JP2004048041A - Support member with semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a low-stress/low-temperature adhesive film which can be suitably applied to a 42 alloy lead frame, a copper lead frame, and an insulating support for die bonding. <P>SOLUTION: The support member with the semiconductor device has a structure composed of the semiconductor device and the support member. The semiconductor device and the support member, bonded together as an adhesive film, is interposed in between. The adhesive film contains polyimide resin. The polyimide resin is obtained as follows. Tetracarboxylic acid dianhydride, containing 30 mol% or higher tetracarboxylic acid dianhydride represented by formula (I) (where, n represents an integer of 2 to 20) in an image 1 and diamine containing 10 mol% or higher diamine represented by formula (II): H<SB>2</SB>N-Q<SB>1</SB>-O-[Q<SB>2</SB>-O-]<SB>p</SB>-Q<SB>3</SB>-NH<SB>2</SB>, (where, Q<SB>1</SB>, Q<SB>2</SB>, and Q<SB>3</SB>denote alkylene, whose number of carbons is 1 to 10; p denotes an integer of 0 to 10) are made to react on each other for obtaining the above polyimide resin. <P>COPYRIGHT: (C)2004,JPO

Description

The present invention relates to an adhesive film used as a bonding material of 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.

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 elastic modulus, so that it is easily broken when applied to a large chip, and is expensive. Solder is inexpensive but has poor heat resistance, and its elasticity is as high as Au-Si eutectic alloy, making it difficult to apply to a large chip. 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, in recent years, as ICs and LSIs have been highly integrated and the chips have become larger in size, when joining ICs and LSIs and lead frames with silver paste, the silver paste is spread over the entire surface of the chip and applied. Comes with difficulties.

接着 Microelectronic Manufacturing and Testing (October 1985) reported an adhesive film for die bonding in which a conductive filler was filled in a thermoplastic resin. In this method, the temperature is raised to around the melting point of the thermoplastic resin and pressure bonding is performed.

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 (for example, Patent Document 1, Patent Document 2). reference).
JP-A-6-145639 JP-A-7-228697

The adhesive film reported by the microelectronic manufacturing and testing can reduce the bonding temperature by using a thermoplastic resin having a low melting point, and the damage to the chip, such as oxidation of the lead frame, is small. However, since the adhesive strength at the time of heat is low, 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.

接着 The adhesive films proposed by the present inventors can be adhered at a relatively low temperature and have good hot adhesion. However, bonding to a copper lead frame (which is susceptible to oxidation) and an insulating support substrate with low thermal conductivity (which tends to warp during heat bonding due to its large thermal expansion), which has begun to be used in recent years, is bonded at a lower temperature. There is a strong need for an adhesive film that can be made. The present invention provides a low-stress, low-temperature adhesive adhesive film that 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. It is intended to be.

（ただし、ｎ＝２〜２０の整数を示す。）で表されるテトラカルボン酸二無水物が全テトラカルボン酸二無水物の３０モル％以上を含むテトラカルボン酸二無水物、と式（II）
Ｈ₂Ｎ−Ｑ₁−Ｏ−［Ｑ₂−Ｏ−］_p−Ｑ₃−ＮＨ₂ （II）
（ただし、Ｑ₁、Ｑ₂及びＱ₃は炭素数１〜１０のアルキレンを示し、ｐは０〜１０の整数を示す。）で表されるジアミンが全ジアミンの１０モル％以上を含むジアミンを反応させて得られるポリイミド樹脂を含有してなる接着フィルムを挟み、両者を接着させた構造を有する半導体素子付き支持部材に関する。 According to the present invention, the formula (I) is provided between the semiconductor element and the support member.

(Where n is an integer of 2 to 20), wherein the tetracarboxylic dianhydride represented by the formula (II) contains at least 30 mol% of all tetracarboxylic dianhydrides. )
_{H 2 N-Q 1 -O- [} Q 2 -O-] p -Q 3 -NH 2 (II)
(Wherein Q ₁ , Q ₂ and Q ₃ represent alkylene having 1 to 10 carbon atoms and p represents an integer of 0 to 10). The present invention relates to a support member with a semiconductor element having a structure in which an adhesive film containing a polyimide resin obtained by a reaction is sandwiched and both are adhered.

