JPH10183079A - Adhesive tape for electronic part - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an adhesive tape which can be adhered at relatively low temps., hardly damages semiconductor chips when adhered, and does not cause a part adhered at a first thermal pressing step to be softened at a second thermal pressing step by forming, on both sides of a substrate, polyimide-contg. layers having glass transition points different from each other. SOLUTION: This adhesive tape is prepd. by forming, on each side of a 5-200μm - thick substrate, an at least 5μm - thick adhesive layer which contains at least one polyimide comprising 100-40mol% at least one kind of structural unit selected from among units represented by formulas I and II (wherein Ar is a divalent group selected from among groups represented by formula III; and R<1> to R<4> are each H, a 1-4C alkyl, or a 1-4C alkoxy) and 0-60mol% at least one kind of structural unit selected from among units represented by formulas IV and V. Pref. the adhesive layers on both sides of the substrate are different in glass transition point from each other by at least 30 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electronic component for use in bonding 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 a semiconductor chip itself. Related to adhesive tape.

[0002]

2. Description of the Related Art Conventionally, adhesive tapes and the like used in a resin-sealed semiconductor device include an adhesive tape for fixing a lead frame and a TAB tape. For example, in the case of an adhesive tape for fixing a lead frame, It is used for fixing the lead pins of the lead frame and for improving the production yield and productivity of the lead frame itself and the entire semiconductor assembly process.It is generally taped on the lead frame by a lead frame maker and brought to the semiconductor maker, After mounting the IC, it is sealed with resin. Therefore, the adhesive tape for fixing lead frames has not only general reliability at the semiconductor level and workability during taping, but also sufficient room temperature adhesive strength immediately after taping and sufficient heat resistance to withstand heating in the semiconductor device assembly process. Etc. are required.

Conventionally, adhesive tapes used in such applications include, for example, a synthetic rubber resin such as polyacrylonitrile, polyacrylate or acrylonitrile-butadiene copolymer on a support such as a polyimide film. Is used alone or modified with another resin, or an adhesive made of a mixture of another resin or another curing component is applied to form a B-stage state.

In recent years, a resin-sealed semiconductor device (semiconductor package) having a structure as shown in FIGS. 1 to 3 has been developed and manufactured. In FIG. 1, a lead pin 3 and a metal radiator plate 2 are connected by an adhesive layer 6, the semiconductor chip 1 is mounted on the metal radiator plate 2, and a bonding wire 4 between the semiconductor chip 1 and the lead pin 3 is provided. In addition, it has a structure sealed with a resin 5. In FIG. 2, the lead pins 3 of the lead frame are fixed to the semiconductor chip 1 by an adhesive layer 6, and have a structure that is sealed by a resin 5 together with the bonding wires 4. In FIG. 3, the semiconductor chip 1 is mounted on the die pad 7, the electrodes 8 are fixed by the adhesive layer 6, and the space between the semiconductor chip 1 and the electrodes 8 and between the electrode 8 and the lead pins 3 are formed. Between
Each has a structure in which they are connected by bonding wires 4 and sealed by a resin 5.

[0005]

When an adhesive tape coated with a conventional thermosetting adhesive is used for the adhesive layer in the resin-encapsulated semiconductor device having the structure shown in FIGS. However, since the heat resistance is not sufficient, there is a problem that the generated gas contaminates the lead and lowers the adhesive strength, or causes a package crack. In addition, when a resin having a molecular structure that is too different is used on both surfaces of the base material, significant distortion is likely to occur during heating unless the resin has a similar thermal expansion coefficient. Therefore, an adhesive for electronic components having sufficient heat resistance and reliability and an adhesive tape for electronic components using the same are desired.

The present inventors have previously made an invention of an adhesive tape using an adhesive containing a polyimide comprising a structural unit represented by the following formula (1a) or (2b) (Japanese Patent Application No. 7-1).
No. 55474, Japanese Patent Application No. 7-245149) can solve the above-mentioned problem. However, these adhesive tapes also have problems. For example, in the semiconductor device having the structure shown in FIG. 2, the punched adhesive tape is first attached to the lead pin 3, and then the semiconductor chip 1 is attached. Since the adhesive having the same glass transition temperature is used for the other surface, the adhesive on the side of the lead pin 3 is also softened at the bonding temperature of the semiconductor chip 1, and the lead pin 3 can be used because it is distorted or moves and comes into contact. There was a problem that disappeared. Further, the bonding to the lead pin 3 side can be performed by heating the lead pin 3 at a temperature about 80 ° C. higher than the glass transition temperature, but since the semiconductor chip 1 cannot be directly heated, heating is performed from the lead pin 3 side at the temperature. Then, it is necessary to bond the semiconductor chip by applying time or pressure, and there is a possibility that the semiconductor chip may be damaged. The same problem was found in the thermoplastic polyimide single-layer adhesive tape. Furthermore, in the case of a single-layer adhesive tape, since there is no support, distortion due to thermal expansion of the lead pin easily occurs in the heating step, and processing becomes difficult. Even in the semiconductor device shown in FIG. 1 or FIG. 3 in which the semiconductor chip is not directly bonded, the thermocompression bonding process is performed twice, and if the second process is performed at the same temperature as the first time, distortion or movement of the lead pin due to softening of the adhesive occurs. There is a problem to do.

The present invention has been made to solve the above problems. That is, an object of the present invention is to enable bonding at a relatively low temperature, minimize the damage to the semiconductor chip when bonding the semiconductor chip to the lead pins, and minimize the damage in the second thermocompression bonding step.
It is an object of the present invention to provide an adhesive tape for electronic parts having sufficient reliability without causing softening of the adhesive part at the time of the round.

[0008]

According to the present invention, at least one of a structural unit represented by the following formula (1a) and a structural unit represented by the following formula (1b) is provided on both sides of a substrate. 1
0 to 40 mol%, and at least one kind of polyimide comprising 0 to 60 mol% of at least one of the structural unit represented by the following formula (2a) and the structural unit represented by the following formula (2b): An adhesive tape provided with an adhesive layer containing the adhesive tape, wherein the adhesive layers on both surfaces have different glass transition temperatures from each other.

Embedded image (In the formula, Ar represents a divalent group selected from the following structures having an aromatic ring.)

Embedded image (Wherein, 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 having 1 to 4 carbon atoms. Are not hydrogen atoms at the same time.)

Embedded image (In the formula, R represents —CH ₂ OC ₆ H ₄ — in which an alkylene group having 1 to 10 carbon atoms or a methylene group is bonded to Si, and n represents an integer of 1 to 20.)

In the adhesive tape for electronic parts of the present invention,
An adhesive layer having a different glass transition temperature (hereinafter, referred to as Tg) means that an adhesive layer having a high Tg is formed on one surface of a substrate and an adhesive layer having a low Tg is formed on another surface of the substrate. It becomes. Further, it is preferable that the glass transition temperature has a difference of 30 ° C. or more. Further, at least one adhesive layer of the electronic component adhesive tape of the present invention has a particle diameter of 1 μm.
m of 0.1 to 50 parts by weight of a filler, and it is also possible to provide a peelable film on at least one surface of the adhesive layer.

[0010]

Embodiments of the present invention will be described below in detail. The substrate used in the present invention is a heat-resistant resin film made of polyimide, polyamide imide, polyphenylene sulfide, polysulfone, or the like, and preferably has insulating properties in addition to heat resistance. Tg of the heat-resistant resin film is preferably 300 ° C. or higher,
More preferably, a resin that does not show a clear glass transition temperature, such as a polyimide film commercially available from Ube Industries under the trade name: Upilex, is preferable. The thickness of the base material is preferably selected according to the size of the package to be used, which is 5 to 200 μm, and more preferably 10 to 100 μm.
Is used.

The polyimide used in the present invention has the formula (1)
It contains at least one of the structural unit represented by a) and the structural unit represented by formula (1b) in an amount of 100 to 40 mol%. In this case, at least one of the structural unit represented by the formula (1a) and the structural unit represented by the formula (1b) includes the structural unit represented by the formula (1a) alone,
It includes both a structural unit represented by the formula (1b) alone and a structural unit composed of both structural units.

Embedded image The polyimide used in the present invention contains at least one of the structural unit represented by the formula (2a) and the structural unit represented by the formula (2b) in an amount of 0 to 60 mol%.
In this case, the structural unit represented by the formula (2a) and the formula (2)
At least one of the structural units represented by b) is represented by the formula (2)
one consisting of the structural unit represented by a) alone, formula (2b)
And both those consisting of a single structural unit and those consisting of both structural units.

Embedded image

The polyimide used in the present invention is:
As the number of structural units represented by the formulas (1a) and (1b) (hereinafter referred to as [(1a) + (1b)]) increases, Tg increases.
On the other hand, as the number of structural units represented by the formulas (2a) and (2b) (hereinafter referred to as [(2a) + (2b)]) increases, the Tg decreases. For this reason, in the polyimide, it is possible to control the temperature at which the adhesive can be pressed by controlling the Tg by variously changing the content ratio of the formulas (1a) and (2b).

