JP2002121530A - Adhesive film, its manufacturing method and semiconductor device having adhesive film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive film which bonds an electronic part such as a semiconductor element to a lead frame and an insulating support substrate and has high adhesion at a high temperature, low stress properties, and low temperature adhesion with or without a substrate, a method for manufacturing the film, and a semiconductor device using the film. SOLUTION: The method for manufacturing the adhesive film comprises steps of (I) mixing 100 pts.wt. polyimide resin, 0.01-50 pts.wt. silane coupling agent to be represented by the formula (wherein X is a vinyl, amino, glycidoxy, methacryloxy, mercapto or isocyanate group; n is 1-10; and R1 is a 1-10C alkyl group), 0-200 pts.wt. thermosetting resin, and 0-8,000 pts.wt. filler in an organic solvent, (II) coating the resulting mixed fluid on a substrate, and (III) heating and drying the coated film. A semiconductor element is obtained by bonding a support member having the above adhesive film to the back surface of a semiconductor. The semiconductor device has an electronic part to which the semiconductor element has been bonded.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive film, a method for producing the same, a support member with an adhesive film, a semiconductor element with an adhesive film, and a semiconductor device. More specifically, an adhesive material for an electronic component such as a semiconductor element and a support member such as a lead frame and an insulating support substrate, that is, an adhesive film suitable for die bonding and a method for producing the same, and the adhesive film are used. The present invention relates to a support member with an adhesive film, a semiconductor element with an adhesive film, and a semiconductor device.

[0002]

2. Description of the Related Art Au-Si eutectic alloys, solders, silver pastes, adhesive films and the like are conventionally known as adhesive materials for electronic components such as semiconductor elements and supporting members such as lead frames and insulating supporting substrates. ing. Among them, Au-S
Since i-eutectic alloys and solders have a large elastic modulus and are difficult to apply to large chips corresponding to high integration of semiconductor elements, silver pastes and adhesive films having a small elastic modulus are mainly used in recent years. .

The mainstream of silver paste is mainly composed of a thermosetting resin from the viewpoint of heat resistance, and the mainstream of adhesive film is mainly composed of thermoplastic resin from the viewpoint of film forming properties.

A semiconductor package in which an electronic component such as a semiconductor element and a supporting member such as a lead frame and an insulating support substrate are bonded by using the above-mentioned adhesive material and sealed with a resin sealing material is soldered to a mounting substrate. Implemented in At this time, the entire package is exposed to a high temperature of about 240 ° C., which is the melting temperature of the solder.

In recent years, along with environmental conservation measures on a global scale,
Legal regulations on lead have been increasingly tightened, mainly in Europe. Accordingly, lead-free solder is being promoted for mounting solder, and in the field where high reliability is required, Sn-Ag solder is the most powerful alternative to the current Sn-Pb solder.

When the mounting solder is switched to Sn-Ag,
Since the melting point is higher than that of the Sn—Pb system, the maximum temperature of the reflow furnace is higher by 20 ° C. to 30 ° C. than the current system. Therefore, an adhesive material for die bonding is required to be a material that can withstand an increase in reflow temperature and has higher reliability than before.

In addition, copper lead frames (which are easily oxidized by heat) and insulating supporting substrates (which have low thermal conductivity), which have begun to be used in recent years, both have large thermal expansion coefficients.
When the adhesive film is easily warped at the time of heat bonding and is used for bonding to such a support substrate, a material which can be bonded at low stress and at low temperature is strongly desired.

A silver paste containing a thermosetting resin as a main component must be in a liquid state, so that it is difficult to achieve both reliability and low stress in terms of material design.

In the case of an adhesive film containing 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 damage to the chip such as oxidation of a lead frame is reduced. be able to. However, an adhesive film using a thermoplastic resin having a low melting point has a problem in that it cannot withstand heat treatment after die bonding, such as a wire bonding step and a mounting step, because of low adhesive strength when heated.

[0010] An adhesive film using both a thermoplastic resin and a thermosetting resin has also been proposed. Such an adhesive film uses a thermoplastic resin having a low melting point to reduce the bonding temperature, and by using a thermosetting resin, has a high adhesive force when heated and 240 ° C. when mounted. It can withstand the heat treatment before and after soldering.

However, when the reflow temperature is increased from about 240 ° C. to about 270 ° C. in accordance with the lead-free mounting solder, the composition of the adhesive film is reduced to the above-mentioned thermoplastic resin and thermosetting resin having a low melting point. It is becoming difficult to secure high reliability while maintaining low stress and low-temperature adhesiveness only by the combination of.

