JP2002226824A - Adhesive composition, adhesive film and semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive composition for bonding an electronic part such as semiconductor element to a lead frame or an insulating supporting substrate and durable to the thermal history of the high-temperature soldering in mounting and provide an adhesive film and a semiconductor device. SOLUTION: The adhesive composition contains a resin and a filler. The filler has spherical form having an average particle diameter of <=10 μm and a maximum particle diameter of <=25 μm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive composition, an adhesive film, and a semiconductor device. More specifically, the present invention relates to 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, the present invention relates to an adhesive composition and an adhesive film suitable for die bonding and a semiconductor device using the same.

[0002]

2. Description of the Related Art Conventionally, as an adhesive material between an electronic component such as a semiconductor element and a supporting member such as a lead frame or an insulating support substrate, Au-Si eutectic alloy, solder, resin paste,
A resin film and the like are known. Among them, Au-
Si eutectic alloys have the problem of being expensive and having a high modulus of elasticity, and solder cannot withstand temperatures higher than the melting point, and have the problem of having a high modulus of elasticity. Resin films are mainly used.

[0003] A resin paste mainly contains a thermosetting resin from the viewpoint of heat resistance reliability, and a resin film mainly contains a thermoplastic resin from the viewpoint of film forming property.

On the other hand, with the rapid increase in demand for high-density packaging due to the miniaturization and thinning of electronic devices, surface-mount type semiconductor packages suitable for high-density packaging have become mainstream instead of the conventional pin insertion type. Have been.

[0005] In order to directly solder the leads or bumps to a printed circuit board or the like, the surface mount package is mounted by heating the entire package by infrared reflow, vapor phase reflow, solder dip, or the like. At this time, since the entire package is exposed to a high temperature of about 240 ° C., if moisture absorption exists inside the package, explosive vaporization of the moisture causes a package crack (hereinafter referred to as a reflow crack). The reflow crack significantly reduces the reliability of the semiconductor package, and is a serious problem and technical problem.

The mechanism of occurrence of reflow cracks caused by the die bonding material is as follows. While the semiconductor package is stored, (1) the die bonding material absorbs moisture, (2) the absorbed moisture is turned into steam by heating at the time of reflow soldering, and (3) the vapor pressure destroys the die bonding layer. And peeling occur,
(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 has become a serious problem particularly in a thin package.

Furthermore, in recent years, with the environmental protection measures on a global scale, legal regulations on lead have been increasingly tightened mainly in Europe and the like. In fields where high reliability is demanded, Sn-A with a higher melting point than the current Sn-Pb system is used.
It is said to switch to g-based solder. When the mounting solder is switched to the above-mentioned Sn-Ag system, the melting point becomes high.
The maximum temperature of the reflow furnace will be 20 to 30C higher than the current temperature. Therefore, an adhesive material for die bonding is required to be a material that can withstand an increase in reflow temperature and has improved reliability more than ever.

Conventionally, the most commonly used silver filler-filled resin paste (hereinafter referred to as silver paste) has become difficult to apply the silver paste uniformly over the entire application area due to the enlargement of the chip. In addition, since the adhesive layer is paste-like, voids are easily generated in the adhesive layer, so that reflow cracks are easily generated.

In order to solve the above problems, a resin film in which a resin paste is formed into a film has been proposed. By making it into a film, a uniform bonding area can be secured,
In addition, since voids can be greatly reduced, reflow crack resistance better than that of paste can be ensured.

The mainstream resin film is a thermoplastic resin as a main component. If a thermoplastic resin having a low melting point is selected and used, the bonding temperature can be lowered, and the chip may be oxidized by a lead frame. The damage done can be reduced. However, a resin film using a thermoplastic resin having a low melting point has a low adhesive strength when heated, and cannot withstand a soldering heat treatment during mounting.

[0011]

SUMMARY OF THE INVENTION An object of the present invention is to provide an adhesive composition for bonding an electronic component such as a semiconductor element to a lead frame or an insulating support substrate. It is an object of the present invention to provide an adhesive composition, an adhesive film, and a semiconductor device that can withstand the same.

That is, the present invention provides an adhesive composition that withstands a high-temperature soldering heat history at the time of mounting and has excellent adhesive strength. The inventions of claims 5 and 6 exhibit the effects of the inventions of claims 1 to 4, and provide an adhesive composition having more excellent adhesive strength.
The invention described in claim 7 provides the effects of the inventions described in claims 5 and 6, and further provides an adhesive composition which does not generate voids and has excellent film-forming properties.

The invention according to claim 8 has the effects of the invention according to claim 7, and has an adhesive composition excellent in low-temperature adhesion, low stress, hydrolysis resistance, and reliability under high temperature and high humidity conditions. It provides things. The invention according to claim 9 is
It is an object of the present invention to provide an adhesive composition exhibiting the effects of the invention of claim 7 and having more excellent low-temperature adhesion, low stress, hydrolysis resistance, and reliability under high temperature and high humidity conditions.

[0014] The tenth aspect of the invention provides the effects of the fifth to ninth aspects of the invention and provides an adhesive composition having more excellent adhesive strength. The inventions of claims 11 to 13 exhibit the effects of the inventions of claims 1 to 10 and provide an adhesive composition having more excellent adhesive strength.

The invention according to claim 14 withstands high-temperature soldering heat history during mounting, has excellent adhesive strength, and has excellent low-temperature adhesion, low stress resistance, hydrolysis resistance, and reliability under high-temperature and high-humidity conditions. And an adhesive film having excellent workability.

A fifteenth aspect of the present invention provides a semiconductor device which ensures high reliability under high temperature and high humidity conditions.

[0017]

The present invention relates to an adhesive composition comprising a resin and a filler, wherein the filler has a spherical shape, an average particle diameter of 10 μm or less, and a maximum particle diameter of not more than 10 μm. The present invention relates to an adhesive composition having a size of 25 μm or less. The present invention also relates to the above adhesive composition, wherein the filler is a metal filler or an inorganic filler. The present invention also relates to the above adhesive composition, wherein the filler is silver powder.
The present invention also relates to the adhesive composition, wherein the content of the filler is 1 to 50% by volume.

The present invention also relates to the above adhesive composition, wherein the resin comprises a thermoplastic resin and a thermosetting resin. The present invention also relates to the above adhesive composition, wherein the resin comprises 100 parts by weight of a thermoplastic resin and 0.1 to 200 parts by weight of a thermosetting resin. The present invention also relates to the above adhesive composition, wherein the thermoplastic resin is a phenoxy resin or a polyimide resin.

