JP2001303015A - Adhesive film, method for producing the same and method for bonding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an adhesive film capable of carrying out bonding at a lower temperature than that of a conventional adhesive film for die bonding and to provide a method for producing the adhesive film and a method for bonding. SOLUTION: This adhesive film comprises (A) an oxetane compound and (B) a curing agent. The method for producing the adhesive film comprises mixing respective components containing one or more selected from (C) a polyimide resin, (D) an electroconductive filler and/or (E) an insulating filler and (F) a solvent and the oxetane compound (A) and the curing agent (B), preparing a pasty or a varnishlike mixture, applying the resultant mixture onto a base film, heating and drying the applied mixture and forming the adhesive film. The method for bonding comprises sandwiching the adhesive film between a semiconductor element and a supporting member, carrying out the thermocompression bonding and bonding the semiconductor element to the supporting member.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive film used as a bonding material between a semiconductor element such as an IC or an LSI and a supporting member such as a lead frame or an insulating support substrate, that is, an adhesive film used as a die bonding material, a method of manufacturing the same, and an adhesive film About the method.

[0002]

2. Description of the Related Art Conventionally, an Au-Si eutectic alloy, solder, silver paste, or the like has been used for joining an IC or LSI to a lead frame. The Au-Si eutectic alloy has high heat resistance and high moisture resistance, but has a large elasticity, so that it is easily broken when applied to a large chip, and is expensive.
Although solder is inexpensive, it has poor heat resistance, and its elastic modulus is as high as Au-Si eutectic alloy, making it difficult to apply it to large chips. On the other hand, silver paste is inexpensive, has high moisture resistance, has the lowest elastic modulus among the above three, and has heat resistance applicable to a thermocompression bonding wire bonder at 350 ° C. It is the mainstream material for bonding frames. However, in recent years, as ICs and LSIs have become highly integrated and the chips have become larger,
When the lead frame is bonded to the C or LSI with the silver paste, it is difficult to spread the silver paste over the entire surface of the chip and apply it.

[0003] MICROELECTRONIC M
ANUFACTURING AND TESTING (October 1985) reported an adhesive film for die bonding in which a conductive resin was filled in a thermoplastic resin. In this method, the temperature is raised to around the melting point of the thermoplastic resin and pressure bonding is performed.

The present inventors have previously proposed an adhesive film using a specific polyimide resin and an adhesive film for die bonding containing a conductive filler or an inorganic filler (Japanese Patent Application Laid-Open No. 6-145639, JP-A-7-228697, JP-A-10-330723, etc.).

[0005]

The adhesive film reported in the above-mentioned microelectronic manufacturing and testing can reduce the bonding temperature by using a thermoplastic resin having a low melting point.
Although damage to the chip, such as oxidation of the lead frame, is small, the adhesive strength at the time of heat is low, so that it cannot withstand heat treatment (for example, wire bonding, a sealing step, etc.) after die bonding. When a thermoplastic resin having a high melting point that can withstand heat treatment is used, the bonding temperature increases, and the lead frame is easily damaged by oxidation or the like.

[0006] The adhesive film proposed by the present inventors can be bonded at a relatively low temperature and has good adhesive strength at hot time. However, recently used copper lead frames (susceptible to oxidation) and insulative supporting substrates with low thermal conductivity (due to large thermal expansion, easily warped during thermal bonding)
An adhesive film that can be adhered at a lower temperature is strongly desired for bonding to a substrate. The present invention provides a die-bonding adhesive film, a method for producing the same, and a method for bonding, wherein the bonding temperature at the time of bonding can be lower than that of a conventional die-bonding adhesive film.

[0007]

According to the first aspect of the present invention,
It is an adhesive film containing an oxetane compound (A) and a curing agent (B), and has excellent low-temperature adhesiveness, can be suitably used for 42 alloy lead frames and copper lead frames, and can also be suitably used for insulating support substrates. An adhesive film is provided. The invention according to claim 2 is the adhesive film according to claim 1, further comprising a polyimide resin (C), and the invention according to claim 3 is such that the polyimide resin (C) is represented by the general formula (1). Is 70 mol% of the total tetracarboxylic dianhydride (C ′).
The adhesive film according to claim 2, which is a polyimide resin (C) obtained by reacting the above tetracarboxylic dianhydride with a diamine (C ").

Embedded image (However, n is an integer of 2 to 20.) The inventions of claims 2 and 3 provide an adhesive film having excellent shear adhesion in addition to the effect of the invention of claim 1.

The invention according to claim 4 is the adhesive film according to any one of claims 1 to 3, further comprising a conductive filler (D) and / or an insulating filler (E). The invention according to claim 5 is that the conductive filler (D) 0 to 100 parts by weight of the oxetane compound (A) is used.
8000 parts by weight and / or insulating filler (E) 0
The adhesive film according to any one of claims 1 to 4, comprising 8000 parts by weight. The inventions according to claims 4 and 5 provide an adhesive film excellent in adhesion between substrates having different thermal expansion coefficients in addition to the effects of the inventions according to claims 1 to 3. According to a sixth aspect of the present invention, the curing agent (B) is a curing agent (B ′) for ring-opening polymerization of the oxetane compound (A), and comprises a cationically polymerizable catalyst, an anionic polymerizable catalyst, and a latent cationic polymerization initiator. The adhesive film according to any one of claims 1 to 5, wherein the adhesive film is at least one selected from an agent and a latent anionic polymerizable catalyst. The invention according to claim 7 is the adhesive film according to claim 6, wherein the curing agent (B ′) is a latent cationic polymerization initiator (B1). The inventions of claims 6 and 7 provide an adhesive film having excellent storage stability in addition to the effects of the inventions of claims 1 to 5. According to an eighth aspect of the present invention, the curing agent (B) is a curing agent (B ″) that undergoes an addition reaction with the oxetane compound (A), and is a bifunctional or more carboxylic acid, a difunctional or more polythiol, or a difunctional or more. The adhesive film according to any one of claims 1 to 5, wherein the adhesive film is at least one selected from carboxylic acid anhydrides and difunctional or higher phenols. ”)
Is the phenolic compound (B2).

The inventions of claims 8 and 9 are the first to fifth aspects of the invention.
An object of the present invention is to provide an adhesive film that can provide high adhesion reliability in addition to the effects of the described invention. The invention according to claim 10 is selected from the polyimide resin (C), the conductive filler (D) and / or the insulating filler (E), and the solvent (F) according to any one of claims 1 to 9. 1
The above and the respective components including the oxetane compound (A) and the curing agent (B) are mixed to prepare a paste-like or varnish-like mixture, which is applied on a base film, and heated and dried to form an adhesive film. A method for producing an adhesive film, which provides a method for producing an adhesive film. According to an eleventh aspect of the present invention, the adhesive film according to any one of the first to ninth aspects is sandwiched between the semiconductor element and the support member, and the semiconductor element and the support member are heat-pressed. It is a bonding method. According to a twelfth aspect of the present invention, there is provided the method for bonding a semiconductor element and a support member according to the eleventh aspect, wherein the adhesive film is irradiated with actinic rays. The invention according to claims 11 and 12 is the invention according to claims 1 to
9. A method for bonding a semiconductor element and a support member using the adhesive film according to 9.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, an adhesive film according to the present invention, a production method thereof and an adhesion method will be described. The oxetane compound (A) in the present invention is not particularly limited as long as it has an oxetane ring in the molecule, and any compound can be used. Of these, oxetane compounds having 1 to 4 oxetane rings in the molecule are preferred because cracks are less likely to occur after bonding.