[0012]

The invention according to claims 1 to 6 is an adhesive film for bonding an electronic component such as a semiconductor element to a lead frame or an insulating support substrate. An object of the present invention is to provide an adhesive film having low stress and low-temperature adhesiveness, which can be suitably used for a copper lead frame or an insulating support substrate. The invention according to claim 7 provides an adhesive film that can withstand the soldering heat history of about 270 ° C. required at the time of lead-free solder mounting, in addition to the above-mentioned problems.

According to the eighth and ninth aspects of the present invention, in addition to the above objects, a thick film can be obtained.
The present invention provides an adhesive film with a base material which is also suitable for use in LOC and LOC. The tenth aspect of the present invention provides an adhesive film for a semiconductor used in the manufacture of the semiconductor device, which does not require a step of temporarily stretching a film and equipment used in the process.

An eleventh aspect of the present invention is to provide a method for producing an adhesive film which can produce the adhesive film which solves the above-mentioned problems, in which variations in film thickness and characteristics can be extremely reduced and which can be produced with high productivity. is there. Claim 12
The described invention is to provide a method for producing the above-mentioned adhesive film which can produce the adhesive film which solves the above-mentioned problem with extremely small variations in film thickness and characteristics and can be produced with high productivity.

According to a thirteenth aspect of the present invention, there is provided the above-mentioned supporting member with an adhesive film which imparts durability and heat resistance to a semiconductor device using the same. Claim 1
The invention described in 4 provides the above-described semiconductor element with an adhesive film which imparts durability and heat resistance to a semiconductor device using the semiconductor element. The invention according to claim 15 provides a semiconductor device having excellent durability and heat resistance.

[0016]

The present invention provides (A) a polyimide resin and (B) a compound represented by the following general formula (1):

Embedded image (Wherein, X represents a vinyl group, an amino group, a glycidoxy group, a methacryloxy group, a mercapto group, an organic group selected from the group consisting of isocyanate groups, n is an integer of 1 to 10, each of the three R ¹ Independently represents an alkyl group having 1 to 10 carbon atoms).

The present invention also relates to the adhesive film, wherein the adhesive film further contains (C) a thermosetting resin. In the present invention, the adhesive film preferably comprises (D)
The present invention relates to the above adhesive film containing a filler.

Further, the present invention provides the following general formula (2)

Embedded image (Wherein, n represents an integer of 2 to 20) or the following formula (3)

Embedded image The above adhesive film, which is 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 the tetracarboxylic dianhydrides represented by About.

Further, the present invention provides a polyimide resin wherein the content of the tetracarboxylic dianhydride represented by the above general formula (2) or (3) is 30% of the total tetracarboxylic dianhydride.
Mol% or more of tetracarboxylic dianhydride and the following general formula (4)

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), wherein the siloxane-based diamine represented by the formula: (5)

Embedded image (Wherein Q ⁷ , Q ⁸ and Q ⁹ each independently have 1 to 10 carbon atoms)
Represents an alkylene group, and p represents an integer of 1 to 10).
The present invention relates to the above adhesive film, which is a polyimide resin obtained by reacting a diamine containing at least mol%.

The present invention also relates to the above adhesive film, wherein X in the above general formula (1) is a glycidoxy group or a mercapto group. The present invention also relates to the adhesive film, wherein the adhesive film is for a lead-free solder-mounted semiconductor device.

The present invention also relates to an adhesive film with a substrate, wherein the above-mentioned adhesive film is laminated on one or both sides of a substrate, directly or via another layer. Further, the present invention relates to the adhesive film with a substrate, wherein the substrate is a heat-resistant film. The present invention also relates to an adhesive film for a semiconductor integrated by laminating the adhesive film and a dicing tape.

The present invention also relates to (I) a polyimide resin 1
With respect to 00 parts by weight, 0.01 to 50 parts by weight of the silane coupling agent of the above general formula (1) and 0 to 50 parts by weight of the thermosetting resin.
200 parts by weight of a filler and 0 to 8000 parts by weight of a filler are mixed in an organic solvent to form a layer of the mixed solution on a substrate, and (III) a step of heating and drying, the method comprising the step of heating and drying. The present invention relates to a method for producing a film. The present invention also relates to a method for producing the above-mentioned adhesive film, which further comprises the step of (IV) removing the substrate.