In the present invention, the polyimide resin may be represented by the following general formula (1):

Embedded image (Where n represents an integer of 2 to 20), or a tetracarboxylic dianhydride represented by the following formula (2):

Embedded image The adhesive, which is a polyimide resin obtained by reacting a tetracarboxylic dianhydride having a content of tetracarboxylic dianhydride of 30 mol% or more of all tetracarboxylic dianhydrides and a diamine with the diamine Composition.

The present invention also relates to a polyimide resin, wherein the content of the tetracarboxylic dianhydride of the general formula (1) or the tetracarboxylic dianhydride of the general formula (2) is 30% of the total tetracarboxylic dianhydride. Mol% or more of tetracarboxylic dianhydride and the following general formula (3)

Embedded image (Wherein Q ¹ and Q ² each independently represent an alkylene group having 1 to 5 carbon atoms or a phenylene group which may have a substituent, and Q ³ , Q ⁴ , Q ⁵ and Q ⁶ each independently represent Represents an alkyl group having 1 to 5 carbon atoms, a phenyl group or a phenoxy group, and m represents an integer of 1 to 50). The present invention relates to the above adhesive composition which is a polyimide resin obtained by the above method.

The present invention also relates to the above adhesive composition, wherein the thermosetting resin is an epoxy resin. The present invention also relates to the above-mentioned adhesive composition further comprising a coupling agent. The present invention also relates to the above adhesive composition, wherein the coupling agent is a silane coupling agent. The present invention also relates to a thermoplastic resin 100 parts by weight, a coupling agent 0.0
The present invention relates to the adhesive composition containing 1 to 50 parts by weight.

The present invention also relates to an adhesive film formed by using the above-mentioned adhesive composition. Further, the present invention relates to a semiconductor device having a structure in which a semiconductor element is bonded to a support member using the adhesive composition or the adhesive film.

[0023]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The adhesive composition of the present invention is an adhesive composition containing a resin and a filler, wherein the filler has a spherical shape and an average particle diameter of 10 μm.
m or less, and the maximum particle diameter is 25 μm or less. With such a configuration, an effect of improving the adhesive strength and the fracture toughness is imparted to the adhesive composition, and the destruction or peeling of the adhesive layer in the heat history of soldering can be suppressed, and as a result, reflow crack resistance The performance is improved.

The shape of the filler used in the adhesive composition of the present invention is "spherical".
It also includes lumps, granules, sponges and the like. Above all, a true sphere is preferable in that it exhibits excellent adhesive strength. FIG. 1 (A) shows an SEM photograph of a typical spherical filler, and FIG. 1 (B) shows an SEM photograph of a typical flaky filler.

The above-mentioned spherical filler has a degree (N) and a degree of flatness (M), each of which is known as a shape index, of 0.
It is preferable that 5 ≦ 1 / N ≦ 1.0 and 0.5 ≦ 1 / M ≦ 1.0. In addition, the major and minor degrees (N) are as follows: N = major axis (L)
/ Minor axis (B), and flatness (M) is represented by M = minor axis (B) / thickness (T). Here, the long diameter (L) is the maximum value of the distance between two planes when particles in the same state are sandwiched between two perpendicular planes, and the short diameter (B) is
In the direction perpendicular to the major axis (L), the distance between the two planes when sandwiched between two vertical planes, and the thickness (T) is the distance between the two planes when the particle is sandwiched between two horizontal planes. (References: Kubo, K. et al., Powder-Basics and Applications (Maruzen)). On the other hand, scaly (flake-like) refers to those having the above 1 / M of less than 0.5, and the adhesive strength of the adhesive film filled with such a filler is the adhesive strength filled with a spherical filler. Inferior to film.

The average particle diameter of the spherical filler is 10 μm
Hereinafter, the maximum particle diameter is preferably 25 μm or less, the average particle diameter is preferably 5 μm or less, and the maximum particle diameter is preferably 20 μm or less. If the average particle size exceeds 10 μm and the maximum particle size exceeds 25 μm, the effect of improving fracture toughness cannot be obtained. The lower limit is not particularly limited, but both are usually 0.00
1 μm.

The spherical filler has an average particle diameter of 10 μm.
Hereinafter, it is necessary that the maximum particle diameter satisfy both of 25 μm or less. When a filler having a maximum particle diameter of 25 μm or less but an average particle diameter of more than 10 μm is used, high adhesive strength cannot be obtained. When a filler having an average particle diameter of 10 μm or less but a maximum particle diameter of more than 25 μm is used, the particle diameter distribution is widened and the adhesive strength tends to vary. When the adhesive composition of the present invention is processed into a thin film and used, the surface is roughened and the adhesive strength is reduced.

As a method for measuring the average particle diameter and the maximum particle diameter of the filler contained in the adhesive composition of the present invention, for example, using a scanning electron microscope (SEM), the particle diameter of about 200 fillers is measured. And the like.

As a measuring method using an SEM, for example, a semiconductor element and a semiconductor supporting substrate are bonded using an adhesive composition, and then cured by heating (preferably 150 to 200).
(1 ° C. for 1 to 10 hours), a center portion of the sample is cut, and a cross section thereof is observed with an SEM.

When the filler used is a metal filler or an inorganic filler, the adhesive composition is heated in an oven at 600 ° C. for 2 hours to decompose and volatilize the resin component.
A method of observing and measuring the remaining filler by SEM can also be adopted. When observing the filler itself by SEM, a sample obtained by attaching a double-sided adhesive tape on a sample stage for SEM observation, sprinkling the filler on the adhesive surface, and then vapor-depositing by ion sputtering may be used. At this time, it is assumed that the existence probability of the filler is 80% or more of all the fillers.

In the adhesive composition of the present invention, the reason why the above filler is preferable as the filler used is as follows.
The following reasons can be considered.

FIG. 2 is a cross-sectional photograph of an adhesive film filled with scale-like and spherical silver fillers, respectively. FIG.
Fig. 1 shows a conceptual diagram of resin / filler interface peeling in an adhesive film filled with a flaky or spherical filler.

As can be seen from FIG. 2, in the adhesive film filled with the flaky silver filler, it is observed that the silver filler is oriented horizontally with respect to the surface of the adhesive film. As a cause of this, when the adhesive composition containing the flaky filler is thinly applied, particularly when the adhesive film is produced by coating on the base film, the flaky filler tends to be oriented in the coating direction. It became clear that there was. On the other hand, an adhesive composition filled with a spherical silver filler does not have anisotropy in the shape of the filler, and thus does not have the orientation as seen in a flaky filler.

