JP2006117949A - Die bonding material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a die bonding material for an electronic component and its support element which has a good adhesiveness in a high temperature and a good resistance against high temperature soldering and is excellent in low stress property and adhesiveness in a low temperature. <P>SOLUTION: This die bonding material is a film die bonding material for adhering semiconductor devices and comprises: a polyamide resin having a Tg of not more than 200°C obtained by the reaction between tetracarboxylic acid dianhydride and a diamine containing at least 3 mol%, against all the diamine, of 1,1,3,3-tetramethyl-1,3-bis(3-aminopropyl)disiloxane; 1-100 pts wt., against 100 pts.wt. of the polyimide resin, of an epoxy resin of the glycidyl ether type of phenol whose elastic modulus after heat-cured at 270°C is at least 5 MPa; not more than 4,000 pts.wt., against 100 pts.wt. of the polyimide resin, of a filler selected from the group consisting of silica, alumina, boron nitride, titania, glass, iron oxide, ceramics and copper powder; and a curing agent. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an adhesive composition and a semiconductor device, and more specifically, an adhesive material between an electronic component such as a semiconductor element and a support member such as a lead frame or an insulating support substrate, that is, an adhesive composition suitable for die bonding. And a semiconductor device including the adhesive composition.

As an adhesive material between an electronic component such as a semiconductor element and a support member such as a lead frame or an insulating support substrate, an Au—Si eutectic alloy, solder, silver paste, an adhesive film, and the like are conventionally known. Among these, Au-Si eutectic alloy has a problem that it is expensive and has a high elastic modulus, and solder has a problem that it cannot withstand a temperature above the melting point and has a high elastic modulus. Silver paste and adhesive film with low elastic modulus are mainly used.
The silver paste is mainly composed of a thermosetting resin from the viewpoint of heat resistance reliability, and the adhesive film is mainly composed of a thermoplastic resin from the viewpoint of film formation (Patent Document 1). 2).
JP 2004-277572 A JP 2000-178519 A

The demand for high-density mounting due to the miniaturization and thinning of electronic devices has been increasing rapidly, and the surface mounting type suitable for high-density mounting has become the mainstream for semiconductor devices (semiconductor packages) instead of the conventional pin insertion type. I came.
This surface-mount package is mounted by heating the entire package by infrared reflow, vapor phase reflow, solder dip, or the like in order to directly solder leads or bumps to a printed circuit board or the like. At this time, since the entire package is exposed to a high temperature of around 240 ° C., if moisture absorption moisture exists inside the package, package cracks (hereinafter referred to as reflow cracks) occur due to explosive vaporization of the moisture.
The reflow crack is a serious problem / technical problem because it significantly reduces the reliability of the semiconductor package.

The generation mechanism of the reflow crack caused by the die bonding material is as follows. While the semiconductor package is being stored, (1) the die bonding material absorbs moisture, (2) this moisture absorption is vaporized by heating during reflow soldering mounting, and (3) the die bonding layer is destroyed by this vapor pressure. Peeling occurs and (4) reflow cracks occur.
While the reflow crack resistance of the sealing material has been improved, the reflow crack caused by the die bonding material is a serious problem particularly in a thin package.

In addition, in recent years, legal regulations related to lead have been strengthened mainly in Europe and other countries due to environmental conservation measures on a global scale. In fields where high reliability is required, it is said that the current Sn-Pb series will be switched to Sn-Ag series solder with a higher melting point.
When the mounting solder is switched to the above Sn-Ag system, the melting point becomes high, so that the maximum temperature of the reflow furnace is 20 ° C. to 30 ° C. higher than the current temperature. Therefore, an adhesive material for die bonding is required to have a material that can withstand the increase in reflow temperature and has higher reliability than ever.

  In the silver paste that has been most commonly used in the past, it has become difficult to uniformly apply the silver paste to the entire surface of the coating portion due to the increase in size of the chip. Reflow cracks are likely to occur due to the tendency to occur.

  In order to solve the above problems, an adhesive film obtained by forming a silver paste into a film has been proposed. By forming a film, a uniform adhesion area can be secured, and voids can be greatly reduced. Therefore, better reflow crack resistance than paste can be secured.

  On the other hand, copper lead frames (which are susceptible to oxidation due to heat) and insulating support substrates (which have low thermal conductivity), which have begun to be used in recent years, have a large coefficient of thermal expansion, so they tend to warp during heat bonding. When applying an adhesive film for adhesion to a substrate, a material that can be adhered at low temperature and at low temperature is strongly desired.

  Adhesive films are mainly composed of thermoplastic resin as the main component, and if a thermoplastic resin with a low melting point is selected and used, the adhesive temperature can be lowered and damage to the chip, such as lead frame oxidation, can be caused. Can be reduced. However, since a resin film using a thermoplastic resin having a low melting point has low adhesive force when heated, it cannot withstand heat treatment after die bonding (wire bonding process, mounting process, etc.).