The polyimide used in the present invention can be obtained by using a general polyimide production method. That is, it can be produced from a tetracarboxylic anhydride corresponding to each repeating structural unit and a diamine or diisocyanate corresponding to each repeating structural unit. Specifically, the polyimide is a tetracarboxylic dianhydride represented by the following formula (3a), a compound represented by the following formula (3b), a compound represented by the following formula (4), and a compound represented by the following formula (5) Can be produced by reacting with the siloxane compound represented by the formula (1).

Embedded image Y-Ar-Y (4) (wherein, Ar represents a divalent group selected from the above-described structures having an aromatic ring, and Y represents an amino group or an isocyanate group.)

Embedded image (Wherein, R represents —CH ₂ OC ₆ H ₄ — in which an alkylene group having 1 to 10 carbon atoms or a methylene group is bonded to Si, and n represents an integer of 1 to 20. Y represents an amino group) Or an isocyanate group.)

In the present invention, the tetracarboxylic dianhydride represented by the above formula (3a) or (3b), which is used as a raw material for producing a polyimide and constitutes a basic repeating structural unit of the obtained polyimide, is 3,3 ', 4,4'
-Diphenylsulfonetetracarboxylic dianhydride and ethylene glycol bistrimellitate dianhydride.

The compound represented by the above formula (4) is
Ar is a divalent group selected from the above-described structures having an aromatic ring, and specific examples of the diamines in which the functional group Y is an amino group include the following. Can be 3,3′-diaminobiphenyl, 3,4 ′
-Diaminobiphenyl, 4,4'-diaminobiphenyl, 3,3'-diaminodiphenylmethane, 3,4'-
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'-
Diaminodiphenyl sulfide, 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) -1-methylethyl] benzene, 1,4-bis [1- (4-aminophenyl) -1-methylethyl] 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, 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, 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, 9,9-bis (3-aminophenyl) fluorene, 9,9-bis (4-aminophenyl) fluorene,
3,3′-diamino-2,2 ′, 4,4′-tetramethyldiphenylmethane, 3,3′-diamino-2,2 ′,
4,4'-tetraethyldiphenylmethane, 3,3'-
Diamino-2,2 ', 4,4'-tetrapropyldiphenylmethane, 3,3'-diamino-2,2', 4,4 '
-Tetraisopropyldiphenylmethane, 3,3'-diamino-2,2 ', 4,4'-tetrabutyldiphenylmethane, 3,4'-diamino-2,3', 4,5'-tetramethyldiphenylmethane, 3,4 '-Diamino-
2,3 ′, 4,5′-tetraethyldiphenylmethane,
3,4'-diamino-2,3 ', 4,5'-tetrapropyldiphenylmethane, 3,4'-diamino-2,
3 ′, 4,5′-tetraisopropyldiphenylmethane, 3,4′-diamino-2,3 ′, 4,5′-tetrabutyldiphenylmethane, 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'-tetraisopropoxydiphenylmethane, 4,4'-diamino-
3,3 ', 5,5'-tetrabutoxydiphenylmethane, 4,4'-diamino-3,3'-dimethoxydiphenylmethane, 4,4'-diamino-3,3'-diethoxydiphenylmethane and the like. In the compound represented by the formula (4), as the diisocyanates in which the functional group Y is an isocyanate group, the diamines exemplified above in which “amino” is replaced with “isocyanate” Can be mentioned.

In the siloxane compound represented by the formula (5) used as a raw material for producing polyimide, the diamines in which the functional group Y is an amino group include bis (3-aminopropyl) tetramethyldisiloxane and bis (3-aminopropyl) tetramethyldisiloxane. 10
-Aminodecamethylene) tetramethyldisiloxane, aminopropyl-terminated dimethylsiloxane tetramers and octamers, 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 diisocyanates in which the functional group Y is an isocyanate group include those obtained by replacing “amino” with “isocyanate” in the diamines exemplified above. In the compounds represented by the formulas (4) and (5), the diisocyanates in which the functional group Y is an isocyanate group can be easily obtained by reacting the corresponding diamine with phosgene according to a conventional method. Can be manufactured.

The polyimide used in the present invention can be produced as follows. When tetracarboxylic dianhydride and diamine are used as raw materials, they may be used in an organic solvent, if necessary, in the presence of a catalyst such as tributylamine, triethylamine, and triphenyl phosphite (20% by weight of the reaction product). Part or less), heating to 100 ° C. or higher, preferably 180 ° C. or higher to directly obtain a polyimide, and reacting tetracarboxylic dianhydride and diamine in an organic solvent at 100 ° C. or lower to obtain a polyimide precursor. After obtaining the polyamic acid that is the body, if necessary,
A method of obtaining a polyimide by adding a dehydration catalyst such as p-toluenesulfonic acid (1 to 5 times the molar amount of tetracarboxylic dianhydride) and heating to cause an imidization reaction, or a method in which this polyamic acid is treated with acetic anhydride, Dehydration ring closure agents such as acid anhydrides such as propionic acid and benzoic anhydride, carbodiimide compounds such as dicyclohexylcarbodiimide, and, if necessary, ring closure catalysts such as pyridine, isoquinoline, imidazole and triethylamine (dehydration ring closure catalysts and There is a method of adding a carboxylic acid dianhydride (2 to 10 times the mole of carboxylic acid dianhydride) and chemically closing the ring at a relatively low temperature (from room temperature to about 100 ° C.).

The organic solvent used in the above reaction is 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. Further, if necessary, benzene, toluene, xylene, methyl ethyl ketone, acetone, tetrahydrofuran, dioxane, monoglyme, diglyme, methyl cellosolve, cellosolve acetate, methanol, ethanol, isopropanol, methylene chloride, chloroform, tricrene, nitrobenzene, etc. Can also be used as a mixture.

When tetracarboxylic dianhydride and diisocyanate are used as raw materials, they can be produced according to the above-mentioned method for directly obtaining polyimide, and the reaction temperature at this time is as follows. It is preferably room temperature or higher, particularly preferably 60 ° C. or higher. By reacting tetracarboxylic dianhydride with a diamine or diisocyanate in an equimolar amount, a polyimide having a high degree of polymerization can be obtained. It is also possible to produce a polyimide using an excess amount in the above.

The molecular weight of the polyimide used in the present invention is preferably set appropriately in accordance with the film-forming property, since the expression of the film-forming property varies depending on the type of the repeating structural unit constituting the polyimide. When used for the double-sided adhesive tape for electronic parts of the present invention, the adhesive layer needs to have a certain degree of film formability, and the heat resistance is also reduced. In the present invention, the number average molecular weight generally needs to be 4,000 or more. Also, when used as a thermoplastic adhesive,
If the viscosity at the time of melting is too high, the adhesiveness is significantly reduced. The molecular weight is one of the factors that determine the viscosity at the time of melting. The polyimide used in the present invention has a number average molecular weight of about 400,000 or less. , Making it difficult to use as an adhesive. The GPC used for the measurement of molecular weight
The measurement conditions are shown after Table 1 and Table 2.

In the present invention, the adhesive layer provided on both sides with the base material interposed therebetween may contain a polyimide selected from the above-mentioned polyimides alone. However, in order to adjust Tg, two or more of these polyimides may be used. May be appropriately mixed and contained. The difference in Tg of the polyimide forming the adhesive layer provided on both sides via the base material preferably has a difference of 30 ° C. or more, more preferably 40 ° C., from the relationship of the bonding time to the electronic component, the pressure, and the temperature. That is all. Since both adhesive layers constituting the adhesive tape of the present invention are made of similar polyimide, the adhesive layers on both surfaces have almost the same coefficient of thermal expansion. Therefore, the adhesive tape of the present invention has little distortion from normal temperature to the time of heating, and has good workability.
As described above, the adhesive tape for electronic components of the present invention has an adhesive layer having a different Tg formed on both surfaces thereof via a base material. The adhesive layer in this adhesive tape,
It can be obtained by forming a polyimide film on both sides of the substrate using a conventionally known method. This film is formed, for example, by applying a coating solution containing polyimide on one surface of a substrate made of a heat-resistant film, drying the coating solution, and drying the first solution.
Is formed on the other surface of the base material, and then a coating liquid containing polyimide is applied to the other surface of the base material so as to form an adhesive layer having a Tg different from that of the first adhesive layer. Although there is a method of forming a layer, other formation methods can be adopted. For example, a method of simultaneously applying and drying a coating solution containing a polyimide having a different Tg on both surfaces of a substrate,
Alternatively, a method of forming an adhesive layer film containing polyimide and then thermocompression bonding the substrate and the film can be employed. Although the thickness of the adhesive tape for electronic parts in the present invention is appropriately selected, it is usually preferably 15 to 250 μm. Further, the thickness of the adhesive layers on both surfaces of the substrate is preferably 5 μm or more in order to maintain the minimum adhesive strength.