It is considered that such a difference in the shape of the filler affects the tensile strength (that is, adhesive strength) in the thickness direction of the adhesive layer. That is, as shown in FIG. 3 (A), when the shape of the filler is scaly, the peeling surface at the interface between the resin 1 and the filler 2 is flat, so that a tensile stress is applied in the thickness direction of the adhesive layer. It is considered that the propagation of the cracks 3 proceeds easily in the orientation direction (horizontal direction) of the filler, whereas in the case of a spherical filler, the spherical surface suppresses the propagation of the cracks 3 as shown in FIG. Resin 1 / Filler 4 compared to scaly filler
It is considered that peeling of the interface tends to be suppressed. It is considered that such a difference in the propagation behavior of the crack 3 affects the adhesive strength in the thickness direction of the adhesive layer as a result. Also, when the particle diameter of the filler is reduced, the resin / filler interface area is increased, so that the fracture toughness of the adhesive layer is increased, and accordingly, the adhesive strength in the thickness direction of the adhesive layer is considered to be improved. Can be

Examples of the filler include metal fillers such as silver powder, gold powder, copper powder, and nickel powder; inorganic fillers such as silica, alumina, boron nitride, titania, glass, iron oxide, and ceramics; carbon, and rubber-based fillers. Organic fillers.

The above fillers can be used properly according to the desired functions. For example, a metal filler is added for the purpose of imparting conductivity, thermal conductivity, thixotropy and the like to the adhesive composition, and a non-metallic inorganic filler adds thermal conductivity, low thermal expansion, low moisture absorption and the like to the adhesive film. The organic filler is added for the purpose of imparting toughness or the like to the adhesive film. These metal fillers, inorganic fillers or organic fillers can be used alone or in combination of two or more. Above all, metal fillers and inorganic fillers are preferable in that the characteristics required for the semiconductor device can be imparted, and silver powder is more preferable among the metal fillers.

The content of the filler is preferably 1 to 50% by volume, more preferably 1 to 40% by volume, particularly preferably 1 to 30% by volume.
It is extremely preferred that the content is ２５25% by volume. If it is less than 1% by volume, the effect of improving fracture toughness tends not to be obtained. If it exceeds 50% by volume, the adhesiveness tends to decrease.

The resin contained in the adhesive composition of the present invention comprises:
In terms of being able to obtain high adhesive strength, it is preferable to contain either a thermoplastic resin or a thermosetting resin,
It is more preferable to contain both.

The thermoplastic resin is not particularly restricted but includes, for example, polyimide resin, polyamide resin, polyetherimide resin, polyester resin, polyesterimide resin, phenoxy resin, polysulfone resin, polyethersulfone resin, polyphenylene. Sulfide resin, polyetherketone resin and the like,
Phenoxy resin or polyimide resin is preferred in that high adhesive strength can be obtained.

The phenoxy resin is a high-molecular-weight epoxy resin having a weight average molecular weight of 5000 or more determined by gel permeation chromatography. Like the epoxy resin, bisphenol A type, F type, AD type
Types, AF copolymerization type, S type and the like. The weight average molecular weight is preferably from 5,000 to 150,000, and more preferably from 10,000 to 80,000 from the viewpoint of melt viscosity, compatibility with other resins, and the like.

The above polyimide resin can be usually produced by subjecting a tetracarboxylic dianhydride and a diamine to a condensation reaction in an organic solvent. The tetracarboxylic dianhydride and the diamine are preferably used in equimolar or almost equimolar, and the order of addition of each component is arbitrary.

In this case, first, a polyamic acid is generated, and further heated to cause dehydration and ring closure to produce a polyimide resin. 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.

The organic solvent to be used is not particularly limited as long as the raw material and the polyimide to be produced are completely dissolved. Examples thereof include dimethylacetamide, dimethylformamide, N
-Methyl-2-pyrrolidone, dimethylsulfoxide, hexamethylphosphorylamide, m-cresol, o-chlorophenol and the like.

The reaction temperature at the beginning of the reaction is preferably from 0 to 80 ° C, more preferably from 0 to 50 ° C. As the reaction proceeds and polyamic acid is generated, the viscosity of the reaction solution gradually increases.
The polyimide resin can be obtained by subjecting the generated polyamic acid to dehydration and ring closure by heat treatment or chemical treatment.

The reaction temperature in the case of heat treatment varies depending on the raw materials used, but is preferably 120 to 250 ° C. The reaction is preferably performed while removing water generated by the dehydration reaction out of the system. At this time, water may be azeotropically removed using benzene, toluene, xylene, or the like.

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

The tetracarboxylic dianhydride that can be used includes 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 Anhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, bis (2,3-
Dicarboxyphenyl) methane dianhydride, bis (3,4
-Dicarboxyphenyl) methane dianhydride, bis (3,
4-dicarboxyphenyl) sulfone dianhydride, 3,
4,9,10-perylenetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 3,4 3 ', 4'-benzophenonetetracarboxylic dianhydride, 2,3,2', 3-benzophenonetetracarboxylic dianhydride, 2,3,3 ', 4'-benzophenonetetracarboxylic dianhydride, , 2,5,6-
Naphthalenetetracarboxylic dianhydride, 2,3,6,7
-Naphthalenetetracarboxylic dianhydride, 1,2,4
5-naphthalenetetracarboxylic dianhydride, 1,4
5,8-naphthalenetetracarboxylic 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, thiophenin-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 (trimellitate 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 (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, 2,2-bis [4- (3,4-dicarboxy) Phenoxy) phenyl]
Hexafluoropropane dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 1,4-bis (2-hydroxyhexafluoroisopropyl) benzene bis (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, the following general formula (1)

Embedded image (Where n represents an integer of 2 to 20) and a tetracarboxylic dianhydride represented by the following formula (2):

Embedded image The tetracarboxylic dianhydride represented by the above general formula (1) is preferable in that it can impart low-temperature adhesiveness to the adhesive film, and the moisture resistance reliability is particularly preferable. The tetracarboxylic dianhydride represented by the above formula (2) is preferable from the viewpoint of superiority. These tetracarboxylic dianhydrides can be used alone or in combination of two or more.

The content of the tetracarboxylic dianhydride represented by the above general formula (1) is preferably at least 30 mol% with respect to all the tetracarboxylic dianhydrides. % Or more, more preferably 70% or more.