[0023] The present invention also relates to a support member with an adhesive film obtained by bonding the adhesive film on a support member. Further, the present invention relates to a semiconductor device with an adhesive film formed by bonding the adhesive film to the back surface of the semiconductor device. The present invention also relates to a semiconductor device having a semiconductor element and an electronic component in which the semiconductor element is adhered to the support member using the adhesive film.

[0024]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The adhesive film of the present invention comprises a polyimide resin and the following general formula (1):

Embedded image (Wherein, X represents a vinyl group, an amino group, a glycidoxy group, a methacryloxy group, a mercapto group, an organic group selected from the group consisting of isocyanate groups, n is an integer of 1 to 10, each of the three R ¹ Independently represents an alkyl group having 1 to 10 carbon atoms), the adhesive film comprising a silane coupling agent represented by the following formula: Excellent humidity resistance and heat resistance can be imparted to the obtained semiconductor device.

In this respect, the adhesive film of the present invention is effective in suppressing reflow cracks and peeling in a reflow step at a higher temperature than before. Since such characteristics are required when electronic components are mounted using lead-free solder such as Sn-Ag solder, the adhesive film of the present invention is most suitable for lead-free solder mounting.

As R ¹ in the above general formula (1), for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isopropyl And a methyl group, an ethyl group and a pentyl group are preferable in that they are easily available.

X in the above general formula (1) includes, for example, organic functional groups such as vinyl group, amino group, glycidoxy group, methacryloxy group, mercapto group, and isocyanate group. Conditions required for the film, for example, amino groups, glycidoxy groups, in that it can impart excellent resistance to high reflow temperatures, etc.
Mercapto groups and isocyanate groups are preferred, and glycidoxy groups and mercapto groups are more preferred.

In the general formula (1), n is an integer of 1 to 10, preferably 1 to 5, and more preferably 2 to 4.
When n exceeds 10, the adhesive strength becomes weak.

Examples of such a 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-ureidopropyltriethoxysilane, N-
(1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine, N, N'-bis (3-
(Trimethoxysilyl) propyl) ethylenediamine,
Polyoxyethylene propyl trialkoxysilane, polyethoxydimethylsiloxane, etc.
-Aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and 3-mercaptopropyltrimethoxysilane are preferred, and 3-glycidoxypropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane are preferred. Methoxysilane is more preferred. These silane coupling agents can be used alone or in combination of two or more.

The content of the silane coupling agent is 0.01 to 50 parts by weight, preferably 0.05 to 20 parts by weight, based on 100 parts by weight of the polyimide resin.
0.5 to 50% in that characteristics suitable for lead-free solder mounting can be provided.
10 parts by weight are highly preferred. If the amount is less than 0.01 part by weight, the effect of improving the adhesive strength during heating cannot be obtained, and if it exceeds 50 parts by weight, the storage stability deteriorates.

Examples of the tetracarboxylic dianhydride that can be used include pyromellitic dianhydride, 3,3 ', 4,4'-
Diphenyltetracarboxylic dianhydride, 2,2 ', 3
3'-diphenyltetracarboxylic dianhydride, 2,2-
Bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride 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)-
Octo (7) -ene, 2,3,5,6-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, the following general formula (2)

Embedded image (Where n is an integer of 2 to 20) and a tetracarboxylic dianhydride represented by the following formula (3):

Embedded image The tetracarboxylic dianhydride represented by the above general formula (2) 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 (3) is preferable from the viewpoint of being excellent. 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 (2) is preferably at least 30 mol% based on all the tetracarboxylic dianhydrides, and the adhesive film has excellent low-temperature adhesion. From the viewpoint, 50% or more is more preferable,
70% or more is very preferable.

The tetracarboxylic dianhydride of the general formula (2) 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 (3) is preferably at least 30 mol% based on all the tetracarboxylic dianhydrides, and the adhesive film is excellent in the moisture resistance reliability. Is more preferably 50% or more, and 70% or more.
% Or more is very preferable.

The starting diamines of the above polyimide resin include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7 Aliphatic diamines such as -diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, o- (or m-, p-) phenylenediamine,
3,3 '-(or 3,4'-) diaminodiphenyl ether, 4,4'-diaminodiphenyl 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'
-) Diaminodiphenyl sulfone, 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-methylethylidene)) bisaniline, 3,4 ′-(1,4-phenylenebis (1-methylethylidene)) bisaniline,
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, bis (4- (4-aminophenoxy) phenyl) Unsaturated bond-containing diamines such as sulfones and the following general formula (4)

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), a siloxane-based diamine represented by the following general formula (5):

Embedded image (However, Q ⁷ , Q ⁸ and Q ⁹ are alkylene having 1 to 10 carbon atoms, and p represents an integer of 1 to 10), and the like. 4) and the diamine represented by the general formula (5),
It is preferable because low stress property and low-temperature adhesive property can be imparted to the adhesive film. These diamines can be used alone or in combination of two or more.