  An object of the present invention is an adhesive composition for adhering an electronic component such as a semiconductor element and a lead frame or an insulating support substrate, which can withstand a high temperature soldering heat history during mounting, and a copper lead frame or It is to provide an adhesive composition having both low stress and low temperature adhesiveness that can be suitably used for an insulating support substrate.

  The present inventors have earnestly devised means for improving the reliability of high temperature soldering heat history at the time of mounting, in addition to low stress and low temperature adhesiveness, for an adhesive composition mainly composed of a thermoplastic resin. As a result of the study, the present invention has been completed.

That is, the die bonding material of the present invention is a film-like die bonding for bonding a semiconductor element containing a thermoplastic resin having a Tg of 200 ° C. or less, a thermosetting resin, a curing agent, and a filler. Material,
The thermoplastic resin includes tetracarboxylic dianhydride and a diamine containing 1,1,3,3-tetramethyl-1,3-bis (3-aminopropyl) disiloxane in an amount of 3 mol% or more of the total diamine. A polyimide resin obtained by reaction,
The thermosetting resin is a phenol glycidyl ether type epoxy resin having an elastic modulus at 270 ° C. of 5 MPa or more after heat curing, and in the range of 1 to 100 parts by weight with respect to 100 parts by weight of the thermoplastic resin. Included in the
The filler is one or more selected from silica, alumina, boron nitride, titania, glass, iron oxide, ceramic and copper powder, and is contained in 4000 parts by weight or less with respect to 100 parts by weight of the thermoplastic resin. It is characterized by that.

  The adhesive composition of the present invention is excellent as an adhesive material for electronic components such as semiconductor elements and supporting members such as lead frames and insulating support substrates, and withstands good thermal adhesive strength and high temperature soldering heat history during mounting. In addition, it has excellent reliability, low stress and low temperature adhesion. Therefore, it can also be suitably used as a die bond material for copper lead frames and insulating support substrates.

  The adhesive composition of the present invention contains 0.1 to 200 parts by weight of a thermosetting resin having an elastic modulus of 5 MPa or more at 270 ° C. after heat curing with respect to 100 parts by weight of a thermoplastic resin having a Tg of 200 ° C. or less. The thermoplastic resin is not limited as long as Tg is 200 ° C. or lower. For example, polyimide resin, polyamide resin, polyetherimide resin, polyester resin, polyesterimide resin, phenoxy resin, polysulfone resin , Polyethersulfone resin, polyphenylene sulfide resin, polyetherketone resin, etc., but preferred are phenoxy resin and polyimide resin. When the Tg of the thermoplastic resin exceeds 200 ° C., the temperature required for adhesion of the adhesive composition increases.

  The phenoxy resin that can be used corresponds to a high molecular weight epoxy resin having an average molecular weight of 5000 or more determined by high performance liquid chromatography (HLC), and as with the epoxy resin, both bisphenol A type, F type, AD type, and AF are used. There are types such as polymerization type and S type. The larger the molecular weight, the easier it is to obtain film formability. The average molecular weight is from 5,000 to 150,000, and a molecular weight of about 10,000 to 80,000 is more preferable from the viewpoints of melt viscosity and compatibility with other resins.

The polyimide resin that can be used can be usually produced by reacting tetracarboxylic dianhydride and diamine. Below, the tetracarboxylic dianhydride which can be used is illustrated.
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-dilboxyphenyl) 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,
1,2,5,6-naphthalenetetracarboxylic dianhydride,
2,3,6,7-naphthalenetetracarboxylic dianhydride,
1,2,4,5-naphthalene-tetracarboxylic dianhydride,
1,4,5,8-naphthalene-tetracarboxylic dianhydride,

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,
Funansulene-1,8,9,10-tetracarboxylic dianhydride,
Pyrazine-2,3,5,6-tetracarboxylic dianhydride,
Thiophenine-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) 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 (trimellitic anhydride),

Ethylenetetracarboxylic 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 (exobicyclo [2,2,1] heptane-2,3-dicarboxylic dianhydride) sulfone,
Bicyclo- (2,2,2) -oct (7) -ene 2,3,5-tetracarboxylic dianhydride,
2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride,
2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] hexafluoropropane dianhydride,
4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride,
1,4-bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimellitic dianhydride),
1,3-bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimellitic dianhydride),
5- (2,5-dioxotetrahydrofuryl) -3-cyclohexene-1,2-dicarboxylic dianhydride,
Tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride,