The tetracarboxylic dianhydride of the general formula (1) can be synthesized, for example, from trimellitic anhydride monochloride and the corresponding diol. Specifically, 1,2- (ethylene) bis ( Trimellitate dianhydride), 1,3- (trimethylene) bis (trimellitate dianhydride), 1,4- (tetramethylene) bis (trimellitate dianhydride), 1,5- (pentamethylene) bis (trimellitate dianhydride) Product), 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), 1,12- (dodecamethylene ) Bis (trimellitate dianhydride), 1,16- (hexadecamethylene) bistrimellitate dianhydride, 1,18-
(Octadecamethylene) bis (trimellitate dianhydride) and the like, and these can be used alone or in combination of two or more.

The content of the tetracarboxylic dianhydride represented by the above formula (2) is preferably at least 30 mol% with respect to all the tetracarboxylic dianhydrides. 50% or more is more preferable in that it can be provided,
70% or more is very preferable.

Examples of the raw material diamine for the polyimide resin include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-
Aliphatic diamines such as diaminoundecane and 1,12-diaminododecane, o- (or m-, p-) phenylenediamine, 3,3 '-(or 3,4'-) diaminodiphenyl ether, 4,4'-diamino Diphenyl ether, 3,3 '-(or 3,4'-) diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,
3 '-(or 3,4'-, 4,4 '-) diaminodiphenyldifluoromethane, 3,3'-(or 3,4'-,
4,4 '-) diaminodiphenylsulfone, 3,3'-
(Or 3,4'-, 4,4'-) diaminodiphenyl sulfide, 3,3'- (or 3,4'-, 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- (or 1,4-) bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 3,3 '-(1-phenylenebis (1-methylethyleridene)) 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 An unsaturated bond-containing diamine such as, bis (4- (4-aminophenoxy) phenyl) sulfide, bis (4- (3-aminophenoxy) phenyl) sulfone, bis (4- (4-aminophenoxy) phenyl) sulfone, The following general formula (3)

Embedded image (Wherein Q ¹ and Q ² each independently represent an alkylene group having 1 to 5 carbon atoms or a phenylene group which may have a substituent, and Q ³ , Q ⁴ , Q ⁵ and Q ⁶ represent Each independently has 1 to 1 carbon atoms
5 represents an alkyl group, a phenyl group or a phenoxy group,
m represents an integer of 1 to 50), and among others, the diamine represented by the above general formula (3) is added to the adhesive composition to obtain a low stress property and a low temperature after heat curing. It is preferable in that it can provide adhesiveness. These diamines can be used alone or in combination of two or more.

Examples of the siloxane-based diamine of the general formula (3) include 1,1,3,3-tetramethyl-diamine.
1,3-bis (4-aminophenyl) disiloxane,
1,1,3,3-tetraphenoxy-1,3-bis (4
-Aminoethyl) disiloxane, 1,1,3,3-tetraphenyl-1,3-bis (2-aminoethyl) disiloxane, 1,1,3,3-tetraphenyl-1,3-bis (3 -Aminopropyl) disiloxane, 1,1,3
3-tetramethyl-1,3-bis (2-aminoethyl)
Disiloxane, 1,1,3,3-tetramethyl-1,3
-Bis (3-aminopropyl) disiloxane, 1,1,
3,3-tetramethyl-1,3-bis (3-aminobutyl) disiloxane, 1,3-dimethyl-1,3-dimethoxy-1,3-bis (4-aminobutyl) disiloxane, 1,1 , 3,3,5,5-hexamethyl-1,5-
Bis (4-aminophenyl) trisiloxane, 1,1,
5,5-tetraphenyl-3,3-dimethyl-1,5-
Bis (3-aminopropyl) trisiloxane, 1,1,
5,5-tetraphenyl-3,3-dimethoxy-1,5
-Bis (4-aminobutyl) trisiloxane, 1,1,
5,5-tetraphenyl-3,3-dimethoxy-1,5
-Bis (5-aminopentyl) trisiloxane, 1,
1,5,5-tetramethyl-3,3-dimethoxy-1,
5-bis (2-aminoethyl) trisiloxane, 1,
1,5,5-tetramethyl-3,3-dimethoxy-1,
5-bis (4-aminobutyl) trisiloxane, 1,
1,5,5-tetramethyl-3,3-dimethoxy-1,
5-bis (5-aminopentyl) trisiloxane, 1,
1,3,3,5,5-hexamethyl-1,5-bis (3
-Aminopropyl) trisiloxane, 1,1,3,3
5,5-hexaethyl-1,5-bis (3-aminopropyl) trisiloxane, 1,1,3,3,5,5-hexapropyl-1,5-bis (3-aminopropyl) trisiloxane, Examples thereof include siloxane diamines represented by the formula, and these can be used alone or in combination of two or more.

[0053]

Embedded image

The content of the siloxane-based diamine represented by the general formula (3) is preferably at least 3 mol%, more preferably at least 5 mol%, and most preferably at least 10 mol%, based on all diamines. When the content of the diamine is less than 3 mol%, there is a tendency that properties such as low hygroscopicity, low-temperature adhesion and low stress after heat curing cannot be exhibited.

The thermosetting resin is a reactive compound that causes a crosslinking reaction by heat. Examples of such a compound include an epoxy resin, a cyanate resin, a bismaleimide resin, a phenol resin, a urea resin, a melamine resin, an alkyd resin, an acrylic resin, an unsaturated polyester resin, a diallyl phthalate resin, a silicone resin, a resorcinol formaldehyde resin, Xylene resin, furan resin, polyurethane resin, ketone resin, triallyl cyanurate resin, polyisocyanate resin, tris (2
(Hydroxyethyl) isocyanurate-containing resin, triallyl trimellitate-containing resin, resin synthesized from cyclopentadiene, thermosetting resin obtained by trimerizing aromatic dicyanamide, and the like. Among them,
Epoxy resins, cyanate resins, and bismaleimide resins are preferred, and epoxy resins are more preferred, in that they can have excellent adhesion at high temperatures. In addition,
These thermosetting resins can be used alone or in combination of two or more.

The content of the thermosetting resin is preferably 200 parts by weight or less based on 100 parts by weight of the thermoplastic resin, and 10 parts when the adhesive composition is processed into a film.
0 parts by weight or less is more preferable. If it exceeds 200 parts by weight, the film-forming properties tend to be poor. The lower limit is not particularly limited, but is usually 0.1 part by weight.