Examples of the siloxane-based diamine of the general formula (4) include 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, 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 and the like Diamine and the following formula

Embedded image And the like, and these can be used alone or in combination of two or more.

The content of the siloxane-based diamine of the general formula (4) 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%, the properties of low stress, low temperature adhesion and low moisture absorption tend not to be exhibited.

Examples of the aliphatic ether diamine represented by the general formula (5) include, for example,

Embedded image And the like, and these can be used alone or in combination of two or more.

The content of the aliphatic ether diamine represented by the general formula (5) 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 low stress properties and low temperature adhesive properties cannot be exhibited.

The polyimide resin used 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 an equimolar or almost equimolar manner, and the addition order of each component is arbitrary.

In this case, first, a polyamic acid is generated, and further heated to cause dehydration and ring closure to form 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, polyamic acid 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 produced polyamic acid to dehydration and ring closure by heat treatment or chemical treatment. The reaction temperature in the case of the 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, for example, acid anhydrides such as acetic anhydride, propionic anhydride and benzoic anhydride, and carbodiimide compounds such as dicyclohexylcarbodiimide are used as a 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 the tetracarboxylic dianhydride.

The adhesive film of the present invention may contain a thermosetting resin or a filler in addition to the polyimide resin and the silane coupling agent of the general formula (1).

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, thermosetting resin synthesized from cyclopentadiene, thermosetting resin obtained by trimerizing aromatic dicyanamide, and the like.
Among them, epoxy resin, cyanate resin, and bismaleimide resin are preferable because they can have excellent adhesive strength at high temperatures. In addition, these thermosetting resins can be used alone or in combination of two or more.

When the above-mentioned thermosetting resin is used, its amount is preferably at most 200 parts by weight, more preferably at most 100 parts by weight, based on 100 parts by weight of the polyimide resin. If it exceeds 200 parts by weight, the film-forming properties tend to be poor. The lower limit is not particularly limited, but is preferably 0.1 part by weight or more.

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 anhydrides, dicyandiamide, and organic acids. Examples include dihydrazide, boron trifluoride amine complex, imidazoles, and tertiary amines.

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

The amount of the curing agent used is preferably 0 to 200 parts by weight based on 100 parts by weight of the thermosetting resin. The amount of the curing accelerator used is 100 parts of the thermosetting resin.
0 to 50 parts by weight is preferable with respect to parts by weight.

The epoxy resin, which is one of preferred thermosetting resins, is more preferably one containing at least two epoxy groups in the molecule, and glycidyl ether type of phenol 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, and 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
Glycidyl ether of novolak resin, glycidyl ether of naphthalene resin, glycidyl ether of trifunctional (or tetrafunctional), glycidyl ether of dicyclopentadiene phenol resin, glycidyl ester of dimer acid, trifunctional (or tetrafunctional) Glycidylamine,
Glycidylamine of naphthalene resin and the like are 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 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, dicyclopentadienephenol novolak resin, xylylene-modified phenol novolak resin, naphthol novolak resin, trisphenol novolak resin, tetrakisphenol novolak resin, bisphenol A novolak resin, poly-p-
Vinyl phenol resin, phenol aralkyl resin and the like can be mentioned.

The cyanate resin, which is one of preferred thermosetting resins, is, for example, 2,2'-bis (4
-Cyanate phenyl) 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-dicyclopentanedienene adduct, cyanated novolak, bis (4-cyanatophenyl) thioether,
Bis (4-cyanatophenyl) ether, resorcinol dicyanate, 1,1,1-tris (4-cyanatophenyl) ethane, 2-phenyl-2- (4-cyanatophenyl) isopropylidene, and the like, 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 a phenol novolak is used as a cocatalyst. be able to.

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 (6) to (9) And the like.

[0057]

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 ² 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)

[0058]

Embedded image (Where Y is O, CH ₂ , CF ₂ , SO ₂ , S, CO, C
(CH ₃ ) ₂ or C (CF ₃ ) ₂ , wherein four R ³ are each independently hydrogen, a lower alkyl group, a lower alkoxy group, fluorine,
Represents chlorine or bromine, and two Ds represent a dicarboxylic acid residue having an ethylenically unsaturated double bond)

[0059]

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.)

