JP2000256627A - Adhesive tape - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a tape which enables bonding and curing at a relatively low temperature, is excellent in heat resistance and has low permittivity by providing a heat-resistant film with an adhesive layer comprising a resin composition containing a siloxane-modified polyimide, an allylated compound and a compound having two or more maleimide groups. SOLUTION: The resin composition contains a siloxane-modified polyimide having structural units of formula I and those of formula II arranged therein, a compound represented by formula III or formula IV, and a compound having two or more maleimide groups (e.g. a compound of formula V). In formulas I and II, Z is a direct bond, -O-, -SO2-, -CO-, -C(CH3)2-, -C(CF3)2-, or -COOCH2CH2 OCO-; Ar is a divalent group having an aromatic ring; R is a 1-10C alkylene, or -CH2OC6H4- having a methylene group bonded to an Si atom; and n is 1 to 20. In formulas III and IV, R is H or CH3. The siloxane-modified polyimide preferably has a glass transition temperature of 150 deg.C or lower.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a tape having heat resistance and adhesiveness, and more particularly to a tape between members around a lead frame constituting a semiconductor device, for example, a lead pin, a substrate for mounting a semiconductor chip, a heat sink, and the like. The present invention relates to an adhesive tape suitable for bonding a semiconductor chip or the like.

[0002]

2. Description of the Related Art Conventionally, adhesive tapes used in a resin-encapsulated semiconductor device include a lead frame fixing tape and a TAB tape. For example, an adhesive tape for fixing a lead frame is used for fixing a lead pin of the lead frame, thereby contributing to an improvement in production yield and productivity in the lead frame itself and the entire semiconductor assembly process. This fixing adhesive tape is usually taped on a lead frame by a lead frame maker, shipped to a semiconductor maker, mounted with an IC by a semiconductor maker, and sealed with a resin. Therefore, the adhesive tape for fixing a lead frame has not only general reliability at the semiconductor level and workability at the time of taping, but also a sufficient room temperature adhesive force immediately after taping, and a sufficient resistance to heating during the semiconductor device assembly process. Heat resistance is required. Conventionally, as an adhesive tape used for such an application, for example, on a support film such as a polyimide film, a polyacrylonitrile, a polyacrylic acid ester or a synthetic rubber-based resin such as an acrylonitrile-butadiene copolymer alone may be used. Or a resin modified with another resin, or a semi-cured state obtained by applying an adhesive mixed with another resin.

In recent years, a resin-sealed semiconductor device (semiconductor package) having a structure as shown in FIGS. 1 to 3 has been developed or manufactured. In the resin-encapsulated semiconductor device shown in FIG. 1, the lead pins 3 and the plane 2 are adhered by a double-sided adhesive tape 6, the semiconductor chip 1 is mounted on the plane 2, and the bonding between the semiconductor chip 1 and the lead pins 3 is performed. It has a structure sealed with a resin 5 together with the wire 4. The device shown in FIG. 2 has a structure in which the lead pins 3 and the semiconductor chip 1 are fixed by a double-sided adhesive tape 6 and are sealed together with the bonding wires 4 by a resin 5. In the device shown in FIG. 3, the semiconductor chip 1 is mounted on the die pad 7, the electrodes 8 are fixed on the die pad 7 by the double-sided adhesive tape 6, and further, between the semiconductor chip 1 and the electrodes 8, and Between the lead pin 3 and the bonding wire 4
And are sealed by a resin 5.

[0004]

However, when a conventional adhesive tape coated with an adhesive is used as each adhesive tape 6 in the resin-sealed semiconductor device having the structure shown in FIGS. And the heat resistance is not sufficient. Further, when a polyimide resin or the like is used, it is necessary to increase the taping temperature, pressure, and the like, and there is a possibility that a metal material such as a lead frame may be damaged. Further, it is necessary to cope with a fine pitch of a semiconductor chip and an increase in an arithmetic processing speed. Therefore, it can be bonded and cured at a relatively low temperature, and has sufficient heat resistance and reliability,
It has been desired to develop an adhesive tape having a low dielectric constant or the like.
The present invention has been made to solve the above-mentioned problems, and provides an adhesive tape which can be bonded and cured at a relatively low temperature, has a low dielectric property and has sufficient heat resistance and reliability, and is suitable for electronic components and the like. It is in.

[0005]

According to a first aspect of the present invention, there is provided an adhesive tape comprising: a siloxane-modified polyimide comprising a component (a): a structural unit represented by the following formula (2a) and a structural unit represented by the following formula (2b): And component (b): the following formula (b-1) or the following formula (b-2)
And an adhesive layer comprising a resin composition containing a compound represented by the following formula: and a component (c): a compound having two or more maleimide groups, and a heat-resistant film.

Embedded image (In the above formulas (2a) and (2b), Z is a direct bond,
_{-O -, - SO 2 -,} - CO -, - C (CH 3) 2 -, -
Represents a bond of C (CF ₃ ) ₂ — or —COOCH ₂ CH ₂ OCO—, and Ar represents a divalent group having an aromatic ring;
Is an alkylene group having 1 to 10 carbon atoms or a methylene group represented by S
i represents —CH ₂ OC ₆ H ₄ — bonded to i, and n represents 1 to
Means an integer of 20. )

Embedded image (In the above formulas (b-1) and (b-2), R represents a hydrogen atom or a methyl group.)

The adhesive tape according to claim 2 comprises the component (b)
Is a compound represented by the following formula (b-3), and the total of the components (b) and (c) is 10 to 900 parts by weight with respect to 100 parts by weight of the component (a). (C)
Wherein the methylallyl group of component (b) is 0.1 to 2.0 molar equivalents per 1 molar equivalent of the maleimide group.

Embedded image The adhesive tape according to claim 3, wherein the component (b) has the following formula (b)
-2).

Embedded image (In the above formula (b-2), R represents a hydrogen atom or a methyl group.) The adhesive tape according to claim 4 is represented by the following formula (d1) and / or formula (d2) in the resin composition. It is characterized by further containing a diamine compound. H ₂ N—R ⁵ —NH ₂ (d1)

Embedded image (In the formulas (d1) and (d2), R ⁵ represents a divalent aliphatic group, an aromatic group, or an alicyclic group;
Represents an integer of 1 to 8. )

In the adhesive tape according to the first or third aspect, the total of the components (b) and (c) is 10 to 900 parts by weight with respect to 100 parts by weight of the component (a), and the component (c) The allyl group or methylallyl group of component (b) is preferably 0.1 to 2.0 molar equivalents per 1 molar equivalent of the maleimide group. Further, the ratio of the structural unit represented by the formula (2a) and the structural unit represented by the formula (2b) in the siloxane-modified polyimide of the component (a) is desirably 90 to 40:10 to 60 in a molar ratio. . Further, the siloxane-modified polyimide of the component (a) contains 90 to 40 mol% of a structural unit represented by the following formula (3a) and 10 to 60 mol% of a structural unit represented by the following formula (3b). Is desirable.

Embedded image (In the formula, Arm is a tetravalent aromatic group and 3,3 ′, 4,4′-
It means any of a diphenylsulfone structure, a 3,3 ', 4,4'-biphenyl structure and a 2,3', 3,4'-biphenyl structure. Ar means a divalent group having an aromatic ring. R represents —CH ₂ OC ₆ H ₄ — in which an alkylene group or a methylene group having 1 to 10 carbon atoms is bonded to Si;
Represents an integer of 1 to 20. )

It is desirable that Ar is a group selected from the following chemical formula group.

Embedded image (In the formula, R ¹ , R ² , R ³ and R ⁴ may be the same or different and each represent a hydrogen atom, an alkyl group or an alkoxy group having 1 to 4 carbon atoms. The siloxane-modified polyimide of the component (a) preferably has a glass transition temperature of 150 ° C. or lower. Further, the siloxane-modified polyimide of the component (a) has a weight average molecular weight of 5,000.
It is desirably from 0 to 500,000. Component (a)
It is desirable that the siloxane-modified polyimide has a dielectric constant of 3.0 or less. The compound having two or more maleimide groups of the component (c) is preferably selected from the group of compounds represented by the following formula.

Embedded image (In the formula (c-4), p represents an integer of 1 to 8.)

Further, based on 100 parts by weight of the component (a),
The sum of the components (b), (c) and (d) is 10 to 9
It is preferable that the amount of the amino group of the component (d) is 0.1 to 2.0 molar equivalent relative to 1 molar equivalent of the maleimide group of the component (c). Further, the resin composition desirably has a dielectric constant of 3.2 or less in a cured state. Furthermore, the resin composition desirably contains a filler having a particle size of 1 μm or less in an amount of 1 to 40% by weight of the total solids. The heat-resistant film is preferably made of polyimide.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The adhesive tape of the present invention includes at least a heat-resistant film and a specific adhesive layer having adhesiveness. The resin composition used for the adhesive layer of the adhesive tape according to claim 1 comprises a siloxane-modified polyimide as the component (a), a compound having two or more allyl groups or methylallyl groups as the component (b), and a component (c). ) And a compound having two or more maleimide groups. [Component (a)] The siloxane-modified polyimide used in the present invention has a structural unit represented by the following formula (2a) and a structural unit represented by the following formula (2b) arranged.

Embedded image Here, Z is a direct _{bond, -O -, - SO 2 -} , - CO
_{-, - C (CH 3)} 2 -, - C (CF 3) 2 -, - COOC
Indicate any bond of H ₂ CH ₂ OCO—. Ar
Is a divalent group having an aromatic ring, and R is -C in which an alkylene group having 1 to 10 carbon atoms or a methylene group is bonded to Si.
H ₂ OC ₆ H ₄ —, wherein n represents an integer of 1 to 20. The arrangement of each of these structural units may be regular or irregular.

