone tetracarboxylic acid dianhydride, 1 , 2, 5, 6-
Naphthalenetetracarboxylic dianhydride, 2,3,6,7
-Naphthalene tetracarboxylic 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,
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-dicarboxyphenyl) hexafluoropropane dianhydride Thing, 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 acid dianhydride, tetrahydrofuran-2,3,4,5-tetracarboxylic acid dianhydride, etc. You may use it in mixture of 2 or more types.

As the diamine used in the present invention,
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 '
-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, 2,2 '-(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
-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 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.

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 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 dehydration ring closure by a chemical method, acetic anhydride, propionic anhydride, acid anhydride of benzoic acid, 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 added to the polyimide resin as appropriate.

The adhesive film of the present invention is manufactured as follows. First, the polyimide resin is dissolved in an organic solvent.
The organic solvent used here is not particularly limited as long as it can be uniformly dissolved or kneaded, and examples thereof include dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, diethylene glycol dimethyl ether, and toluene. Examples thereof include benzene, xylene, methyl ethyl ketone, tetrahydrofuran, ethyl cellosolve, ethyl cellosolve acetate, butyl cellosolve and dioxane. Then, add additives as needed and mix

The varnish thus obtained is applied evenly on a base film such as a polyester sheet, and the solvent used is sufficiently evaporated, that is, about 6
It is heated at a temperature of 0 to 200 ° C. for 0.1 to 30 minutes to form an adhesive film, which is usually used for adhesion by removing the base film at the time of use.

The adhesive film of the present invention has a content of (A) the tetracarboxylic dianhydride of the formula (I), which is 70 mol% or more of the total tetracarboxylic dianhydride. And a polyimide resin obtained by reacting diamine with 100 parts by weight of (B) thermosetting resin; 0.1 to 200 parts by weight.

Here, the thermosetting resin is an epoxy resin,
A resin containing a phenolic resin and a curing accelerator, and
It is selected from imide compounds having at least two thermosetting imide groups in one molecule.

Further, the adhesive film of the present invention, that is, the adhesive film in the case where the thermosetting resin is a resin containing an epoxy resin, a phenol resin and a curing accelerator,
(1) The content of the tetracarboxylic dianhydride of formula (I) is
Polyimide resin (A) obtained by reacting tetracarboxylic dianhydride, which is 70 mol% or more of all tetracarboxylic dianhydrides, with diamine; 100 parts by weight, epoxy resin; 0.01 to 200 parts by weight, Phenol resin: 2-150 parts by weight with respect to 100 parts by weight of epoxy resin, and curing accelerator: 0.01 with respect to 100 parts by weight of epoxy resin
˜50 parts by weight is dissolved in an organic solvent, (2) coated on a base film and heated, and the thermosetting resin has at least two thermosetting imide groups in one molecule. The adhesive film when the imide compound has,
(1) The content of the tetracarboxylic dianhydride of formula (I) is
Polyimide resin (A) obtained by reacting tetracarboxylic dianhydride, which is 70 mol% or more of all tetracarboxylic dianhydrides, with diamine; 100 parts by weight, and at least two thermosettings in one molecule An imide compound having a hydrophilic imide group; 0.1 to 200 parts by weight, is dissolved in an organic solvent,
(2) It is manufactured by coating on a base film and heating.

The adhesive film containing the thermosetting resin is characterized by high shear adhesive strength when heated. But,
On the contrary, since the peel adhesive strength when heated decreases, 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 0.1 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 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
1 to 200 parts by weight to 100 parts by weight of polyimide resin,
It is preferably from 5 to 100 parts by weight, and when it exceeds 200 parts by weight, the film forming property is deteriorated.

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 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, 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 0.01 to 50 parts by weight, preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the epoxy resin. If it exceeds the limit, the storage stability will deteriorate.

The production of such an adhesive film is as follows. First, an epoxy resin, a phenol resin, and a polyimide resin are dissolved in an organic solvent. The organic solvent used here is not particularly limited as long as it can dissolve or knead the above materials uniformly, and examples thereof include the above-mentioned solvents such as dimethylformamide.

Then, a curing accelerator and, if necessary, additives are added, and a varnish is obtained in the same manner as described above.
This is applied uniformly on a base film and heated to form an adhesive film.