[0060]

Embedded image (Wherein, two R ⁴ each independently represent a divalent hydrocarbon group, four R ⁵ each independently represent a monovalent hydrocarbon group, and two Ds each independently represent an ethylenically unsaturated double bond. 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.

The bismaleimide resin represented by the general formula (6) includes, for example, 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 (7) include 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, 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 amount of the radical polymerization agent used 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,
Octanoyl peroxide, acetyl peroxide, dicumyl peroxide, cumene hydroperoxide, azobisisobutyronitrile and the like can be mentioned.

Examples of the filler 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 ceramics; and organic fillers such as carbon and rubber-based fillers. And the like.

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 or thixotropy to the adhesive film, a non-metallic inorganic filler is added for the purpose of imparting a low thermal expansion property and low moisture absorption to the adhesive film, and an organic filler is bonded. It is added for the purpose of imparting toughness to the film. These metal fillers, inorganic fillers or organic fillers,
They can be used alone or in combination of two or more. Mixing and kneading in the case of using a filler can be performed by appropriately combining ordinary dispersers such as a stirrer, a grinder, a three-roll mill, and a ball mill.

When a filler is contained, the amount is preferably 8,000 parts by weight or less, more preferably 4,000 parts by weight or less, based on 100 parts by weight of the polyimide resin. The lower limit is not particularly limited, but is usually 5 parts by weight or more. If it exceeds 8000 parts by weight, the adhesiveness tends to decrease.

Next, a method for producing the adhesive film of the present invention will be described. The adhesive film of the present invention can be used alone or as a substrate-attached adhesive film in which the above-mentioned adhesive film is laminated directly or through another layer on one or both sides of a substrate.

The substrate used in the production of the adhesive film is
There is no particular limitation as long as it can withstand the heating and drying conditions during the production of the adhesive film. For example, there are a polyester film, a polypropylene film, a polyethylene terephthalate film, a polyimide film, a polyetherimide film, a polyethernaphthalate 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.

When the adhesive film with a substrate is used as it is as an adhesive for a semiconductor device, the substrate is preferably a heat-resistant film. Examples of the heat-resistant film include a polyimide film, a polyetherimide film, a methylpentene film, and a polyethernaphthalate film.

Further, the adhesive film of the present invention can be made into an adhesive film for a semiconductor in which the adhesive film and the dicing film are integrated by, for example, laminating the adhesive film on the adhesive layer surface of the dicing tape in advance. This adhesive film for a semiconductor can be used for the manufacture of a semiconductor device by, for example, laminating the back surface of a wafer, dicing the wafer and the adhesive film, and then picking up as a semiconductor element with an adhesive film.

The adhesive film is prepared by mixing (I) a polyimide resin, a silane coupling agent, and, if necessary, a thermosetting resin, a filler and other additives in an organic solvent, and Form a layer of the mixture, (II
It can be produced by (I) heating and drying, and (IV) removing the substrate.

Further, the adhesive film with a base material is the same as the above (I)
The steps (I) to (III) may be performed without performing the step V). The production of an adhesive film with a base material having an adhesive film layer laminated on both sides is carried out by the above (I) to (III)
After performing the step (4), a layer of the mixture is formed on the unpainted surface, and (V) heating and drying can be carried out.

In the adhesive film with a substrate, another layer may be interposed between the substrate and the adhesive film for the purpose of improving workability and the like. Examples of such a layer include a release layer for increasing the releasability between the substrate and the adhesive film, and an adhesive layer for increasing the adhesion strength between the substrate and the adhesive film.

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

The heating and drying conditions in the production of the adhesive film may be any conditions under which the used solvent is sufficiently evaporated. The drying temperature is preferably in the range of 60C to 200C, and the drying time is preferably in the range of 0.1 to 90 minutes.

The obtained adhesive film is made of a semiconductor element such as an IC or an LSI, a lead frame such as a 42 alloy lead frame or a copper lead frame, a plastic film such as a polyimide resin or an epoxy resin, or a base material such as a glass non-woven fabric. It can be used for bonding with a support member such as a material impregnated and cured with a plastic such as an epoxy resin or a ceramic such as alumina. That is, the adhesive film of the present invention is sandwiched between the above-described semiconductor element and the supporting member, and the two are bonded by heating and pressing. The heating temperature is preferably from 100 to 300 ° C, and the heating time is from 0 to 300 ° C.
Preferably from 1 to 300 seconds. After that, a semiconductor device (semiconductor package) is obtained through a wire bonding step and a sealing step using a sealing material.