Examples of the compound having one oxetane ring include a compound represented by the following general formula (2).

[0012]

Embedded image

In the general formula (2), R ¹ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group or a butyl group; a fluoroalkyl group having 1 to 6 carbon atoms; Group, aryl group, furyl group or thienyl group. R ² represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group or a butyl group, a 1-propenyl group, a 2-propenyl group, a 2-methyl-1-propenyl group, C2-C6 alkenyl such as methyl-2-propenyl, 1-butenyl, 2-butenyl or 3-butenyl, phenyl, benzyl, fluorobenzyl, methoxybenzyl or phenoxyethyl; Having 2 to 6 carbon atoms such as a group having an aromatic ring, an ethylcarbonyl group, a propylcarbonyl group or a butylcarbonyl group, and an alkoxy group having 2 to 6 carbon atoms such as an ethoxycarbonyl group, a propoxycarbonyl group or a butoxycarbonyl group. Carbonyl group, ethylcarbamoyl group, propylcarbamoyl group, butylcarbamoyl group or Is like N- alkylcarbamoyl group having 2 to 6 carbon atoms such as pentyl carbamoyl group.

Next, examples of the compound having two oxetane rings include a compound represented by the following general formula (3).

[0015]

Embedded image

In the general formula (3), R ¹ is the same group as in the general formula (2). R ³ represents, for example, a linear or branched alkylene group such as an ethylene group, a propylene group or a butylene group, and poly (ethyleneoxy)
Linear or branched unsaturated hydrocarbon groups such as linear or branched poly (alkyleneoxy) groups such as a group or poly (propyleneoxy) group, propenylene group, methylpropenylene group or butenylene group, carbonyl group, Examples include an alkylene group including a carbonyl group, an alkylene group including a carboxyl group, and an alkylene group including a carbamoyl group.

Further, R ³ is represented by the following general formulas (4) to (1)
It is also a polyvalent group selected from the groups represented by 5).

[0018]

Embedded image

In the general formula (4), R ⁴ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group or a butyl group, a methoxy group, an ethoxy group, a propoxy group or a butoxy group. And a halogen atom such as a chlorine atom or a bromine atom, a nitro group, a cyano group, a mercapto group, a lower alkylcarboxyl group, a carboxyl group, or a carbamoyl group.

[0020]

Embedded image

In the general formula (5), R ⁵ represents an oxygen atom, a sulfur atom, a methylene group,

Embedded image It is NH, SO, SO ₂ , C (CF ₃ ) ₂ or C (CH ₃ ) ₂ .

[0022]

Embedded image

In the general formula (6), R ⁶ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group or a butyl group, a methoxy group, an ethoxy group, a propoxy group or a butoxy group. A C1-C4 alkoxy group such as a group, a halogen atom such as a chlorine atom or a bromine atom, a nitro group, a cyano group, a mercapto group, a lower alkylcarboxyl group, a carboxyl group, or a carbamoyl group.

[0024]

Embedded image

In the general formula (7), R ⁷ is an oxygen atom, a sulfur atom, a methylene group,

Embedded image NH, SO, SO ₂ , C (CF ₃ ) ₂ or C
(CH ₃ ) ₂ , C (C ₆ H ₅ ) (CH ₃ ) and C (C ₆ H ₅ ) ₂ .

[0026]

Embedded image

In the general formulas (8) and (9),
R ⁸ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group or a butyl group, or an alkoxy group having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group or a butoxy group. , A halogen atom such as a chlorine atom or a bromine atom, a nitro group, a cyano group, a mercapto group,
It is a lower alkyl carboxyl group, a carboxyl group or a carbamoyl group. Further, R ⁸ represents 2 to 2 on the naphthalene ring.
Four may be replaced.

[0028]

Embedded image However, in the general formulas (14) and (15), n is 0 to 10, and a mixture of compounds having different numerical values may be used.

Preferred examples of the compound having two oxetane rings other than the above-mentioned compounds include a compound represented by the following formula (16). In the general formula (16), R ¹ is the same group as in the general formula (2).

[0030]

Embedded image

Examples of the compound having 3 to 4 oxetane rings include a compound represented by the following general formula (17).

[0032]

Embedded image

In the general formula (17), R ¹ is the same group as in the general formula (2), and m is 3 or 4. R ⁹ is, for example, a group having 1 to 1 carbon atoms such as a group represented by the following general formulas (18), (19) and (20).
And a branched poly (alkyleneoxy) group such as a group represented by the following general formula (21).

[0034]

Embedded image (In the general formula (18), R ¹⁰ is a lower alkyl group such as a methyl group, an ethyl group or a propyl group.)

[0035]

Embedded image

[0036]

Embedded image

[0037]

Embedded image (In the general formula (21), n is an integer of 1 to 10.)

Preferred specific examples of the oxetane compound used in the present invention include the following compounds.

[0039]

Embedded image

[0040]

Embedded image

[0041]

Embedded image

[0042]

Embedded image However, R is a methyl group or an ethyl group

In addition, besides these, the molecular weight is 1,000.
A compound having 1 to 4 oxetane rings having a relatively high molecular weight of about 5,000 to about 5,000 is also included. Further, as a polymer containing oxetane, a polymer having an oxetane ring in a side chain (for example, K. Sato, A. Kameyama and T. Nishikubo,
Macromolecules, 25, 1198 (1992)) can be used in the same manner. In the present invention, two or more oxetane compounds can be used in combination.

Further, in the adhesive film of the present invention, an epoxy compound may be used in combination with the oxetane compound (A). The epoxy compound is not particularly limited as long as it has an epoxy group in the molecule. Specific examples of epoxy compounds include bisphenol A, bisphenol AD, bisphenol S, bisphenol F or a condensate of halogenated bisphenol A and epichlorohydrin, glycidyl ether of phenol novolak resin, glycidyl ether of cresol novolak resin, and glycidyl ether of bisphenol A novolak resin. And the like. The amount of the epoxy compound used is not particularly limited, but is 0.01 to 2 parts by weight per 100 parts by weight of the oxetane compound (A).
00 parts by weight.

In order to improve the adhesive strength, a silane coupling agent, a titanium coupling agent, a nonionic surfactant, a fluorine surfactant, a silicone additive and the like are appropriately added to the oxetane compound (A). You may.