（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、
次の式（II）

で表されるテトラカルボン酸二無水物が挙げられる。これら２種以上を併用してもよい。
特に好ましいテトラカルボン酸二無水物は、前記の式（Ｉ）の酸二無水物および前記の式（II）の酸二無水物である。式（Ｉ）および式（II）のテトラカルボン酸二無水物のうち少なくとも一方の含量が全テトラカルボン酸二無水物の３０モル％以上であるのがさらに好ましい。 The following formula (I)

(Wherein n represents an integer of 2 to 20), tetracarboxylic dianhydride represented by
The following formula (II)

The tetracarboxylic dianhydride represented by these is mentioned. Two or more of these may be used in combination.
Particularly preferred tetracarboxylic dianhydrides are the acid dianhydrides of formula (I) and the acid dianhydrides of formula (II). More preferably, the content of at least one of the tetracarboxylic dianhydrides of the formulas (I) and (II) is 30 mol% or more of the total tetracarboxylic dianhydrides.

As the tetracarboxylic dianhydride of the formula (I), when n is 2 to 5,
1,2- (ethylene) bis (trimellitate dianhydride),
1,3- (trimethylene) bis (trimellitate dianhydride),
1,4- (tetramethylene) bis (trimellitate dianhydride),
There are 1,5- (pentamethylene) bis (trimellitate dianhydride) and the like, and two or more of these may be used in combination.
When n is 6-20,
1,6- (hexamethylene) bis (trimellitate dianhydride),
1,7- (heptamethylene) bis (trimellitic dianhydride),
1,8- (octamethylene) bis (trimellitate dianhydride),
1,9- (nonamethylene) bis (trimellitate dianhydride),
1,10- (decamethylene) bis (trimellitate dianhydride),
1,12- (dodecamethylene) bis (trimellitate dianhydride),
1,16- (hexadecamethylene) bis (trimellitate dianhydride),
1,18- (octadecamethylene) bis (trimellitate dianhydride) and the like, and two or more of these may be used in combination.

  The tetracarboxylic dianhydride of the above formula (I) can be synthesized from trimellitic anhydride monochloride and the corresponding diol. The amount of the tetracarboxylic dianhydride contained in the total tetracarboxylic dianhydride is preferably 30 mol% or more in order to maintain the low-temperature adhesiveness of the adhesive film.

  The reason why the tetracarboxylic dianhydride of the formula (II) is preferably 30 mol% or more based on the total tetracarboxylic dianhydride is to maintain the moisture resistance reliability of the adhesive film.

Examples of diamine, which is one of the other raw materials of the polyimide resin, are given below.
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,
Aliphatic diamines such as 1,12-diaminododecane,

o-phenylenediamine,
m-phenylenediamine,
p-phenylenediamine,
3,3′-diaminodiphenyl ether,
3,4'-diaminodiphenyl ether,
4,4′-diaminodiphenyl ether,
3,3′-diaminodiphenylmethane,
3,4'-diaminodiphenylmethane,
4,4'-diaminodiphenylmethane,
3,3′-diaminodiphenyldifluoromethane,
3,4'-diaminodiphenyldifluoromethane,
4,4′-diaminodiphenyldifluoromethane,
3,3′-diaminodiphenyl sulfone,
3,4'-diaminodiphenyl sulfone,
4,4′-diaminodiphenyl sulfone,
3,3′-diaminodiphenylsulfide,
3,4'-diaminodiphenylsulfide,
4,4'-diaminodiphenylsulfide,

（式中、Q₁及びQ₂はそれぞれ独立に炭素数が１〜５のアルキレン基、又はフェニレン基を示し、Q₃、Q₄、Q₅及びQ₆はそれぞれ独立に炭素数が１〜５のアルキル基、フェニル基又はフェノキシ基を示し、ｍは１〜５０の整数を示す。）で表されるシロキサン系ジアミン等が挙げられる。これらは２種以上を併用してもよい。 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-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- (4-aminophenoxy) phenyl) hexafluoropropane,
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,
In addition, the following formula (III)

(Wherein Q ₁ and Q ₂ each independently represent an alkylene group having 1 to 5 carbon atoms or a phenylene group, and Q ₃ , Q ₄ , Q ₅ and Q ₆ each independently represent 1 to 5 carbon atoms. The alkyl group, the phenyl group, or the phenoxy group, and m represents an integer of 1 to 50). Two or more of these may be used in combination.

As the siloxane diamine of the formula (III), when m is 1,
1,1,3,3-tetramethyl-1,3-bis (4-aminophenyl) disiloxane,
1,1,3,3-tetraphenoxy-1,3-bis (4-aminoethyl) disiloxane,
1,1,3,3-tetraphenyl-1,3-bis (2-aminoethyl) disiloxane,
1,1,3,3-tetraphenyl-1,3-bis (3-aminopropyl) disiloxane,
1,1,3,3-tetramethyl-1,3-bis (2-aminoethyl) disiloxane,
1,1,3,3-tetramethyl-1,3-bis (3-aminopropyl) disiloxane,
1,1,3,3-tetramethyl-1,3-bis (3-aminobutyl) disiloxane,
Examples include 1,3-dimethyl-1,3-dimethoxy-1,3-bis (4-aminobutyl) disiloxane.