[0079]

The present invention will be described below with reference to examples. However, the present invention is not limited to this embodiment.

Examples 1 to 8 and Comparative Examples 1 to 4 << Synthesis of Polyimide and Preparation of Varnish >> Polyimides of the following A to D were synthesized, and Examples 1 to 8 and The varnishes of Comparative Examples 1 to 4 were prepared.

[Polyimide A] Stirrer, nitrogen inlet tube,
In a 1 liter four-necked flask equipped with a drying tube,
20.5 g (0.05 mol) of 2-bis (4- (4-aminophenoxy) phenyl) propane and the following formula

Embedded image Was added and N-methyl-2-pyrrolidone (NM) was added under a nitrogen stream.
P) 250 g was added to make a solution. Transfer the flask to a water bath and, with vigorous stirring, 1,10- (decamethylene)
52.2 g of bis (trimellitate dianhydride) (0.10
Mol) was added in small portions. When the acid dianhydride was almost dissolved, the reaction was carried out for 6 hours while stirring slowly to obtain a polyamic acid solution.

Next, a distillation apparatus was attached to the four-necked flask containing the polyamic acid solution, and 160 g of xylene was added. The condensed water generated by the imidization was azeotropically distilled off together with xylene with vigorous stirring on a 180 ° C. oil bath under a nitrogen stream. The reaction solution was poured into water, and the precipitated polymer was separated by filtration and dried to obtain polyimide A.

[Polyimide B] Stirrer, nitrogen inlet tube,
In a 1 liter four-necked flask equipped with a drying tube,
8.2 g (0.02 mol) of 2-bis (4- (4-aminophenoxy) phenyl) propane and the following formula

Embedded image Was added and N-methyl-2-pyrrolidone (NM) was added under nitrogen stream.
P) was added to make a solution. The flask was transferred to a water bath, and 52.0 g (0.10 mol) of 4,4 '-(4,4'-isopropylidenediphenoxy) -bis (phthalic anhydride) was added little by little with vigorous stirring. . When the acid dianhydride almost dissolves, 6
The reaction was carried out for a time to obtain a polyamic acid solution.

Next, a distillation apparatus was attached to the four-necked flask containing the polyamic acid solution, and 210 g of xylene was added. Condensed water generated by imidization was azeotropically distilled off with xylene while heating on a 180 ° C. oil bath under a nitrogen stream with vigorous stirring. The reaction solution was poured into water, and the precipitated polymer was separated by filtration and dried to obtain polyimide B.

[Polyimide C] Stirrer, nitrogen inlet tube,
In a 1 liter four-necked flask equipped with a drying tube,
41.0 g (0.10 mol) of 2-bis (4- (4-aminophenoxy) phenyl) propane was added, and 250 g of N-methyl-2-pyrrolidone (NMP) was added under a nitrogen stream to form a solution. The flask was transferred to a water bath, and 41.0 g (0.10 mol) of 1,2- (ethylene) bis (trimellitate dianhydride) was added little by little with vigorous stirring. When the acid dianhydride was almost dissolved, the reaction was carried out for 6 hours while slowly stirring to obtain a polyamic acid solution.

Next, a distillation apparatus was attached to the four-necked flask containing the polyamic acid solution, and 220 g of xylene was added. The condensed water generated by the imidization was azeotropically distilled off together with xylene with vigorous stirring on a 180 ° C. oil bath under a nitrogen stream. The reaction solution was poured into water, and the precipitated polymer was separated by filtration and dried to obtain polyimide C.

[Polyimide D] Stirrer, nitrogen inlet tube,
In a 1 liter four-necked flask equipped with a drying tube,
19.8 g of 4'-diaminodiphenylmethane (0.10 g)
Mol), and 215 g of N-methyl-2-pyrrolidone (NMP) was added under a nitrogen stream to form a solution. Transfer the flask to a water bath and, with vigorous stirring, 52.2 g of 1,10- (decamethylene) bis (trimellitate dianhydride)
(0.10 mol) was added in small portions. When the acid dianhydride is almost dissolved, react for 6 hours while stirring slowly.
A polyamic acid solution was obtained.