The present invention also provides an adhesive film comprising: (A) a tetracarboxylic dianhydride wherein the tetracarboxylic dianhydride of the formula (I) comprises at least 30 mol% of all tetracarboxylic dianhydrides; (B) thermosetting resin: 0 to 200 parts by weight, and 100 parts by weight of a polyimide resin obtained by reacting a diamine represented by the following formula with a diamine containing 10 mol% or more of all diamines, and (C) The present invention relates to the support member with a semiconductor element described above, which is an adhesive film containing 0 to 8000 parts by weight of a filler.

The present invention also provides a support member comprising a 42 alloy lead frame, a copper lead frame, a plastic film of a polyimide, a plastic film of an epoxy resin, a plastic film of a polyimide resin, The present invention relates to the above-mentioned support member with a semiconductor element, wherein the support member is selected from those impregnated and cured with a plastic such as, and alumina.

Since the adhesive film of the present invention has low stress and low temperature adhesiveness, it 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. it can.

The tetracarboxylic dianhydride of the formula (I), which is one of the raw materials for producing the polyimide resin according to the adhesive film of the present invention, includes 1,2- (ethylene) bis (trimellitate) when n is 2 to 5. Dianhydride), 1,3- (trimethylene) bis (trimellitate dianhydride), 1,4- (tetramethylene) bis (trimellitate dianhydride), 1,5- (pentamethylene) bis (trimellitate dianhydride) ), When n is 6 to 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), 1,10- (decamethylene) bis (trimellitate dianhydride), 1,1 -(Dodecamethylene) bis (trimellitate dianhydride), 1,16- (hexadecamethylene) bistrimellitate dianhydride, 1,18- (octadecamethylene) bis (trimellitate dianhydride), and the like, 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. Further, the amount of the above-mentioned tetracarboxylic dianhydride contained in all tetracarboxylic dianhydrides is 30 mol% or more, preferably 50 mol% or more, more preferably 70 mol% or more. If the amount is less than 30 mol%, the temperature at the time of bonding the adhesive film is undesirably high.

Examples of the tetracarboxylic dianhydride that can be used together with the tetracarboxylic dianhydride of the formula (I) include pyromellitic dianhydride, 3,3 ′, 4,4′-diphenyltetracarboxylic dianhydride, 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, 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-perylenetetraca Boric acid dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 3,4,3 ', 4'-benzophenone tetra Carboxylic dianhydride, 2,3,2 ', 3-benzophenonetetracarboxylic dianhydride, 2,3,3', 4'-benzophenonetetracarboxylic dianhydride, 1,2,5,6-naphthalene Tetracarboxylic 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, 2,3,2', 3'-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) dimethylsilane dianhydride, bis (3,4- Dicarboxyphenyl) methylphenyl Ran 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 acid Acid dianhydride) sulfone, bicyclo- (2,2,2) -oct (7) -ene 2,3,5,6-tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxy) Phenyl) hexafluoropropane dianhydride 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] hexafluoropropane dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 1,4-bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimellitic 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. More than one kind may be mixed and used.

Formula (II), which is another one of the raw materials for producing the polyimide resin according to the adhesive film of the present invention.
_{H 2 N-Q 1 -O- [} Q 2 -O-] p-Q 3 -NH 2 (II)
(Q ₁ , Q ₂ and Q ₃ are alkylene having 1 to 10 carbon atoms, and examples of such alkylene include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, There are decamethylene, propylene, butylene, amylene, hexylene and the like, and p is an integer of 0 to 10.) The diamine of the above formula (II) is a diamine containing at least 10 mol%, preferably at least 20 mol%, more preferably at least 30 mol%, based on the total diamine. If it is less than 10 mol%, the low-stress and low-temperature adhesive properties cannot be exhibited.

The formula Specific examples of compounds of formula _{(II), H 2 N- (CH 2)} 3 -O- (CH 2) 4 -O- (CH 2) 3 -NH 2, H 2 N- (CH 2) _{3 -O- (CH 2) 6 -O-} (CH 2) 3 -NH 2, H 2 N- (CH 2) 3 -O- (CH 2) 2 -O- (CH 2) 2 -O- ( _{CH 2) 3 -NH 2, H} 2 N- (CH 2) 3 -O- (CH 2) 2 -O- (CH 2) 2 -O- (CH 2) 2 -O- (CH 2) 3 - There are NH _{2 and the} like, and two or more kinds may be used as a mixture.