As the curing agent (B) which is a component of the present invention, any compound capable of subjecting the oxetane compound (A) to ring-opening polymerization and / or any compound capable of undergoing an addition reaction with the oxetane compound can be used. Polymerizable catalyst, anionic polymerizable catalyst, latent cationic polymerization initiator,
Latent anionic polymerizable catalyst, difunctional or higher carboxylic acid,
A bifunctional or higher polythiol, a difunctional or higher carboxylic anhydride, a difunctional or higher phenol compound, or the like is preferably used. These can be used alone or in combination of two or more. The amount of the curing agent (B ′) used for ring-opening polymerization of the oxetane compound (A), such as a cationic polymerizable catalyst, an anionic polymerizable catalyst, a latent cationic polymerization initiator, a latent anionic polymerizable catalyst, etc. A) 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight, per 100 parts by weight. If the amount of the curing agent (B ′) for ring-opening polymerization of the oxetane compound (A) is less than 0.01 part by weight, the curability tends to be insufficient, and if it exceeds 20 parts by weight, the adhesive film is stored before use. Stability tends to decrease.

Further, difunctional or higher carboxylic acid, difunctional or higher polythiol, difunctional or higher carboxylic anhydride,
The amount of the curing agent (B ″) that undergoes an addition reaction with the oxetane compound (A) such as a phenol compound having more than one functionality is preferably 2 to 500 parts by weight, more preferably 50 to 300 parts by weight, per 100 parts by weight of the oxetane compound (A). If the amount of the curing agent (B ″) that undergoes an addition reaction with the oxetane compound (A) is less than 2 parts by weight, the curability tends to be insufficient, and if it exceeds 500 parts by weight, the adhesive film before use is used. Storage stability tends to decrease.

Among these, the latent cationic polymerization initiator (B1) described later as a curing agent (B ') for ring-opening polymerization of the oxetane compound (A) can provide an adhesive film having excellent storage stability. As a curing agent (B ″) that undergoes an addition reaction with the oxetane compound (A), a phenol compound (B2) described below is preferable because an adhesive film having high connection reliability can be obtained. (B1) and the phenol compound (B2) can be used alone or simultaneously.

The cationically polymerizable catalyst forms a cationically polymerizable catalyst by irradiating and / or heating with actinic rays, and catalyzes a curing reaction by ring-opening cationic polymerization of the oxetane ring in the oxetane compound (A). is there. Among these, the so-called latent cationic polymerization initiator (B1), which forms a cationically polymerizable catalyst by irradiating and / or heating with actinic rays, is blended with an adhesive film containing an oxetane compound (A). As long as it is left at room temperature, it is stable for a long period of time, but as soon as the latch is removed by the action of actinic rays and / or heat, a cationically polymerizable catalyst can be formed and the curing reaction can be started and accelerated. it can.

Specific examples of the latent cationic polymerization initiator (B1) include various onium salts as shown below. For example, a quaternary ammonium salt represented by the following general formula (22), a phosphonium salt represented by the following general formula (23) and the following general formula (24):
And the sulfonium salt represented by (25) or (26).

[0051]

Embedded image

(However, in the general formula (22), R ^{1 to} R ⁴
Is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 3 to 12 carbon atoms, an aryl group, an alkaryl group, an alkanol group having 1 to 20 carbon atoms, or a cycloalkyl having 5 to 10 carbon atoms, respectively. And may be the same or different from each other, and may or may not have a substituent. Two of R ^{1 to} R ⁴ may be bonded to each other to form a heterocyclic ring having N, P, O or S as a hetero atom. Further, X is BF ₄ , PF ₆ ,
AsF ₆ , SbF ₆ , SbCl ₆ , (C ₆ F ₅ ) ₄ B,
_{SbF 5 (OH), HSO 4} , p-CH 3 C 6 H 4 SO
₃ , a counter ion selected from the group consisting of HCO ₃ , H ₂ PO ₄ , CH ₃ COO and a halogen atom, ie, 1
Represents a valent anion. )

[0053]

Embedded image

(However, in the general formula (23), R ^{1 to} R ⁴
And X each represent R in the general formula (22).
Is the same as ¹ to R ⁴ and X. )

[0055]

Embedded image

(However, in the general formula (24), R ^{1 to} R ³
And X each represent R in the general formula (22).
^{1 to} R ³ and X are the same, and two of R ^{1 to} R ³ may be bonded to each other to form a heterocyclic ring having N, P, O or S as a hetero atom. )

[0057]

Embedded image

(However, in the general formula (25), R ¹ , R ²
And X each represent R in the general formula (22).
It is the same as ¹ , R ² and X, and R ¹ and R ² may combine with each other to form a heterocyclic ring having N, P, O or S as a hetero atom. Ar represents an aryl group which may or may not have a substituent. )

[0059]

Embedded image

(However, in the general formula (26), R ^{1 to} R ⁴
And X each represent R in the general formula (22).
Is the same as ¹ to R ⁴ and X. Ar is the same as Ar in the general formula (25). )

In the formulas (22) to (26), the alkyl group having 1 to 20 carbon atoms as R ¹ , R ² , R ³ or R ⁴ has a substituent. And straight-chain or branched alkyl groups which may or may not have, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group , N-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, n-heptyl, n-octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl , A hexadecyl group, an octadecyl group, a nonadecyl group and an eicosyl group. As the alkenyl group having 3 to 12 carbon atoms as R ¹ , R ² , R ³ or R ⁴ , a linear or branched alkenyl group which may or may not have a substituent. And, for example, an n-propenyl group,
n-butenyl group, sec-butenyl group, tert-butenyl group, n-pentenyl group, sec-pentenyl group, hexenyl group, n-heptenyl group, sec-heptenyl group, octenyl group, nonenyl group, decenyl group, uncenyl group, etc. Is mentioned.

The aryl group as R ¹ , R ² , R ³ or R ⁴ includes, for example, a substituted or unsubstituted phenyl group, naphthyl group or anthracene group, and a phenyl group is particularly preferred. As the alkaryl group as R ¹ , R ² , R ³ or R ⁴ , the alkaryl group described above includes the alkyl group having 1 to 20 carbon atoms and the aryl group. The alkanol group having 1 to 20 carbon atoms as R ¹ , R ² , R ³ or R ⁴ may be a straight-chain or branched alkanol group which may or may not have a substituent. And, for example, an ethanol group, an n-propanol group, an isopropanol group, n
-Butanol group, sec-butanol group, tert-butanol group, n-pentanol group, sec-pentanol group, 1-hexanol group, 1-heptanol group, 1-
Octanol group, 1-nonanol group, 1-decanol group, 1-undecanol group, 1-dodecanol group, 1-
Tridecanol group, 1-tetradecanol group, 1-pentadecanol group, 1-hexadecanol group, 1-heptadecanol group, 1-octadecanol group, 1-nonadecanol group, 1-eicosanol group and the like. Can be Further, as the cycloalkyl group having 5 to 10 carbon atoms as R ¹ , R ² , R ³ or R ⁴ ,
A cycloalkyl group which may or may not have a substituent and which may have a branch is included, and examples thereof include a cyclopentyl group, a 2-methylcyclopentyl group, a cyclohexyl group and a cycloheptyl group. On the other hand, in the general formulas (25) and (26), examples of the aryl group which may or may not have a substituent as Ar include a substituted or unsubstituted phenyl group and a naphthyl group.