In the present invention, in order to form the adhesive layer by coating, a varnish for coating polyimide is obtained by dissolving the polyimide in an appropriate solvent. As a solvent for dissolving the polyimide used in the present invention, N-methyl-
2-pyrrolidone, N, N-dimethylacetamide, N,
Aprotic polar solvents such as N-dimethylformamide, dimethylsulfoxide, sulfolane, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidone, phenolic solvents such as phenol, cresol, xylenol, p-chlorophenol, isophorone , Cyclohexanone, carbitol acetate, diglyme,
A wide range of organic solvents such as dioxane, tetrahydrofuran and the like can be mentioned. Furthermore, methanol, ethanol, alcohol solvents such as isopropanol, methyl acetate, ethyl acetate, ester solvents such as butyl acetate, acetonitrile, nitrile solvents such as benzonitrile, benzene, toluene, aromatic solvents such as xylene, It is also possible to use a mixture of a halogen-based solvent such as chloroform and dichloromethane to such an extent that the polyimide is not precipitated. It is preferable that the concentration and viscosity of the polyimide solution are appropriately changed according to the coating conditions. In the present invention, the adhesive layers provided on both surfaces of the base material may each contain a filler having a particle size of 1 μm or less in order to control the characteristics at the time of bonding. When the filler is blended, the content is 0.1 to 5 of the total solid content.
0 parts by weight or less, more preferably 0.4 to 25 parts by weight.
Parts by weight. When the amount of the filler is more than 50 parts by weight, the adhesive strength is remarkably reduced, while when the amount is less than 0.1 part by weight, the effect of adding the filler cannot be obtained. As the filler, for example, silica, quartz powder, mica, alumina, diamond powder, zircon powder, calcium carbonate, magnesium oxide, fluororesin and the like are used.

In the present invention, a film having a thickness of 1 to
It is also possible to provide a releasable film of 200 μm as a protective layer. Specifically, polyethylene, polypropylene, fluororesin, polyethylene terephthalate,
A resin film or paper of polyimide or the like, or those obtained by subjecting their surfaces to release treatment using a silicone-based release agent are used.

[0024]

The present invention will be described below in detail with reference to examples. First, synthetic examples of the polyimide used in the present invention and a coating varnish containing the same will be described. Synthesis Example 1 In a flask equipped with a stirrer, 12.34 g (67 mmol) of 3,4′-diaminobiphenyl and 1,3-bis (3
-Aminopropyl) -1,1,3,3-tetramethyldisiloxane 8.20 g (33 mmol) and 3,3 ′,
35.83 g (100 mmol) of 4,4'-diphenylsulfonetetracarboxylic dianhydride and N-methyl-2
-Pyrrolidone (hereinafter referred to as "NMP") 300 ml
Was introduced under ice temperature, and stirring was continued for 1 hour. Next, this solution was reacted at room temperature for 3 hours to synthesize a polyamic acid. 50 ml of toluene and 1.
0 g of p-toluenesulfonic acid was added, and the mixture was heated to 160 ° C., and an imidization reaction was performed for 3 hours while separating water azeotropic with toluene as the reaction proceeded. After that, toluene was distilled off, and the obtained polyimide varnish was poured into methanol, and the obtained precipitate was separated, pulverized, washed and dried, thereby obtaining each of the structural units represented by the above formula. When the molar ratio is [(1a) + (1b)]:
[(2a) + (2b)] = 67:33, [(1a):
(1b) = 100: 0, (2a): (2b) = 100:
0] (50.0 g, yield 95%). When the infrared absorption spectrum of the obtained polyimide was measured, typical imide absorption was observed at 1718 cm ^-1 and 1783 cm ^-1 . Also, its molecular weight, T
g and pyrolysis onset temperature were measured. Table 1 shows the results.
Shown in This polyimide was dissolved in tetrahydrofuran (hereinafter referred to as “THF”) to a concentration of 25% by weight to obtain a coating varnish.

Synthesis Example 2 13.41 g (67 mmol) of 4,4'-oxydianiline and 1,3-bis (3-aminopropyl) -1,1,1
Synthesis Example 1 Using 8.20 g (33 mmol) of 3,3-tetramethyldisiloxane, 35.83 g (100 mmol) of 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride and 300 ml of NMP The molar ratio of each structural unit is [(1a) + (1
b)]: [(2a) + (2b)] = 67:33, [(1
a): (1b) = 100: 0, (2a): (2b) = 1
00: 0] (51.0 g, yield 95).
%). When the infrared absorption spectrum of the obtained polyimide was measured, 1718 cm ⁻¹ and 1783 cm
^{At -1} , typical imide absorption was observed. Further, its molecular weight, Tg and thermal decomposition onset temperature were measured. Table 1 shows the results. This polyimide was dissolved in THF to a concentration of 25% by weight to obtain a coating varnish.

Synthesis Example 3 13.29 g of 4,4'-diaminodiphenylmethane (6
7 mmol) and 1,3-bis (3-aminopropyl)-
8.20 g of 1,1,3,3-tetramethyldisiloxane
(33 mmol) and 35.83 g of 3,3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride (100
Mmol) and 300 ml of NMP, and the molar ratio of each structural unit is [(1a) + (1
b)]: [(2a) + (2b)] = 67:33, [(1
a): (1b) = 100: 0, (2a): (2b) = 1
00: 0] (52.0 g, yield 97).
%). When the infrared absorption spectrum of the obtained polyimide was measured, 1718 cm ⁻¹ and 1783 cm ⁻¹
A typical imide absorption was observed. Further, its molecular weight, Tg and thermal decomposition onset temperature were measured. Table 1 shows the results. 25% by weight of this polyimide in THF
To obtain a coating varnish.

Synthesis Example 4 14.49 g of 4,4′-diaminodiphenyl sulfide
(67 mmol) and 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane 8.
20 g (33 mmol) and 35.83 g of 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride
(100 mmol) and 300 ml of NMP,
In the same manner as in Synthesis Example 1, the molar ratio of each structural unit was [(1
a) + (1b)]: [(2a) + (2b)] = 67: 3
3, [(1a) :( 1b) = 100: 0, (2a):
(2b) = 100: 0] polyimide 51.0
g (93% yield). When the infrared absorption spectrum of the obtained polyimide was measured, it was 1718 cm ^-1 and 1
Typical imide absorption was observed at 780 cm ^-1 . Further, its molecular weight, Tg and thermal decomposition onset temperature were measured.
Table 1 shows the results. This polyimide is converted to THF
To a concentration of 25% by weight
A varnish for coating was obtained.

Synthesis Example 5 16.64 g of 3,3′-diaminodiphenyl sulfone
(67 mmol) and 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane 8.
20 g (33 mmol) and 35.83 g of 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride
(100 mmol) and 300 ml of NMP,
In the same manner as in Synthesis Example 1, the molar ratio of each structural unit was [(1
a) + (1b)]: [(2a) + (2b)] = 67: 3
3, [(1a) :( 1b) = 100: 0, (2a):
(2b) = 100: 0] polyimide 51.5
g (yield 90%) was obtained. The infrared absorption spectrum of the obtained polyimide was measured to be 1715 cm ^-1 and 1
Typical imide absorption was observed at 783 cm ^-1 . Further, its molecular weight, Tg and thermal decomposition onset temperature were measured.
Table 1 shows the results. This polyimide is converted to THF
To a concentration of 25% by weight
A varnish for coating was obtained.

Synthesis Example 6 2,2-bis (4-aminophenyl) propane 15.1
6 g (67 mmol), 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane 8.20 g (33 mmol) and 3,3 ′, 4,4′-diphenylsulfone 35.83 Tetracarboxylic dianhydride
g (100 mmol) and 300 ml of NMP, and in the same manner as in Synthesis Example 1, the molar ratio of each structural unit was [(1a) + (1b)]: [(2a) + (2b)] = 6.
7:33, [(1a) :( 1b) = 100: 0, (2
a): Polyimide 5 represented by (2b) = 100: 0]
4.0 g (97% yield) was obtained. When the infrared absorption spectrum of the obtained polyimide was measured, it was 1718 cm ^-1.
And 1783 cm ^-1 typical absorption of imide was observed. Further, its molecular weight, Tg and thermal decomposition onset temperature were measured. Table 1 shows the results. This polyimide,
A coating varnish was obtained by dissolving in THF to a concentration of 25% by weight.

Synthesis Example 7 2,2-bis (4-aminophenyl) hexafluoropropane 22.40 g (67 mmol) and 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyl 8.20 g (33 mmol) of disiloxane and 3,
35.83 g (100 mmol) of 3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride and NMP3
In the same manner as in Synthesis Example 1, the molar ratio of each structural unit was [(1a) + (1b)]: [(2a) +
(2b)] = 67:33, [(1a) :( 1b) = 10
0: 0, (2a) :( 2b) = 100: 0] to obtain 60.0 g (95% yield) of a polyimide. The infrared absorption spectrum of the obtained polyimide was measured.
Typical imide absorption was observed at 721 cm ^-1 and 1783 cm ^-1 . Further, its molecular weight, Tg and thermal decomposition onset temperature were measured. Table 1 shows the results. This polyimide was dissolved in THF to a concentration of 25% by weight to obtain a coating varnish.

Synthesis Example 8 1,4-bis (4-aminophenoxy) benzene
58 g (67 mmol), 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane 8.20 g (33 mmol), 3,3 ′, 4,4′-diphenylsulfone 35.83 Tetracarboxylic dianhydride
g (100 mmol) and 300 ml of NMP, and in the same manner as in Synthesis Example 1, the molar ratio of each structural unit was [(1a) + (1b)]: [(2a) + (2b)] = 6.
7:33, [(1a) :( 1b) = 100: 0, (2
a): Polyimide 5 represented by (2b) = 100: 0]
8.0 g (97% yield) was obtained. When the infrared absorption spectrum of the obtained polyimide was measured, it was 1718 cm ^-1.
And 1780 cm ^-1 typical absorption of imide was observed. Further, its molecular weight, Tg and thermal decomposition onset temperature were measured. Table 1 shows the results. This polyimide,
A coating varnish was obtained by dissolving in THF to a concentration of 25% by weight.