Further, the divalent group having an aromatic ring of Ar is preferably a group selected from the following chemical formula group.
However, in the formula, R ¹ , R ² , R ³ and R ⁴ may be the same or different and each represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group. It cannot be an atom.

Embedded image

Accordingly, the following can be specifically exemplified. 4,4′-diamino-3,3 ′, 5,5′-tetramethyldiphenylmethane, 4,4′-diamino-3,3 ′,
5,5′-tetraethyldiphenylmethane, 4,4′-diamino-3,3 ′, 5,5′-tetrapropyldiphenylmethane, 4,4′-diamino-3,3 ′, 5,5′-tetraisopropyldiphenylmethane, 4,4'-diamino-
3,3 ', 5,5'-tetrabutyldiphenylmethane, 4,
4'-diamino-3,3'-diethyl-5,5'-dimethyldiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3 '
-Diethyldiphenylmethane, 4,4'-diamino-3,
3 ', 5,5'-tetramethoxydiphenylmethane, 4,
4'-diamino-3,3 ', 5,5'-tetraethoxydiphenylmethane, 4,4'-diamino-3,3', 5,5 '
-Tetrapropoxydiphenylmethane, 4,4'-diamino-3,3 ', 5,5'-tetrabutoxydiphenylmethane, 4,4'-diamino-3,3'-dimethoxydiphenylmethane, 1,3-bis (3-amino Phenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene,
1,4-bis (4-aminophenoxy) benzene, 9,9
-Bis (3-aminophenyl) fluorene, 9,9-bis (4-aminophenyl) fluorene, 1,3-bis [1- (3-aminophenyl) -1-methylethyl] benzene, 1,3-bis [1- (4-aminophenyl)-
1-methylethyl] benzene, 1,4-bis [1- (3
-Aminophenyl) -1-methylethyl] benzene,
1,4-bis [1- (4-aminophenyl) -1-methylethyl] benzene, 3,3′-bis (3-aminophenoxy) biphenyl, 3,3′-bis (4-aminophenoxy) biphenyl, 3,4'-bis (3-aminophenoxy) biphenyl, 3,4'-bis (4-aminophenoxy) biphenyl, 4,4'-bis (3-aminophenoxy) biphenyl, 4,4'-bis (4 -Aminophenoxy) biphenyl, 3,3'-bis (3-aminophenoxy) diphenyl ether, 3,3'-bis (4-aminophenoxy) diphenyl ether, 3,4'-bis (3-aminophenoxy) diphenyl ether,
4'-bis (4-aminophenoxy) diphenyl ether, 4,4'-bis (3-aminophenoxy) diphenyl ether, 4,4'-bis (4-aminophenoxy)
Diphenyl ether, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, 2,2-bis [3- (3
-Aminophenoxy) phenyl] propane, 2,2-bis [3- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [ 4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3- (3
-Aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [3- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4-
(3-Aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy)
Phenyl] hexafluoropropane and the like.

The siloxane-modified polyimide of the component (a) is more preferably a siloxane-modified polyimide in which a structural unit represented by the following formula (3a) and a structural unit represented by the following formula (3b) are arranged.

Embedded image In the formula, Arm is a tetravalent aromatic group having a 3,3 ′, 4,4′-diphenyl sulfone structure, a 3,3 ′, 4,4′-biphenyl structure, 2,3 ′, 3,4′-biphenyl. Means any of the structures. Ar means a divalent group having an aromatic ring.
R represents —CH ₂ OC ₆ H ₄ — in which an alkylene group or a methylene group having 1 to 10 carbon atoms is bonded to Si;
It means an integer of up to 20. In this case, the amount of the structural unit represented by the formula (3a) is 90 to 40 mol%, and
Is preferably 10 to 60 mol%. If the structural unit represented by the formula (3a) is more than 90 mol%, Tg becomes too low, and the adhesive layer may be tacky. If it is less than 40 mol%, Tg becomes high, and This is because the temperature increases.

The siloxane-modified polyimide of the component (a) in the present invention comprises 90 to 40 mol% of at least one of the structural units represented by the formula (2a) and 90% by mol of the structural unit represented by the formula (2b). Those containing at least one kind in an amount of 10 to 60 mol% are preferred.

The siloxane-modified polyimide of component (a) has a weight average molecular weight of 5,000 to 500,000, a glass transition temperature (Tg) of 150 ° C. or less, and a dielectric constant of 3.0.
The following are preferred. Weight average molecular weight of 5,000 or more
Those having a glass transition temperature of 140 ° C. or lower and a dielectric constant of 3.0 or lower are more preferable, and a weight average molecular weight of 10,000 to 300,000 and a glass transition temperature of 13 are preferable.
Those having a temperature of 0 ° C. or lower and a dielectric constant of 3.0 or lower are more preferable. When the weight average molecular weight is less than 5,000, thermal stability becomes poor, and heat resistance decreases. When it exceeds 500,000, workability and adhesiveness become poor due to an increase in melt viscosity. If the glass transition temperature is higher than 150 ° C., the melting temperature increases, which causes an increase in the working temperature or poor adhesion. When the dielectric constant is higher than 3.0, it is difficult to reduce the dielectric constant of the resin composition, and it is difficult to cope with miniaturization of electronic components such as a lead frame.

The siloxane-modified polyimide used in the present invention can be obtained by using a general polyimide production method. That is, for example, it can be produced from a tetracarboxylic dianhydride corresponding to each repeating structural unit and a diamine or diisocyanate corresponding to each repeating structural unit. Specifically, as the tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3 ′,
4,4′-benzophenonetetracarboxylic dianhydride,
3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,3', 3,4'-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, ethylene glycol bistrimellitate dianhydride, 2,2-bis [4-
(3,4-dicarboxyphenoxy) phenyl] propane dianhydride and the like, more preferably 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3 ′,
4,4'-biphenyltetracarboxylic dianhydride, 2,
It can be produced by reacting 3 ', 3,4'-biphenyltetracarboxylic dianhydride with an aromatic diamine corresponding to Ar and a siloxane compound represented by the following chemical formula (5).

Embedded image Here, R is —CH ₂ OC ₆ H ₄ — in which a C ₁ -C ₁₀ alkylene group or methylene group is bonded to Si, and n is 1
Represents an integer of from 20 to 20, and Q is a functional group such as an amino group or an isocyanate group.

In the siloxane compound represented by the formula (5) used as a raw material for producing polyimide, the diamines in which the functional group Q is an amino group include bis (3-aminopropyl) tetramethyldisiloxane and bis (3-aminopropyl) tetramethyldisiloxane. 10
-Aminodecamethylene) tetramethyldisiloxane, aminopropyl-terminated dimethylsiloxane tetramer, octamer, bis (3-aminophenoxymethyl) tetramethyldisiloxane, and the like, and these can be used in combination. . Further, in the compound represented by the formula (5),
Examples of the diisocyanates in which the functional group Q is an isocyanate group include diamines shown above in which each "amino" is replaced with "isocyanate". In the compound represented by the above formula (5),
Diisocyanates in which the functional group Q is an isocyanate group can be easily produced by reacting the corresponding diamine exemplified above with phosgene according to a conventional method.

Specific examples of the siloxane-modified polyimide used in the present invention include the following production examples.
When tetracarboxylic dianhydride and diamine are used as raw materials, they may be used in an organic solvent in the presence of a catalyst such as tributylamine, triethylamine, or triphenyl phosphite as needed (20 parts by weight or less of the reactant). ), 10
A method of heating directly to 0 ° C. or higher, preferably 180 ° C. or higher to directly obtain polyimide. Tetracarboxylic dianhydride and diamine are reacted in an organic solvent at a temperature of 100 ° C. or lower to obtain a polyamic acid which is a precursor of polyimide.
-A method of obtaining a polyimide by adding a dehydration catalyst such as toluenesulfonic acid (1 to 5 times mol of tetracarboxylic dianhydride) and performing imidization by heating. Alternatively, this polyamic acid can be used as an acid anhydride such as acetic anhydride, propionic anhydride, and benzoic anhydride; a dehydration ring-closing agent such as a carbodiimide compound such as dicyclohexylcarbodiimide; and a ring-closing catalyst such as pyridine, isoquinoline, imidazole, and triethylamine, if necessary. (Dehydration ring-closing agent and ring-closing catalyst are added 2 to 10 times the molar amount of tetracarboxylic dianhydride), and a method of chemically closing the ring at a relatively low temperature (about room temperature to about 100 ° C.) is available.

As the organic solvent used in the above reaction, N
-Methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, sulfolane, hexamethylphosphoric triamide,
Aprotic polar solvents such as 1,3-dimethyl-2-imidazolidone, phenol, cresol, xylenol,
Phenol solvents such as p-chlorophenol are exemplified. If necessary, benzene, toluene, xylene, methyl ethyl ketone, acetone, tetrahydrofuran, dioxane, monoglyme, diglyme, methyl cellosolve, cellosolve acetate, methanol, ethanol, isopropanol, methylene chloride, chloroform, trichlene, nitrobenzene, etc. Can also be used as a mixture. In addition, when using tetracarboxylic dianhydride and diisocyanate as raw materials, it is possible to produce according to the method of directly obtaining the above polyimide, the reaction temperature at this time is room temperature or more, In particular, the temperature is preferably 60 ° C. or higher. By reacting the tetracarboxylic dianhydride with the diamine or diisocyanate in an equimolar amount, it is possible to obtain a polyimide having a high degree of polymerization. It is also possible to produce polyimide using an excess amount in the following range.