For curing, a curing agent and a curing accelerator, or a catalyst and a co-catalyst can be appropriately used.

Examples of the curing agent include phenol compounds, aliphatic amines, alicyclic amines, aromatic polyamines, polyamides, aliphatic acid anhydrides, alicyclic acid anhydrides,
Aromatic acid anhydride, dicyandiamide, organic acid dihydrazide, boron trifluoride amine complex, imidazoles, third
Secondary amine and the like.

The curing accelerator is not particularly limited as long as it cures the thermosetting resin. Examples thereof include imidazoles, dicyandiamide derivatives, dicarboxylic dihydrazide, triphenylphosphine, tetraphenylphosphonium tetraphenylborate, and the like. -Ethyl-4
-Methylimidazole-tetraphenylborate, 1,
8-diazabicyclo [5.4.0] undecene-7-tetraphenylborate and the like.

The content of the curing agent is preferably from 0 to 200 parts by weight based on 100 parts by weight of the thermosetting resin. The content of the curing accelerator is the same as that of the thermosetting resin 100.
0 to 50 parts by weight is preferable with respect to parts by weight.

As the epoxy resin, which is one of the preferred thermosetting resins, those containing at least two epoxy groups in the molecule are more preferable, and glycidyl ether type of phenol is preferred from the viewpoint of curability and properties of the cured product. Are particularly preferred. Examples of such a resin include bisphenol A type (or AD type, S type, F type) glycidyl ether, water-added bisphenol A type glycidyl ether, ethylene oxide adduct bisphenol A type glycidyl ether, and propylene oxide adduct Glycidyl ether of bisphenol A type, glycidyl ether of phenol novolak resin, glycidyl ether of cresol novolak resin, bisphenol A
Novolak resin glycidyl ether, naphthalene resin glycidyl ether, trifunctional (or tetrafunctional) glycidyl ether, dicyclopentadiene phenol resin glycidyl ether, dimer acid glycidyl ester, trifunctional (or tetrafunctional) Glycidylamine,
Glycidylamine of naphthalene resin and the like can be mentioned. These can be used alone or in combination of two or more.

Examples of the curing agent for the epoxy resin include phenol compounds, aliphatic amines, alicyclic amines, aromatic polyamines, polyamides, aliphatic acid anhydrides,
Alicyclic acid anhydride, aromatic acid anhydride, dicyandiamide,
Examples thereof include organic acid dihydrazide, boron trifluoride amine complex, imidazoles, and tertiary amines. Among them, phenol compounds are preferable, and phenol compounds having at least two phenolic hydroxyl groups in the molecule are more preferable.

Examples of the phenolic compound having at least two phenolic hydroxyl groups in the molecule include phenol novolak resin, cresol novolak resin, t-butylphenol novolak resin, dicyclopentadiene cresol novolak resin, and dicyclopentadiene phenol. Novolak resin, xylylene-modified phenol novolak resin, naphthol novolak resin,
Trisphenol novolak resin, tetrakisphenol novolak resin, bisphenol A novolak resin,
Poly-p-vinylphenol resin, phenol aralkyl resin and the like can be mentioned.

The cyanate resin, which is one of preferred thermosetting resins, includes, for example, 2,2'-bis (4
-Cyanatephenyl) isopropylidene, 1,1'-
Bis (4-cyanatephenyl) ethane, bis (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-cyanatophenyl) ether, resorcinol dicyanate, 1,1,1-tris (4-cyanatephenyl) ethane, 2-phenyl-2- (4-cyanatephenyl) isopropylidene, etc., are exemplified. They can be used alone or in combination of two or more.

When a cyanate resin is used as the thermosetting resin, a metal salt or a metal complex such as cobalt, zinc or copper is used as a catalyst and a phenolic compound such as an alkylphenol, a bisphenol compound or phenol novolak is used as a cocatalyst. It can be.

The bismaleimide resin, which is one of the preferred thermosetting resins, includes, for example, o- (or m-
-, P-) bismaleimidobenzene, 4-bis (p-maleimidocumyl) benzene, 1,4-bis (m-maleimidocumyl) benzene and compounds represented by the following general formulas (4) to (7) And the like.

[0067]

Embedded image (Where X is O, CH ₂ , CF ₂ , SO ₂ , S, CO, C
(CH ₃ ) ₂ or C (CF ₃ ) ₂ , four R ¹ each independently represent hydrogen, a lower alkyl group, a lower alkoxy group, fluorine, chlorine or bromine, and two Ds each independently represent ethylene. Dicarboxylic acid residue having an unsaturated double bond)

[0068]

Embedded image (Where Y is O, CH ₂ , CF ₂ , SO ₂ , S, CO, C
(CH ₃ ) ₂ or C (CF ₃ ) ₂ ; four R ² each independently represent hydrogen, a lower alkyl group, a lower alkoxy group, fluorine, chlorine or bromine; (Indicates a dicarboxylic acid residue having a heavy bond)

[0069]

Embedded image (In the formula, q represents an integer of 0 to 4, and a plurality of Ds each independently represent a dicarboxylic acid residue having an ethylenically unsaturated double bond.)

[0070]

Embedded image (Wherein two R ³ are each independently a divalent hydrocarbon group, four R ⁴ each independently represents a monovalent hydrocarbon group, an ethylenically unsaturated double bond each independently two D Represents a dicarboxylic acid residue having the formula: wherein r represents an integer of 1 or more)

In each of the above structural formulas, examples of the dicarboxylic acid residue having an ethylenically unsaturated double bond represented by D include a maleic acid residue and a citraconic acid residue.

Examples of the bismaleimide resin represented by the general formula (4) include 4,4-bismaleimidediphenyl ether, 4,4-bismaleimidediphenylmethane,
4,4-bismaleimide-3,3'-dimethyl-diphenylmethane, 4,4-bismaleimidediphenylsulfone, 4,4-bismaleimidediphenylsulfide,
4,4-bismaleimide diphenyl ketone, 2'-bis (4-maleimidophenyl) propane, 4-bismaleimidodiphenylfluoromethane, 1,1,1,3,3,
3-hexafluoro-2,2-bis (4-maleimidophenyl) propane and the like.

Examples of the bismaleimide resin represented by the general formula (5) 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-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 bismaleimide resins, a radical polymerization agent may be used. The content of the radical polymerization agent is preferably 0.01 to 1.0 part by weight based on 100 parts by weight of the bismaleimide resin.

