JP3430020B2 - Adhesive tape for electronic components - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a TAB tape for forming a semiconductor device, a lead frame fixing tape, a member around the lead frame, for example, a lead pin, a semiconductor chip mounting substrate, a heat sink, the semiconductor chip itself, etc. The present invention relates to an adhesive tape for electronic parts, which is used for adhering a resin.

[0002]

2. Description of the Related Art Conventionally, adhesive tapes and the like used in resin-sealed semiconductor devices include lead frame fixing adhesive tapes and TAB tapes. For example, in the case of lead frame fixing adhesive tapes, It is used to fix the lead pins of the lead frame and to improve the production yield and productivity of the lead frame itself and the entire semiconductor assembly process.It is generally taped onto the lead frame by the lead frame maker and brought to the semiconductor maker. After mounting the IC, resin sealing is performed.
Therefore, the adhesive tape for fixing the lead frame has not only general reliability and taping workability at the semiconductor level, 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, as an adhesive tape used for such an application, for example, a synthetic rubber resin such as polyacrylonitrile, polyacrylic acid ester or acrylonitrile-butadiene copolymer is provided on a support such as a polyimide film. In the B-stage state, an adhesive is applied, which is composed of the above-mentioned one or modified with other resin, or is mixed with other resin or other curing component. Recently, a double-sided adhesive tape using a highly reliable and highly heat-resistant thermoplastic polyimide resin has come into use.

In recent years, a resin-sealed semiconductor device (semiconductor package) having a structure as shown in FIG. 2 has been developed and manufactured. In FIG. 2, the lead pin 3 and the metal heat sink 2 are connected by an adhesive layer 6, the semiconductor chip 1 is mounted on the metal heat sink 2, and a bonding wire 4 between the semiconductor chip 1 and the lead pin 3 is used. At the same time, it has a structure sealed by the resin 5. A single-layer adhesive or double-sided adhesive tape is generally used for the adhesive layer 6.

[0005]

When the adhesive tape using the conventional thermosetting adhesive as described above is used in the adhesive layer in the resin-encapsulated semiconductor device having the structure shown in FIG. However, there is a problem that the gas generated at the time of curing contaminates the leads to reduce the adhesive strength and causes the generation of package cracks, and the heat resistance was insufficient. Therefore, an adhesive for electronic parts having sufficient heat resistance and reliability and an adhesive tape for electronic parts using the same are desired.

The present inventors have previously made an adhesive tape using an adhesive made of a polyimide resin having structural units represented by the following formulas (1a) and (2) (Japanese Patent Laid-Open No. 8-32553).
No. 3, gazette and Japanese Patent Laid-Open No. 9-67559), and it was possible to solve the above problems. However, these adhesive tapes also have other problems. That is, in the case of an adhesive tape in which the adhesive layer is provided on the heat resistant film, there is a problem that interface separation between the heat resistant film and the adhesive layer is likely to occur. Interfacial peeling, especially when wet and humid,
This is a big problem because it significantly reduces the reliability of the package. Further, the tape having a single layer of adhesive has a problem that, for example, the lead frame is buried and penetrates in the adhesive layer during thermocompression bonding, which makes it difficult to secure insulation.

Further, in the conventional semiconductor device, first, a lead frame and a heat sink are manufactured, and then the both are laminated via a double-sided adhesive tape cut by a mold and heat-pressed. Therefore, the die for cutting the tape must be changed for each shape of the lead frame and the heat sink. Moreover, since there are many manufacturing processes, the manufacturing cost becomes high.

Further, Japanese Patent Laid-Open No. 6-291236 discloses a technique of fixing a heat dissipation plate and a lead frame by using an adhesive layer having a different glass transition temperature (Tg). However, this patent publication does not disclose a specific adhesive composition, molecular weight, or the like. Moreover, when the molecular structures of the resins constituting the adhesive are different from each other, peeling is likely to occur at the adhesive layer and the adhesive interface, and it is impossible to secure the adhesion and electrical reliability between the adhesive layers only by defining the glass transition temperature. There was a problem to say.

Furthermore, a method has also been proposed in which two adhesive layers are sequentially laminated on a metal foil (plate), the adhesive property close to that of a metal is used to secure the insulation, and the other layer is used to secure the adhesiveness to the lead frame. ing. By the way, the adhesive layer for fixing the lead frame is required to be made of a resin having a relatively low Tg from the viewpoints of preventing oxidation of the lead frame, preventing the occurrence of distortion, and adhering work time. On the other hand, if the glass transition temperature is too low, lead pins may be shifted or package cracks may easily occur during the semiconductor device assembly process. On the other hand, if the glass transition temperature is set high, it is necessary to stick at a high temperature, and if sticking at a low temperature to avoid oxidation, the working time of the sticking process tends to be long.