When m is 2,
1,1,3,3,5,5-hexamethyl-1,5-bis (4-aminophenyl) trisiloxane,
1,1,5,5-tetraphenyl-3,3-dimethyl-1,5-bis (3-aminopropyl) trisiloxane,
1,1,5,5-tetraphenyl-3,3-dimethoxy-1,5-bis (4-aminobutyl) trisiloxane,
1,1,5,5-tetraphenyl-3,3-dimethoxy-1,5-bis (5-aminopentyl) trisiloxane,
1,1,5,5-tetramethyl-3,3-dimethoxy-1,5-bis (2-aminoethyl) trisiloxane,
1,1,5,5-tetramethyl-3,3-dimethoxy-1,5-bis (4-aminobutyl) trisiloxane,
1,1,5,5-tetramethyl-3,3-dimethoxy-1,5-bis (5-aminopentyl) trisiloxane,
1,1,3,3,5,5-hexamethyl-1,5-bis (3-aminopropyl) trisiloxane,
1,1,3,3,5,5-hexaethyl-1,5-bis (3-aminopropyl) trisiloxane,
Examples include 1,1,3,3,5,5-hexapropyl-1,5-bis (3-aminopropyl) trisiloxane.

これらシロキサン系ジアミンは２種以上を併用してもよい。好ましいシロキサン系ジアミンは、式（III）のシロキサン系ジアミンである。ジアミンは、式（III）のシロキサン系ジアミンが、全ジアミンに対して３モル％以上含まれるのがさらに好ましい。より好ましい式（III）のシロキサン系ジアミンの含量は、５モル％以上、更に好ましくは１０モル％以上である。３モル％未満では、低応力性、低温接着性、低吸湿性の特性を発揮できない。 Furthermore, when m is 3 to 50, the following formula (III-a), the following formula (III-b), the following formula (III-c) and the like can be mentioned.

Two or more of these siloxane-based diamines may be used in combination. A preferred siloxane diamine is a siloxane diamine of formula (III). More preferably, the diamine contains 3 mol% or more of the siloxane diamine of the formula (III) with respect to the total diamine. The content of the siloxane diamine of the formula (III) is more preferably 5 mol% or more, further preferably 10 mol% or more. If it is less than 3 mol%, the properties of low stress, low temperature adhesion and low hygroscopicity cannot be exhibited.

  The condensation reaction of tetracarboxylic dianhydride and diamine is carried out in an organic solvent. In this case, tetracarboxylic dianhydride and diamine are preferably used in equimolar or almost equimolar amounts, and the order of addition of the components is arbitrary. Examples of the organic solvent to be used include dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, hexamethylphosphorylamide, m-cresol, o-chlorophenol and the like.

  The condensation reaction temperature is preferably 80 ° C. or lower, more 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 polyimide precursor, is generated.

  Polyimide can be obtained by dehydrating and ring-closing the reactant (polyamic acid). Dehydration ring closure can be performed using a heat treatment method at 120 ° C. to 250 ° C. or a chemical method. In the case of the heat treatment at 120 ° C. to 250 ° C., it is preferable to carry out while removing water generated by the dehydration reaction out of the system. At this time, water may be removed azeotropically using benzene, toluene, xylene or the like. In the present invention, the polyimide resin is a general term for polyimide and its precursor. In addition to polyamide acid, polyimide precursors include those in which polyamide acid is partially imidized.

  In the case of dehydration and ring closure by a chemical method, acetic anhydride, propionic anhydride, acid anhydride of benzoic acid, carbodiimide compounds such as dicyclohexylcarbodiimide, and the like are used as the ring closure agent. At this time, a ring-closing catalyst such as pyridine, isoquinoline, trimethylamine, aminopyridine, or imidazole may be used as necessary. The ring-closing agent or the ring-closing catalyst is preferably used in the range of 1 to 8 moles per 1 mole of tetracarboxylic dianhydride.