In the present invention, by containing the specific siloxane-modified polyimide, the film forming ability of the resin composition after drying is improved, the flexibility of the molded product is improved, and punching and cutting are performed. During the operations such as the above, the scattering of the resin is extremely reduced, the handleability is improved, and the yield is improved. In particular, since the polyimide is modified with siloxane, the solubility in a solvent is remarkably improved. Furthermore, it has a low dielectric property, and the above-mentioned dielectric constant of 3.0 or less can be easily achieved.

[Component (b)] As a compound having two or more allyl groups or methylallyl groups, the following formula (b-)
1) or (b-2) is particularly preferred. These compounds are generally commercially available and can be easily obtained.

Embedded image (In the formula, R represents a hydrogen atom or a methyl group.) In particular, as in the invention according to claim 2, in (b-1), R is preferably a methyl group.
As shown in the invention according to (1), the one shown in (b-2) is desirable.

[Component (c)] As the compound having two or more maleimide groups, any compound can be used.
Those represented by (c-5) to (c-5) are particularly preferred. These compounds are generally commercially available and can be easily obtained. Further, it can be synthesized by a conventionally known method.

Embedded image (In the formula (c-4), p represents an integer of 1 to 8.)

[Component (d)] In the adhesive tape according to the first aspect of the present invention, the resin composition has the following formula (d)
It is preferable that the composition further contains a diamine compound represented by 1) and / or the formula (d2). H ₂ N—R ⁵ —NH ₂ (d1)

Embedded image (In the formulas (d1) and (d2), R ⁵ represents a divalent aliphatic group, an aromatic group, or an alicyclic group;
Represents an integer of 1 to 8. Examples of the diamine compound represented by the formula (d1) include the following. 3,3′-diaminobiphenyl, 3,4′-diaminobiphenyl, 4,4′-diaminobiphenyl, 3,3′-diaminodiphenylmethane,
4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 2,2- (3,3'-diaminodiphenyl) propane, 2,2- (3,4'-diaminodiphenyl) propane, 2,2- (4 , 4'-Diaminodiphenyl) propane, 2,2- (3,3'-diaminodiphenyl) hexafluoropropane, 2,2- (3,4'-diaminodiphenyl) hexafluoropropane, 2,2-
(4,4'-diaminodiphenyl) hexafluoropropane, 3,3'-oxydianiline, 3,4'-oxydianiline, 4,4'-oxydianiline, 3,3'-diaminodiphenylsulfide, 3 , 4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfone, 3,4 '
-Diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 1,3-bis [1- (3-aminophenyl) -1-methylethyl] benzene, 1,3-bis [1- (4-aminophenyl) -1-methylethyl] benzene, 1,4-bis [1- (3-aminophenyl)]
Benzene, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene,
1,4-bis (4-aminophenoxy) benzene, 3,
3′-bis (3-aminophenoxy) diphenyl ether, 3,3′-bis (4-aminophenoxy) diphenyl ether, 3,4′-bis (3-aminophenoxy)
Diphenyl ether, 3,4'-bis (4-aminophenoxy) diphenyl ether, 4,4'-bis (3-aminophenoxy) diphenyl ether, 4,4'-bis (4-aminophenoxy) diphenyl ether, 1,4
-Bis [1- (4-aminophenyl) -1-methylethyl-bis (3-aminophenoxy)] biphenyl, 3,
3'-bis (4-aminophenoxy) biphenyl, 3,
4'-bis (3-aminophenoxy) biphenyl, 3,
4'-bis (4-aminophenoxy) biphenyl, 4,
4'-bis (3-aminophenoxy) biphenyl, 4,
4'-bis (4-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] sulfone,
Bis [4- (4-aminophenoxy) phenyl] sulfone, 2,2-bis [3- (3-aminophenoxy) phenyl] propane, 2,2-bis [3- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (3
-Aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3- (3-aminophenoxy) phenyl] hexafluoropropane, 2,2- Screw [3-
(4-Aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (3-aminophenoxy)
Phenyl] hexafluoropropane, 2,2-bis [4
Biphenyl structures such as-(4-aminophenoxy) phenyl] hexafluoropropane, 9,9-bis (3-aminophenyl) fluorene, 9,9-bis (4-aminophenyl) fluorene, methylenediamine, and hexamitylenediamine , Diphenylmethane structure, diphenylpropane structure, diphenylhexafluoropropane structure, benzidine structure, diphenylsulfide structure, diphenylsulfone structure, bisphenylbenzene structure, bisphenoxybenzene structure, bisphenoxydiphenylether structure, bisphenylbisphenoxybisphenyl structure,
An aromatic diamine having a bisphenoxybiphenyl structure, a bisphenoxybisphenylsulfone structure, a bisphenoxybisphenylpropane structure, a bisphenoxybisphenylhexafluoropropane structure, a fluorene structure, or an aliphatic diamine having 1 to 12 carbon atoms is preferably used.
The diamine compound represented by (d2) is preferably a polysiloxane compound having a weight average molecular weight of 7000 or less. When the weight average molecular weight is 7000 or less, reactivity with a compound having two or more maleimide groups is improved. Represented by the general formula (d2),
Weight average molecular weight having amino groups at both ends is 7,000
Examples of the following polysiloxane compounds include bis (3-aminopropyl) tetramethyldisiloxane, aminopropyl-terminated dimethylsiloxane tetramers and octamers, and bis (3-aminophenoxymethyl) tetramethyldisiloxane. These can be used in combination. Preferred H ₂ N-R ⁵ is an aminoalkyl group of C ₁ -C ₆ Among the polysiloxane compound, aminophenyl group, an amino phenoxymethyl group.

In the resin composition of the present invention, when the components (a) to (c) or the component (d) is contained, the mixing ratio of the components (a) to (d) is 100% by weight of the component (a). Parts (b) and (c) or (b)
(D) is 10 to 900 parts by weight, and 50 to 9
00 parts by weight is more preferable, and 100 to 900 parts by weight is further preferable. When the total of the component (b) and the components (c) or (b) to (d) is less than 10 parts by weight, the resin composition is cured, and the heat resistance of the resin composition, particularly, the glass transition temperature (Tg) and the Young's modulus are lowered. It becomes remarkable and is not suitable for the intended use. If the amount exceeds 900 parts by weight, when the resin composition is cured to a semi-cured state, the resin composition itself becomes brittle and causes scattering of the resin. The mixing ratio of the component (b) to the component (c) is such that the methylallyl group of the component (b) is 0.1 to 2.0 molar equivalents per 1 molar equivalent of the maleimide group of the component (c). Is desirable. Preferably it is 0.3 to 1.8 molar equivalents, more preferably 0.5 to 1.5 molar equivalents. When the allyl group or methylallyl group equivalent is less than 0.1 molar equivalent, after the resin composition is cured, the electric reliability is deteriorated, and when the equivalent is more than 2.0 molar equivalent, gelation occurs during mixing,
The adhesive cannot be prepared.

The mixing ratio of component (c) to component (d) is such that component (d) is equivalent to 1 mole equivalent of the maleimide group of component (c).
It is necessary to make the amino group of 0.1 to 2.0 molar equivalents, preferably 0.1 to 1.5 molar equivalents, more preferably 0.1 to 1.0 molar equivalents. If the amino group equivalent is less than 0.1 molar equivalent, after curing of the adhesive,
If the dielectric properties are poor and more than 2.0 molar equivalents,
Since gelation occurs during mixing, the adhesive cannot be prepared.

Component (a), component (b) and component (c)
Can also be performed in a solvent in which they are dissolved. As the solvent, for example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, sulfolane, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidone, hexane , Benzene, toluene, xylene, methyl ethyl ketone, acetone, diethyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxymethane, diethylene glycol dimethyl ether,
Methyl cellosolve, cellosolve acetate, methanol, ethanol, propanol, isopropanol, methyl acetate, ethyl acetate, acetonitrile, methylene chloride, chloroform, carbon tetrachloride, chlorobenzene, dichlorobenzene, dichloroethane, trichloroethane, and the like. The type and amount are appropriately selected and used so that the components are dissolved.