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 (II) to (IV), etc. But.

[Chemical 3] [In Formula (II), 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. ]

[Chemical 4] [In Formula (III), 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 5] [In formula (IV), n shows the integer of 0-4. ]

The amount of the imide compound used in the present invention is
The amount is 0.1 to 200 parts by weight, preferably 1 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.

Examples of the imide compound of the formula (II) include 4,4-bismaleimide diphenyl ether, 4,
4-bismaleimide diphenylmethane, 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- Hexafluoro-2,2-bis (4-maleimidophenyl) propane, and the like.

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, 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.

The adhesive film in this case is manufactured as follows. First, the polyimide resin (A) and the above imide compound are taken, dissolved in an organic solvent in the same manner as described above, an additive is added if necessary to obtain a varnish, and this is uniformly applied onto a base film, Heat to form an adhesive film.

Semiconductor elements such as ICs and LSIs, lead frames, ceramics wiring boards, glass epoxy wiring boards,
When the adhesive film obtained in the present invention is sandwiched between a supporting member such as a glass-polyimide wiring board and heat-pressed, the both adhere to each other.

[0038]

EXAMPLES The present invention will be described below with reference to examples. Synthesis example 1 500 m equipped with thermometer, stirrer and calcium chloride tube
41 g (0.1 mol) of 2,2-bis (4-aminophenoxyphenyl) propane and 150 g of dimethylacetamide were placed in a four-necked 1-liter flask and stirred. After dissolution of the diamine, while cooling the flask in an ice bath,
-(Ethylene) bis (trimellitate dianhydride) 41g
(0.1 mol) was added in small portions. After reacting for 3 hours at room temperature, 30 g of xylene was added, and the mixture was heated at 150 ° C. while blowing N ₂ gas to remove xylene azeotropically 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 ₁ ).

Synthesis Example 2 500 m equipped with a thermometer, stirrer and calcium chloride tube
43.2 g (0.1 mol) of bis (4- (3-aminophenoxy) phenyl) sulfone and 150 g of N-methyl-2-pyrrolidone were placed in a four-necked 4-liter flask and stirred. After dissolving the diamine, at room temperature, 43.8 g of 1,4- (tetramethylene) bis (trimellitate dianhydride)
(0.1 mol) was added. React at 5 ° C or below for 5 hours,
20.4 g (0.2 mol) of acetic anhydride and pyridine 15.
8 g (0.2 mol) was added and stirred at room temperature for 1 hour. The reaction solution was poured into water, and the precipitated polymer was collected by filtration and dried to obtain a polyimide resin (A ₂ ).

Synthesis Example 3 500 ml equipped with a thermometer, stirrer and calcium chloride tube
, 2-bis (4-aminophenoxyphenyl) propane 32.8 g (0.08 mol),
5.08 g (0.02 mol) of 3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane and 100 g of dimethylacetamide were taken and stirred. After dissolution of the diamine, while cooling the flask in an ice bath,
0- (decamethylene) bis (trimellitate dianhydride)
41.8 g (0.08 mol) and benzophenone tetracarboxylic dianhydride 6.44 g (0.02 mol) were added in small portions. After the addition was completed, the reaction was allowed to proceed for 3 hours in an ice bath and further for 4 hours at room temperature, and then 25.5 g (0.25
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 taken by filtration, and dried to give a polyimide resin (A _3).

Example 1 First, a varnish was prepared according to the composition table shown in Table 1.

[Table 1] Table 1 Recipe (Unit: parts by weight) ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Material No. 1 No. 2 No. 3 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Polyimide resin A ₁ A ₂ A ₃ 100 parts 100 parts 100 parts Part ──────────────────────────────────── Solvent 300 300 300 300 (Dimethylacetamide) ━━━━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━

This varnish was applied on a polyester film in a thickness of 30 to 50 μm and heated at 80 ° C. for 10 minutes and then at 150 ° C. for 30 minutes to obtain three kinds of adhesive films. The film forming properties were all good (Table 2).