と と も に Other diamines can be used in combination with the above formula (II). Examples of the diamine that can be used in combination include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, Aliphatic diamines such as 8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, o-phenylenediamine, m-phenylenediamine, p-phenylene Diamine, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenyldifluorome 3,4'-diaminodiphenyldifluoromethane, 4,4'-diaminodiphenyldifluoromethane, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 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-phenylene) Bis (1-methylethylidene)) bisaniline, 4,4 '-(1,4-phenylenebis (1-methylethylidene)) bisaniline, 2,2-bis (4- (3-aminophenoxy) phenyl) propane, , 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, bis ( Aromatic diamines such as 4- (4-aminophenoxy) phenyl) sulfone can be given.

縮合 The condensation reaction between the tetracarboxylic dianhydride and the diamine is performed in an organic solvent. In this case, the tetracarboxylic dianhydride and the diamine are preferably used in an equimolar or almost equimolar manner, 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, o-chlorophenol and the like.

The reaction temperature is 80 ° C or lower, preferably 0 to 50 ° 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 dehydrating and ring-closing the above reactant (polyamic acid). The dehydration ring closure can be performed using a method of heat treatment at 120 ° 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, those in which polyamic acid is partially imidized.

In the case of ring closure by dehydration 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 and imidazole may be used, if necessary. The ring-closing agent or the ring-closing catalyst is preferably used in an amount of 1 to 8 mol per 1 mol of tetracarboxylic dianhydride.

In addition, a silane coupling agent, a titanium-based coupling agent, a nonionic surfactant, a fluorine-based surfactant, a silicone-based additive, or the like may be appropriately added to the polyimide resin in order to improve the adhesive strength.

接着 The adhesive film of the present invention can also be obtained by adding a thermosetting resin and / or a filler to the polyimide resin. When a thermosetting resin is used, as the thermosetting resin (B), a resin containing an epoxy resin, 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 (1) is obtained by converting the tetracarboxylic dianhydride of the formula (I) into all tetracarboxylic dianhydrides. 100 parts by weight of a polyimide resin (A) obtained by reacting a tetracarboxylic dianhydride containing 30 mol% or more of the product with a diamine of the formula (II) containing 10 mol% or more of the total diamine; 0 to 200 parts by weight of an epoxy resin; 0 to 150 parts by weight of a phenol resin; 100 parts by weight of an epoxy resin; and 0 to 50 parts by weight of a curing accelerator; 100 parts by weight of an epoxy resin are dissolved in an organic solvent. (2) coating on a base film and heating.

When the thermosetting resin is an imide compound having at least two thermosetting imide groups in one molecule, (1) the tetracarboxylic dianhydride of the formula (I) is all tetracarboxylic dianhydrides 100 parts by weight of a polyimide resin (A) obtained by reacting a tetracarboxylic dianhydride containing 30 mol% or more of the above with a diamine in which the diamine of the formula (II) contains 10 mol% or more of all diamines; An imide compound having at least two thermosetting imide groups in one molecule; 0 to 200 parts by weight is dissolved in an organic solvent, (2) applied on a base film and heated.

(4) When a filler is contained, examples of the filler (C) include conductive fillers such as silver powder, gold powder, and copper powder, and inorganic fillers such as silica, alumina, titania, glass, iron oxide, and ceramic.

The filler-containing adhesive film is prepared by dissolving the 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.

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

(4) When a 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 the amount exceeds 200 parts by weight, the film-forming properties deteriorate.

When selecting a resin containing an epoxy resin, a phenolic resin and a curing accelerator as the thermosetting resin, the epoxy resin used has at least two epoxy groups in the molecule and has curability and properties of a cured product. In view of this, a glycidyl ether type epoxy resin of phenol is preferred. Examples of such resins include bisphenol A, bisphenol AD, bisphenol S, bisphenol F or condensates 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 the epoxy 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.

The phenolic 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, poly-p-vinylphenol, and phenol. Aralkyl resins and the like. 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 will be insufficient.