In the resin composition, diazabicyclooctane, methyl ethyl ketone peroxide, cyclohexane peroxide, 3, 3
3,5-trimethylcyclohexanone peroxide,
Methylcyclohexanone peroxide, methyl acetoacetate peroxide, acetylacetone peroxide, 1,1-bis (t-butylperoxy) -3,
3,5-trimethylhexane, 1,1-bis (t-butylperoxy) -cyclohexane, 2,2-bis (t-butylperoxy) octane, n-butyl-4,4-bis (t-butylperoxy) ) Valate, 2,2-bis (t
-Butylperoxy) butane, t-butyl hydroperoxide, cumene hydroperoxide, di-isopropylbenzene hydroperoxide, p-menthane hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, di-cumyl peroxide, α, α′-bis (t-
Butylperoxy-m-isopropyl) benzene, 2,
5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne, acetyl peroxide, isobutyl peroxide, octanoyl peroxide , Decanoyl peroxide, benzoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, succinic acid peroxide, 2,4-dichlorobenzoyl peroxide,
m-toluoyl peroxide, di-isopropylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, di-n-propylperoxydicarbonate, bis- (4-t-butylcyclohexyl)
Peroxydicarbonate, di-myristyl peroxydicarbonate, di-2-ethoxyethylperoxydicarbonate, di-methoxyisopropylperoxydicarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, Di-allyl peroxy dicarbonate, t-butyl peroxy acetate, t
-Butylperoxyisobutyrate, t-butylperoxypivalate, t-butylperoxyneodecanate, cumylperoxyneodecanate, t-butylperoxy-2-ethylhexanate, t-butylperoxy- 3,5,5-trimethylhexanate, t-butylperoxylaurate, t-butylperoxybenzoate, di-t-butylperoxyisophthalate, 2.5
-Dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxymaleic acid, t-butylperoxyisopropyl carbonate, cumylperoxyoctate, t-hexylperoxyneodecanate,
Organic peroxides such as t-hexylperoxypivalate, t-butylperoxyneohexanate, acetylcyclohexylsulfonyl peroxide, t-butylperoxyallylcarbonate, 1,2-dimethylimidazole, 1-methyl-2- Ethyl imidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenyl Imidazole, 1-benzyl-2-phenylimidazole trimellitate, 1-benzyl-2-ethylimidazole, 1-benzyl-2-ethyl-5-methylimidazole, 2-ethylimidazole, 2-isopropylimidazole, 2 -Phenyl-4-benzylimidazole, 1-cyanoethyl-2-methylimidazole, 1
-Cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole,
1-cyanoethyl-2-isopropylimidazole, 1
-Cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazolium trimellitate,
1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,
4-diamino-6- [2′-ethyl-4-methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4
-Diamino-6- [2'-undecylimidazolyl-
(1 ′)]-ethyl-s-triazine, 2-methylimidazolium isocyanuric acid adduct, 2-phenylimidazolium isocyanuric acid adduct, 2,4-diamino-6- [2′-methylimidazolyl- ( 1 ′)]-ethyl-s-triazine-isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2
-Phenyl-4-benzyl-5-hydroxymethylimidazole, 4,4'-methylene-bis- (2-ethyl-
5-methylimidazole), 1-aminoethyl-2-methylimidazole, 1-cyanoethyl-2-phenyl-
4,5-di (cyanoethoxymethyl) imidazole, 1
-Dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazole / benzotriazole adduct, 1-aminoethyl-2-ethylimidazole, 1- (cyanoethylaminoethyl) -2-methylimidazole, N, N '-[2-methylimidazolyl-
(1) -ethyl] -adipoyldiamide, N, N′-bis- (2-methylimidazolyl-1-ethyl) urea, N
-(2-methylimidazolyl-1-ethyl) urea, N,
N '-[2-Methylimidazolyl- (1) -ethyl] dodecandioyldiamide, N, N'-[2-methylimidazolyl- (1) -ethyl] eicosandioilodiamide, 1-benzyl-2-phenylimidazole A reaction accelerator such as imidazoles such as hydrochloride and triphenylphosphine can also be added.

A silane coupling agent can be added to the resin composition. In addition, the resin composition may contain a filler having a particle size of 1 μm or less in order to stabilize taping characteristics when applied to an adhesive tape. Stability of taping characteristics means that when an adhesive tape is thermocompressed onto a lead, it is prevented from protruding from the end face of the tape due to the melting of the adhesive, and the adhesive layer is kept at an appropriate thickness to improve adhesiveness. Means to maintain. The content of the filler is 1 to 40% by weight of the total solids, preferably 4 to 4%.
0% by weight, more preferably 9 to 24% by weight. When the content is lower than the lower limit of the above range, the effect of stabilizing the taping characteristics is reduced, and when the content is more than 40% by weight, the adhesive strength of the adhesive tape is reduced, and the workability of laminating or the like is unfavorably deteriorated. As the filler, for example, silica, quartz powder, alumina, calcium carbonate, magnesium oxide, diamond powder, mica, fluororesin, zircon powder and the like are used. In addition, the resin composition, if necessary, is isolated after completion of the reaction, and washed with an organic solvent, water, or a mixture of an organic solvent and water, and then dissolved again in the above organic solvent to form a liquid adhesive. It may be used for forming an adhesive layer. Organic solvents that can be used for washing include acetone, methyl ethyl ketone,
Hexane, benzene, toluene, xylene, methanol, ethanol, propanol, diethyl ether, tetrahydrofuran, methyl acetate, ethyl acetate, acetonitrile, methylene chloride, chloroform, carbon tetrachloride, chlorobenzene, dichlorobenzene, dichloroethane, trichloroethane and the like.

The low dielectric thermosetting resin composition thus obtained, when cured, preferably has a dielectric constant of 3.2 or less, more preferably 3.0 or less. 3.2
This is because the following can sufficiently cope with miniaturization of electronic components such as a lead frame.

The adhesive tape of the present invention comprises an adhesive layer made of the above resin composition and a heat-resistant film. The adhesive tape of the present invention is a two-layered single-sided tape in which the adhesive layer is formed only on one side of the heat-resistant film, a double-sided tape in which the adhesive layer is formed on both sides of the heat-resistant film, and any other arbitrary tape. It has a layer. Examples of using the adhesive tape of the present invention for electronic components such as semiconductor devices include:
For example, if it is a single-sided tape, it can be pressed down and pasted directly on the lead frame, or if it is a double-sided tape,
It can be used in a method as shown in FIGS. In order to produce the adhesive tape for electronic parts of the present invention, the above-mentioned liquid adhesive may be applied to one or both sides of a heat-resistant film and dried. At this time, the coating thickness is 5 to 1
It is preferably in the range of 00 μm, especially 10 to 50 μm.

Examples of the heat-resistant film include heat-resistant resin films such as polyimide, polyphenylene sulfide, polyether, polyparabanic acid, and polyethylene terephthalate; Although a film etc. are mentioned, especially a film of a polyimide resin is preferable since its dimensional temperature dependency is small. The thickness of the heat-resistant film is 7.5 to 130 μm, preferably 12.
It is set in the range of 5-75 μm. If the thickness is too thin, the adhesive tape will have insufficient stiffness, and if it is too thick, the punching operation of the adhesive tape becomes difficult. Therefore, the above range is preferable. When the liquid adhesive is applied to one or both surfaces of the heat-resistant film to form an adhesive layer, a peelable protective film may be further provided on the adhesive layer.
As the protective film, a film having a thickness of 1 to 200 μm, preferably 10 to 100 μm is used. Examples of the peelable film that can be used include a polypropylene film, a fluororesin-based film, a polyethylene film, a polyethylene terephthalate film, paper, and in some cases, those obtained by imparting a peelability with a silicone resin or the like.

It is desirable that these peelable films have a 90 ° peel strength in the range of 0.01 to 10.0 g / cm. If the peel strength is smaller than the above range, there is a problem that the peelable film is easily peeled off when the adhesive tape is conveyed. Worse.

[0033]

EXAMPLES [Synthesis Example of Siloxane-Modified Polyimide] [Synthesis Example 1] 2,2-bis [4- (aminophenoxy) phenyl] propane was placed in a flask equipped with a stirrer.
42 g (72 mmol) and Q = N in the above formula (5)
6.96 g (28 mmol) of diaminosiloxane in which H ₂ , R = propylene and n is 1 and 35.83 of 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride
g (100 mmol) and 300 ml of N-methyl-2-pyrrolidone (NMP) were introduced at an ice temperature, and stirring was continued for 1 hour. Next, this solution was reacted at room temperature for 2 hours to synthesize a polyamic acid. 50 ml of toluene and 1.0 g of p-toluenesulfonic acid were added to the obtained polyamic acid,
The mixture was heated to 160 ° C., and an imidization reaction was performed for 3 hours while separating water azeotroped with toluene as the reaction proceeded. The toluene is distilled off, the obtained siloxane-modified polyimide varnish is poured into methanol, and the obtained precipitate is separated, pulverized, washed and dried, whereby the above formula (2a): (2b) = 72 : 28, molecular weight 18,
As a result, 61.9 g (94% yield) of a siloxane-modified polyimide having a Tg of 30 ° C. and a dielectric constant of 2.8 was obtained. When the infrared absorption spectrum of the obtained siloxane-modified polyimide was measured, typical imide absorption was observed at 1718 and 1783 cm ^-1 .

Synthesis Example 2 30.39 g of 2,2-bis [4- (4-aminophenoxy) phenyl] propane (7
4 mmol) and Q = NH ₂ , R
= Propylene, diaminosiloxane where n is 8 19.
94 g (26 mmol), 29.42 g (100 mmol) of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and N-methyl-2-pyrrolidone (NMP) 30
Siloxane having a molecular weight of (2a) :( 2b) = 74: 26, a molecular weight of 19,000, a Tg of 45 ° C., and a dielectric constant of 2.9, in the same manner as in Synthesis Example 1 using 0 ml. 72.3 g (95% yield) of the modified polyimide was obtained. When the infrared absorption spectrum of the obtained siloxane-modified polyimide was measured, typical imide absorption was observed at 1718 and 1783 cm ^-1 . [Synthesis Example 3] 41.48 g of 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane
(80 mmol) and Q = N in the above formula (5).
15.54 g (20 mmol) of diaminosiloxane having H ₂ , R = propylene and n = 8 was mixed with 2,3 ′, 3,4′-
29.42 g of biphenyltetracarboxylic dianhydride (1
00 mmol) and N-methyl-2-pyrrolidone (NM
P) Using 300 ml, in the same manner as in Synthesis Example 1,
The molar ratio of each structural unit is (2a) :( 2b) = 80: 20
81.2 g (94% yield) of a siloxane-modified polyimide having a molecular weight of 10,000, Tg of 60 ° C. and a dielectric constant of 2.9 was obtained. When the infrared absorption spectrum of the obtained siloxane-modified polyimide was measured, it was 1718 and 1783 cm ^-1.
A typical imide absorption was observed.