  The thermosetting resin contained in the adhesive composition of the present invention is a reactive compound that causes a crosslinking reaction by heat. Such compounds include epoxy resins, cyanate resins, bismaleimide resins, phenol resins, urea resins, melamine resins, alkyd resins, acrylic resins, unsaturated polyester resins, diallyl phthalate resins, silicone resins, resorcinol formaldehyde resins, xylene resins. , Furan resin, polyurethane resin, ketone resin, triallyl cyanurate resin, polyisocyanate resin, resin containing tris (2-hydroxyethyl) isocyanurate, resin containing triallyl trimellitate, thermosetting from cyclopentadiene Resin, thermosetting resin by trimerization of aromatic dicyanamide and the like. Among these, a resin composition having an elastic modulus at 270 ° C. of 5 MPa or more after heat curing is selected. In addition, you may use 2 or more types for these thermosetting resins. In the adhesive composition of the present invention, the reflow temperature of a surface-mount type semiconductor device is generally about 270 ° C. or slightly lower than that, so the elastic modulus at 270 ° C. of the thermosetting resin is 5 MPa or more. It is necessary. When the elastic modulus is less than 5 MPa, the adhesive strength of the adhesive composition when heated is lowered.

  For curing, a curing agent and a curing accelerator (catalyst) can be appropriately used. For example, when an epoxy resin is used, the curing agent is a phenol compound, aliphatic amine, alicyclic amine, aromatic polyamine, polyamide, aliphatic acid anhydride, alicyclic acid anhydride, aromatic acid. Anhydrides, dicyandiamides, organic acid dihydrazides, boron trifluoride amine complexes, imidazoles, tertiary amines and the like can be mentioned. The curing accelerator (catalyst) is not particularly limited as long as it can cure the thermosetting resin. When a cyanate resin is used, a metal salt or metal complex such as cobalt, zinc or copper can be used as a catalyst, and a phenolic compound such as alkylphenol, bisphenol compound or phenol novolak can be used as a cocatalyst.

The epoxy resin contains at least two epoxy groups in the molecule, and is preferably a phenol glycidyl ether type epoxy resin from the viewpoint of curability and cured product characteristics. As such resin,
Bisphenol A type glycidyl ether,
Bisphenol AD type glycidyl ether,
Bisphenol S-type glycidyl ether,
Bisphenol F type glycidyl ether,
Water added bisphenol A type glycidyl ether,
Ethylene oxide adduct bisphenol A type glycidyl ether,
Propylene oxide adduct bisphenol A type glycidyl ether,
Glycidyl ether of phenol novolac resin,
Glycidyl ether of cresol novolac resin,
Glycidyl ether of bisphenol A novolac resin,
Glycidyl ether of naphthalene resin,
Trifunctional glycidyl ether,
Tetrafunctional glycidyl ether,
Glycidyl ether of dicyclopentagen phenol resin,
Glycidyl ester of dimer acid,
Trifunctional glycidylamine,
Tetrafunctional glycidylamine,
Examples thereof include glycidylamine of naphthalene resin. Two or more of these may be used.

The epoxy resin curing agent is not particularly limited. For example, the phenolic compounds, aliphatic amines, alicyclic amines, aromatic polyamines, polyamides, aliphatic acid anhydrides, alicyclic acid anhydrides, aromatic acid anhydrides, dicyandiamide, organic acid dihydrazides, trifluoride, etc. Examples thereof include boron amine complexes, imidazoles, and tertiary amines. Phenol compounds having at least two phenolic hydroxyl groups in the molecule are preferred. As such,
Phenol novolac resin,
Cresol novolac resin,
t-butylphenol novolac resin,
Dicyclopentagencresol novolak resin,
Dicyclopentagen phenol novolac resin,
Xylylene-modified phenol novolac resin,
Naphthol novolac resin,
Trisphenol novolac resin,
Tetrakisphenol novolac resin,
Bisphenol A novolac resin,
Poly-p-vinylphenol resin,
Examples thereof include phenol aralkyl resins.

As cyanate resin, for example,
2,2'-bis (4-cyanatephenyl) isopropylidene
1,1'-bis (4-cyanatephenyl) ethanebis (4-cyanate-3,5-dimethylphenyl) methane
1,3-bis (4-cyanatephenyl-1- (1-methylethylidene)) benzene cyanated phenol-dicyclopentanediene adduct cyanated novolak bis (4-cyanatophenyl) thioether bis (4-cyanate) Phenyl) ether resorcinol dicyanate
1,1,1-tris (4-cyanatephenyl) ethane
There are 2-phenyl-2- (4-cyanatephenyl) isopropylidene and the like, and two or more of these may be used.

（式中、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。）

（式中、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。）

（式中、ｑは０〜４の整数を示し、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。）

（式中、Ｒ₁₀及びＲ₁₁はそれぞれ二価の炭化水素基、Ｒ₁₂、Ｒ₁₃、R₁₄及びR₁₅はそれぞれ一価の炭化水素基を示し、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し、ｌは１以上の整数を表す。） As a compound having a bismaleimide group (bismaleimide resin),
Orthobismaleimidebenzene,
Metabismaleimidebenzene,
Parabismaleimidobenzene,
1,4-bis (p-maleimidocumyl) benzene,
In addition to 1,4-bis (m-maleimidocumyl) benzene, there are imide compounds represented by the following formulas (IV) to (VII).