Synthesis Example 9 1,3-bis (4-aminophenoxy) benzene
58 g (67 mmol), 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane 8.20 g (33 mmol), 3,3 ′, 4,4′-diphenylsulfone 35.83 Tetracarboxylic dianhydride
g (100 mmol) and 300 ml of NMP, and in the same manner as in Synthesis Example 1, the molar ratio of each structural unit was [(1a) + (1b)]: [(2a) + (2b)] = 6.
7:33, [(1a) :( 1b) = 100: 0, (2
a): Polyimide 5 represented by (2b) = 100: 0]
8.0 g (97% yield) was obtained. When the infrared absorption spectrum of the obtained polyimide was measured, it was 1718 cm ^-1.
And 1780 cm ^-1 typical absorption of imide was observed. Further, its molecular weight, Tg and thermal decomposition onset temperature were measured. Table 1 shows the results. This polyimide,
A coating varnish was obtained by dissolving in THF to a concentration of 25% by weight.

Synthesis Example 10 23.08 g (67 mmol) of 1,3-bis [1- (4-aminophenyl) -1-methylethyl] benzene and 1,3-bis (3-aminopropyl) -1,1 , 3,3
As in Synthesis Example 1, using 8.20 g (33 mmol) of tetramethyldisiloxane, 35.83 g (100 mmol) of 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride and 300 ml of NMP. And the molar ratio of each structural unit is [(1a) + (1b)]:
[(2a) + (2b)] = 67:33, [(1a):
(1b) = 100: 0, (2a): (2b) = 100:
0] (62.5 g, yield 98%). When the infrared absorption spectrum of the obtained polyimide was measured, typical imide absorption was observed at 1718 cm ^-1 and 1783 cm ^-1 . Also, its molecular weight, T
g and pyrolysis onset temperature were measured. Table 1 shows the results.
Shown in This polyimide was dissolved in THF to a concentration of 25% by weight to obtain a coating varnish.

Synthesis Example 11 4,4'-bis (4-aminophenoxy) biphenyl 2
4.68 g (67 mmol), 8.20 g (33 mmol) of 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane and 3,3 ′, 4,4 ′
-Diphenylsulfonetetracarboxylic dianhydride 35.
Using 83 g (100 mmol) and 300 ml of NMP in the same manner as in Synthesis Example 1, the molar ratio of each structural unit was [(1a) + (1b)]: [(2a) + (2b)] = 6.
7:33, [(1a) :( 1b) = 100: 0, (2
a): Polyimide 6 represented by (2b) = 100: 0]
4.0 g (98% yield) was obtained. When the infrared absorption spectrum of the obtained polyimide was measured, it was 1718 cm ^-1.
And 1780 cm ^-1 typical absorption of imide was observed. Further, its molecular weight, Tg and thermal decomposition onset temperature were measured. Table 1 shows the results. This polyimide,
A coating varnish was obtained by dissolving in THF to a concentration of 25% by weight.

Synthesis Example 12 25.75 g (67 mmol) of 4,4'-bis (4-aminophenoxy) diphenyl ether and 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldiphenylether 8.20 g (33 mmol) of siloxane and 3,
35.83 g (100 mmol) of 3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride and NMP3
In the same manner as in Synthesis Example 1, the molar ratio of each structural unit was [(1a) + (1b)]: [(2a) +
(2b)] = 67:33, [(1a) :( 1b) = 10
0: 0, (2a) :( 2b) = 100: 0], to obtain 64.0 g of a polyimide (yield 97%). The infrared absorption spectrum of the obtained polyimide was measured.
Typical imide absorption was observed at 718 cm ^-1 and 1783 cm ^-1 . Further, its molecular weight, Tg and thermal decomposition onset temperature were measured. Table 1 shows the results. This polyimide was dissolved in THF to a concentration of 25% by weight to obtain a coating varnish.

Synthesis Example 13 28.98 g (67 mmol) of bis [4- (4-aminophenoxy) phenyl] sulfone and 1,3-bis (3-
8.20 g (33 mmol) of aminopropyl) -1,1,3,3-tetramethyldisiloxane and 3,3 ′, 4
4'-diphenylsulfonetetracarboxylic dianhydride 3
Using 5.83 g (100 mmol) and 300 ml of NMP, the molar ratio of each structural unit was [(1a) + (1b)]: [(2a) + (2b)] in the same manner as in Synthesis Example 1.
= 67: 33, [(1a) :( 1b) = 100: 0,
(2a): (2b) = 100: 0], and 65.0 g (94% yield) of polyimide was obtained. When the infrared absorption spectrum of the obtained polyimide was measured, 1719c
Typical imide absorptions were observed at m ^-1 and 1785 cm ^-1 . Further, its molecular weight, Tg and thermal decomposition onset temperature were measured. Table 1 shows the results. This polyimide was dissolved in THF to a concentration of 25% by weight to obtain a coating varnish.

Synthesis Example 14 27.50 g (67 mmol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane and 1,3-
8.20 g (33 mmol) of bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane and 3,
35.83 g (100 mmol) of 3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride and NMP3
In the same manner as in Synthesis Example 1, the molar ratio of each structural unit was [(1a) + (1b)]: [(2a) +
(2b)] = 67:33, [(1a) :( 1b) = 10
0: 0, (2a) :( 2b) = 100: 0] to obtain 65.0 g (96% yield) of a polyimide. The infrared absorption spectrum of the obtained polyimide was measured.
Typical imide absorptions were observed at 720 cm ^-1 and 1783 cm ^-1 . Further, its molecular weight, Tg and thermal decomposition onset temperature were measured. Table 1 shows the results. This polyimide was dissolved in THF to a concentration of 25% by weight to obtain a coating varnish.

Synthesis Example 15 34.74 g (67 mmol) of 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane and 1,3-bis (3-aminopropyl) -1,1,1
Example of synthesis using 8,20 g (33 mmol) of 3,3-tetramethyldisiloxane, 35.83 g (100 mmol) of 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride and 300 ml of NMP 1, the molar ratio of each structural unit is [(1a) + (1
b)]: [(2a) + (2b)] = 67:33, [(1
a): (1b) = 100: 0, (2a): (2b) = 1
00: 0] of 74.0 g (yield 98
%). When the infrared absorption spectrum of the obtained polyimide was measured, it was found to be 1715 cm ^-1 and 1786 cm ^-1.
A typical imide absorption was observed. Further, its molecular weight, Tg and thermal decomposition onset temperature were measured. Table 1 shows the results. 25% by weight of this polyimide in THF
To obtain a coating varnish.

Synthesis Example 16 9,9-bis (4-aminophenoxy) fluorene 2
3.35 g (67 mmol), 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane 8.20 g (33 mmol) and 3,3 ′, 4,4 ′
-Diphenylsulfonetetracarboxylic dianhydride 35.
Using 83 g (100 mmol) and 300 ml of NMP in the same manner as in Synthesis Example 1, the molar ratio of each structural unit was [(1a) + (1b)]: [(2a) + (2b)] = 6.
7:33, [(1a) :( 1b) = 100: 0, (2
a): Polyimide 6 represented by (2b) = 100: 0]
0.5 g (95% yield) was obtained. When the infrared absorption spectrum of the obtained polyimide was measured, it was found to be 1,720 cm ^-1.
And 1780 cm ^-1 typical absorption of imide was observed. Further, its molecular weight, Tg and thermal decomposition onset temperature were measured. Table 1 shows the results. This polyimide,
A coating varnish was obtained by dissolving in THF to a concentration of 25% by weight.

Synthesis Example 17 13.82 g (75 mmol) of 3,4′-diaminobiphenyl and 1,3-bis (3-aminopropyl) -1,
6.21 g of 1,3,3-tetramethyldisiloxane (2
5 mmol), 41.03 g (100 mmol) of ethylene glycol bistrimellitate dianhydride and NMP3
In the same manner as in Synthesis Example 1, the molar ratio of each structural unit was [(1a) + (1b)]: [(2a) +
(2b)] = 75:25, [(1a) :( 1b) = 0:
100, (2a) :( 2b) = 0: 100] to obtain 54.0 g (94% yield) of a polyimide. The infrared absorption spectrum of the obtained polyimide was measured.
Typical imide absorption was observed at 718 cm ^-1 and 1783 cm ^-1 . Further, its molecular weight, Tg and thermal decomposition onset temperature were measured. Table 1 shows the results. This polyimide was dissolved in THF to a concentration of 25% by weight to obtain a coating varnish.

Synthesis Example 18 15.02 g (75 mmol) of 4,4′-oxydianiline and 1,3-bis (3-aminopropyl) -1,1,1
6.21 g (25 mmol) of 3,3-tetramethyldisiloxane, 41.03 g (100 mmol) of ethylene glycol bistrimellitate dianhydride and NMP300
and the molar ratio of each structural unit is [(1a) + (1b)]: [(2a) + (2
b)] = 75:25, [(1a) :( 1b) = 0: 10
0, (2a) :( 2b) = 0: 100] to obtain 52.0 g (yield: 89%) of a polyimide. The infrared absorption spectrum of the obtained polyimide was measured.
Typical absorption of imide was observed in 8 cm ^-1 and 1783 cm ^-1. Further, its molecular weight, Tg and thermal decomposition onset temperature were measured. Table 1 shows the results. This polyimide was dissolved in THF to a concentration of 25% by weight to obtain a coating varnish.