In the general formulas (22) to (26), examples of the substituent include a halogen atom such as a fluorine atom, a methyl group, an ethyl group, an n-propyl group,
Isopropyl group, n-butyl group, sec-butyl group, t
tert-butyl group, n-pentyl group, isopentyl group,
Neopentyl group, n-hexyl group, isohexyl group, n
1 carbon atom such as heptyl group and n-octyl group
-8 alkyl groups, cyclopentyl groups, cyclohexyl groups, cycloheptyl groups and other cycloalkyl groups having 5 to 7 carbon atoms, or methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec- Alkoxy groups having 1 to 8 carbon atoms such as butoxy group, tert-butoxy group, pentyloxy group, isopentyloxy group, sec-pentyloxy group, hexyloxy group, isohexyloxy group, heptyloxy group and octyloxy group Is mentioned.

The quaternary ammonium salt represented by the general formula (22) includes, for example, tetrabutylammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphate, tetrabutylammonium hydrogen sulfate, tetraethylammonium tetrafluoroborate, tetraethylammonium p-toluenesulfonate, N, N-dimethyl-N-benzylanilinium antimony hexafluoride, N, N-dimethyl-N-benzylanilinium boron tetrafluoride,
N-dimethyl-N-benzylpyridinium antimony hexafluoride, N, N-diethyl-N-benzyltrifluoromethanesulfonic acid, N, N-dimethyl-N- (4-methoxybenzyl) pyridinium antimony hexafluoride, N,
N-diethyl-N- (4-methoxybenzyl) toluidinium antimony hexafluoride and the like can be mentioned.
Specific examples of the phosphonium salt represented by the general formula (23) include, for example, ethyltriphenylphosphonium antimony hexafluoride and tetrabutylphosphonium antimony hexafluoride.

Examples of the sulfonium salt represented by formula (24), (25) or (26) include, for example, triphenylsulfonium boron tetrafluoride, triphenylsulfonium antimony hexafluoride, and triphenylsulfonium hexafluoride. Arsenic arsenide, tri (4-methoxyphenyl) sulfonium arsenic hexafluoride, diphenyl (4-phenylthiophenyl) sulfonium arsenic hexafluoride, Adekaopton SP-150 (manufactured by Asahi Denka Kogyo KK, counter ion: PF ₆ ), adekaopton SP-170 (manufactured by Asahi Denka Kogyo KK, counter ion: SbF ₆ ), Adeka Opton CP-66 (manufactured by Asahi Denka Kogyo KK, counter ion: SbF)
₆ ), Adeka Opton CP-77 (manufactured by Asahi Denka Kogyo KK, counter ion: SbF ₆ ), Sun-Aid SI-60L
(Manufactured by Sanshin Chemical Co., Ltd., counter ion: SbF ₆ ), Sun Aid SI-80L (manufactured by San Shin Chemical Co., Ltd., counter ion: SbF ₆ ), San Aid SI-100L (manufactured by San Shin Chemical Co., Ltd., Ion: SbF ₆ ), San-Aid SI-150 (manufactured by Sanshin Chemical Industry Co., Ltd., counter ion: S
bF ₆ ), CYRACURE UVI-6974 (manufactured by Union Carbide Co., counter ion: SbF ₆ ), CYR
ACURE UVI-6990 (manufactured by Union Carbide, counter ion: PF ₆ ), UVI-508 (manufactured by General Electric), UVI-509 (general
Electric), FC-508 (Minnesota Mining and Manufacturing), FC
-509 (manufactured by Minnesota Mining and Manufacturing Co., Ltd.), CD-1010 (manufactured by Sartomer Co., Ltd.), CD-1011 (manufactured by Sartomer Co., Ltd.) and CI series (manufactured by Nippon Soda Co., Ltd., counter ion: PF _6, Sb
F ₆ ).

Further, as the latent cationic polymerization initiator (B1), a diazonium salt represented by the following general formula (27) and an iodonium salt represented by the following general formula (28) can also be used.

[0067]

Embedded image

(In the general formula (27), Ar and X are the same as Ar in the general formula (25) and X in the general formula (22), respectively.)

[0069]

Embedded image

[0070] (wherein, in the general formula (28), X is the same as X in the general formula (22), R ⁵ and R
⁶ is an aryl group which may be the same or different, and may or may not have a substituent. )

Here, the general formulas (27) and (2)
In 8), specific examples of the aryl group which may or may not have a substituent as Ar, and the monovalent anion as X are as described above. Examples of the aryl group which may or may not have a substituent as R ⁵ and R ⁶ include, for example, a substituted or unsubstituted phenyl group, a naphthyl group and an anthracene group. Is preferred. As the substituent, for example,
Halogen atom such as fluorine atom, chlorine atom, bromine atom, iodine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, te
rt-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, isohexyl group, n-
1 to 1 carbon atoms such as a heptyl group and an n-octyl group
8 alkyl groups, cyclopentyl groups, cyclohexyl groups, cycloheptyl groups and other cycloalkyl groups having 5 to 7 carbon atoms, or methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy. Group, a tert-butoxy group, a pentyloxy group, an isopentyloxy group, a sec-pentyloxy group, a hexyloxy group, an isohexyloxy group, a heptyloxy group, and an octyloxy group. No.

Specific examples of the diazonium salt represented by the general formula (27) include AM manufactured by American Can Inc.
ERICURE (counter ion: BF ₄ ) and ULTRASET (counter ion: BF ₄ , P
F ₆ ). Specific examples of the iodonium salt represented by the general formula (28) include:
Arsenic diphenyliodonium hexafluoride, arsenic di-4-chlorophenyliodonium hexafluoride, arsenic di-4-bromophenyliodonium hexafluoride, arsenic phenyl (4-methoxyphenyl) iodonium hexafluoride, general
Electric Co., Ltd. of UVE series, Minnesota Mining and Manufacturing Co., Ltd. of the FC series, Toshiba Silicone Co., Ltd. of UV-9310C (counter ion: SbF ₆₎ and Rhone Poulenc of Photoini
tiator 2074 (counter ion: (C ₆ F ₅ ) ₄ B) and the like.

The amount of the latent cationic polymerization initiator (B1) to be used is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, per 100 parts by weight of the oxetane compound (A). If the amount of the latent cationic polymerization initiator (B1) is less than 0.01 part by weight, the curability tends to be insufficient, and if it exceeds 20 parts by weight, the storage stability of the adhesive film before use tends to decrease. is there.

As the phenol compound (B2), a phenol resin having two or more phenol structures in its molecule can be used. Examples of such a resin include a phenol novolak resin, a cresol novolak resin, a bisphenol A novolak resin, and a poly-novolak resin.
p-Vinylphenol, phenol aralkyl resin and the like. The amount of the phenol resin used is preferably 2 to 500 parts by weight, more preferably 50 to 300 parts by weight, per 100 parts by weight of the oxetane compound (A). If the amount of the phenol compound (B2) is less than 2 parts by weight, the curability tends to be insufficient, and if it exceeds 500 parts by weight, the storage stability of the adhesive film before use tends to decrease.