[Table 2] Table 2 Film forming properties of varnish ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Item No. ． 1 No. 2 No. 3 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Film forming ability 〇 〇 〇 ━ ━━━━━━━━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ In addition, in Table 2 (or Table 4 and Table 6 described later), ○ and × have the following meanings. Good: There is no stickiness and it can be easily peeled off from the polyester film. X: Sticky or the film was brittle and difficult to peel off from the polyester film.

Example 2 According to the formulation table shown in Table 3, six kinds of paste-like mixtures No. 4 to No. 9 (however, No. 8 is a comparison) were prepared.

[Table 3] Table 3 Recipe (Unit: parts by weight) ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Material No.4 5 6 7 8 9 (Comparison) ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Epoxy YDCN-702 N-865 ESCN-195 N-865 N-865 YDCN-702 Resin 50 parts 20 parts 10 parts 10 parts 7 parts 100 parts ─────────────────── ───────────────── pheno H-1 H-1 VH-4170 VH-4170 VH-4170 H-1 resin 24 10 6 6 5 48 ────── ────────────────────────────── Curing acceleration 2P4MHZ TPPK 2MA-0K TPPK TPPK 2P4MHZ agent 0.5 0.4 0.1 0.5 0.7 1 ─── ───────────────────────────────── Polyimi A ₁ A ₂ A ₃ A ₁ A ₁ − Resin 100 100 100 100 100 0 ────────── ────────────────────────── SOLVENT DMAA NMP DMF DMF DMF DMAA 400 200 100 100 67 1000 ━━━━━━━━━━━ ━━━━━━━━━━━━━━━━━━━━━━━━━━

In Table 3, various symbols have the following meanings. YDCH-702: Toto Kasei, Cresol Novolac Epoxy
(Epoxy equivalent 220) N-865: Dainippon Ink, bisphenol novolac type epoxy (epoxy equivalent 208) ESCN-195: Nippon Kayaku, cresol novolac type epoxy (epoxy equivalent 200) H-1: Meiwa Kasei, phenol novolac ( OH equivalent 106) VH-4170: Dainippon Ink, Bisphenol A Novolac
(OH equivalent 118) DMAA: dimethylacetamide NMP: N-methylpyrrolidone DMF: dimethylformamide

This varnish was applied on a polyester film to a thickness of 30 to 50 μm and heated at 80 ° C. for 10 minutes and then at 150 ° C. for 30 minutes to obtain an adhesive film. The film forming properties are shown in Table 4.

[Table 4] Table 4 Film forming properties of varnish ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Item No. 4 5 6 7 8 9 (Comparison) ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ ━ Film formability 〇 〇 〇 〇 〇 〇 × ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━

Example 3 Five types of paste-like mixtures No. 9 to No. 13 were prepared according to the formulation table shown in Table 5.

[Table 5] Table 5 Recipe (unit: parts by weight) ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Material No. 10 11 12 12 13 14 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Polyimide A ₁ A ₂ A ₃ A ₁ A ₁ resin 100 parts 100 parts 100 parts 100 parts 100 parts ────────────────────────────────── ─── Imide compound BMDADPM BMDADPM BMPPP BMPPP BMDADPE 20 50 10 50 30 ─────────────────────────────────── ─ Solvent DMAA DMAA NMP DMF DMAA ──────────────────────────────────── Other BPO DCPO BPO CHPO DCPO 0.1 0.2 0.01 0.003 0.1 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━

However, the symbols in Table 5 have the following meanings. BMDADPM: 4,4'-bismaleimidodiaminodiphenylmethane BMPPP: 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane BMDADPE: 4,4'-bismaleimidodiaminodiphenyl ether DMAA: dimethylacetamide NMP: N-methyl Pyrrolidone DMP: Dimethylformamide BPO: Benzoyl peroxide DCPO: Dicumyl peroxide CHPO: Cumene hydroperoxide

The varnish is applied to a polyester film in a thickness of 30 to 50 μm, and the temperature is 80 ° C. for 10 minutes, followed by 15 minutes.
It heated at 0 degreeC for 15 minutes, and obtained the adhesive film. The film forming properties are shown in Table 6.