(In the formula, 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 are each 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.)

(In the formula, 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 are each 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.)

(In the formula, q represents an integer of 0 to 4, and D represents a dicarboxylic acid residue having an ethylenically unsaturated double bond.)

Wherein R ₁₀ and R ₁₁ are each a divalent hydrocarbon group, R ₁₂ , R ₁₃ , R ₁₄ and R ₁₅ are each a monovalent hydrocarbon group, and D is an ethylenically unsaturated double bond. And 1 represents an integer of 1 or more.)

As an imide compound of the formula (IV), for example,
4,4-bismaleimide diphenyl ether,
4,4-bismaleimide diphenylmethane,
4,4-bismaleimide-3,3′-dimethyl-diphenylmethane,
4,4-bismaleimide diphenyl sulfone,
4,4-bismaleimide diphenyl sulfide,
4,4-bismaleimide diphenyl ketone,
2,2′-bis (4-maleimidophenyl) propane,
3,4-bismaleimide diphenylfluoromethane,
There are 1,1,1,3,3,3-hexafluoro-2,2-bis (4-maleimidophenyl) propane and the like.

As an imide compound of the formula (V), for example,
Bis (4- (4-maleimidophenoxy) phenyl) ether,
Bis (4- (4-maleimidophenoxy) phenyl) methane,
Bis (4- (4-maleimidophenoxy) phenyl) fluoromethane,
Bis (4- (4-maleimidophenoxy) phenyl) sulfone,
Bis (4- (3-maleimidophenoxy) phenyl) sulfone,
Bis (4- (4-maleimidophenoxy) phenyl) sulfide,
Bis (4- (4-maleimidophenoxy) phenyl) ketone,
1,2-bis (4- (4-maleimidophenoxy) phenyl) propane,
1,1,1,3,3,3-hexafluoro-2,2-bis (4- (4-maleimidophenoxy) phenyl) propane and the like.

  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 with respect to 100 parts by weight of the bismaleimide resin.

  The content of the thermosetting resin contained in the adhesive composition of the present invention is 0.1 to 200 parts by weight, preferably 0.1 to 100 parts by weight with respect to 100 parts by weight of the thermoplastic resin. If it exceeds 200 parts by weight, the film formability will deteriorate.

Moreover, the adhesive composition of this invention may contain a silane coupling agent. As a silane coupling agent contained in the adhesive composition of the present invention, for example,
Vinyltrimethoxysilane,
Vinyltriethoxysilane,
Vinyltris (2-methoxyethoxy) silane,
N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane,
N- (2-aminoethyl) 3-aminopropyltrimethoxysilane,
3-aminopropyltriethoxysilane,
3-aminopropyltrimethoxysilane,
3-glycidoxypropyltrimethoxysilane,
3-glycidoxypropylmethyldimethoxysilane,
2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane,
3-isocyanatopropyltriethoxysilane,
3-methacryloxypropyltrimethoxysilane,
3-mercaptopropyltrimethoxysilane,
3-ureidopropyltriethoxysilane,
N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine,
N, N′-bis (3- (trimethoxysilyl) propyl) ethylenediamine, polyoxyethylenepropyltrialkoxysilane,
There are polyethoxydimethylsiloxane and the like, and two or more of these may be used.

  The content of the silane coupling agent is preferably 0.01 to 50 parts by weight, and more preferably 0.05 to 20 parts by weight with respect to 100 parts by weight of the thermoplastic resin. If it exceeds 50 parts by weight, the storage stability will deteriorate.

  You may mix | blend a filler with the adhesive composition of this invention in the range which does not impair adhesiveness. Examples of such fillers include metal fillers such as silver powder, gold powder, and copper powder, inorganic fillers such as silica, alumina, boron nitride, titania, glass, iron oxide, and ceramic, carbon, and rubber-based organic fillers. Among the fillers, the metal filler is added for the purpose of imparting conductivity or thixotropy to the adhesive composition, and the inorganic filler is added for the purpose of imparting low thermal expansion and low hygroscopicity to the adhesive composition. The organic filler is added for the purpose of imparting toughness to the adhesive composition. Two or more kinds of these metal fillers, inorganic fillers or organic fillers can be used. Mixing and kneading in the case of using a filler can be carried out by appropriately combining dispersers such as ordinary stirrers, crackers, three rolls, and ball mills.

  When the filler is contained, the amount of the filler is 0 to 8000 parts by weight, preferably 0 to 4000 parts by weight with respect to 100 parts by weight of the thermoplastic resin. When it exceeds 8000 parts by weight, the adhesiveness is lowered.