In the present invention, the glass transition temperature (T
g) is measured under the following conditions. Apparatus: Shear modulus measurement device (HAAKE “Rheo Stress RS”)
75 ”) Measurement temperature range: -10 to 300 ° C Temperature rise rate: 3 ° C / min Measurement frequency: 1 Hz Distortion rate: 0.01% ± 0.0025%

[Resin Composition Preparation Example] [Resin Composition Preparation Example 1] 100 parts by weight of the siloxane-modified polyimide resin obtained in Synthesis Example 3 was added to the above-mentioned formula (c).
-2) 272 parts by weight of the compound represented by the formula (b)
The compound of the formula (3) is 128 parts by weight (the molar equivalent of methylallyl group is 1 mole equivalent of 1 mole equivalent of maleimide group).
5) is added to tetrahydrofuran and mixed well,
By dissolving, a liquid adhesive having a solid content of 30% by weight was obtained. [Resin Composition Preparation Example 2] In the resin composition preparation example 1, the compound represented by the formula (c-2) was added to 206 parts by weight,
Liquid adhesion was carried out in the same manner as in Resin Composition Preparation Example 1, except that the compound represented by the formula (b-3) was changed to 193 parts by weight (the molar equivalent of methylallyl group to one molar equivalent of maleimide group was 1.0). Agent was obtained. [Resin Composition Preparation Example 3] The compound represented by the formula (c-2) was added to 166 parts by weight, and the compound represented by the formula (b-3) was added to 234 parts by weight (a methylallyl group was added to one mole equivalent of a maleimide group). A liquid adhesive was obtained in the same manner as in Resin Composition Preparation Example 1, except that the molar equivalent was changed to 1.5).

[Resin Composition Preparation Example 4] The above formula (c-2)
Is a resin composition except that the compound represented by the formula is changed to 52 parts by weight and the compound represented by the formula (b-3) is changed to 49 parts by weight (the molar equivalent of the methylallyl group is 1.0 relative to 1 molar equivalent of the maleimide group). A liquid adhesive was obtained in the same manner as in Preparation Example 1. [Resin Composition Preparation Example 5] The compound represented by the above formula (c-2) was added to 464 parts by weight, and the compound represented by the above formula (b-3) was added to 435 parts by weight (a methylallyl group was added to one mole equivalent of a maleimide group). A liquid adhesive was obtained in the same manner as in Resin Composition Preparation Example 1 except that the molar equivalent was changed to 1.0). [Resin Composition Preparation Example 6] 272 parts by weight of the compound represented by the formula (c-2) is added to 251 parts by weight of the compound represented by the formula (c-1), and then represented by the formula (b-3). A liquid adhesive was obtained by operating in the same manner as in Resin Composition Preparation Example 1, except that the compound was changed from 128 parts by weight to 148 parts by weight (the molar equivalent of methylallyl group to 1 molar equivalent of maleimide group was 1.0).

[Resin Composition Preparation Example 7] The above formula (c-2)
272 parts by weight of the compound represented by the formula (c-3) and 173 parts by weight of the compound represented by the formula (b-3) (the amount of the methylallyl group relative to 1 mole equivalent of the maleimide group) A liquid adhesive was obtained in the same manner as in Resin Composition Preparation Example 1 except that the molar equivalent was changed to 1.0). [Resin Composition Preparation Example 8] 272 parts by weight of the compound represented by the formula (c-2) is added to 218 parts by weight of the compound represented by the formula (c-4) wherein p is 1. The same procedure as in Resin Composition Preparation Example 1 was carried out except that 128 parts by weight of the compound represented by (b-3) was changed to 180 parts by weight (the molar equivalent of methylallyl group to 1.0 mole equivalent of maleimide group was changed to 1.0). A liquid adhesive was obtained. [Resin Composition Preparation Example 9] 272 parts by weight of the compound represented by the formula (c-2) is added to 298 parts by weight of the compound represented by the formula (c-4), wherein p is 8, and A liquid adhesive was prepared in the same manner as in Resin Composition Preparation Example 1, except that the compound represented by (b-3) was changed to 104 parts by weight (the molar equivalent of methylallyl group to 1 molar equivalent of maleimide group was 1.0). I got

[Resin Composition Preparation Example 10] The above formula (c-
The compound of the formula (c-5)
Preparation of a resin composition except that the compound represented by the formula (b-3) was changed to 155 parts by weight (the molar equivalent of methylallyl group to 1 mol equivalent of maleimide group was 1.0) to 247 parts by weight of the compound represented by A liquid adhesive was obtained in the same manner as in Example 1. [Resin Composition Preparation Example 11] A liquid adhesive was prepared in the same manner as in Resin Composition Preparation Example 2, except that the siloxane-modified polyimide obtained in Synthesis Example 3 was replaced with the siloxane-modified polyimide obtained in Synthesis Example 1. Obtained. [Resin Composition Preparation Example 12] A liquid adhesive was prepared in the same manner as in Resin Composition Preparation Example 2, except that the siloxane-modified polyimide obtained in Synthesis Example 3 was replaced with the siloxane-modified polyimide obtained in Synthesis Example 2. Obtained.

[Resin Composition Preparation Example 13] 100 parts by weight of the siloxane-modified polyimide resin obtained in Synthesis Example 3, 314 parts by weight of the compound represented by the formula (c-2), and In the compound represented by -2), 86 parts by weight of the compound in which R is a methyl group (the molar equivalent of a methylallyl group is 0.5 with respect to 1 molar equivalent of a maleimide group)
Add to tetrahydrofuran, mix well and dissolve,
A liquid adhesive having a solid content of 30% by weight was obtained. [Resin Composition Preparation Example 14] In the above resin composition preparation example 13, the compound represented by the formula (c-2) was added to 259 parts by weight, and the compound represented by the formula (b-2) was substituted by a methyl group. A liquid adhesive was obtained by operating in the same manner as in Resin Composition Preparation Example 13 except that the compound was changed to 141 parts by weight (the molar equivalent of methylallyl group to 1 molar equivalent of maleimide group was 1.0). [Resin Composition Preparation Example 15] 221 parts by weight of the compound represented by the formula (c-2) and 179 parts by weight of the compound represented by the formula (b-2) wherein R is a methyl group A liquid adhesive was obtained in the same manner as in Resin Composition Preparation Example 13, except that the molar equivalent of methylallyl group was changed to 1.5 with respect to 1 molar equivalent of maleimide group.

[Resin Composition Preparation Example 16]
The compound of the formula (c-1)
And 298 parts by weight of a compound represented by the formula (b-2) wherein R is a methyl group
A liquid adhesive was obtained in the same manner as in Resin Composition Preparation Example 13, except that the amount was changed to 02 parts by weight (the molar equivalent of methylallyl group per mol equivalent of maleimide group was 1.0).

[Resin Composition Preparation Example 17]
The compound of the formula (c-3)
Is added to 278 parts by weight of the compound represented by the formula (b-2)
A liquid adhesive was obtained by operating in the same manner as in Resin Composition Preparation Example 13, except that the amount was changed to 22 parts by weight (the molar equivalent of methylallyl group per mol equivalent of maleimide group was 1.0). [Resin Composition Preparation Example 18] 314 parts by weight of the compound represented by the formula (c-2) is added to 271 parts by weight of the compound represented by the formula (c-4) wherein p is 1, and the compound represented by the formula (b) Resin composition Preparation Example 13 except that the compound represented by -2), in which R was a methyl group, was changed to 129 parts by weight (the molar equivalent of methylallyl group to 1.0 mole equivalent of maleimide group was 1.0). The same operation was performed to obtain a liquid adhesive. [Resin Composition Preparation Example 19] 314 parts by weight of the compound represented by the formula (c-2) is added to 333 parts by weight of the compound represented by the formula (c-4) wherein p is 8, and the compound represented by the formula (b) Resin composition Preparation Example 13 except that the compound represented by -2), in which R is a methyl group, was changed to 67 parts by weight (the molar equivalent of methylallyl group to 1.0 mole equivalent of maleimide group was changed to 1.0). The same operation was performed to obtain a liquid adhesive. [Resin Composition Preparation Example 20] A compound represented by the formula (b-2) is added to 314 parts by weight of the compound represented by the formula (c-2) and 294 parts by weight of the compound represented by the formula (c-5). Liquid bonding was carried out in the same manner as in Resin Composition Preparation Example 13 except that the compound in which R was a methyl group was changed to 106 parts by weight (the molar equivalent of methylallyl group to 1.0 mole equivalent of maleimide group). Agent was obtained.

[Resin Composition Preparation Example 21] A liquid was prepared in the same manner as in Resin Composition Preparation Example 14, except that the siloxane-modified polyimide obtained in Synthesis Example 3 was replaced with the siloxane-modified polyimide obtained in Synthesis Example 1. An adhesive was obtained. [Resin Composition Preparation Example 22] A liquid adhesive was prepared in the same manner as in Resin Composition Preparation Example 14, except that the siloxane-modified polyimide obtained in Synthesis Example 3 was replaced with the siloxane-modified polyimide obtained in Synthesis Example 2. Obtained. [Resin Composition Preparation Example 23] 100 parts by weight of the siloxane-modified polyimide obtained in Synthesis Example 3, 273 parts by weight of the compound represented by the formula (c-2), and the compound represented by the formula (b-2) And 127 parts by weight of the compound in which R is hydrogen (the molar equivalent of allyl group is 1.0 relative to 1 molar equivalent of maleimide group) is added to tetrahydrofuran, mixed and dissolved sufficiently, and the solid content is 30% by weight. Of a liquid adhesive was obtained. [Resin Composition Preparation Example 24] 325 parts by weight of the compound represented by the formula (c-2) is added to 284 parts by weight of the compound represented by the formula (c-4), wherein p is 1. Resin composition except that the compound represented by (b-2), in which R is hydrogen, was changed from 127 parts by weight to 116 parts by weight (the molar equivalent of allyl group to 1.0 molar equivalent of maleimide group was 1.0). A liquid adhesive was obtained in the same manner as in Preparation Example 23.