The curing accelerator is not particularly limited as long as it is used for curing the epoxy resin. Such compounds include, for example, imidazoles, dicyandiamide derivatives, dicarboxylic dihydrazide, triphenylphosphine, tetraphenylphosphonium tetraphenylborate, 2-ethyl-4-methylimidazole-tetraphenylborate, 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 from 0 to 50 parts by weight, preferably from 0 to 20 parts by weight, based on 100 parts by weight of the epoxy resin, 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 particularly limited as long as the material can be uniformly dissolved, kneaded or dispersed.For example, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, diethylene glycol dimethyl ether, Examples include toluene, benzene, xylene, methyl ethyl ketone, tetrahydrofuran, ethyl cellosolve, ethyl cellosolve acetate, butyl cellosolve, and dioxane.

When an imide compound having at least two thermosetting imide groups in one molecule is used as the thermosetting resin, examples of the compound include ortho-bismaleimide benzene, meta-bismaleimide benzene, para-bismaleimide benzene, In addition to 1,4-bis (p-maleimidocumyl) benzene and 1,4-bis (m-maleimidocumyl) benzene, there are imide compounds represented by the following formulas (III) to (V).

〔式（III）中、ＸはＯ、ＣＨ₂、ＣＦ₂、ＳＯ₂、Ｓ、ＣＯ、Ｃ（ＣＨ₃）₂ 又はＣ（ＣＦ₃）₂を示し、Ｒ₁、Ｒ₂、Ｒ₃及びＲ₄はそれぞれ独立に水素、低級アルキル基、低級アルコキシ基、フッ素、塩素又は臭素を示し、Ｄはエチレン性不飽和二重結合を有するジカルボン酸残基を示す。〕

[In the formula (III), X represents O, CH ₂ , CF ₂ , SO ₂ , S, CO, C (CH ₃ ) ₂ or C (CF ₃ ) ₂ , and R ₁ , R ₂ , R ₃ and R ₄ independently represents 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. ]

〔式（IV）中、ＹはＯ、ＣＨ₂、ＣＦ₂、ＳＯ₂、Ｓ、ＣＯ、Ｃ（ＣＨ₃）₂又はＣ（ＣＦ₃）₂を示し、Ｒ₅、Ｒ₆、Ｒ₇及びＲ₈はそれぞれ独立に水素、低級アルキル基、低級アルコキシ基、フッ素、塩素又は臭素を示し、Ｄはエチレン性不飽和二重結合を有するジカルボン酸残基を示する。〕

[In the formula (IV), Y represents O, CH ₂ , CF ₂ , SO ₂ , S, CO, C (CH ₃ ) ₂ or C (CF ₃ ) ₂ , and R ₅ , R ₆ , R ₇ and R ₈ independently represents 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. ]

〔式（Ｖ）中、ｍは０〜４の整数を示す。〕

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

The amount of the imide compound used in the present invention 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 the amount exceeds 200 parts by weight, the film-forming properties deteriorate.

Examples of the imide compound of the formula (III) include 4,4-bismaleimide diphenyl ether, 4,4-bismaleimide diphenylmethane, 4,4-bismaleimide-3,3′-dimethyl-diphenylmethane, and 4,4-bismaleimide Diphenylsulfone, 4,4-bismaleimidediphenylsulfide, 4,4-bismaleimidediphenylketone, 2,2′-bis (4-maleimidophenyl) propane, 4,4-bismaleimidediphenylfluoromethane, 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, and bis [4- (4-maleimidophenoxy) phenyl 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.

ラ ジ カ ル A radical polymerization agent may be used to accelerate the curing of these imide compounds. Examples of the radical polymerization agent include acetylcyclohexylsulfonyl 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 about 0.01 to 1.0 part by weight based on 100 parts by weight of the imide compound.

Among the fillers, conductive fillers such as silver powder, gold powder, and copper powder are added for the purpose of imparting conductivity or thixotropy to the adhesive, and inorganic fillers such as silica, alumina, titania, glass, iron oxide, and ceramic are bonded. It is added for the purpose of imparting a low thermal expansion property and a low moisture absorption rate to the agent. 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 the physical properties are not impaired.

(4) The amount of the filler is in the range of 0 to 8000 parts by weight, preferably 0 to 4000 parts by weight, based on 100 parts by weight of the polyimide resin. If the amount is more than 8000 parts by weight, the adhesiveness decreases.