When a curing agent (B ″) that undergoes an addition reaction with the oxetane compound (A) is used as the curing agent (B) of the present invention, a curing accelerator may be further added. As the curing accelerator, imidazole is used. , Dicyandiamide derivative, dicarboxylic dihydrazide, triphenylphosphine, tetraalkylammonium halides (alkyl = C ₁
To C ₈ , halide = F, Cl, Br, I), tetraalkylphosphonium halides (alkyl = C _{1 to} C ₈ , halide = F, Cl, Br, I), tetraphenylphosphonium halides (halide = F, Cl, Br, I),
Benzyltrialkylammonium halides (alkyl = C ₁ -C ₈ , halide = F, Cl, Br, I), 2-
Ethyl-4-methylimidazole-tetraphenyl borate, 1,8-diazabicyclo (5,4,0) undecene-7-tetraphenyl borate, and the like can be mentioned. Further, the latent cationic polymerization initiator (B1) can also be used. When a curing accelerator is used, the amount thereof is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the oxetane compound.
The amount of the latent cationic polymerization initiator (B1) used is 0.01
When the amount is less than 20 parts by weight, a substantial addition effect tends not to be observed, and when the amount exceeds 20 parts by weight, the storage stability of the adhesive film before use tends to decrease.

The polyimide resin (C) in the present invention comprises:
There is no particular limitation as long as it has an imide bond in the molecule, and any resin can be used. The number average molecular weight of the polyimide resin (C) in the present invention is 5,000.
３００300,000, preferably 10,000
More preferably, it is set to １５０150,000. If the number average molecular weight is less than 5,000, the mechanical strength tends to decrease when bonded using an adhesive film.
If it exceeds 000, the film formability tends to decrease. The number average molecular weight is a value measured by a gel permeation chromatography method and converted using a standard polystyrene calibration curve. Among these, polyimide resin (C) synthesized from tetracarboxylic dianhydride (C ′) and diamine (C ″) shown below has excellent shear adhesive strength when used in an adhesive film. Is preferred.

The tetracarboxylic dianhydride (C ′) of the general formula (1) used as a raw material of the polyimide resin (C) of the present invention includes 1,2- (ethylene ) Bis (trimellitate dianhydride), 1,3-
(Trimethylene) bis (trimellitate dianhydride),
1,4- (tetramethylene) bis (trimellitate dianhydride), 1,5- (pentamethylene) bis (trimellitate dianhydride), and when n is 6 to 20, 1,6- (hexamethylene) bis ( Trimellitate dianhydride), 1,7
-(Heptamethylene) bis (trimellitate dianhydride), 1,8- (octamethylene) bis (trimellitate dianhydride), 1,9- (nonamethylene) bis (trimellitate dianhydride), 1,10- (decamethylene ) Bis (trimellitate dianhydride), 1,12- (dodecamethylene) bis (trimellitate dianhydride), 1,16-
(Hexadecamethylene) bistrimellitate dianhydride,
1,18- (octadecamethylene) bis (trimellitate dianhydride) and the like may be used in combination.

The above tetracarboxylic dianhydride (C ′)
Can be synthesized from trimellitic anhydride monochloride and the corresponding diol. On the other hand, if the content of the tetracarboxylic dianhydride (C ′) is 70 mol% or less with respect to all the tetracarboxylic dianhydrides, the temperature at the time of bonding the adhesive film is undesirably high.

The tetracarboxylic anhydride usable together with the tetracarboxylic dianhydride (C ′) of the general formula (1) includes, for example, pyromellitic dianhydride, 3,3 ′,
4,4'-diphenyltetracarboxylic dianhydride, 2,
2 ', 3,3'-diphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane Dianhydride, 1,1-bis (2,3-
Dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride,
Bis (3,4-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, bis (3 4-dicarboxyphenyl) ether dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 3,4,3 ′, 4′-benzophenonetetracarboxylic dianhydride, 2,3 2 ', 3-benzophenonetetracarboxylic dianhydride, 2,3,3',
4'-benzophenonetetracarboxylic dianhydride, 1,
2,5,6-naphthalenetetracarboxylic dianhydride,
2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,4,5-naphthalene-tetracarboxylic dianhydride, 1,4,5,8-naphthalene-tetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4
5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,
4,5,8-tetracarboxylic dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride,
Thiophene-2,3,4,5-tetracarboxylic dianhydride, 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride, 3,4,3', 4'-biphenyltetracarboxylic dianhydride Anhydride, 2,3,2 ', 3'-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) dimethylsilane dianhydride, bis (3,4-dicarboxyphenyl) methylphenylsilane Dianhydride, bis (3,4-dicarboxyphenyl) diphenylsilane dianhydride, 1,4-bis (3,4-dicarboxyphenyldimethylsilyl) benzene dianhydride, 1,3-bis (3,4 -Dicarboxyphenyl) -1,1,3,3-
Tetramethyldicyclohexane dianhydride, p-phenylbis (trimellitic acid monoester 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 anhydride) sulfone, bicyclo -(2,2,2) -oct (8) -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 anhydride),
1,3-bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimellitic anhydride), 5-
(2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride,
There are tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride and the like, and two or more kinds may be used as a mixture.

The diamine (C ″) used as another raw material of the polyimide resin (C) of the present invention includes:
1,2-diaminoethane, 1,3-diaminopropane,
1,4-diaminobutane, 1,5-diaminopentane,
Fats such as 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane Group diamine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3 '
-Diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane,
3,3'-diaminodiphenyldifluoromethane, 3,
4'-diaminodiphenyldifluoromethane, 4,4 '
-Diaminodiphenyldifluoromethane, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfide, 3,
4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide,

3,3′-diaminodiphenyl ketone,
3,4'-diaminodiphenyl ketone, 4,4'-diaminodiphenyl ketone, 2,2-bis (3-aminophenyl) propane, 2,2 '-(3,4'-diaminodiphenyl) propane, 2,2 -Bis (4-aminophenyl) propane, 2,2-bis (3-aminophenyl) hexafluoropropane, 2,2- (3,4'-diaminodiphenyl) hexafluoropropane, 2,2-bis (4- Aminophenyl) hexafluoropropane, 1,
3-bis (3-aminophenoxy) benzene, 1,4-
Bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 3,3 '-(1,
4-phenylenebis (1-methylethylidene)) bisaniline, 3,4 '-(1,4-phenylenebis (1-methylethylidene)) bisaniline, 4,4'-(1,4
-Phenylenebis (1-methylethylidene)) bisaniline, 2,2-bis (4- (3-aminophenoxy) phenyl) propane, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 2, 2-bis (4-
(3-aminophenoxy) phenyl) hexafluoropropane, 2,2-bis (4- (4-aminophenoxy)
Phenyl) hexafluoropropane, bis (4- (3-
Aminophenoxy) phenyl) sulfide, bis (4-
(4-aminophenoxy) phenyl) sulfide, bis (4- (3-aminophenoxy) phenyl) sulfone,
Aromatic diamines such as bis (4- (4-aminophenoxy) phenyl) sulfone can be given.