[Resin Composition Preparation Example 25] A liquid composition was prepared in the same manner as in Resin Composition Preparation Example 23 except that the siloxane-modified polyimide obtained in Synthesis Example 3 was replaced with the siloxane-modified polyimide obtained in Synthesis Example 1. An adhesive was obtained. [Resin Composition Preparation Example 26] A liquid adhesive was prepared in the same manner as in Resin Composition Preparation Example 23 except that the siloxane-modified polyimide obtained in Synthesis Example 3 was replaced with the siloxane-modified polyimide obtained in Synthesis Example 2. Obtained.

[Resin Composition Preparation Example 27] 100 parts by weight of the siloxane-modified polyimide resin obtained in Synthesis Example 3, 69 parts by weight of the compound represented by the formula (c-2),
-1) 24 parts by weight of a compound in which R is a methyl group (the molar equivalent of a methylallyl group is 0.37 relative to 1 molar equivalent of a maleimide group), and in the compound represented by the formula (d2), R ⁵ is 7 parts by weight of a compound in which n is 1 in propylene (the molar equivalent of the amino group is 0.14 with respect to 1 molar equivalent of the maleimide group) are added to tetrahydrofuran, mixed and dissolved sufficiently, and the solid content of 30% by weight is obtained. A liquid adhesive was obtained. [Resin Composition Preparation Example 28] The compound of the formula (b-1) was added to 273 parts by weight of 69 parts by weight of the compound represented by the formula (c-2).
In the compound represented by the formula (d2), 24 parts by weight of the compound in which R is a methyl group was added to 97 parts by weight (the molar equivalent of methylallyl group was 1.0 with respect to 1 molar equivalent of maleimide group).
A resin composition preparation example except that 7 parts by weight of the compound represented by the formula (1) in which R ⁵ is propylene and n is 1 was changed to 30 parts by weight (the molar equivalent of the amino group to 0.1 mole equivalent of the maleimide group was 0.16) The same operation as in Example 27 was performed to obtain a liquid adhesive having a solid content of 30% by weight.

[Resin Composition Preparation Example 29]
69 parts by weight of the compound represented by 2) is added to 306 parts by weight, and 24 parts by weight of the compound represented by the formula (b-1) in which R is a methyl group is added to 64 parts by weight (based on 1 mole equivalent of the maleimide group). The molar equivalent of methylallyl group is 0.5),
In the compound represented by the formula (d2), 30 parts by weight of 7 parts by weight of the compound in which R ⁵ is propylene and n is 1 (the molar equivalent of the amino group is 0.1 mole equivalent to 1 mole equivalent of the maleimide group).
A liquid adhesive having a solid content of 30% by weight was obtained in the same manner as in Resin Composition Preparation Example 27 except for changing to 14). [Resin Composition Preparation Example 30] The compound of the formula (b-1) was added to 69 parts by weight of the compound represented by the formula (c-2) in 300 parts by weight.
24 parts by weight of a compound represented by the formula (b-2) wherein R is a methyl group is added to 70 parts by weight of a compound represented by the formula (b-2) wherein R is a methyl group. Of the compound represented by the formula (d2), wherein 7 parts by weight of the compound represented by the formula (d2) wherein R ⁵ is propylene and n is 1 is 30 parts by weight (the molar equivalent of the amino group with respect to 1 molar equivalent of the maleimide group is 0.1
A liquid adhesive having a solid content of 30% by weight was obtained in the same manner as in Resin Composition Preparation Example 27 except for changing to 4).

[Resin Composition Preparation Example 31]
69 parts by weight of the compound represented by 2) are added to 307 parts by weight, and 24 parts by weight of the compound represented by the formula (b-1) in which R is a methyl group is a compound represented by the formula (b-2) In 63 parts by weight of a compound in which R is hydrogen (the molar equivalent of the allyl group is 0.4 per mole of the maleimide group)
4) In the compound represented by the formula (d2), 7 parts by weight of the compound in which R ⁵ is propylene and n is 1 is changed to 30 parts by weight (the molar equivalent of the amino group is 0.14 relative to 1 molar equivalent of the maleimide group). A liquid adhesive having a solid content of 30% by weight was obtained in the same manner as in Resin Composition Preparation Example 27 except that the above procedure was repeated. [Resin Composition Preparation Example 32] The compound of the formula (b-1) was added to 278 parts by weight of 69 parts by weight of the compound represented by the formula (c-2).
24 parts by weight of the compound represented by the formula (b) in which R is a methyl group is added to 92 parts by weight of the compound represented by the formula (b-1) in which R is hydrogen (the molar equivalent of the allyl group to 1 molar equivalent of the maleimide group) Is 0.38), and in the compound represented by the formula (d2), 30 parts by weight of 7 parts by weight of the compound in which R ⁵ is propylene and n is 1 (the molar equivalent of the amino group to 0.15 molar equivalent of the maleimide group is 0.15). )) Except that the solid content ratio was 3
A 0% by weight liquid adhesive was obtained.

[Resin Composition Preparation Example 33]
69 parts by weight of the compound represented by 2) is added to 306 parts by weight of the compound represented by the formula (c-1), and 24 parts by weight of the compound represented by the formula (b-1) wherein R is a methyl group. To 74 parts by weight (the molar equivalent of the methylallyl group to one mole equivalent of the maleimide group is 0.41), 7 parts by weight of the compound represented by the formula (d2) wherein R ⁵ is propylene and n is 1 are 20 parts by weight. A liquid adhesive having a solid content of 30% by weight was obtained in the same manner as in Resin Composition Preparation Example 27 except that the molar equivalent of the amino group was changed to 0.15 with respect to 1 molar equivalent of the maleimide group. [Resin Composition Preparation Example 34] A compound represented by the formula (b-1) was added to 69 parts by weight of the compound represented by the formula (c-2) and 289 parts by weight of the compound represented by the formula (c-3). Of 24 parts by weight of a compound in which R is a methyl group is added to 86 parts by weight (the molar equivalent of a methylallyl group is 0.39 based on 1 molar equivalent of a maleimide group), and in the compound represented by the formula (d2), R ⁵ is The same procedure as in Resin Composition Preparation Example 27 was carried out except that 7 parts by weight of the compound wherein n was 1 was changed to 25 parts by weight (molar equivalent of amino group per mole of maleimide group was 0.15), and the solid content was changed. A 30% by weight liquid adhesive was obtained.

[Resin Composition Preparation Example 35]
69 parts by weight of the compound of the formula (c-4) are added to 284 parts by weight of the compound of the formula (c-4) wherein p is 1, and R in the compound of the formula (b-1) is methyl. 24 parts by weight of the compound, which is a group, to 90 parts by weight (the molar equivalent of methylallyl group is 0.1 mole equivalent to 1 mole equivalent of maleimide group).
38), in the compound represented by the formula (d2), R ⁵
Resin composition Preparation Example 27 except that 7 parts by weight of the compound in which n is 1 was changed to 26 parts by weight (the molar equivalent of the amino group was 0.15 with respect to 1 molar equivalent of the maleimide group)
A liquid adhesive having a solid content of 30% by weight was obtained in the same manner as described above. [Resin Composition Preparation Example 36] 69 parts by weight of the compound represented by the formula (c-2) was added to 336 parts by weight of the compound represented by the formula (c-4) in which p is 8, and b-
Compound 2 wherein R is a methyl group among the compounds represented by 1)
4 parts by weight to 52 parts by weight (molar equivalent of methylallyl group to 1 mole equivalent of maleimide group is 0.44), and 7 parts by weight of a compound represented by the above formula (d2) wherein R ⁵ is propylene and n is 1. To 12 parts by weight (molar equivalent of amino group to 0.1 mole equivalent of maleimide group is 0.14)
A liquid adhesive having a solid content of 30% by weight was obtained in the same manner as in Resin Composition Preparation Example 27 except that the composition was changed to.

[Resin Composition Preparation Example 37]
69 parts by weight of the compound represented by 2) is added to 302 parts by weight of the compound represented by the formula (c-5), and 24 parts by weight of the compound represented by the formula (b-1) wherein R is a methyl group. To 77 parts by weight (the molar equivalent of methylallyl group to one mole equivalent of the maleimide group was 0.41), 21 parts by weight of 7 parts by weight of the compound represented by the formula (d2) in which R ⁵ was propylene and n was 1 was added. A liquid adhesive having a solid content of 30% by weight was obtained in the same manner as in Resin Composition Preparation Example 27 except that the molar equivalent of the amino group was changed to 0.15 with respect to 1 molar equivalent of the maleimide group. [Resin Composition Preparation Example 38] The compound of the formula (b-1) was added to 231 parts by weight of 69 parts by weight of the compound represented by the formula (c-2).
In the compound represented by the formula, 24 parts by weight of the compound in which R is a methyl group is added to 97 parts by weight (the molar equivalent of methylallyl group is 0.45 based on 1 molar equivalent of maleimide group), and the compound represented by the formula (d)
In the compound represented by 2), 7 parts by weight of the compound in which R ⁵ is propylene and n is 1 is changed to 72 parts by weight of the compound in which n is 8 (the molar equivalent of the amino group is 0.14 relative to 1 molar equivalent of the maleimide group). Except that the resin composition preparation example 27
A liquid adhesive having a solid content of 30% by weight was obtained in the same manner as described above.