Synthesis Example 19 14.87 g of 4,4′-diaminodiphenylmethane (7
5 mmol) and 1,3-bis (3-aminopropyl)-
6.21 g of 1,1,3,3-tetramethyldisiloxane
(25 mmol), 41.03 g (100 mmol) of ethylene glycol bistrimellitate dianhydride and NM
Using P300 ml and the same method as in Synthesis Example 1, the molar ratio of each structural unit was [(1a) + (1b)]: [(2
a) + (2b)] = 75:25, [(1a) :( 1b)
= 0: 100, (2a) :( 2b) = 0: 100] to obtain 55.0 g (94% yield) of a polyimide. When the infrared absorption spectrum of the obtained polyimide was measured, typical imide absorption was observed at 1718 cm ^-1 and 1783 cm ^-1 . Further, its molecular weight, Tg and thermal decomposition onset temperature were measured. Table 1 shows the results.
This polyimide was dissolved in THF to a concentration of 25% by weight to obtain a coating varnish.

Synthesis Example 20 16.22 g of 4,4′-diaminodiphenyl sulfide
(75 mmol) and 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane6.
Using 21 g (25 mmol), 41.03 g (100 mmol) of ethylene glycol bistrimellitate dianhydride and 300 ml of NMP, in the same manner as in Synthesis Example 1, the molar ratio of each structural unit was [(1a) + ( 1b)]:
[(2a) + (2b)] = 75:25, [(1a):
(1b) = 0: 100, (2a) :( 2b) = 0: 10
0] (54.0 g, yield 90%). When the infrared absorption spectrum of the obtained polyimide was measured, typical imide absorption was observed at 1718 cm ^-1 and 1780 cm ^-1 . Also, its molecular weight, T
g and pyrolysis onset temperature were measured. Table 1 shows the results.
Shown in This polyimide was dissolved in THF to a concentration of 25% by weight to obtain a coating varnish.

Synthesis Example 21 18.63 g of 3,3′-diaminodiphenyl sulfone
(75 mmol) and 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane6.
Using 21 g (25 mmol), 41.03 g (100 mmol) of ethylene glycol bistrimellitate dianhydride and 300 ml of NMP, in the same manner as in Synthesis Example 1, the molar ratio of each structural unit was [(1a) + ( 1b)]:
[(2a) + (2b)] = 75:25, [(1a):
(1b) = 0: 100, (2a) :( 2b) = 0: 10
0] (55.5 g, yield 89%). When the infrared absorption spectrum of the obtained polyimide was measured, typical imide absorption was observed at 1715 cm ^-1 and 1783 cm ^-1 . Also, its molecular weight, T
g and pyrolysis onset temperature were measured. Table 1 shows the results.
Shown in This polyimide was dissolved in THF to a concentration of 25% by weight to obtain a coating varnish.

Synthesis Example 22 2,2-bis (4-aminophenyl) propane 16.9
7 g (75 mmol), 6.21 g (25 mmol) of 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane and 41.03 g of ethylene glycol bistrimellitate dianhydride ( 100 mmol) and 300 ml of NMP, and the molar ratio of each structural unit was [(1a) + (1
b)]: [(2a) + (2b)] = 75:25, [(1
a): (1b) = 0: 100, (2a): (2b) =
0: 100] 57.0 g of polyimide (yield 9
4%). When the infrared absorption spectrum of the obtained polyimide was measured, 1718 cm ⁻¹ and 1783 cm
^{At -1} , typical imide absorption was observed. Further, its molecular weight, Tg and thermal decomposition onset temperature were measured. Table 1 shows the results. This polyimide was dissolved in THF to a concentration of 25% by weight to obtain a coating varnish.

Synthesis Example 23 25.07 g (75 mmol) of 2,2-bis (4-aminophenyl) hexafluoropropane and 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyl 6.21 g (25 mmol) of disiloxane and 41.03 g of ethylene glycol bistrimellitate dianhydride
(100 mmol) and 300 ml of NMP,
In the same manner as in Synthesis Example 1, the molar ratio of each structural unit was [(1
a) + (1b)]: [(2a) + (2b)] = 75: 2
5, [(1a): (1b) = 0: 100, (2a):
(2b) = 0: 100] polyimide 67.0
g (98% yield). When the infrared absorption spectrum of the obtained polyimide was measured, it was 1721 cm ^-1 and 1
Typical imide absorption was observed at 783 cm ^-1 . Further, its molecular weight, Tg and thermal decomposition onset temperature were measured.
Table 1 shows the results. This polyimide is converted to THF
To a concentration of 25% by weight
A varnish for coating was obtained.

Synthesis Example 24 1,4-bis (4-aminophenoxy) benzene 21.
92 g (75 mmol), 6.21 g (25 mmol) of 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane and 41.03 g of ethylene glycol bistrimellitate dianhydride ( 100 mmol) and 300 ml of NMP, and the molar ratio of each structural unit is [(1a) + (1
b)]: [(2a) + (2b)] = 75:25, [(1
a): (1b) = 0: 100, (2a): (2b) =
0: 100] 62.0 g of polyimide (yield 9
5%). When the infrared absorption spectrum of the obtained polyimide was measured, 1718 cm ^-1 and 1780 cm
^{At -1} , typical imide absorption was observed. Further, its molecular weight, Tg and thermal decomposition onset temperature were measured. Table 1 shows the results. This polyimide was dissolved in THF to a concentration of 25% by weight to obtain a coating varnish.

Synthesis Example 25 1,3-bis (4-aminophenoxy) benzene 21.
92 g (75 mmol), 6.21 g (25 mmol) of 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane and 41.03 g of ethylene glycol bistrimellitate dianhydride ( 100 mmol) and 300 ml of NMP, and the molar ratio of each structural unit is [(1a) + (1
b)]: [(2a) + (2b)] = 75:25, [(1
a): (1b) = 0: 100, (2a): (2b) =
0: 100], 64.0 g of polyimide (yield 9).
7%). When the infrared absorption spectrum of the obtained polyimide was measured, 1718 cm ^-1 and 1780 cm
^{At -1} , typical imide absorption was observed. Further, its molecular weight, Tg and thermal decomposition onset temperature were measured. Table 2 shows the results. This polyimide was dissolved in THF to a concentration of 25% by weight to obtain a coating varnish.

Synthesis Example 26 25.84 g (75 mmol) of 1,3-bis [1- (4-aminophenyl) -1-methylethyl] benzene and 1,3-bis (3-aminopropyl) -1,1 , 3,3
6.21 g (25 mmol) of tetramethyldisiloxane, 41.03 g (100 mmol) of ethylene glycol bistrimellitate dianhydride and 300 ml of NMP
In the same manner as in Synthesis Example 1, the molar ratio of each structural unit is [(1a) + (1b)]: [(2a) + (2
b)] = 75:25, [(1a) :( 1b) = 0: 10
0, (2a) :( 2b) = 0: 100] to obtain 67.0 g (96% yield) of a polyimide. The infrared absorption spectrum of the obtained polyimide was measured.
Typical absorption of imide was observed in 8 cm ^-1 and 1783 cm ^-1. Further, its molecular weight, Tg and thermal decomposition onset temperature were measured. Table 2 shows the results. This polyimide was dissolved in THF to a concentration of 25% by weight to obtain a coating varnish.

Synthesis Example 27 4,4′-Bis (4-aminophenoxy) biphenyl 2
7.63 g (75 mmol), 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane 6.21 g (25 mmol) and ethylene glycol bistrimellitate dianhydride In the same manner as in Synthesis Example 1 using 03 g (100 mmol) and 300 ml of NMP, the molar ratio of each structural unit was [(1a) + (1
b)]: [(2a) + (2b)] = 75:25, [(1
a): (1b) = 0: 100, (2a): (2b) =
0: 100] of 69.5 g of polyimide (yield 9).
8%). When the infrared absorption spectrum of the obtained polyimide was measured, 1718 cm ^-1 and 1780 cm
^{At -1} , typical imide absorption was observed. Further, its molecular weight, Tg and thermal decomposition onset temperature were measured. Table 2 shows the results. This polyimide was dissolved in THF to a concentration of 25% by weight to obtain a coating varnish.

Synthesis Example 28 28.82 g (75 mmol) of 4,4′-bis (4-aminophenoxy) diphenyl ether and 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldiphenyl ether 6.21 g (25 mmol) of siloxane and 41.03 g of ethylene glycol bistrimellitate dianhydride
(100 mmol) and 300 ml of NMP,
In the same manner as in Synthesis Example 1, the molar ratio of each structural unit was [(1
a) + (1b)]: [(2a) + (2b)] = 75: 2
5, [(1a): (1b) = 0: 100, (2a):
(2b) = 0: 100] polyimide 70.0
g (yield 97%) was obtained. When the infrared absorption spectrum of the obtained polyimide was measured, it was 1718 cm ^-1 and 1
Typical imide absorption was observed at 783 cm ^-1 . Further, its molecular weight, Tg and thermal decomposition onset temperature were measured.
Table 2 shows the results. This polyimide is converted to THF
To a concentration of 25% by weight
A varnish for coating was obtained.