The condensation reaction between tetracarboxylic dianhydride (C ′) and diamine (C ″) can be carried out in an organic solvent. In this case, tetracarboxylic dianhydride (C ′) 1
The diamine (C ″) is preferably used in an amount of 0.5 to 2 molar equivalents, more preferably 0.75 to 1.5 molar equivalents, and more preferably 0.8 to 1.2 molar equivalents. Diamine (C ″) is preferably 0.5 to 1 mole equivalent of tetracarboxylic dianhydride (C ′).
If the molar equivalent is less than or greater than 2.0, the number average molecular weight of the polyimide resin (C) tends to be low. The order of addition of the tetracarboxylic dianhydride (C ′), the diamine (C ″) and the organic solvent is arbitrary. Examples of the organic solvent used include dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, Hexamethylphosphorylamide, m-cresol, o-chlorophenol and the like.

The reaction temperature is 80 ° C. or lower, preferably 0 to 5
0 ° C. As the reaction proceeds, the viscosity of the reaction solution gradually increases. In this case, polyamic acid, which is a precursor of polyimide, is generated.

The polyimide can be obtained by subjecting the above reaction product (polyamic acid) to dehydration and ring closure. Dehydration ring closure is 1
The heat treatment can be performed at 20 ° C. to 250 ° C. or a chemical method. In the case of a method of performing heat treatment at 120 ° C. to 250 ° C., the heat treatment is preferably performed while removing water generated in the dehydration reaction outside the system. At this time, water may be azeotropically removed using benzene, toluene, xylene, or the like. In the present invention, the polyimide resin (C) is a general term for polyimide and its precursor. Polyimide precursors include, in addition to polyamic acid, polyamic acid partially imidized.

In the case of ring closure by dehydration by a chemical method, acetic anhydride, propionic anhydride, acid anhydrides of benzoic anhydride, carbodiimide compounds such as dicyclohexylcarbodiimide and the like are used as a ring closing 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 tetracarboxylic dianhydride (C ′) 1
It is preferable to use 1 to 8 moles with respect to the moles.

When the polyimide resin (C) is used, it is preferably used in an amount of 0.01 to 10000 parts by weight based on 100 parts by weight of the oxetane compound (A).
More preferably, 0.5 to 5000 parts by weight is used.
Most preferably, it is used in an amount of up to 1000 parts by weight. If the amount of the polyimide resin (C) used is less than 0.01 part by weight, the substantial addition effect tends not to be exhibited, and
When the amount is more than the weight part, the film-forming property tends to decrease.

The conductive filler (D) used in the present invention comprises:
It is added for the purpose of imparting conductivity to the adhesive film, and examples thereof include conductive metal powders such as gold powder, silver powder, copper powder, and stainless steel powder, and carbon black. These may be used alone or as a mixture of two or more. The conductive filler (D) is added in an amount of 0 to 8000 parts by weight, preferably 10 to 400 parts by weight, per 100 parts by weight of the oxetane compound (A).
0 parts by weight. If it exceeds 8000 parts by weight, the adhesiveness tends to decrease.

Further, an insulating filler (E) can be added. Specific examples of the insulating filler (E) include:
Silica powder, alumina powder, titania, glass, iron oxide, quartz powder, magnesia, silicon carbide, particulate inorganic filler (filler) such as boron nitride, MBS (methyl methacrylate-butadiene-styrene) resin, silicone resin,
Organic fine particles such as a fluororesin are exemplified. The amount of the insulating filler (E) to be added is as follows: the oxetane compound (A) 100
0 to 8000 parts by weight, preferably 10 to 4 parts by weight per part by weight
000 parts by weight. If it exceeds 8000 parts by weight, the adhesiveness tends to decrease. Furthermore, conductive filler (D)
When used together with the insulating filler (E), the total amount of the conductive filler (D) and the insulating filler (E) is 1 with respect to 100 parts by weight of the oxetane compound (A).
The amount is from 8,000 to 8,000 parts by weight, preferably from 10 to 4,000 parts by weight. If the total of the conductive filler (D) and the insulating filler (E) is less than 1 part by weight, sufficient conductivity tends not to be obtained even when it is desired to impart conductivity to the adhesive film, and exceeds 8000 parts by weight. And the adhesiveness tends to decrease.

The solvent (F) used in the present invention can be suitably selected from those capable of mixing and dispersing each component in producing an adhesive film. Specific examples of the solvent (F) include 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 and the like. The solvent (F) can be used alone or in combination of two or more. The boiling point of the solvent (F) is preferably from 50C to 300C, more preferably from 70C to 250C. When the boiling point of the solvent (F) is less than 50 ° C., the solvent is liable to be scattered during the production of the adhesive film described later, and only the surface of the adhesive film is dried.
So-called leather upholstery tends to occur.
If the temperature is higher than 00 ° C., the solvent tends to be less likely to be scattered during the production of the film.

In the method for producing an adhesive film of the present invention, first, each component is mixed to prepare a paste-like mixture, which is uniformly applied on a base film such as a polyester film, and a solvent (F) is used. In such cases, the conditions under which the solvent used is sufficiently volatilized, that is, approximately 60 to 20
Heating is performed at a temperature of 0 ° C. for 0.1 to 30 minutes. The adhesive film is usually used for bonding after removing the base film at the time of use. The method for producing the paste-like mixture in the production of the adhesive film of the present invention is not particularly limited. For example, an oxetane compound (A) and a curing agent (B), and if necessary, a solvent (F) and additives are added. A method in which a dispersing machine such as a stirrer, a mill, a three-roll mill, and a ball mill is appropriately combined and kneaded. The polyimide resin (C) is dissolved in the solvent (F), and then, as necessary, the conductive filler (D) and And / or adding an insulating filler (E) and an additive, kneading the mixture by appropriately combining an ordinary stirrer, a mill, a three-roller, a disperser such as a ball mill, and further mixing the oxetane compound (A) and the curing agent (B). Is added and mixed, the polyimide resin (C) is dissolved in the oxetane compound (A), and then, if necessary, the conductive filler (D) and / or the insulating filler (E), an additive In addition, kneading by appropriately combining and mixing ordinary dispersers such as a stirrer, a mill, a three-roll mill, and a ball mill, further adding a curing agent (B) and mixing, a polyimide resin (C), an oxetane compound (A) A method in which a conductive filler (D) and / or an insulating filler (E) and a solvent (F) are kneaded, if necessary, and a curing agent (B) is added and mixed, a polyimide resin (C), an oxetane compound A method of kneading the conductive filler (D) and / or the insulating filler (E) and the solvent (F) with the curing agent (A) and the curing agent (B), if necessary, may be used. In the method for producing a paste-like mixture in the production of the adhesive film of the present invention, when an oxetane compound that is liquid at room temperature is used as the oxetane compound (A), the paste-like mixture can be produced without using the solvent (F). The paste mixture thus obtained can also be used for the production of an adhesive film.