[Table 6] Table 6 Film forming properties of varnish ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Item No. 10 11 12 13 14 14 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Film forming property 〇 〇 〇 〇 〇 〇 ━━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━

Test Example 1 The shear adhesive strength of the adhesive film obtained in Example 1 was measured and the results are shown in Table 7. The test method was to cut the adhesive film into a size of 4 × 4 mm, and cut this into 4 × 4 mm.
It is sandwiched between a 4 mm silicon chip and a silver-plated lead frame, a load of 1000 g is applied, and pressure is applied for 3 seconds at 260 ° C. Then, using a push-pull gauge, heat at room temperature and at 350 ° C for 20 seconds. At times, shear adhesion was measured.

[Table 7] Table 7 Shear adhesive strength of the adhesive film ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Item No. ． 1 No. 2 No. 3 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Shear adhesive strength Room temperature 12.0 11.3 10.7 ( kgf / chip) 350 ℃ 0.3 0.5 0.5 0.4 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━

Test Example 2 The shear adhesive strength of the adhesive film obtained in Example 2 was measured and the results are shown in Table 8. The test method was to cut the adhesive film into a size of 4 × 4 mm, and cut this into 4 × 4 mm.
It is sandwiched between a 4 mm silicon chip and a silver-plated lead frame, a load of 50 g is applied, and pressure is applied for 3 minutes at 200 ° C. Then, using a push-pull gauge, heat at room temperature and at 350 ° C for 20 seconds. At times, shear adhesion was measured. Comparing Table 7 and Table 8, the adhesive film containing the thermosetting resin (No. 4 to 8) is more shear bonded at 350 ° C. than the adhesive film containing no thermosetting resin (No. 1 to 3). You can see that the power is high.

[Table 8] Table 8 Shear adhesion of adhesive film ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Item No. .4 5 6 7 8 9 (Comparison) ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Shear adhesive strength Room temperature 10.7 12.7 10.4 12.9 11.8 − * (kgf / chip) 350 ° C 2.1 3.2 1.7 2.0 2.2 − * ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ ━━━━━ *: Measurement was not possible because a film could not be formed.

Test Example 3 The shear adhesive strength of the adhesive film obtained in Example 3 was measured and the results are shown in Table 9. The test method was the same as in Test Example 2.

[Table 9] Table 9 Shear adhesion of adhesive film ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Item No. .10 11 12 13 13 14 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Shear adhesive strength Room temperature 11.0 13.2 16.6 15.5 10.9 (kgf / chip) 350 ℃ 1.9 3.0 2.8 2.0 2.5 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━

Test Example 4 The peel adhesive strengths of the adhesive films obtained in Examples 1 and 2 were measured and the results are shown in Table 10. The peel adhesion is obtained by cutting the adhesive film into a size of 8 × 8 mm, sandwiching it between a silicon chip of 8 × 8 mm and a lead frame with silver plating, applying a load of 1000 g, and heating at 300 ° C. for 5 After crimping for seconds, 250 ℃,
It was measured during heating for 20 seconds.

[Table 10] Table 10 Peel adhesion of adhesive film ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Item No. .1 2 3 4 5 6 7 8 9 (Comparison) ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Peel adhesion Power 2.5 2.2 2.4 1.7 1.2 1.6 2.4 1.8 ― * (kgf / chip) 250 ℃ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ ━━━ *: Cannot be measured because the film could not be formed. From the results of Table 10, the adhesive film containing no thermosetting resin (No. 1-3) was an adhesive film containing a thermosetting resin (N
It can be seen that the peel adhesive strength at 250 ° C. is higher than that of o.

[0053]

The adhesive film of the present invention is a die-bonding adhesive film that can be formed at a relatively low temperature.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yasuo Miyadera 48, Wadai, Tsukuba, Ibaraki Hitachi Chemical Co., Ltd. Tsukuba Development Laboratory

Claims (2)

[Claims] 1. A formula (I) of the formula 1 (However, the integer of n = 2-20 is shown.) Tetracarboxylic dianhydride whose content of the tetracarboxylic dianhydride is 70 mol% or more of all tetracarboxylic dianhydrides, An adhesive film containing a polyimide resin obtained by reacting a diamine. 2. The content of (A) tetracarboxylic dianhydride of formula (I) is 70 mol% of the total tetracarboxylic dianhydride.
An adhesive film containing the polyimide resin obtained by reacting the above tetracarboxylic dianhydride with a diamine; (B) a thermosetting resin.