Synthesis Example 29 32.08 g (75 mmol) of bis [4- (4-aminophenoxy) phenyl] sulfone and 1,3-bis (3-
(Aminopropyl) -1,1,3,3-tetramethyldisiloxane 6.21 g (25 mmol) and ethylene glycol bistrimellitate dianhydride 41.03 g (100
Synthesis Example 1
In the same manner as described above, the molar ratio of each structural unit is [(1a) +
(1b)]: [(2a) + (2b)] = 75:25,
[(1a) :( 1b) = 0: 100, (2a) :( 2
b) = 0: 100] 74.0 g of a polyimide represented by the following formula:
(97% yield). When the infrared absorption spectrum of the obtained polyimide was measured, it was 1719 cm ^-1 and 17
Typical imide absorption was observed at 85 cm ^-1 . Further, its molecular weight, Tg and thermal decomposition onset temperature were measured.
Table 2 shows the results. This polyimide is converted to THF
To a concentration of 25% by weight
A varnish for coating was obtained.

Synthesis Example 30 30.78 g (75 mmol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane and 1,3-bis
6.21 g (25 mmol) of bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane and 41.03 of ethylene glycol bistrimellitate dianhydride
g (100 mmol) and 300 ml of NMP, and in the same manner as in Synthesis Example 1, the molar ratio of each structural unit was [(1a) + (1b)]: [(2a) + (2b)] = 7.
5:25, [(1a) :( 1b) = 0: 100, (2
a): Polyimide 7 represented by (2b) = 0: 100]
3.0 g (98% yield) was obtained. When the infrared absorption spectrum of the obtained polyimide was measured, it was found to be 1,720 cm ^-1.
And 1783 cm ^-1 typical absorption of imide was observed. Further, its molecular weight, Tg and thermal decomposition onset temperature were measured. Table 2 shows the results. This polyimide,
A coating varnish was obtained by dissolving in THF to a concentration of 25% by weight.

Synthesis Example 31 38.89 g (75 mmol) of 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane and 1,3-bis (3-aminopropyl) -1,1,1
6.21 g (25 mmol) of 3,3-tetramethyldisiloxane, 41.03 g (100 mmol) of ethylene glycol bistrimellitate dianhydride and NMP300
and the molar ratio of each structural unit is [(1a) + (1b)]: [(2a) + (2
b)] = 75:25, [(1a) :( 1b) = 0: 10
0, (2a) :( 2b) = 0: 100] to obtain 80.0 g (97% yield) of a polyimide. The infrared absorption spectrum of the obtained polyimide was measured.
Typical absorption of imide was observed in 5 cm ^-1 and 1786 cm ^-1. Further, its molecular weight, Tg and thermal decomposition onset temperature were measured. Table 2 shows the results. This polyimide was dissolved in THF to a concentration of 25% by weight to obtain a coating varnish.

Synthesis Example 32 9,9-bis (4-aminophenoxy) fluorene 2
6.14 g (75 mmol), 6.23 g (25 mmol) of 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane and ethylene glycol bistrimellitate dianhydride In the same manner as in Synthesis Example 1 using 03 g (100 mmol) and 300 ml of NMP, the molar ratio of each structural unit was [(1a) + (1
b)]: [(2a) + (2b)] = 75:25, [(1
a): (1b) = 0: 100, (2a): (2b) =
0: 100] 66.0 g of polyimide (yield 9).
5%). When the infrared absorption spectrum of the obtained polyimide was measured, 1720 cm ⁻¹ and 1780 cm
^{At -1} , typical imide absorption was observed. Further, its molecular weight, Tg and thermal decomposition onset temperature were measured. Table 2 shows the results. This polyimide was dissolved in THF to a concentration of 25% by weight to obtain a coating varnish.

Synthesis Example 33 20.53 g (50 mmol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane and 1,3-
12.43 g (50 mmol) of bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane and 35.83 g of 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride ( 100 mmol) and NM
Using P300 ml and the same method as in Synthesis Example 1, the molar ratio of each structural unit was [(1a) + (1b)]: [(2
a) + (2b)] = 50:50, [(1a) :( 1b)
= 100: 0, (2a) :( 2b) = 100: 0] to obtain 61.0 g (yield 93%) of a polyimide. When the infrared absorption spectrum of the obtained polyimide was measured, typical imide absorption was observed at 1715 cm ^-1 and 1786 cm ^-1 . Further, its molecular weight, Tg and thermal decomposition onset temperature were measured. Table 2 shows the results.
This polyimide was dissolved in THF to a concentration of 25% by weight to obtain a coating varnish.

Synthesis Example 34 30.79 g (75 mmol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane and 1,3-
6.21 g (25 mmol) of bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane and 3,
35.83 g (100 mmol) of 3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride and NMP3
In the same manner as in Synthesis Example 1, the molar ratio of each structural unit was [(1a) + (1b)]: [(2a) +
(2b)] = 75:25, [(1a) :( 1b) = 10
0: 0, (2a) :( 2b) = 100: 0] to obtain 65.0 g (yield 94%) of a polyimide. The infrared absorption spectrum of the obtained polyimide was measured.
Typical imide absorptions were observed at 720 cm ^-1 and 1783 cm ^-1 . Further, its molecular weight, Tg and thermal decomposition onset temperature were measured. Table 2 shows the results. This polyimide was dissolved in THF to a concentration of 25% by weight to obtain a coating varnish.

Synthesis Example 35 32.84 g (80 mmol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane and 1,3-
4.97 g (20 mmol) of bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane and 3,
35.83 g (100 mmol) of 3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride and NMP3
In the same manner as in Synthesis Example 1, the molar ratio of each structural unit was [(1a) + (1b)]: [(2a) +
(2b)] = 80:20, [(1a) :( 1b) = 10
0: 0, (2a) :( 2b) = 100: 0], to obtain 68.0 g of a polyimide (yield 97%). The infrared absorption spectrum of the obtained polyimide was measured.
Typical imide absorptions were observed at 720 cm ^-1 and 1783 cm ^-1 . Further, its molecular weight, Tg and thermal decomposition onset temperature were measured. Table 2 shows the results. This polyimide was dissolved in THF to a concentration of 25% by weight to obtain a coating varnish.

Synthesis Example 36 36.95 g (90 mmol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane and 1,3-
2.49 g (10 mmol) of bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane and 3,
35.83 g (100 mmol) of 3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride and NMP3
In the same manner as in Synthesis Example 1, the molar ratio of each structural unit was [(1a) + (1b)]: [(2a) +
(2b)] = 90:10, [(1a) :( 1b) = 10
0: 0, (2a) :( 2b) = 100: 0] to obtain 69.0 g of a polyimide (yield 97%). The infrared absorption spectrum of the obtained polyimide was measured.
Typical imide absorptions were observed at 720 cm ^-1 and 1783 cm ^-1 . Further, its molecular weight, Tg and thermal decomposition onset temperature were measured. Table 2 shows the results. This polyimide was dissolved in THF to a concentration of 25% by weight to obtain a coating varnish.

Synthesis Example 37 30.79 g (75 mmol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane and 1,3-
6.21 g (25 mmol) of bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane and 3,
17.91 g (50 mmol) of 3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride and 20.53 g (50 mmol) of ethylene glycol bistrimellitate dianhydride
Synthesis Example 1
In the same manner as described above, the molar ratio of each structural unit is [(1a) +
(1b)]: [(2a) + (2b)] = 75:25,
[(1a) :( 1b) = 50: 50, (2a) :( 2
b) = 50: 50], 68.5 g of polyimide
(95% yield). The infrared absorption spectrum of the obtained polyimide was measured to be 1715 cm ^-1 and 17
A typical imide absorption was observed at 86 cm ^-1 . Further, its molecular weight, Tg and thermal decomposition onset temperature were measured.
Table 2 shows the results. This polyimide is converted to THF
To a concentration of 25% by weight
A varnish for coating was obtained.

Synthesis Example 38 30.79 g (75 mmol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane and 1,3-
6.21 g (25 mmol) of bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane and 3,
Using 8.96 g (25 mmol) of 3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride, 30.77 g (75 mmol) of ethylene glycol bistrimellitate dianhydride and 300 ml of NMP, Synthesis Example 1 was used. In a similar manner, the molar ratio of each structural unit is [(1a) + (1
b)]: [(2a) + (2b)] = 75:25, [(1
a): (1b) = 25: 75, (2a): (2b) = 2
5:75] of polyimide (69.5 g, yield 95).
%). When the infrared absorption spectrum of the obtained polyimide was measured, it was found to be 1715 cm ^-1 and 1786 cm ^-1.
A typical imide absorption was observed. Further, its molecular weight, Tg and thermal decomposition onset temperature were measured. Table 2 shows the results. 25% by weight of this polyimide in THF
To obtain a coating varnish.