The adhesive film obtained by the present invention can be used for IC,
It is used for bonding support members such as lead frames of semiconductor devices such as LSIs, ceramic wiring boards, glass epoxy wiring boards, and glass polyimide wiring boards.

The adhesive film of the present invention can be adhered to a semiconductor element such as an IC or LSI and a lead frame by the following method. First, there is a method in which an adhesive film is formed in a tape ribbon shape, cut in accordance with the size of a semiconductor element, and sandwiched between a support member such as a lead frame and the semiconductor element, followed by heat bonding. In the case of bonding by this method, the bonding can be performed by an apparatus to which a die bonding apparatus for a solder ribbon or the like is applied, for example.

Second, there is a method in which an adhesive film is first formed on a support member such as a lead frame, and then the semiconductor element is heated and bonded. In order to form an adhesive film on a lead frame, there is a method in which the adhesive film is cut in accordance with the size of a semiconductor element, and is bonded by heating or a method in which a solvent is applied and bonded. Further, it can also be formed by a method of printing and applying a varnish of an adhesive film on a lead frame. After the adhesive film is formed on the lead frame, the semiconductor element can be bonded by, for example, a device using a die bonding device or the like that has been conventionally used with a silver paste.

Third, there is a method in which an adhesive film is formed on the back surface of the wafer, and then the wafer and the adhesive film are cut in a dicing step and adhered to a lead frame. In order to form an adhesive film on the back surface of the wafer, there are a method of applying the adhesive film by heating, and a method of applying a solvent and attaching the adhesive film. Alternatively, the varnish of the adhesive film may be formed by printing or spin coating on the back surface of the wafer. After forming an adhesive film on the backside of the wafer, to bond the semiconductor elements, for example,
Bonding can be carried out by using a device such as a die bonding device used for silver paste. The bonding temperature at the time of performing the bonding is preferably from 60 to 350 ° C, and from 60 to 350 ° C.
300 ° C is more preferable, and 60 to 250 ° C is most preferable. If the temperature is lower than 60 ° C., the time required for bonding tends to be long, and productivity tends to decrease. If the temperature is 350 ° C. or higher, long-term bonding reliability tends to decrease. The bonding time at this time is not particularly limited, but is approximately 0.1 second to 3 seconds.
0 minutes. The pressure of the pressure bonding at the time of performing the bonding can be adjusted depending on the type of the adherend to be bonded, but is generally about 0.1 KPa to 10 MPa.

In addition to the above method, an adhesive film is formed on an adhesive dicing film used in the dicing step, and a wafer is attached to the adhesive film. Then, the semiconductor element and the adhesive film are bonded in the dicing step. There is a method of cutting and attaching to a lead frame, but the adhesive film of the present invention is not limited to any of the methods exemplified above. In addition, when performing the above-mentioned bonding, before the thermocompression bonding, simultaneously with the thermocompression bonding, and after the thermocompression bonding, a carbon arc, a mercury vapor arc, a xenon arc, a photo flood bulb, a solar lamp, and an actinic ray generated from other light sources. To the adhesive film. When irradiating the adhesive film with actinic rays simultaneously with and after the thermocompression bonding, the adhesive film may be irradiated with light from any direction if the adherend transmits the actinic rays. When light does not pass through, the adhesive film can be irradiated with actinic rays from the gap between the adherends. Irradiating the adhesive film with actinic rays is preferable because the heating temperature at the time of pressing can be reduced and the pressing time can be further reduced.

[0097]

The present invention will be described below in more detail with reference to examples. (Synthesis Example 1) In a 500 ml four-necked flask equipped with a thermometer, a stirrer, and a calcium chloride tube, 2,2-bis (4
-Aminophenoxyphenyl) propane 41 g (0.1
Mol) and 150 g of dimethylacetamide and stirred. After dissolution of the diamine, 41 g (0.1 mol) of 1,2- (ethylene) bis (trimellitate dianhydride) was added little by little while the flask was cooled in an ice bath. After reacting at room temperature for 3 hours, 30 g of xylene was added, and N ₂ was added.
The mixture was heated at 150 ° C. while blowing gas to azeotropically remove xylene with water. The reaction solution was poured into water, and the precipitated polymer was collected by filtration, dried and dried to obtain a number-average molecular weight of 4
0000 polyimide resin (C-1) was obtained.

(Synthesis Example 2) Bis (4- (3-aminophenoxy) phenyl) sulfone was placed in a 500 ml four-necked flask equipped with a thermometer, a stirrer, and a calcium chloride tube.
43.2 g (0.1 mol) and 150 g of N-methyl-2-pyrrolidone were taken and stirred. After dissolution of the diamine, 43.8 g (0.1 mol) of 1,4- (tetramethylene) bis (trimellitate dianhydride) was added at room temperature. 5 ℃
The mixture was reacted for 5 hours as follows, and 20.4 g (0.2 mol) of acetic anhydride and 15.8 g (0.2 mol) of pyridine were added.
Stirred at room temperature for hours. The reaction solution was poured into water, and the precipitated polymer was collected by filtration, dried and dried to obtain a number average molecular weight of 5
000 polyimide resin (C-2) was obtained.

(Synthesis Example 3) In a 500 ml four-necked flask equipped with a thermometer, a stirrer, and a calcium chloride tube, 2,2
-Bis (4-aminophenoxyphenyl) propane 3
2.8 g (0.08 mol), 3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane
08 g (0.02 mol) and dimethylacetamide 10
0 g was taken and stirred. After dissolution of the diamine, 41.8 g (0.08 mol) of 1,10- (decamethylene) bis (trimellitate dianhydride) and benzophenonetetracarboxylic dianhydride were cooled while cooling the flask in an ice bath.
44 g (0.02 mol) were added in small portions. After completion of the addition, the mixture was reacted in an ice bath for 3 hours and further at room temperature for 4 hours.
Acetic anhydride 25.5 g (0.25 mol) and pyridine 1
9.8 g (0.25 mol) was added and stirred for 2 hours at room temperature. The reaction solution was poured into water, and the precipitated polymer was collected by filtration and dried to obtain a polyimide resin (C-3) having a number average molecular weight of 60,000.

(Examples 1 to 8, Comparative Example 1) According to the composition table shown in Table 1, the polyimide resin (C) was dissolved in the solvent (F), and then the conductive filler (D) and / or the insulating filler Add (E), knead for 10 minutes with a mill,
Further, the oxetane compound (A) and the curing agent (B) were added and mixed with a three-blade stirring device for 10 minutes to prepare a paste-like mixture.