Examples of the radical polymerization agent include acetylcyclohexylsulfonyl peroxide, isobutyryl peroxide, benzoyl peroxide,
Examples include octanoyl peroxide, acetyl peroxide, dicumyl peroxide, cumene hydroperoxide, azobisisobutyronitrile, and the like.

It is preferable that the adhesive composition of the present invention further contains a coupling agent. Examples of the coupling agent include a titanium-based coupling agent and a silane coupling agent, and a silane coupling agent is preferable because it is easily available.

Examples of the silane coupling agent include 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-ureidopropyl Triethoxysilane, N-
(1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine, N, N'-bis (3-
(Trimethoxysilyl) propyl) ethylenediamine,
Examples thereof include polyoxyethylene propyl trialkoxy silane and polyethoxy dimethyl siloxane, and these can be used alone or in combination of two or more.

The content of the above-mentioned coupling agent is determined based on the resin 10
It is preferably 0.01 to 50 parts by weight, more preferably 0.05 to 20 parts by weight, based on 0 parts by weight.
If it exceeds 50 parts by weight, the storage stability tends to be poor, and if it is less than 0.01 part by weight, the effect of the coupling agent tends not to be sufficiently obtained.

The adhesive composition of the present invention comprises a thermoplastic resin,
It can be obtained by mixing and kneading a thermosetting resin, a filler and, if necessary, other components in an organic solvent. Mixing and kneading can be performed by appropriately combining ordinary dispersing machines such as a stirrer, a mill, a three-roll mill, and a ball mill.

The adhesive composition of the present invention can be used not only for improving workability in manufacturing a semiconductor device, improving the reliability of a semiconductor device, etc.
It is preferable to use a film-like adhesive from the viewpoint of making the most of its characteristic high adhesive strength.

As a method for obtaining the adhesive composition of the present invention as a film adhesive, for example, a method of forming a layer of the adhesive composition on a base film, heating and drying, and then removing the base material is used. Method and the like. The conditions for the heating and drying are not particularly limited as long as the solvent used is sufficiently volatilized, but the heating and drying are usually performed by heating at 60 ° C to 200 ° C for 0.1 to 90 minutes.

At this time, an adhesive film with a substrate may be used as a film support without removing the substrate. For the purpose of simplifying the semiconductor device manufacturing process, an integrated adhesive film obtained by laminating a dicing film on the obtained adhesive film may be used. The integrated adhesive film is preferably laminated on the back surface of the semiconductor wafer while heating the adhesive layer of the integrated adhesive film, diced, and then picked up and used as a semiconductor element with an adhesive film.

The organic solvent used in the production of the above-mentioned adhesive composition is not limited as long as it can dissolve, knead or disperse the material uniformly. For example, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl Sulfoxide, diethylene glycol dimethyl ether, toluene, benzene, xylene, methyl ethyl ketone, tetrahydrofuran, ethyl cellosolve, ethyl cellosolve acetate, butyl cellosolve, dioxane,
Cyclohexanone, ethyl acetate and the like can be mentioned.

When the adhesive composition of the present invention is used as a film adhesive, the thickness of the film (the thickness of the adhesive layer) is 10
１００100 μm is preferred. When the thickness of the film is 25 μm or less, it is preferable that the maximum particle diameter of the filler to be used is not more than the thickness of the film in terms of excellent smoothness of the film adhesive.

The substrate film used in the production of the adhesive film is not particularly limited as long as it can withstand the heating and drying conditions described above. For example, a polyester film, a polypropylene film, a polyethylene terephthalate film, a polyimide film, Examples include an etherimide film, a polyether naphthalate film, and a methylpentene film. These films may be used in combination of two or more kinds to form a multilayer film, and the surface of which may be treated with a release agent such as a silicone-based or silica-based release agent.

The adhesive composition of the present invention can suppress a significant decrease in the adhesive strength and fracture toughness due to the high filler loading when it is necessary to highly fill the filler for the purpose of imparting functionality. Reflow crack resistance can be maintained.

For example, when an adhesive material having high heat conductivity such as silver is highly filled as an adhesive material in a field where heat dissipation is important, the composition of the adhesive composition of the present invention has been difficult. Thus, an adhesive material that enables a high degree of compatibility between high thermal conductivity and high reflow crack resistance can be obtained. In this case, the thermal conductivity is preferably 1.0 W / mK or more.

The obtained adhesive composition or adhesive film is composed of a semiconductor element such as an IC and an LSI, a lead frame such as a 42 alloy lead frame and a copper lead frame, a plastic film such as a polyimide resin and an epoxy resin,
A material obtained by impregnating and curing a plastic such as a polyimide resin or an epoxy resin into a base material such as a glass non-woven fabric, and a joining with a support member such as a ceramic such as alumina can be used. That is, the adhesive composition of the present invention is sandwiched between the above-described semiconductor element and the supporting member, and the two are bonded by heating and pressing. The heating temperature is usually 100 to 300
C. for 0.1 to 300 seconds. After that, a semiconductor device (semiconductor package) is obtained through a wire bonding process and, if necessary, a sealing process using a sealing material.

The adhesive composition and the adhesive film of the present invention can be used as an adhesive material for an electronic component such as a semiconductor element and a supporting member such as a lead frame and an insulating support substrate, with good adhesive strength at hot and high temperature soldering at mounting. It has excellent reliability against the heat history of mounting, and can be suitably used as a die-bonding material for a lead-free semiconductor package. Further, a semiconductor device comprising a structure in which a semiconductor element and a support member are bonded using the adhesive composition or the adhesive film of the present invention,
Excellent reliability.

[0090]

The present invention will be described below by way of examples.

Examples 1 to 6 and Comparative Examples 1 to 3 Adhesive compositions of Examples 1 to 6 and Comparative Examples 1 to 3 using polyimides of the following A to C as shown in the composition tables of Tables 1 to 3. Was prepared.

<< Synthesis of Polyimide >> Polyimide A: A 2-liter 2-neck (4-liter) flask was placed in a 1-liter four-necked flask equipped with a stirrer, a nitrogen inlet tube, and a drying tube.
8.2 g of (4-aminophenoxy) phenyl) propane
(0.02 mol) and a diamine 72.0 represented by the following formula:
g (0.08 mol), N-methyl-
320 g of 2-pyrrolidone (NMP) was added to make a solution.

[0093]

Embedded image

The flask was transferred to a water bath and 52.0 g (0.1%) of 4,4 '-(4,4'-isopropylidenediphenoxy) -bis (phthalic anhydride) was stirred with vigorous stirring.
0 mol) was added in small portions. When the acid dianhydride was almost dissolved, the mixture was stirred slowly and reacted for 6 hours to obtain a polyamic acid solution.