Synthesis Example 39 30.79 g (75 mmol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane and 1,3-
6.21 g (25 mmol) of bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane and 3,
26.87 g (75 mmol) of 3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride and 10.26 g of ethylene glycol bistrimellitate dianhydride (25
Synthesis Example 1
In the same manner as described above, the molar ratio of each structural unit is [(1a) +
(1b)]: [(2a) + (2b)] = 75:25,
[(1a) :( 1b) = 75: 25, (2a) :( 2
b) = 75: 25] 66.0 g of a polyimide represented by the following formula:
(94% yield). The infrared absorption spectrum of the obtained polyimide was measured to be 1715 cm ^-1 and 17
A typical imide absorption was observed at 86 cm ^-1 . Further, its molecular weight, Tg and thermal decomposition onset temperature were measured.
Table 2 shows the results. This polyimide is converted to THF
To a concentration of 25% by weight
A varnish for coating was obtained.

Synthesis Example 40 30.79 g (75 mmol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane and 1,3-
Bis [(aminophenoxy) methyl] -1,1,3,3
-As in Synthesis Example 1, using 9.42 g (25 mmol) of tetramethyldisiloxane, 35.83 g (100 mmol) of 3,3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride and 300 ml of NMP. And the molar ratio of each structural unit is [(1a) + (1b)]:
[(2a) + (2b)] = 75:25, [(1a):
(1b) = 100: 0, (2a): (2b) = 100:
0] (69.0 g, yield 95%). The infrared absorption spectrum of the obtained polyimide was measured, typical absorption of imide was observed in 1720 cm ^-1 and 1783 cm ^-1. Also, its molecular weight, T
g and pyrolysis onset temperature were measured. Table 2 shows the results.
Shown in This polyimide was dissolved in THF to a concentration of 25% by weight to obtain a coating varnish.

Synthesis Example 41 30.79 g (75 mmol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane and an aminopropyl-terminated dimethylsiloxane tetramer represented by the following general formula (5) ( Y = NH ₂ , R = propylene, n = 3)
10.72 g (25 mmol)

Embedded image 35.83 g (100 mmol) of 3,3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride and NM
Using P300 ml and the same method as in Synthesis Example 1, the molar ratio of each structural unit was [(1a) + (1b)]: [(2
a) + (2b)] = 75:25, [(1a) :( 1b)
= 100: 0, (2a) :( 2b) = 100: 0] to obtain 67.0 g (yield 91%) of a polyimide. When the infrared absorption spectrum of the obtained polyimide was measured, typical imide absorption was observed at 1712 cm ^-1 and 1783 cm ^-1 . Further, its molecular weight, Tg and thermal decomposition onset temperature were measured. Table 2 shows the results.
This polyimide was dissolved in THF to a concentration of 25% by weight to obtain a coating varnish.

Synthesis Example 42 31.04 g (100 mmol) of 4,4′-diamino-3,3 ′, 5,5′-tetraethyldiphenylmethane and 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride 35.83 g (100 mmol) and NM
Using P300 ml and the same method as in Synthesis Example 1, the molar ratio of each structural unit was [(1a) + (1b)]: [(2
a) + (2b)] = 100: 0, [(1a) :( 1b)
= 100: 0, (2a): (2b) = 0: 0] to obtain 58.8 g of a polyimide (93% yield). When the infrared absorption spectrum of the obtained polyimide was measured,
Typical imide absorptions were observed at 1720 cm ^-1 and 1780 cm ^-1 . Further, its molecular weight, Tg and thermal decomposition onset temperature were measured. Table 2 shows the results. This polyimide was dissolved in THF to a concentration of 25% by weight to obtain a coating varnish.

Synthesis Example 43 15.52 g (50 mmol) of 4,4′-diamino-3,3 ′, 5,5′-tetraethyldiphenylmethane and 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride 13.34 g (37.5 mmol) of ethylene glycol bistrimellitate dianhydride 5.13 g
(12.5 mmol) and 300 ml of NMP, and in the same manner as in Synthesis Example 1, the molar ratio of each structural unit was [(1a) + (1b)]: [(2a) + (2b)] = 1
00: 0, [(1a) :( 1b) = 75: 25, (2
a): Polyimide represented by (2b) = 0: 0]
6 g (92% yield) was obtained. When the infrared absorption spectrum of the obtained polyimide was measured, typical imide absorption was observed at 1720 cm ^-1 and 1780 cm ^-1 .
Further, its molecular weight, Tg and thermal decomposition onset temperature were measured. Table 2 shows the results. This polyimide is
By dissolving in HF to a concentration of 25% by weight, a coating varnish was obtained.

Synthesis Example 44 4,4'-Diamino-3,3 ', 5,5'-tetraethyl
15.52 g (50 mmol) of rudiphenylmethane
3,3 ', 4,4'-diphenylsulfonetetracarbo
Acid dianhydride (8.89 g, 25 mmol) and ethylene glycol
10.26 g of recall bistrimellitate dianhydride (2
5 mmol) and 300 ml of NMP
In the same manner as in Example 1, the molar ratio of each structural unit is [(1a) +
(1b)]: [(2a) + (2b)] = 100: 0,
[(1a) :( 1b) = 50: 50, (2a) :( 2
b) = 0: 0] 29.6 g of polyimide (yield
92%). Infrared absorption spectrum of the obtained polyimide
It was 1720cm^-1 And 1780c
m^-1A typical imide absorption was observed. Also,
The molecular weight, Tg and pyrolysis onset temperature were measured. Them
Table 2 shows the results. This polyimide is added to THF 25 times.
By dissolving it to a concentration of
I got a varnish.

Synthesis Example 45 7.76 g (25 mmol) of 4,4′-diamino-3,3 ′, 5,5′-tetraethyldiphenylmethane and bis (3-aminopropyl) tetramethyldisiloxane
21 g (25 mmol) and 17.91 g of 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride
(50 mmol) and 300 ml of NMP, and the molar ratio of each structural unit was [(1
a) + (1b)]: [(2a) + (2b)] = 50: 5
0, [(1a) :( 1b) = 100: 0, (2a):
(2b) = 100: 0] polyimide 27.4
g (yield 91%) was obtained. The infrared absorption spectrum of the obtained polyimide was measured to be 1720 cm ^-1 and 1
Typical imide absorption was observed at 780 cm ^-1 . Further, its molecular weight, Tg and thermal decomposition onset temperature were measured.
Table 2 shows the results. This polyimide is converted to THF
To a concentration of 25% by weight
A varnish for coating was obtained.

Synthesis Example 46 11.64 g (37.5 mmol) of 4,4′-diamino-3,3 ′, 5,5′-tetraethyldiphenylmethane
And 3.11 g (12.5 mmol) of bis (3-aminopropyl) tetramethyldisiloxane and 3,3 ′, 4
4'-diphenylsulfonetetracarboxylic dianhydride 1
Using 7.91 g (50 mmol) and 300 ml of NMP, in the same manner as in Synthesis Example 1, the molar ratio of each structural unit was [(1a) + (1b)]: [(2a) + (2b)] =
75:25, [(1a) :( 1b) = 100: 0, (2
a): Polyimide 2 represented by (2b) = 100: 0]
9.6 g (92% yield) were obtained. When the infrared absorption spectrum of the obtained polyimide was measured, it was found to be 1,720 cm ^-1.
And 1780 cm ^-1 typical absorption of imide was observed. Further, its molecular weight, Tg and thermal decomposition onset temperature were measured. Table 2 shows the results. This polyimide,
A coating varnish was obtained by dissolving in THF to a concentration of 25% by weight.

Synthesis Example 47 12.4 g (50 mmol) of 4,4′-diamino-3,3 ′, 5,5′-tetramethyldiphenylmethane and 20.5 g of ethylene glycol bistrimellitate dianhydride
Using 1 g (50 mmol) and 300 ml of NMP, in the same manner as in Synthesis Example 1, the molar ratio of each structural unit was [(1a) + (1b)]: [(2a) + (2b)] = 1
00: 0, [(1a) :( 1b) = 0: 100, (2
a): Polyimide represented by (2b) = 0: 0]
5 g (94% yield) was obtained. When the infrared absorption spectrum of the obtained polyimide was measured, typical imide absorption was observed at 1720 cm ^-1 and 1780 cm ^-1 .
Further, its molecular weight, Tg and thermal decomposition onset temperature were measured. Table 2 shows the results. This polyimide is
By dissolving in HF to a concentration of 25% by weight, a coating varnish was obtained.

Synthesis Example 48 15.52 g (50 mmol) of 4,4′-diamino-3,3 ′, 5,5′-tetraethyldiphenylmethane and 20.5 of ethylene glycol bistrimellitate dianhydride
Using 1 g (50 mmol) and 300 ml of NMP, in the same manner as in Synthesis Example 1, the molar ratio of each structural unit was [(1a) + (1b)]: [(2a) + (2b)] = 1
00: 0, [(1a) :( 1b) = 0: 100, (2
a): Polyimide represented by (2b) = 0: 0].
8 g (93% yield) was obtained. When the infrared absorption spectrum of the obtained polyimide was measured, typical imide absorption was observed at 1720 cm ^-1 and 1780 cm ^-1 .
Further, its molecular weight, Tg and thermal decomposition onset temperature were measured. Table 2 shows the results. This polyimide is
By dissolving in HF to a concentration of 25% by weight, a coating varnish was obtained.