Further, Japanese Unexamined Patent Publication No. 10-140106 discloses an adhesive tape for electronic parts, which comprises two kinds of adhesive layers containing a specific polyimide and showing different glass transition temperatures. . This adhesive tape has a problem that when it is attached to a metal plate, the viscosity of the low Tg adhesive layer becomes low and the thickness of the adhesive layer changes. In order to avoid it, firstly the low Tg of the adhesive tape
When a metal plate is attached to the high Tg adhesive layer after the adhesive layer is attached to the lead frame, high temperature and high pressure are required for pressure bonding, so the lead pin bites deep into the low Tg adhesive layer, leading to lead shift, There was a problem that lead drift, short circuit, etc. are likely to occur.

The present invention has been made for the purpose of solving the above problems. That is, the object of the present invention is capable of bonding in a short time at a relatively low temperature,
An object of the present invention is to provide an adhesive tape for electronic parts, which can ensure the insulation, does not generate gas, and has sufficient reliability without causing interfacial peeling.

[0012]

The adhesive tape for electronic parts of the present invention comprises an adhesive layer A, an adhesive layer B and an adhesive layer C which are sequentially laminated on at least one surface of a metal plate. There is formed of polyimide, glass transition temperature of the adhesive layer a in contact with the metallic plate is higher than the glass transition temperature of the adhesive layer B, the glass transition temperature of the adhesive layer B is rather high than the glass transition temperature of the adhesive layer C, and adhesion The glass transition temperature of layer C
The temperature is 150 ° C. or lower, and the adhesive layer A is represented by the following formula (1a).
100 to 20 mol% of the structural unit represented by the following formula (1b)
At least consisting of 0 to 80 mol% of the structural unit represented by
Contains one polyimide, and the adhesive layer B has the following formula (1a)
And a structural unit represented by the following formula:
A small amount of 0 to 60 mol% of the structural unit represented by (2)
The adhesive layer C contains at least one polyimide and has the following formula.
90 to 40 mol% of the structural unit represented by (3a), and
It is composed of 10 to 60 mol% of the structural unit represented by the formula (3b).
And at least one polyimide .

[0013]

[0014]

[Chemical 6] (In the formula, Ar represents a divalent group having an aromatic ring and selected from the following structures.)

[Chemical 7] (In the formula, R ₁ , R ₂ , R ₃ and R _{4, which} may be the same or different, each represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group, and all of these groups are the same. It cannot be a hydrogen atom.)

[0015]

[Chemical 8] (In the formula, R is —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.
Is shown and n means the integer of 1-20. )

[Chemical 9] (In the formula, X is a 3,3 ′, 4,4′-diphenylsulfone structure, a 3,3 ′, 4,4′-biphenyl structure, and 2,
A tetravalent aromatic group having any of the 3 ', 3,4'-biphenyl structure is shown, and Ar 1 , R and n have the same meanings as defined above. )

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described in detail below. FIG. 1 shows a schematic cross-sectional view of an example of a semiconductor device using the adhesive tape of the present invention. In FIG. 1, the lead pin 3 and the metal plate 2 include an adhesive layer A6a and an adhesive layer B6 containing the polyimide and having different glass transition temperatures.
b and the adhesive layer C6c, the semiconductor chip 1
Is mounted on the metal plate 2, and has a structure in which it is sealed with resin 5 together with the bonding wire 4 between the semiconductor chip 1 and the lead pin 3.

The metal plate constituting the adhesive tape of the present invention is
It is not particularly limited as long as it has a heat dissipation effect, and the thickness of the metal plate is preferably 10 to 300 μm. As the material, copper, white copper, silver, iron, 42 alloy, and stainless steel are preferable.

The adhesive layer A, the adhesive layer B and the adhesive layer C in the adhesive tape of the present invention have a glass transition temperature of the adhesive layer A.
As long as there is a relation of> adhesive layer B> adhesive layer C, it may be composed of any polyimide, but in particular, since each adhesive layer is preferably composed of the above-mentioned polyimide, the case will be described below. ..

Adhesive layer A constituting the adhesive tape of the present invention
Is 100 to 20 mol%, preferably 80 to 20 mol% of the structural unit represented by the above formula (1a), and the above formula (1b)
0-80 mol% of the structural unit represented by, preferably 20
˜80 mol% of one or more polyimides are contained, but in the present invention, these polyimides may contain two or more structural units represented by the above formula (1a), and The structural unit represented by the formula (1b) is 2
More than one species may be included. The polyimide used in the adhesive layer A has a lower glass transition temperature as represented by the formula (1a) and more structural units, and has a higher glass transition temperature as represented by the formula (1b) and more structural units. Therefore, the above-mentioned polyimide can control the glass transition temperature by variously changing the content ratios of the formulas (1a) and (1b), and thus, in the bonding condition of the adhesive layer B, sufficient insulation can be achieved. It is possible to control the flow start temperature of the adhesive layer A so as to ensure the temperature.