Next, a distillation device was attached to the four-necked flask containing the polyamic acid solution, and 210 g of xylene was added.
Was added. 180 ° C under a nitrogen stream with vigorous stirring
The condensed water generated by imidation was distilled off azeotropically with xylene while heating on an oil bath. The reaction solution was poured into water, and the precipitated polymer was collected by filtration and dried to obtain polyimide A (weight average molecular weight 29,300).

Polyimide B: 1,2- (ethylene) bis (trimellitate dianhydride): 41.0 g (0.10 mol) and 2,2-bis (4- (4-aminophenoxy) phenyl) propane Using 0 g (0.10 mol) as a raw material, the others were synthesized in the same manner as polyimide A to obtain polyimide B (weight average molecular weight 126,000).

Polyimide C: 52.2 g of 1,10- (decamethylene) bis (trimellitate dianhydride)
10 mol) and 4,4'-diaminodiphenylmethane 1
Using 9.8 g (0.10 mol) as a raw material, the others were synthesized in the same manner as polyimide A to obtain polyimide C (weight average molecular weight 120,000).

[0098] In Tables 1 to 3, various symbols mean the following. PKHH: Tomo Kogyo Co., Ltd., phenoxy resin ESCN195: Sumitomo Chemical Co., Ltd., Cresol novolak type epoxy resin (epoxy equivalent: 200) Epicoat 834: Yuka Shell Epoxy Co., Ltd., bisphenol type epoxy resin (epoxy equivalent: 250) DME-100: Cyclohexane dimethanol type epoxy resin (epoxy equivalent: 155) manufactured by Shin Nippon Rikagaku Co., Ltd. BMI-M: Novolac bismaleimide resin manufactured by Mitsui Chemicals, Inc. L-10: manufactured by Asahi Chiba Co., Ltd. , Bisphenol F type cyanate resin XU-366: manufactured by Asahi Ciba Co., Ltd., phenyl-1- (1-
Methylethylidene) benzene-type cyanate resin

H-1: Meino Kasei Co., Ltd., phenol novolak (OH equivalent: 106) NH-7000: Nippon Kayaku Co., Ltd., naphthol novolak (OH equivalent: 140) Trisphenol TC: Honshu Chemical Co., Ltd. And trisphenol novolak (OH equivalent: 160) XL-225: manufactured by Mitsui Chemicals, Inc., xylylene-modified phenol novolak (OH equivalent: 175) 2P4MHZ: manufactured by Shikoku Chemicals, Curesol 2P4
MHZ

2MA-OK: an imidazole compound represented by the following formula

Embedded image

S520: 3-Glycidoxypropylmethyldimethoxysilane A-1310 manufactured by Chisso Corporation; 3-Isocyanatopropyltriethoxysilane A-1100 manufactured by Nippon Unicar Co., Ltd .: 3 manufactured by Nippon Unicar Co., Ltd. -Aminopropyltriethoxysilane A-189: Nippon Unicar Co., Ltd., 3-mercaptopropyltrimethoxysilane A-187: Nippon Unicar Co., Ltd., 3-glycidoxypropyltrimethoxysilane

SE-1: Tokuyama Co., Ltd., silica MFP-1110: Mitsui Kinzoku Kogyo Co., Ltd., copper powder C-0083P: Kemet Co., Ltd., silver powder E-03: Tokai Mineral Co., Ltd., silica I-ED: Silver powder made by Degussa Co., Ltd. TCG-1: Silver powder made by Tokuri Chemical Co., Ltd. D-1: Silver powder made by Degussa Co., Ltd. HP-P1: Mizushima Alloy Iron, Boron Nitride

FIG. 5 shows an SEM photograph of the shape of the filler.

DMAc: dimethylacetamide DMF: dimethylformamide NMP: N-methylpyrrolidone

[0105]

[Table 1]

[0106]

[Table 2]

[0107]

[Table 3]

This adhesive composition was applied on a substrate (polypropylene film) to a thickness of 30 to 50 μm,
For 10 minutes and then at 150 ° C. for 30 minutes, and then peeled from the substrate at room temperature to obtain a film-shaped adhesive composition.

<< Evaluation Test >> Examples 1 to 6, Comparative Examples 1 to 3
About the adhesive composition obtained in (1), the peel adhesive force was measured (Table 4).

[0110]

[Table 4]

(Example 7) 100 parts by weight of polyimide A, 20 parts by weight of Epicoat 834 as an epoxy resin, 8.4 parts by weight of NH-7000 as a curing agent, 0.15 parts by weight of 2P4MHZ as a curing accelerator, As a silane coupling agent, 1.0 part by weight of A-189 and a specified amount of a spherical or flaky silver filler (30 vol%) are stirred and mixed in a solvent DMAc, and then vacuum defoamed to obtain an adhesive composition. Was. This was applied on a base film polypropylene to a thickness of 30 μm, dried at 150 ° C. for 30 minutes, and the base film was peeled off to obtain an adhesive film containing a specified content of spherical or flaky filler. FIG. 4 shows the relationship between the average particle size of the silver filler and the peel strength in these adhesive films.

As is apparent from FIG. 4, the peel strength of the spherical filler is higher than that of the flaky filler, and the peel strength increases as the average particle diameter of the filler decreases.

The methods for measuring the peel adhesion and the chip warpage are as follows. <Measurement Method of Peel Adhesion Force> Using a push-pull gauge 11 (manufactured by Hitachi Chemical Co., Ltd.) as shown in FIG. 6, the measurement was performed at a pulling speed of 0.5 mm / sec and an angle of 17 °.
Here, the peel strength is a 90 ° peel strength, the value of which can be measured by an apparatus shown in FIG. The measurement sample was a film-shaped adhesive composition 12 of 5 mm × 5
mm, and this is sandwiched between a 5 × 5 mm silicon chip 13 and a die pad portion 14 of a copper lead frame, a 1000 g load is applied thereto, and the resultant is pressed at 250 ° C. for 5 seconds, and then 180 ° C. Then, heating was performed for 1 hour to cure the adhesive composition. The peel strength when heated on a hot plate 16 at 245 ° C. or 275 ° C. for 20 seconds was measured.