混合 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.

後 After uniformly applying the varnish or paste mixture thus obtained on the base film, heating is performed under conditions in which the solvent used is sufficiently volatilized, that is, at a temperature of approximately 60 to 200 ° C for 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 a semiconductor element such as IC and LSI, a lead frame such as 42 alloy lead frame and copper lead frame, a plastic film such as polyimide, epoxy resin and polyimide resin, and a polyimide such as glass non-woven fabric. It can be used for bonding a support member made of a material impregnated and cured with a plastic such as an epoxy resin or a polyimide resin, or a ceramic material such as an alumina. That is, the adhesive film of the present invention is sandwiched between the semiconductor element and the support member as described above, and the two are bonded by heat and pressure. The heating temperature is usually 100 to 300 ° C. for 0.1 to 300 seconds.

Hereinafter, the present invention will be described with reference to examples.
Synthesis example 1
In a 500 ml four-necked flask equipped with a thermometer, a stirrer and a calcium chloride tube, 20.4 g (0.1 mol) of 4,9-dioxadodecane-1,12-diamine and 150 g of dimethylacetamide were stirred and stirred. . After dissolution of the diamine, 52.2 g (0.1 mol) of decamethylene bistrimellitate dianhydride was added little by little while the flask was cooled in an ice bath. After reacting at room temperature for 3 hours, 30 g of xylene was added, the mixture was heated at 150 ° C. while blowing N ₂ gas, and xylene was removed 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).

Synthesis Example 2
In a 500 ml four-necked flask equipped with a thermometer, a stirrer and a calcium chloride tube, 10.2 g (0.05 mol) of 4,9-dioxadodecane-1,12-diamine and 2,2-bis (4- 20.5 g (0.05 mol) of (4-aminophenoxy) phenyl) propane and 150 g of N-methyl-2-pyrrolidone were taken and stirred. After dissolution of the diamine, 52.2 g (0.1 mol) of decamethylene bistrimellitate dianhydride was added little by little while the flask was cooled 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. 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
In a 500 ml four-necked flask equipped with a thermometer, a stirrer, and a calcium chloride tube, 41 g (0.1 mol) of 2,2-bis (4- (4-aminophenoxy) phenyl) propane and N-methyl-2- 150 g of pyrrolidone was taken and stirred. After dissolution of the diamine, 52.2 g (0.1 mol) of decamethylene bistrimellitate dianhydride was added little by little while the flask was cooled in an ice bath. After reacting at room temperature for 3 hours, 30 g of xylene was added, the mixture was heated at 150 ° C. while blowing N ₂ gas, and xylene was removed 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 (C).

As shown in the composition tables in Tables 1 and 2, Varnishes Nos. 1 to 9 (Examples Nos. 1 to 6 of the present invention and Comparative Examples Nos. 7 to 9) were prepared. In Tables 1 and 2, various symbols have the following meanings.
YDCH-702: Toto Kasei, Cresol novolak type epoxy (epoxy equivalent 220)
N-865: made by Dainippon Ink, bisphenol novolak epoxy (epoxy equivalent 208)
ESCN-195: Nippon Kayaku, Cresol novolak type 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

[Table 1]
Table 1 Composition table (unit: parts by weight)
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Material No. 1 2 3 4 5 6
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Polyimide A A A B B B
100 parts 100 parts 100 parts 100 parts 100 parts 100 parts────────────────────────────────────
Epoxy N-865 N-865 YDCN-702 YDCN-702 N-865 ESCN-195
Resin 10 100 100 50 20 10
────────────────────────────────────
Fenault VH-4170 VH-4170 H-1 H-1 H-1 VH-4170
5.6 70 48 24 10 5.9
────────────────────────────────────
Acceleration of curing TPPK TPPK 2P4MHZ 2P4MHZ TPPK 2MA-0K
0.5 10 1 0.5 0.4 0.1
────────────────────────────────────
Filler TCG-1 No alumina TCG-1 Silica None 100 190 − 80 45 −
────────────────────────────────────
Solvent DMF DMF DMAC DMAC NMP DMF
100 1000 1000 400 200 100
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━