[0101]

[Table 1]

In Table 1, various symbols have the following meanings (blending amounts are parts by weight). XDO: Toa Gosei Co., Ltd., 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene B1: 1,2-bis (3-ethyl-3-oxetanylmethoxy) -4-tertbutylbenzene B2 : 1,3-bis (3-ethyl-3-oxetanylmethoxy) benzene SI100L: Sanshin Chemical Industry Co., Ltd., Sun Aid SI
-100L, cationic latent curing agent SI150: Sanshin Chemical Industry Co., Ltd., Sun-Aid SI-
150, cationic latent curing agent SP-170: Adeka Opton S, Asahi Denka Kogyo Co., Ltd.
P-170, cationic latent curing agent H-1: Meiwa Kasei Co., Ltd., phenol novolak (O
HCG 106) TCG-1: Tokuriki Chemical Co., Ltd., silver powder DMAc: dimethylacetamide NMP: N-methylpyrrolidone DMF: dimethylformamide 2MIZ: 2-methylimidazole ESCN-195: Nippon Kayaku Co., Ltd., cresol novolac epoxy (epoxy) Equivalent 200)

This paste-like mixture was applied on a polyester film to a thickness of 30 to 50 μm,
And then heated at 150 ° C. for 30 minutes to obtain an adhesive film.

(Shear Adhesion Test) With respect to the adhesive films obtained from the compositions of Examples 1 to 8 and Comparative Example 1, a shear adhesion test was carried out. In addition, the test method is as follows.
8. Cut to a size of 4 mm, sandwich this between a 4 mm 4 mm silicon chip and a silver-plated lead frame;
A load of 806N (1000 g) was applied at 120 ° C, 5
It was pressed for 2 seconds to produce an adhesive. The adhesive film obtained with the composition of Example 8 was cut into a size of 4 × 4 mm, and this was attached to a lead frame with silver plating.
Active light was irradiated at 100 mJ / cm ² using a 0 W ultra-high pressure mercury lamp. Thereafter, a silicon chip of 4 × 4 mm was put thereon, a load of 9.806 N (1000 g) was applied, and
It was pressed at 0 ° C. for 3 seconds to produce an adhesive. The shear adhesion test was carried out at room temperature (25 ° C.) using the obtained adherend.
When a load of 0N / chip is applied,
A load of N / chip was applied, and the peeled state of the chip was observed. The results are shown in Table 2.

[0105]

[Table 2] Room temperature: chip does not peel off at 50 N / chip load at room temperature = ○ Chip peels off at 50 N / chip load at room temperature = × 350 ° C .: Apply 10 N / chip load at 350 ° C. Chip does not peel off = ○ Chip peels off at 350 ° C with a load of 10 N / chip = ×

The adhesive films of Examples 1 to 8 containing the oxetane compound (A) and the curing agent (B), which are the components of the present invention, can be bonded at a lower temperature and in a shorter time than conventional adhesive films. The results of the shear adhesion test were also good. On the other hand, the adhesive film of Comparative Example 1, which did not use the oxetane compound (A), which is an essential component of the present invention, peeled off as a result of the shear adhesion test.

[0107]

According to the first aspect of the present invention, there is provided an adhesive film which is excellent in low-temperature adhesiveness, can be suitably used for 42 alloy lead frames and copper lead frames, and can also be suitably used for an insulating support substrate. Is what you do. Claim 2,
The third aspect of the present invention provides an adhesive film having excellent shear adhesive strength in addition to the effects of the first aspect of the present invention. The inventions according to claims 4 and 5 provide an adhesive film excellent in adhesion between substrates having different thermal expansion coefficients in addition to the effects of the inventions according to claims 1 to 3. Claim 6,
The invention described in 7 provides an adhesive film having excellent storage stability in addition to the effects of the inventions described in claims 1 to 5. The inventions according to claims 8 and 9 provide an adhesive film that can provide high adhesion reliability in addition to the effects of the inventions according to claims 1 to 5. The invention according to claim 10 is
It is intended to provide a method for producing an adhesive film according to claims 1 to 9. The invention according to claim 11 is the invention according to claims 1 to 9
It is intended to provide a method for bonding a semiconductor element and a support member using the above-described adhesive film. According to a twelfth aspect of the present invention, there is provided a method for bonding a semiconductor element and a support member, wherein the adhesive film is irradiated with actinic rays.

Continued on the front page F-term (reference) 4J004 AA07 AA11 AA12 AB04 CA06 CC02 FA05 4J040 DB052 EB062 EE031 EH032 EK032 GA05 GA07 GA14 GA22 GA28 HA026 HA066 HA116 HA206 HA306 HA326 HA346 HB10 HB22 HB26 HC01 HD12 HD12 HD03 HD24 JB02 KA14 KA16 KA32 KA42 LA06 LA09 MA03 MA10 NA19 NA20 PA23 PA30 5G301 DA03 DA18 DA33 DA42 DA51 DD03 DD08

Claims (12)

[Claims] 1. An oxetane compound (A) and a curing agent (B)
Adhesive film containing. 2. The adhesive film according to claim 1, further comprising a polyimide resin (C). 3. A tetracarboxylic acid in which the content of the tetracarboxylic dianhydride represented by the general formula (1) is 70 mol% or more of the total tetracarboxylic dianhydride (C ′) in the polyimide resin (C). The adhesive film according to claim 2, which is a polyimide resin (C) obtained by reacting a dianhydride with a diamine (C "). (However, n is an integer of 2 to 20.) 4. The method according to claim 1, further comprising a conductive filler (D) and / or an insulating filler (E).
The adhesive film according to any one of the above. 5. A conductive filler (D) in an amount of 0 to 8000 parts by weight and / or 100 parts by weight of the oxetane compound (A).
The adhesive film according to any one of claims 1 to 4, further comprising 0 to 8000 parts by weight of the insulating filler (E). 6. The curing agent (B) is a curing agent (B ′) for ring-opening polymerization of the oxetane compound (A), and comprises a cationically polymerizable catalyst, an anionic polymerizable catalyst, a latent cationic polymerization initiator, The adhesive film according to any one of claims 1 to 5, wherein the adhesive film is at least one selected from an anionic polymerizable catalyst. 7. The adhesive film according to claim 6, wherein the curing agent (B ′) is a latent cationic polymerization initiator (B1). 8. The curing agent (B) is a curing agent (B ″) that undergoes an addition reaction with the oxetane compound (A), and is a bifunctional or more carboxylic acid, a difunctional or more polythiol, or a difunctional or more carboxylic anhydride. The adhesive film according to any one of claims 1 to 5, wherein the adhesive film is at least one selected from a product and a bifunctional or higher phenol compound. 9. The adhesive film according to claim 8, wherein the curing agent (B ″) is a phenol compound (B2). 10. A polyimide resin (C), a conductive filler (D) and / or an insulating filler (E) according to any one of claims 1 to 9, and at least one selected from solvents (F). Oxetane compound (A) and curing agent (B)
Are mixed to form a paste or varnish-like mixture, which is applied on a base film,
A method for producing an adhesive film, which is dried to form an adhesive film. 11. The semiconductor device according to claim 1, wherein the semiconductor device and the supporting member are provided between the semiconductor device and the supporting member.
A method for bonding a semiconductor element and a support member, wherein the bonding method is performed by sandwiching the adhesive film according to any one of claims 9 to 9 and applying heat and pressure. 12. The method according to claim 11, wherein an actinic ray is irradiated to the adhesive film.