  When the adhesive composition of the present invention is obtained, for example, in the form of a film, a thermoplastic resin, a thermosetting resin, and preferably a coupling agent and / or filler are mixed in an organic solvent to form a varnish. The varnish layer is formed on a base material, dried by heating, and the base material is removed. Alternatively, the varnish layer may be formed directly on the object to be bonded. For example, it can be used by forming a film on the back surface of a semiconductor wafer by spin coating.

  The organic solvent used for the varnish of the adhesive composition is not limited as long as it can uniformly dissolve, knead or disperse the thermoplastic resin as a material. For example, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, Examples include dimethyl sulfoxide, diethylene glycol dimethyl ether, toluene, benzene, xylene, methyl ethyl ketone, tetrahydrofuran, ethyl cellosolve, ethyl cellosolve acetate, butyl cellosolve, dioxane, cyclohexanone, and ethyl acetate.

  The heat drying is performed by heating for 0.1 to 90 minutes under conditions where the solvent used is sufficiently volatilized, that is, in the range of approximately 60 ° C to 200 ° C. Thereafter, the film-like adhesive composition is used after being peeled off from the substrate at room temperature. Or it can also be used with a base material.

  The substrate used for forming the varnish layer is not particularly limited as long as it can withstand the heating and drying conditions. For example, there are a polyester film, a polypropylene film, a polyethylene terephthalate film, a polyimide film, a polyetherimide film, a polyether naphthalate film, a methylpentene film, and the like. Two or more of these films may be combined to form a multilayer film. These films may be treated with a silicone-based or silica-based release agent.

The obtained adhesive composition is used for bonding a semiconductor element such as an IC or LSI and a support member to obtain the semiconductor device of the present invention. For example, the adhesive composition of the present invention is sandwiched between the semiconductor element and the support member as described above, and thermocompression bonded to bond them together. The thermocompression bonding is usually preferably 100 to 300 ° C., 0.1 to 300 seconds, and 0.005 to 2 MPa. Thereafter, a semiconductor device is obtained through a wire bonding process and, if necessary, a semiconductor element sealing process using a sealing material.
As a support member,
42 alloy lead frames, lead frames such as copper lead frames,
Plastic films such as polyimide resin and epoxy resin,
A glass nonwoven fabric or other base material impregnated and cured with a plastic such as polyimide resin or epoxy resin,
Examples thereof include ceramics such as alumina.

ポリイミドB：ビスフェノールAビストリメリテート二無水物：１００モル％と2,2-ビス（4-（4-アミノフェノキシ）フェニル）プロパン：２０モル％及び次式（III−ａ）で表されるジアミン：８０モル％とから合成した。

ポリイミドC： 1,10-(デカメチレン)ビス(トリメリテート二無水物)：１００モル％と2,2-ビス（4-（4-アミノフェノキシ）フェニル）プロパン：１００モル％とから合成した。
ポリイミドD：1,2-（エチレン）ビス（トリメリテート二無水物）：１００モル％と4,4’-ジアミノジフェニルメタン：１００モル％とから合成した。
ポリイミドE：ピロメリット酸二無水物：５０モル％と3,3’,4,4’-ビフェニルテトラカルボン酸二無水物：５０モル％および4,4’-ビス(3-アミノフェノキシ)ビフェニル：１００モル％とから合成した。 Hereinafter, the present invention will be described with reference to examples and comparative examples.
(Examples 1-5, Comparative Examples 1-4)
Using the polyimides of A to E below, as shown in the recipes of Tables 1 and 2, the varnishes of No. 1 to No. 9 (No. 1 to 5: related to Examples 1 to 5 of the present invention, No. 6 To 9: for Comparative Examples 1 to 4).
Polyimide A: 1,10- (decamethylene) bis (trimellitate dianhydride): 100 mol% and 2,2-bis (4- (4-aminophenoxy) phenyl) propane: 50 mol% and the following formula (VIII) The diamine represented: 50 mol%.

Polyimide B: bisphenol A bis trimellitate dianhydride: 100 mol% and 2,2-bis (4- (4-aminophenoxy) phenyl) propane: 20 mol% and a diamine represented by the following formula (III-a) : Synthesized from 80 mol%.

Polyimide C: Synthesized from 1,10- (decamethylene) bis (trimellitate dianhydride): 100 mol% and 2,2-bis (4- (4-aminophenoxy) phenyl) propane: 100 mol%.
Polyimide D: 1,2- (ethylene) bis (trimellitate dianhydride): synthesized from 100 mol% and 4,4′-diaminodiphenylmethane: 100 mol%.
Polyimide E: pyromellitic dianhydride: 50 mol% and 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride: 50 mol% and 4,4'-bis (3-aminophenoxy) biphenyl: It was synthesized from 100 mol%.