<Measurement of Thermal Diffusivity> The thermal diffusivity in the thickness direction of the adhesive film of Example 4 (curing conditions: 5 hours at 180 ° C., 20 μm) was measured, and the thermal conductivity was calculated. Thermal diffusivity is measured by Temperature Wave Analysis
is method (TWA method, reference: T. Hashimoto)
o, et al, Thermochim. Act
a, 304/305, 151, 1997;
Morikawa, et al, Polyme
r, 38, 21, pp. 5397, 1997,
T. Kurihara, et al, Inter
national Journal Thermo
physics, 18, 2, pp. 505-51
3, 1997), measurement temperature: 20 ° C., frequency: 1
The measurement was performed at 0 Hz. The thermal conductivity was calculated by the following mathematical formula. Table 5 shows the results.

Λ = α · Cp · ρ (where λ is thermal conductivity, α is thermal diffusivity, Cp is specific heat capacity, and ρ is density)

[0115]

[Table 5]

[0116]

The adhesive compositions according to the first to fourth aspects are resistant to high-temperature soldering heat history during mounting and have excellent adhesive strength. The adhesive compositions according to claims 5 and 6 exhibit the effects of the inventions according to claims 1 to 4, and are more excellent in adhesive strength. The adhesive composition according to the seventh aspect has the effects of the inventions according to the fifth and sixth aspects, is free from voids, and has excellent film-forming properties.

The adhesive composition according to the eighth aspect is the adhesive composition according to the seventh aspect.
The present invention has the effects of the described invention, and is further excellent in low-temperature adhesion, low stress, hydrolysis resistance, and reliability under high temperature and high humidity conditions. The adhesive composition according to the ninth aspect has the effects of the invention according to the seventh aspect, and is more excellent in low-temperature adhesiveness, low stress resistance, hydrolysis resistance, and reliability under high temperature and high humidity conditions. . The adhesive composition according to the tenth aspect has the effects of the inventions according to the fifth to ninth aspects, and is more excellent in adhesive strength. The adhesive compositions according to claims 11 to 13 exhibit the effects of the inventions according to claims 1 to 10, and are more excellent in adhesive strength.

The adhesive film according to claim 14 withstands high-temperature soldering heat history at the time of mounting, has excellent adhesive strength, low-temperature adhesion, low stress resistance, hydrolysis resistance, and reliability under high temperature and high humidity conditions. It is excellent in workability. Claim 1
The semiconductor device according to the fifth aspect provides high reliability under high temperature and high humidity conditions.

[Brief description of the drawings]

FIG. 1A is an SEM photograph of a representative spherical filler. (B) SEM photograph of a representative flaky filler.

FIG. 2 is a cross-sectional photograph of an adhesive film filled with flaky and spherical silver fillers, respectively.

FIG. 3 is a conceptual diagram of resin / filler interface peeling in an adhesive film filled with a flaky or spherical filler.

FIG. 4 is a graph showing the relationship between the type of silver filler and the peel strength of an adhesive film.

FIG. 5 is an SEM of a filler used in Examples and Comparative Examples.
It is a photograph.

FIG. 6 is a cross-sectional view illustrating a peel strength measuring method using a push-pull gauge.

[Explanation of symbols]

Reference Signs List 1 resin 2 flaky filler 3 crack 4 spherical filler 11 push-pull gauge 12 adhesive composition of the present invention 13 silicon chip 14 die pad part 15 support 16 hot plate 17 support

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09J 183/10 C09J 183/10 H01L 21/52 H01L 21/52 EF Term (Reference) 4J004 AA11 AA13 AA15 AB03 AB04 BA02 CA06 CC02 CE01 EA01 EA05 FA05 FA08 4J040 DH021 EB041 EB061 EB081 EC061 EC071 EC081 EC091 EC121 ED001 EE061 EG001 EH031 EJ011 EJ031 EK111 EL051 HA026 HA066 HA136 HA306 LA04 MA03 HA03 HA04 HA03 HD07 BA53 BB03 BB18

Claims (15)

[Claims] 1. An adhesive composition comprising a resin and a filler, wherein the filler has a spherical shape, and has an average particle diameter of 10 μm or less and a maximum particle diameter of 25 μm or less. . 2. The adhesive composition according to claim 1, wherein the filler is a metal filler or an inorganic filler. 3. The adhesive composition according to claim 2, wherein the filler is silver powder. 4. The adhesive composition according to claim 1, wherein the content of the filler is 1 to 50% by volume. 5. The adhesive composition according to claim 1, wherein the resin comprises a thermoplastic resin and a thermosetting resin. 6. The adhesive composition according to claim 1, wherein the resin comprises 100 parts by weight of a thermoplastic resin and 0.1 to 200 parts by weight of a thermosetting resin. 7. The adhesive composition according to claim 5, wherein the thermoplastic resin is a phenoxy resin or a polyimide resin. 8. A polyimide resin represented by the following general formula (1): (Wherein n is an integer of 2 to 20) or a tetracarboxylic dianhydride represented by the following formula (2): 8. A polyimide resin obtained by reacting a diamine with a tetracarboxylic dianhydride having a content of the tetracarboxylic dianhydride of 30 mol% or more of all tetracarboxylic dianhydrides represented by the formula: The adhesive composition according to claim. 9. The polyimide resin, wherein the content of the tetracarboxylic dianhydride of the general formula (1) or the tetracarboxylic dianhydride of the above formula (2) is at least 30 mol% of the total tetracarboxylic dianhydride. A tetracarboxylic dianhydride,
The following general formula (3) (Wherein Q ¹ and Q ² each independently represent an alkylene group having 1 to 5 carbon atoms or a phenylene group which may have a substituent, and Q ³ , Q ⁴ , Q ⁵ and Q ⁶ each independently represent Represents an alkyl group having 1 to 5 carbon atoms, a phenyl group or a phenoxy group, and m represents an integer of 1 to 50). The adhesive composition according to claim 7, which is a polyimide resin obtained by the above method. 10. The adhesive composition according to claim 5, wherein the thermosetting resin is an epoxy resin. 11. The adhesive composition according to claim 1, further comprising a coupling agent. 12. The adhesive composition according to claim 11, wherein the coupling agent is a silane coupling agent. 13. The composition according to claim 11, comprising 100 parts by weight of a thermoplastic resin and 0.01 to 50 parts by weight of a coupling agent.
Or the adhesive composition according to 12. 14. An adhesive film formed using the adhesive composition according to claim 1. 15. A semiconductor device having a structure in which a semiconductor element is bonded to a support member using the adhesive composition according to claim 1 or the adhesive film according to claim 14.