[Resin Composition Preparation Example 39]
69 parts by weight of the compound represented by 2) is added to 273 parts by weight, and 24 parts by weight of the compound represented by the formula (b-1) in which R is a methyl group is added to 97 parts by weight (based on 1 mole equivalent of the maleimide group). The molar equivalent of methylallyl group is 0.3
8) In the compound represented by the formula (d2), 7 parts by weight of a compound in which R ⁵ is propylene and n is 1 is 15 parts by weight of hexamethylenediamine (the molar equivalent of the amino group is 0.17 relative to 1 molar equivalent of the maleimide group). ) Was performed in the same manner as in Resin Composition Preparation Example 27, except that the liquid adhesive having a solid content of 30% by weight was obtained. [Resin Composition Preparation Example 40] 150 parts by weight of silica filler was dispersed in the liquid adhesive obtained in Resin Composition Preparation Example 28 to obtain a liquid adhesive. [Resin Composition Preparation Example 41] A liquid adhesive was prepared in the same manner as in Resin Composition Preparation Example 28 except that the siloxane-modified polyimide obtained in Synthesis Example 3 was replaced with the siloxane-modified polyimide obtained in Synthesis Example 1. Obtained. [Resin Composition Preparation Example 42] A liquid adhesive was prepared in the same manner as in Resin Composition Preparation Example 28 except that the siloxane-modified polyimide obtained in Synthesis Example 3 was replaced with the siloxane-modified polyimide obtained in Synthesis Example 2. Obtained.

[Resin Composition Preparation Example 43]
69 parts by weight of the compound represented by 2) is added to 152 parts by weight, and 24 parts by weight of the compound represented by the formula (b-1) in which R is a methyl group is added to 142 parts by weight (maleimide group 1
The molar equivalent of methylallyl group to the molar equivalent is 1.
0), 7 parts by weight of the compound represented by the formula (d2) in which R ⁵ is propylene and n is 1 is changed to 105 parts by weight (the molar equivalent of the amino group is 1.0 with respect to 1 molar equivalent of the maleimide group). A liquid adhesive having a solid content of 30% by weight was obtained in the same manner as in Resin Composition Preparation Example 27 except that the above procedure was repeated. [Resin Composition Preparation Example 44] The compound of the formula (b-1) was added to 116 parts by weight of the compound represented by the formula (c-2) and 116 parts by weight.
In the compound represented by the formula (d), 24 parts by weight of the compound in which R is a methyl group is added to 163 parts by weight (the molar equivalent of methylallyl group is 1.5 with respect to 1 molar equivalent of maleimide group),
Resin composition except that 7 parts by weight of the compound represented by 2) in which R ⁵ is propylene and n is 1 are changed to 121 parts by weight (the molar equivalent of amino group to 1 molar equivalent of maleimide group is 1.5) A liquid adhesive having a solid content of 30% by weight was obtained in the same manner as in Preparation Example 27.

[Resin Composition Preparation Example 45 (for Comparative Example 1)]
Nylon epoxy adhesive ("Toresin FS-410")
A product of Teikoku Chemical Industry Co., Ltd. (solid content 20%, solvent: isopropyl alcohol: methyl ethyl ketone = 2: 1) was prepared. [Resin Composition Preparation Example 46 (for Comparative Example 2)] Polyimide (amic acid) (“Lark TPI” Mitsui Chemicals, Inc.)
(N-methyl-2-pyrrolidone) was prepared.

[Resin Composition Preparation Example 47 (for Comparative Example 3)]
A liquid adhesive was obtained in the same manner as in Resin Composition Preparation Example 1, except that the siloxane-modified polyimide obtained in Synthesis Example 3 was replaced with an acrylonitrile-butadiene copolymer.

[Examples 1 to 44] The liquid adhesives of the respective resin composition preparation examples 1 to 44 were applied to both sides of a polyimide film so that the thickness of the adhesive layer after drying was 20 μm, and hot air was applied. The adhesive tape was manufactured by drying at 160 ° C. for 5 minutes in a circulation dryer. [Comparative Examples 1 and 3] Each of the adhesives of the above resin composition preparation examples 45 and 47 was applied to both sides of a polyimide film so that the thickness of the adhesive layer after drying became 20 μm. After drying at 150 ° C. for 15 minutes in the middle, adhesive tapes of Comparative Examples 1 and 3 were produced in order. [Comparative Example 2] The adhesive of Resin Composition Preparation Example 46 was applied on both sides of a polyimide film so that the thickness of the adhesive layer after drying became 20 µm, and the mixture was dried in a hot-air circulation type dryer.
The adhesive tape of Comparative Example 2 was produced by drying at 50 ° C. for 120 minutes and then at 250 ° C. for 60 minutes.

[Manufacture of Semiconductor Package] The semiconductor package shown in FIG. 1 was manufactured using the adhesive tapes of the above Examples and Comparative Examples. [1. Assembly of Lead Frame] Punching of Adhesive Tape: The adhesive tape was punched into a ring shape using a mold. Temporary bonding of adhesive tape: plane 2 on hot plate
Was placed, and the adhesive tape 6 punched in a ring shape was pressed onto the plane 2 with a metal rod and temporarily bonded. At this time, the adhesive layer was hot-melted and bonded under the conditions shown in Table 1. Lead frame assembly: Align the plane 2 to which the adhesive tape 6 has been temporarily adhered in the above process and the lead frame body, apply heat and pressure on a heated hot plate, and connect the lead pins 3 of the lead frame and the plane 2 via the adhesive tape 6. And stuck together. At this time, the adhesive layer was hot-melted and bonded under the conditions shown in Table 1. Adhesive tape cure: Examples 1 to 44 and Comparative Examples 1 and 3
In the case of the above, it was placed in a hot-air circulation type oven purged with nitrogen and thermally cured under the conditions shown in Table 1. The reason why the bonding conditions and the curing conditions are different is that the characteristics of each adhesive tape are different. Here, optimal bonding conditions were selected for each adhesive tape, and the adhesive was cured based on the optimum conditions.

[0057]

[Table 1]

[2. Assembling of Semiconductor Package] A semiconductor package was assembled according to the following procedure using the above-prepared lead frame. Die bonding: A semiconductor chip is bonded to the plane using a silver paste for die bonding,
For 2 hours. Wire bonding: A wire bonder was used to wire the wire pad on the semiconductor chip and the silver-plated portion at the end of the inner lead wire with a gold wire. Molding: Transfer molding was performed with an epoxy-based molding agent. Finishing process We performed processes such as homing, die cutting, and plating of the outer lead part, and finished the package.

[Test and Evaluation] [Evaluation of Adhesive Tape at Lead Frame Assembly] (A) Taping temperature: Evaluation of whether or not the adhesive tape can be easily and quickly adhered to an adherend, that is, a plane or a lead pin. went. Specifically, the temperature range where each adhesive tape could be adhered to the lead frame was measured by a taping machine. As a result, the adhesive tape of this example and the adhesive tapes of Comparative Examples 1 and 3 were 100 to 240 ° C.
In the comparative example 2, a temperature of 350 ° C. or higher was required. (B) Oxidation of Lead Frame: At the time of taping, whether or not oxidation of the lead frame surface had occurred was evaluated by visual judgment on discoloration of the lead frame surface.
As a result, the adhesive tapes of this example and Comparative Examples 1 and 3 did not oxidize, but in Comparative Example 2, the discoloration was observed because the adhesive temperature was too high and required a long time. Oxidation of the lead frame occurred.

(C) Void: When curing the adhesive,
Whether or not voids generated in the adhesive were at a practically problematic level was evaluated by visual judgment using a microscope. As a result, the adhesive tapes of this example and Comparative Examples 2 and 3 did not have any voids, but Comparative Example 1 did. (D) Workability: Handling property (curling, tapping, etc.) of the adhesive tape during lead frame assembly
(Runnability) was evaluated. As a result, the adhesive tape of this example and the adhesive tapes of Comparative Examples 1 and 3 all had good handling properties, and in the case of Comparative Example 2, there was a problem in handling properties.

(E) Wire Bondability: At the time of assembling the package, the wire bondability of the gold wire onto the lead frame during wire bonding was confirmed. As a result, in the case of using the adhesive tapes of this example and Comparative Examples 2 and 3, in the test of 832 pins, the bonding failure was zero. On the other hand, Comparative Example 1
In the case of (1), bonding failure of 123 pins among 832 products was confirmed, and bonding of the gold wire could not be made to have sufficient strength. (F) Evaluation of semiconductor package: For each semiconductor package obtained as described above, a PCBT test (Pres
sure Cooker Biased Test). Conditions were applied at 5 volts, 121 ° C., 2 atm, 100% RH, and the electrical reliability was evaluated. As a result, as shown in Tables 2 to 4, in the case of the present example, no leakage or short circuit occurred in 1000 hours, and the electrical reliability was high.

As is clear from the above results, in the case of the adhesive tape of the present embodiment, a semiconductor package can be manufactured favorably. On the other hand, in the case of the adhesive tape of the comparative example, there are problems such as oxidation of the lead frame, the bonding conditions are not suitable for assembling the lead frame, and the wire bonding of the gold wire cannot be performed.
Not suitable for use in making low dielectric electronic components.