In Tables 1 and 2, various symbols mean the following.
ESCN195: Sumitomo Chemical, cresol novolac type epoxy resin (epoxy equivalent 200)
YH-434L: Toto Kasei, 4-functional glycidylamine type epoxy resin (epoxy equivalent 116)
BEO-60E: New Nippon Rikagaku Co., Ltd., Ethylene oxide 6 mol adduct bisphenol A type epoxy resin (epoxy equivalent 373)
BPO-60E: Shin Nippon Rikagaku, propylene oxide adduct bisphenol type epoxy resin (epoxy equivalent 314)
L-10: Asahi Ciba, bisphenol F type cyanate resin
XU-366: Asahi Ciba, phenyl-1- (1-methylethylidene) benzene cyanate resin
H-1: Meiwa Kasei, phenol novolak (OH equivalent 106)
TrisP-PA: Honshu Chemical, trisphenol novolak (OH equivalent 140)
TrisP-TC: Honshu Chemical, trisphenol novolak (OH equivalent 160)
XL-225: Mitsui Toatsu Chemical Xylylene Modified Phenol Novolak (OH Equivalent 175)
A-1310: Nihon Unicar, 3-isocyanatopropyltriethoxysilane
A-189: Nihon Unicar, 3-mercaptopropyltrimethoxysilane
A-187: Nihon Unicar, 3-glycidoxypropyltrimethoxysilane
A-1100: Nihon Unicar, 3-aminopropyltriethoxysilane
DMAc: Dimethylacetamide
DMF: Dimethylformamide
NMP: N-methylpyrrolidone The elastic modulus values at 270 ° C. after curing of the thermosetting resins shown in Tables 1 and 2 were determined by using a viscoelasticity analyzer RSA-2 manufactured by Rheometrics. It was obtained by storage elastic modulus E ′ at 270 ° C. measured at ° C./min and frequency 1 Hz.

  This varnish is applied to a substrate (polypropylene film) to a thickness of 30 to 50 μm, heated at 80 ° C. for 10 minutes, then heated at 150 ° C. for 30 minutes, and then peeled off from the substrate at room temperature. An adhesive composition (hereinafter referred to as an adhesive film) was obtained.

(Evaluation test)
For the adhesive films obtained in Examples 1 to 5 and Comparative Examples 1 to 4, peel adhesive strength was measured, and using the adhesive films obtained in Examples 1 to 5 and Comparative Examples 1 to 4, copper was used. Chip warpage was measured when a silicon chip was bonded to the lead frame. The measurement results are shown in Tables 3 and 4.

In addition, the peel adhesive force and the chip warpage measuring method are as follows.
<Measurement method of peel adhesion>
Cut the adhesive film into 5mm x 5mm size, sandwich it between the 5x5mm silicon chip and the die pad part of the copper lead frame, apply 1000g load, and press-bond at 180 ° C or 250 ° C for 5 seconds After that, the adhesive film was cured by heating at 180 ° C. for 1 hour. The chip peeling strength when heated at 245 ° C. or 275 ° C. for 20 seconds was measured with a push-pull gauge.
<Measurement method of chip warpage>
The adhesive film is cut to a size of 10 mm x 10 mm, sandwiched between the die pad part of the copper lead frame and the silicon chip of the size of 10 mm x 10 mm, applied with a load of 1000 g, and crimped at 250 ° C for 20 seconds. After returning to room temperature, a surface roughness meter was used, and the chip surface was scanned 10 mm diagonally to determine the maximum height (μm) from the base line, which was taken as chip warpage.

Claims (3)

A film-like die bonding material for bonding a semiconductor element containing a thermoplastic resin having a Tg of 200 ° C. or less, a thermosetting resin, a curing agent, and a filler,
The thermoplastic resin includes tetracarboxylic dianhydride and a diamine containing 1,1,3,3-tetramethyl-1,3-bis (3-aminopropyl) disiloxane in an amount of 3 mol% or more of the total diamine. A polyimide resin obtained by reaction,
The thermosetting resin is a phenol glycidyl ether type epoxy resin having an elastic modulus at 270 ° C. of 5 MPa or more after heat curing, and in the range of 1 to 100 parts by weight with respect to 100 parts by weight of the thermoplastic resin. Included in the
The filler is one or more selected from silica, alumina, boron nitride, titania, glass, iron oxide, ceramic and copper powder, and is contained in 4000 parts by weight or less with respect to 100 parts by weight of the thermoplastic resin. Die bonding material.   The die bonding material according to claim 1, which contains an imidazole curing agent.   The die bonding material according to claim 1 or 2, wherein the polyimide resin is a polyimide resin obtained by reacting one kind of tetracarboxylic dianhydride and two kinds of diamines.