[Table 2]
Table 2 Composition table (unit: parts by weight)
━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Material No. 7 (comparison) 8 (comparison) 9 (comparison)
━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Polyimide C C C
100 parts 100 parts 100 parts────────────────────────────
Epoxy N-865 YDCN-702 N-865
Resin 100 500 10
────────────────────────────
Fenault H-1 H-1 VH-4170
Resin 48 24 5.6
────────────────────────────
Acceleration of curing 2P4MHZ 2P4MHZ TPPK
Agent 1 0.5 0.5
────────────────────────────
Filler TCG-1 Silica None 67 80-
────────────────────────────
Solvent DMAC DMAC DMAC
500 400 500
━━━━━━━━━━━━━━━━━━━━━━━━━━━━

ＮｏNo. Each of varnishes 1 to 9 is applied on a polypropylene film (base 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. Then, an adhesive film was obtained.

Test example 1
The above No. The peel adhesion at each bonding temperature of the adhesive films obtained in Examples 1 to 6 of the present invention (Examples 1 to 6 of the present invention and Comparative Examples 7 to 9) was measured (Table 3). In addition, the peel adhesive force cuts the adhesive film into a size of 8 mm x 8 mm, sandwiches the cut between an 8 mm x 8 mm silicon chip and a copper lead frame, and applies a load of 1000 g at 180 ° C or 250 ° C. After pressing for 3 seconds, the peel strength at the time of heating at 250 ° C. for 20 seconds was measured.
[Table 3]
Table 3 Peel adhesive strength of adhesive film
Peel adhesion (Kgf / chip)
Adhesion temperature No. 1 2 3 4 5 6 7 8 9
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
180 ° C 2.1 1.5 2.2 2.1 1.7 1.9 0.5 0.4 0.3
250 ° C 1.7 1.9 1.9 2.2 2.0 2.0 1.7 2.0 1.8
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━

Test example 2
The above No. Chip warpage when using the adhesive films obtained in Examples 1 to 9 (Examples Nos. 1 to 6 of the present invention and Comparative Examples Nos. 7 to 9) was measured (Table 4). In addition, the chip warpage is performed by cutting the adhesive film into a size of 13 mm × 13 mm, sandwiching the cut between a silicon chip having a size of 13 mm × 13 mm and a copper lead frame, and applying a load of 1000 g at 250 ° C., 5 ° C. After pressing for 2 seconds, the chip warpage was measured. Note that the tip warpage was a measured value of the maximum height (μm) from the baseline when scanning 11 mm linearly using a surface roughness meter.

[Table 4]
Table 4 Chip warpage
Chip warpage (μm)
No. 1 2 3 4 5 6 7 8 9
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
5 6 4 18 20 18 42 43 40
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━

Claims (3)

Formula (I) is provided between the semiconductor element and the support member.

(Where n is an integer of 2 to 20), wherein the tetracarboxylic dianhydride represented by the formula (II) contains at least 30 mol% of all tetracarboxylic dianhydrides. )
_{H 2 N-Q 1 -O- [} Q 2 -O-] p -Q 3 -NH 2 (II)
(Wherein Q ₁ , Q ₂ and Q ₃ represent alkylene having 1 to 10 carbon atoms and p represents an integer of 0 to 10). A support member with a semiconductor element having a structure in which an adhesive film containing a polyimide resin obtained by a reaction is sandwiched and both are adhered. The adhesive film comprises (A) a tetracarboxylic dianhydride in which the tetracarboxylic dianhydride of the formula (I) contains at least 30 mol% of all tetracarboxylic dianhydrides, and a diamine represented by the formula (II) (B) thermosetting resin: 0 to 200 parts by weight, and (C) filler: 0 to 8000 with respect to 100 parts by weight of a polyimide resin obtained by reacting a diamine containing 10 mol% or more of all diamines. The support member with a semiconductor element according to claim 1, which is an adhesive film containing parts by weight. The supporting member is a 42 alloy lead frame, a copper lead frame, a plastic film of polyimide, a plastic film of epoxy resin, a plastic film of polyimide resin, a glass non-woven fabric or the like impregnated with a plastic such as polyimide, epoxy resin or polyimide resin. 3. The support member with a semiconductor element according to claim 1, wherein the support member is selected from a cured product and an alumina.