[Peel strength test] JIS C6481
(Peeling strength), each adhesive tape was applied to a copper plate (1 to 4 in Examples 1 to 44 and Comparative Examples 1 and 3).
After sticking (taping) at 50 ° C. and at 350 ° C. in Comparative Example 2, the 90 ° peel strength of the 10 mm wide tape at room temperature was measured. The results are shown in Tables 2 to 4. Each of the adhesive tapes of Examples 1 to 44 was 1.2 to 1.4 kg / 10
mm, whereas in Comparative Example 1, 0.3 kg /
10 mm, and 1.0 kg / 1 in the case of Comparative Example 2.
It was 0 mm.

[Dielectric constant] Manufacture of Adhesive Tape for Measuring Dielectric Constant (Example) Polyethylene terephthalate obtained by subjecting each of the liquid adhesives of the above resin composition preparation examples 1 to 44 to a release treatment so that the thickness of the adhesive layer after drying becomes 20 μm. It was applied to a film and dried at 160 ° C. for 5 minutes in a hot air circulation type drier to produce an adhesive tape for dielectric constant measurement. (Comparative Examples 1 and 3) The liquid adhesives of the above resin composition preparation examples 45 and 47 were applied to a polyethylene terephthalate film which had been subjected to a release treatment so that the thickness of the adhesive layer after drying was 20 μm, and was heated with hot air. 1 at 150 ° C in a circulation dryer
After drying for 5 minutes, an adhesive tape for measuring a dielectric constant was manufactured. (Comparative Example 2) The liquid adhesive of Resin Composition Preparation Example 46 was applied to a polyethylene terephthalate film that had been subjected to a release treatment so that the thickness of the adhesive layer after drying was 20 μm, and a hot air circulation type dryer was used. After drying at 150 ° C. for 120 minutes and then at 250 ° C. for 60 minutes, an adhesive tape for dielectric constant measurement was prepared. 2. Method of Measuring Dielectric Constant The dielectric constant was determined in accordance with JIS C6481 (relative dielectric constant and dielectric loss tangent) at a frequency of 1 MHz by measuring the capacitance of the cured adhesive layer. Table 2 shows the results.
The results are shown in FIG. The dielectric constant of the adhesive layer in Examples 1 to 44 is 2.4 to 3.0, whereas that of Comparative Example 1 is 3.5, and that of Comparative Example 2 is 3.4. In the case of Comparative Example 3, it was 3.5.

[0065]

[Table 2]

[0066]

[Table 3]

[0067]

[Table 4]

[0068]

The adhesive tape of the present invention is excellent in low dielectric constant, heat resistance, workability, low-temperature adhesiveness, low-temperature curability, reliability and the like. For example, as a tape for fixing a lead frame, a TAB tape, etc. It can be suitably used for bonding between members around a lead frame constituting the device, for example, a lead pin, a semiconductor chip mounting substrate, a heat sink, a semiconductor chip itself, and the like. In particular, by setting the sum of the component (b) and the component (c) to the specific amount with respect to the component (a), the heat resistance and the Young's modulus are improved, and the scattering of the resin can be prevented. Furthermore, the amount of the methylallyl group of the component (b) is 0.1 to 2.2 with respect to 1 mole equivalent of the maleimide group of the component (c).
By setting the molar equivalent to 0, electric reliability and the like are improved, and workability is improved. The siloxane-modified polyimide of the component (a) has a glass transition temperature of 15
When the temperature is 0 ° C. or lower, the melting temperature is lowered, the working temperature is lowered, and the adhesiveness is improved. When the weight average molecular weight is 5,000 to 500,000, thermal stability is improved, heat resistance is improved, and workability and adhesiveness are improved. Further, when the dielectric constant of the resin composition in the cured state is 3.2 or less, it is possible to cope with miniaturization of electronic components such as a lead frame. The adhesive tape according to claim 1, wherein the resin composition further contains a diamine compound represented by the formula (d1) and / or the formula (d2), thereby lowering the cured adhesive layer. Dielectric.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of an example of a resin-sealed semiconductor device.

FIG. 2 is a cross-sectional view of another example of a resin-sealed semiconductor device.

FIG. 3 is a sectional view of still another example of the resin-sealed semiconductor device.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Semiconductor chip 2 Plane 3 Lead pin 4 Bonding wire 5 Resin 6 Adhesive tape 7 Die pad 8 Electrode

 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Ken Sato 3-1, Yosoba Tomoecho, Shizuoka City, Shizuoka Prefecture Inside the Electronic Materials Division of Hamakawa Paper Mills Co., Ltd. (72) Inventor Daisuke Orino Yomune Tomoe, Shizuoka City, Shizuoka Prefecture 3-1 Machi Famagawa Paper Mills Electronic Materials Division F-term (reference) 4J004 AA06 AA11 AA18 CA06 CA07 CB01 CC02 DA01 DA02 DA03 DA04 DB02 EA05 FA05 4J040 EH031 EH032 FA011 FA012 FA181 FA182 FA191 FA192 HD36 JA09 LA01 LA11 LA09 LA09 NA20

Claims (16)

[Claims] 1. A component (a): a siloxane-modified polyimide in which a structural unit represented by the following formula (2a) and a structural unit represented by the following formula (2b) are arranged; ) Or the following formula (b-2)
And a component (c): a resin composition containing a compound having two or more maleimide groups, and a heat-resistant film. Embedded image (In the above formulas (2a) and (2b), Z is a direct bond,
_{-O -, - SO 2 -,} - CO -, - C (CH 3) 2 -, -
Represents a bond of C (CF ₃ ) ₂ — or —COOCH ₂ CH ₂ OCO—, and Ar represents a divalent group having an aromatic ring;
Is an alkylene group having 1 to 10 carbon atoms or a methylene group represented by S
i represents —CH ₂ OC ₆ H ₄ — bonded to i, and n represents 1 to
Means an integer of 20. ) (In the above formulas (b-1) and (b-2), R represents a hydrogen atom or a methyl group.) 2. The component (b) is a compound represented by the following formula (b-3), and the sum of the components (b) and (c) is 100 parts by weight of the component (a). Is 10-9
And the amount of the methylallyl group of the component (b) is 0.1 to 2.0 relative to 1 mole equivalent of the maleimide group of the component (c).
2. The adhesive tape according to claim 1, wherein the adhesive tape has a molar equivalent. Embedded image 3. The adhesive tape according to claim 1, wherein the component (b) is a compound represented by the following formula (b-2). Embedded image (In the above formula (b-2), R represents a hydrogen atom or a methyl group.) 4. The adhesive tape according to claim 1, wherein the resin composition further contains a diamine compound represented by the following formula (d1) and / or (d2). H ₂ N—R ⁵ —NH ₂ (d1) (In the formulas (d1) and (d2), R ⁵ represents a divalent aliphatic group, an aromatic group, or an alicyclic group;
Represents an integer of 1 to 8. ) 5. The method according to claim 5, wherein 100 parts by weight of component (a) is
The total of the component (b) and the component (c) is 10 to 900 parts by weight, and the allyl group or the methyl allyl group of the component (b) is 0.1 to 1 mole equivalent of the maleimide group of the component (c).
5. The adhesive tape according to claim 1, wherein the adhesive tape has a molar equivalent of 2.0. 6. A structural unit represented by the formula (2a) in the siloxane-modified polyimide of the component (a), wherein the structural unit represented by the formula (2)
The ratio of the structural unit represented by b) is 90 to 40 in a molar ratio:
The adhesive tape according to any one of claims 1 to 5, wherein the adhesive tape is 10 to 60. 7. The siloxane-modified polyimide of the component (a) has a structural unit represented by the following formula (3a):
0 mol% and 10 units of the structural unit represented by the following formula (3b).
2 to 60 mol%.
4. The adhesive tape according to any one of 4. Embedded image (In the formula, Arm is a tetravalent aromatic group and 3,3 ′, 4,4′-
It means any of a diphenylsulfone structure, a 3,3 ', 4,4'-biphenyl structure and a 2,3', 3,4'-biphenyl structure. Ar means a divalent group having an aromatic ring. R represents —CH ₂ OC ₆ H ₄ — in which an alkylene group or a methylene group having 1 to 10 carbon atoms is bonded to Si;
Represents an integer of 1 to 20. ) 8. The method according to claim 1, wherein Ar is a group selected from the following chemical formula group.
The adhesive tape according to any one of the above. Embedded image (In the formula, R ¹ , R ² , R ³ and R ⁴ may be the same or different and each represent a hydrogen atom, an alkyl group or an alkoxy group having 1 to 4 carbon atoms. Is not.) 9. The adhesive tape according to claim 1, wherein the siloxane-modified polyimide of the component (a) has a glass transition temperature of 150 ° C. or lower. 10. The adhesive tape according to claim 1, wherein the siloxane-modified polyimide as the component (a) has a weight average molecular weight of 5,000 to 500,000. 11. The adhesive tape according to claim 1, wherein the siloxane-modified polyimide as the component (a) has a dielectric constant of 3.0 or less. 12. The compound according to claim 1, wherein the compound having two or more maleimide groups of the component (c) is selected from the group of compounds represented by the following formula. The adhesive tape as described. Embedded image (In the formula (c-4), p represents an integer of 1 to 8.) 13. The total of component (b), component (c) and component (d) is 10 per 100 parts by weight of component (a).
The adhesive tape according to claim 4, wherein the amount of the amino group of the component (d) is 0.1 to 2.0 molar equivalents with respect to 1 molar equivalent of the maleimide group of the component (c). 14. The adhesive tape according to claim 1, wherein the resin composition has a dielectric constant of 3.2 or less in a cured state. 15. The resin composition according to claim 1, wherein a filler having a particle size of 1 μm or less is contained in the resin composition in an amount of 1 to 40% by weight of the total solid. Adhesive tape. 16. The adhesive tape according to claim 1, wherein the heat-resistant film is made of polyimide.