Next, a distillation apparatus was attached to the four-necked flask containing the polyamic acid solution, and 140 g of xylene was added.
Was added. The condensed water generated by the imidization was azeotropically distilled off together with xylene with vigorous stirring on a 180 ° C. oil bath under a nitrogen stream. The reaction solution was poured into water, and the precipitated polymer was separated by filtration and dried to obtain polyimide D.

In Tables 1 to 3, various symbols mean the following. S510: 3-Glycidoxypropyltrimethoxysilane manufactured by Chisso Co., Ltd. S520: 3-Glycidoxypropylmethyldimethoxysilane manufactured by Chisso Co., Ltd. A-1310: 3-Isocyanatopropyltrimethoxysilane manufactured by Nippon Unicar Co., Ltd. Ethoxysilane A-1100: manufactured by Nippon Unicar Co., Ltd., 3-aminopropyltriethoxysilane A-189: manufactured by Nippon Unicar Co., Ltd., 3-mercaptopropyltrimethoxysilane A-187: manufactured by Nippon Unicar Co., Ltd., 3 -Glycidoxypropyltrimethoxysilane

ESCN195: Cresol novolak type epoxy resin manufactured by Sumitomo Chemical Co., Ltd. (epoxy equivalent: 20)
0) Epicoat 834: Bisphenol type epoxy resin (epoxy equivalent 250) manufactured by Yuka Shell Epoxy Co., Ltd. DME-100: Cyclohexane dimethanol type epoxy resin (epoxy equivalent 155) manufactured by Shin Nippon Chemical Co., Ltd. BPO-60E: Produced by Shin-Nippon Rikagaku Co., Ltd., propylene oxide adduct bisphenol type epoxy resin (epoxy equivalent: 314) BMI-M: manufactured by Mitsui Chemicals, Inc., novolac type bismaleimide resin L-10: manufactured by Asahi Ciba, bisphenol F -Type cyanate resin XU-366: phenyl 1- (1-methylethylidene) benzene-type cyanate resin manufactured by Asahi Ciba Co., Ltd.

H-1: manufactured by Meiwa Kasei Co., Ltd., phenol novolak (OH equivalent: 106) NH-7000: manufactured by Nippon Kayaku Co., Ltd., naphthol novolak (OH equivalent: 140) Trisphenol TC: manufactured by Honshu Chemical Co., Ltd. XL-225, manufactured by Mitsui Chemicals, Inc., xylylene-modified phenol novolak (OH equivalent: 175)

DMAc: dimethylacetamide DMF: dimethylformamide NMP: N-methylpyrrolidone

2MA-OK: an imidazole compound represented by the formula (10), manufactured by Shikoku Chemical Industry Co., Ltd. 2P4MHZ: an imidazole compound represented by the formula (11) manufactured by Shikoku Chemical Industry Co., Ltd.

[0094]

Embedded image

[0095]

[Table 1]

[0096]

[Table 2]

[0097]

[Table 3]

<Manufacture of Adhesive Film>
It was applied on a substrate (polypropylene film) to a thickness of ５０50 μm, heated at 80 ° C. for 10 minutes, subsequently at 150 ° C. for 30 minutes, and then peeled off from the substrate at room temperature to obtain an adhesive film.

<Evaluation Tests> Examples 1 to 8 and Comparative Examples 1 to 4
For the adhesive film obtained in the above, the peel adhesive force was measured, and a chip when a silicon chip was bonded to a lead frame using the adhesive films obtained in Examples 1 to 8 and Comparative Examples 1 to 4 Warpage was measured (Tables 4 to 6)

[0100]

[Table 4]

[0101]

[Table 5]

[0102]

[Table 6]

<Measurement Method of Peel Adhesive Force> The adhesive film was cut into a size of 5 mm × 5 mm, and this was sandwiched between a 5 × 5 mm silicon chip and a copper lead frame. Alternatively, after pressure bonding at 250 ° C. for 5 seconds, the adhesive film was cured by heating at 180 ° C. for 1 hour. The peel strength at the time of heating at 245 ° C. or 275 ° C. for 20 seconds was measured with a push-pull gauge.

<Measurement method of chip warpage>
It was cut into a size of 0 mm x 10 mm, sandwiched between a copper lead frame and a silicon chip of a size of 10 mm x 10 mm, applied with a load of 1000 g, crimped at 250 ° C for 20 seconds, and then cooled to room temperature. This was returned, and a 10 mm diagonal scan was performed using a surface roughness meter, and the maximum height (μm) from the base line was determined to determine chip warpage.