[0071]

[Table 1]

[0072]

[Table 2]

In Tables 1 and 2, the molecular weight of polyimide was measured using THF as an eluent, and the column was Shodex.
Performed using 80M × 2. The molecular weight value is a number average molecular weight by GPC and is based on polystyrene. Tg is differential thermal analysis (temperature rise at 10 ° C / min in nitrogen)
The thermal decomposition onset temperature was measured by thermogravimetric analysis (heating in nitrogen at 10 ° C./min).

Example 1 The coating varnish containing the polyimide obtained in the above Synthesis Example 42 was used as a coating liquid, and the layer thickness when dried using a bar coater on a 50 μm-thick polyimide film as a substrate. 2
The coating was applied to a thickness of 5 μm, and the applied layer was dried at 150 ° C. for 5 minutes using a hot-air circulating drier to form an adhesive layer on one surface of the substrate. Next, a coating varnish containing the polyimide obtained in Synthesis Example 2 (having a different Tg from the polyimide in Synthesis Example 42) is used as a coating liquid on the other surface of the base material, and the layer thickness when dried becomes 25 μm. The adhesive layer was dried in a hot-air circulation type dryer at 150 ° C. for 10 minutes to prepare an adhesive tape having a total thickness of 100 μm in which adhesive layers of polyimide having different Tg were formed on both surfaces of the substrate. .

Examples 2 to 40 Using the polyimides obtained in Synthesis Examples 1 to 48, adhesive tapes according to the present invention of Examples 2 to 40 were produced in exactly the same manner as in Example 1. The low Tg adhesive layer of Example 37 and the high Tg adhesive layer of Example 38 had a particle diameter of 0.05 μm.
m of alumina filler (manufactured by Showa Denko KK) in an amount of 10% by weight. Further, the low Tg adhesive layer of Example 39 and Example 4
The high Tg adhesive layer of No. 0 contained 10% by weight of a 0.07 μm silica filler (manufactured by Arakawa Chemical Co., Ltd.).

Tables 3 and 4 show the types and amounts of the coating varnish and filler used for the adhesive layers used in Examples 1 to 40, and the adhesive temperatures of the formed adhesive layers, respectively. In addition,
The T of the high Tg adhesive layer and the low Tg adhesive layer shown in Tables 3 and 4
g is the Tg of the corresponding synthetic example described in Tables 1 and 2.
Is equivalent to

Comparative Example 1 The coating varnish containing the polyimide obtained in Synthesis Example 10 was used as a coating liquid, and the same Tg was applied to both surfaces of the substrate in the same manner as in Example 1.
A comparative adhesive tape having a polyimide adhesive layer formed thereon was produced.

Comparative Example 2 A 20% by weight solution of a polyimide varnish (Lark TPI, manufactured by Mitsui Toatsu Chemicals, Inc.) in N-methyl-2-pyrrolidone was prepared. This solution was coated on one surface of the 50 μm polyimide film used in Example 1 with a dry adhesive layer having a thickness of 25 μm.
m in a hot-air circulation dryer.
And dried at 150 ° C. for 1 hour in a hot-air circulating drier. After that, the adhesive tape was further dried at 250 ° C. for 1 hour to prepare an adhesive tape for comparison. Table 5 also shows the coating varnish, the amount of filler added, and the bonding temperature of the adhesive layer in Comparative Examples 1 and 2 in the same manner as in Examples.

[0079]

[Table 3]

[0080]

[Table 4]

[0081]

[Table 5]

The following operations were performed to evaluate the adhesive tapes obtained in the above Examples and Comparative Examples. (Assembly of Lead Frame) A lead frame used for the semiconductor package shown in FIG. 2 was assembled by the following procedure. (A) Punching of Adhesive Tape Strip punching of adhesive tape using a mold. (B) Assembling the lead frame Align the adhesive tape punched in the shape of a strip with the lead frame, and heat and press on a heated hot plate.
Assembling a lead frame by bonding high Tg adhesive layer side of the adhesive tape to the lead frame (4kgf / cm ^2/1 sec). The bonding temperature at this time is shown in Tables 3, 4 and 5 as the bonding temperature of the high Tg bonding layer.

(Assembly of Semiconductor Package) Next, a semiconductor package was assembled according to the following procedure using the lead frame obtained above. The reason why the bonding conditions are different at the time of assembling the lead frame is that the characteristics of the respective adhesive tapes are different. Here, the optimum bonding conditions were selected for each adhesive tape, and the bonding was performed based on the optimum bonding conditions. (C) Die bonding A semiconductor chip was bonded to the low Tg bonding layer of the bonding tape bonded to the lead frame obtained in (b). For bonding, heat and press on a hot plate (4
kgf / cm ^2/1 sec) were carried out. The bonding temperature at this time is
Tables 3, 4 and 5 show the bonding temperature of the low Tg bonding layer. (D) Wire bonding A wire bonder is used to wire the wire pad on the semiconductor chip and the silver-plated portion at the end of the inner lead wire using a gold wire. (E) Molding Transfer molding with an epoxy-based molding agent. (F) Finishing process The package is finished including processes such as homing, dam cutting, and plating of the outer lead portion.

(Adhesive tape and semiconductor package (n =
Evaluation result of 10)) (A) Adhesive strength After attaching (taping) an adhesive tape to a copper plate under the conditions at the time of assembling the lead frame, the 90 ° peel strength of the tape having a width of 10 mm at room temperature was measured. as a result,
The strength of the adhesive tape of Examples 1 to 40 was 35 to 50 g /
10 mm, while that of Comparative Example 1 is 35 to 50 mm.
g / 10 mm, which was not a problem, but that of Comparative Example 2 was 10 to 40 g / 10 mm, and the fluctuation range was large. (B) Embedded state of lead The state where the lead pin was embedded in the adhesive tape at the time of assembling the lead frame was observed. In the adhesive tapes of Examples 1 to 40, the lead pins embedded on the high Tg side are:
The bonding state of the lead frame at the time of manufacturing the lead frame was kept as shown in (b). However, in the case of the comparative examples 1 and 2, the lead pins were distorted or moved at the time of bonding the semiconductor chip of (c) and the flatness was deteriorated. There was something. (C) Evaluation of semiconductor package The package obtained as described above was
T Test (Pressure Cooker Base)
d Test). These test conditions were applied at 5 volts, and the test was performed at 121 ° C., 2 atm, and 100% RH to perform an electrical reliability test. As a result, in Examples 1 to 40, no short circuit occurred even after 1000 hours. On the other hand, in Comparative Examples 1 and 2, there was a case where a short circuit occurred due to the contact due to the movement of the lead pin because the first adhesive layer was softened.

From the above results, when the adhesive tape of the present invention is used, a good semiconductor package can be manufactured. On the other hand, when the adhesive tape of the comparative example is used, leads are embedded. There are problems such as the occurrence of short-circuits in the electrical reliability test, and a large variation in the adhesive force, and it is apparent that the method is not suitable for manufacturing electronic components.

[0086]

As can be seen from the above test results, the adhesive tape for electronic parts of the present invention has sufficient heat resistance and adhesiveness, so that it is highly reliable for bonding electronic parts. For example, it is preferably used for fixing a lead frame, for TAB, between members around a lead frame constituting a semiconductor device, that is, for bonding a lead pin, a semiconductor chip mounting substrate, a heat sink, a semiconductor chip itself, and the like. can do.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of an example of a resin-sealed semiconductor device using the present invention or a conventional adhesive tape.

FIG. 2 is a cross-sectional view of another example of the resin-encapsulated semiconductor device using the present invention or a conventional adhesive tape.

FIG. 3 is a sectional view of still another example of a resin-sealed semiconductor device using the present invention or a conventional adhesive tape.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Semiconductor chip, 2 ... Plane (metal heat sink), 3 ...
Lead pin, 4 ... bonding wire, 5 ... resin, 6
... adhesive layer, 7 ... die pad, 8 ... electrode

Claims (4)

[Claims] [Claim 1] The following formula (1)
100 to 40 mol% of at least one of the structural unit represented by a) and the structural unit represented by the following formula (1b), and the structural unit represented by the following formula (2a) and the following formula (2b) An adhesive tape provided with an adhesive layer containing at least one polyimide containing at least one kind of structural unit represented by 0 to 60 mol%, wherein the adhesive layers on both surfaces are different from each other in glass transition. An adhesive tape for electronic parts, which has a temperature. Embedded image (In the formula, Ar represents a divalent group selected from the following structures having an aromatic ring.) (Wherein, 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 having 1 to 4 carbon atoms. Not all groups are hydrogen atoms at the same time.) (In the formula, R represents —CH ₂ OC ₆ H ₄ — in which an alkylene group having 1 to 10 carbon atoms or a methylene group is bonded to Si, and n represents an integer of 1 to 20.) 2. The adhesive tape for electronic parts according to claim 1, wherein the adhesive layers provided on both surfaces of the substrate have a difference in glass transition temperature of 30 ° C. or more. 3. At least one of the adhesive layers has a particle size of 1 μm.
The adhesive tape for electronic parts according to claim 1, comprising 0.1 to 50 parts by weight of the following filler. 4. The adhesive tape for an electronic component according to claim 1, wherein a peelable film is provided on at least one surface of the adhesive layer.