[0105]

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 hot adhesive strength and soldering temperature of about 270 ° C. during mounting. It has high solder heat resistance to withstand application heat history, and also has excellent low stress properties and low temperature adhesion. Therefore, it can be suitably used as a die bond material for a copper lead frame and an insulating support substrate.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09J 7/02 C09J 7/02 Z 183/04 183/04 183/07 183/07 H01L 21/52 H01L 21 / 52 E (72) Inventor Shinji Takeda 1500 Oji, Shimodate-shi, Ibaraki Pref.Hitachi Kasei Kogyo Co., Ltd. F-term (reference) JL11A 4J004 AA11 AB05 BA02 CA04 CA06 CC02 EA03 EA05 FA05 4J040 CA122 DF002 EB042 EB062 EB112 EB132 EC042 EC052 EC062 EC072 ED112 EF002 EF272 EH031 EH032 EK032 EK082 GA01 HA02 HA20 HA20 GA20 GA04 GA20 LA09 MA04 MB05 NA20 PA30 4J043 PA01 PA04 PA08 QB15 QB26 RA34 RA35 SA06 SA42 SA47 SB02 TA22 TB02 UA022 UA0 32 UA052 UA062 UA121 UA122 UA131 UA132 UA151 UA152 UA252 UA262 UA332 UA712 UA761 UA771 UA781 UB011 UB012 UB021 UB022 UB051 UB061 UB121 UB122 UB131 UB132 UB141 UB151 UB152 UB172 UB281 UB301 UB302 UB351 UB352 XA13 YA05 YA06 YA08 ZA12 ZA46 ZB11 ZB50 5F047 AA11 AA13 AA17 BA21 BB03 BB16 BB18

Claims (15)

[Claims] (A) a polyimide resin and (B) the following general formula (1): (Wherein, X represents a vinyl group, an amino group, a glycidoxy group, a methacryloxy group, a mercapto group, an organic group selected from the group consisting of isocyanate groups, n is an integer of 1 to 10, each of the three R ¹ Independently represents an alkyl group having 1 to 10 carbon atoms). 2. The adhesive film according to claim 1, further comprising (C) a thermosetting resin. 3. The adhesive film according to claim 1, further comprising (D) a filler. 4. The polyimide resin is represented by the following general formula (2): (Wherein, n represents an integer of 2 to 20) or the following formula (3): 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: 4. The adhesive film according to any one of claims 1 to 3. 5. A polyimide resin wherein the content of the tetracarboxylic dianhydride represented by the general formula (2) or (3) is 30 mol% or more of the total tetracarboxylic dianhydride. Acid dianhydride and the following general formula (4) (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), wherein the siloxane-based diamine represented by the formula: (5) (Wherein Q ⁷ , Q ⁸ and Q ⁹ each independently have 1 to 10 carbon atoms)
Represents an alkylene group, and p represents an integer of 1 to 10).
The adhesive film according to any one of claims 1 to 3, which is a polyimide resin obtained by reacting with a diamine containing at least mol%. 6. The adhesive film according to claim 1, wherein in the silane coupling agent, X in the general formula (1) is a glycidoxy group or a mercapto group. 7. The adhesive film according to claim 1, wherein the adhesive film is for a lead-free solder-mounted semiconductor device. 8. An adhesive film with a substrate, wherein the adhesive film according to any one of claims 1 to 7 is laminated on one or both surfaces of the substrate directly or via another layer. 9. The adhesive film with a substrate according to claim 8, wherein the substrate is a heat-resistant film. 10. An adhesive film for semiconductor obtained by laminating the adhesive film according to claim 1 and a dicing tape. 11. (I) 0.01 to 50 parts by weight of a silane coupling agent represented by the general formula (1), 0 to 200 parts by weight of a thermosetting resin, and 100 parts by weight of a polyimide resin. 0 to 8000 parts by weight of a filler are mixed in an organic solvent, and (II) a layer of the mixed solution is formed on a substrate,
(III) A method for producing an adhesive film including a step of heating and drying. 12. The method for producing an adhesive film according to claim 11, further comprising (IV) a step of removing the substrate. 13. A support member with an adhesive film, wherein the adhesive film according to claim 1 is adhered on the support member. 14. A semiconductor device with an adhesive film, wherein the adhesive film according to claim 1 is adhered to the back surface of the semiconductor device. 15. A semiconductor device comprising a semiconductor element and an electronic component in which a support member and a semiconductor element are bonded using the adhesive film according to claim 1.