Adhesive layer B constituting the adhesive tape of the present invention
Contains 100 to 40 mol% of the structural unit represented by the above formula (1a) and one or more polyimides composed of 0 to 60 mol% of the structural unit represented by the above formula (2),
In the present invention, these polyimides have the above formula (1a)
Two or more types of structural units represented by the above may be contained, and two or more types of structural units represented by the above formula (2) may be contained. The polyimide used in the adhesive layer B has a higher glass transition temperature as the number of structural units represented by the formula (1a) increases. On the other hand, the more structural units represented by the formula (2), the lower the glass transition temperature and the better the adhesion to the adhesive layer A. Therefore, the polyimide has the formula (1a)
The glass transition temperature can be controlled by variously changing the compounding ratio of the structural units represented by (2) and (2), and thereby the pressure-bondable temperature of the adhesive layer B can be controlled.

The adhesive layer B has the following formula (4a)
And at least one selected from the bisimide compounds represented by (4b) per 1 part by weight of the polyimide.
Up to 100 parts by weight can be contained.

[Chemical 10] (In the formula, Ar has the same meaning as defined above. R
₅ , R ₆ and R _{7, which} may be the same or different, each represents a hydrogen atom, a chlorine atom, a bromine atom, a carboxyl group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group. )

It is known that some of these bisimide compounds have the function of improving the fluidity of the polyimide when it is melted. Therefore, the adhesive layer B can be obtained by adding the bisimide compound represented by the formula (4a) or (4b) to the polyimide used in the present invention in the above amount.
It is possible to lower the pressure-bondable temperature of (1) as compared with the case where it is used alone. In addition, the time required for pressure bonding can be shortened and oxidation of the lead frame and the metal plate can be prevented as compared with the case where these bisimide compounds are not used. Furthermore, it is possible to improve the adhesion between the adhesive layer A and the adhesive layer B. The effect of improving the adhesiveness is particularly remarkable when at least one of R ₅ , R ₆ and R ₇ is a carboxyl group.

The adhesive layer C in the adhesive tape of the present invention is
It has a low melting point and is capable of temporary pressure bonding, and has the above formula (3a)
90 to 40 mol% of the structural unit represented by the formula (3)
It is composed of a polyimide containing 10 to 60 mol% of the structural unit represented by b). In the present invention, these polyimides have a structural unit represented by the above formula (3a) of 2 or less.
One or more types may be contained, and two or more types of structural units represented by the above formula (3b) may be contained. The polyimide used for the adhesive layer C has a lower glass transition temperature as the number of structural units represented by the formula (3b) is larger and the number of repeating units of (OSi) is longer, and the adhesion with the adhesive layer B is improved. To do. Therefore, the polyimide has the formula (3
It is possible to control the glass transition temperature by variously changing the ratio of the structural units represented by a) and the formula (3b) and the length of siloxane, and thereby controlling the temperature at which the adhesive layer C can be pressure-bonded. It becomes possible to do. In the present invention, the adhesive layer C has a relatively low temperature, that is, 100 to 1
It is necessary to be able to crimp the lead frame at 80 ° C. Accordingly, the glass transition temperature is 0.99 ° C. or less, good <br/> Mashiku is 100 ° C. The following polyimide is used.

The above-mentioned polyimides used in the present invention can be synthesized by using a general method for producing a polyimide. That is, 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. More specifically, the polyimide used for the adhesive layer A is a tetracarboxylic acid dianhydride.
It can be produced by reacting 3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride and pyromellitic dianhydride with a compound represented by the following formula (5). Y-Ar-Y (5) (In the formula, Ar has the same meaning as defined above, and Y represents an amino group or an isocyanate group.)

On the other hand, the polyimide used for the adhesive layer B is 3,3 ', 4,4 as tetracarboxylic dianhydride.
Using 4'-diphenylsulfone tetracarboxylic dianhydride, a compound represented by the above formula (5) and the following formula (6)
It can be produced by reacting with a siloxane compound represented by.

[Chemical 11] (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. Y represents an amino group. Or represents an isocyanate group.)

Further, the polyimide used for the adhesive layer C is 3,3 ', 4,4 as tetracarboxylic dianhydride.
4'-diphenylsulfone tetracarboxylic acid dianhydride,
Using 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride or 2,3 ′, 3,4′-biphenyltetracarboxylic dianhydride, the compound represented by the above formula (5) and the above It can be produced by reacting with a siloxane compound represented by the formula (6).

The above-mentioned polyimide in the present invention may be formed by using two or more kinds of the compounds represented by the above formula (5), and the siloxane compound represented by the above formula (6). It may be formed using two or more kinds.

The compound represented by the formula (5) used as a raw material for synthesizing the above polyimide has a divalent group selected from the above-mentioned structure having an aromatic ring as Ar. Specific examples of the diamines in which the group Y is an amino group include the following. Three
3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 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 (4
-Amino-α, α-dimethylbenzyl) 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-
Examples include 3,3'-dimethoxydiphenylmethane and 4,4'-diamino-3,3'-diethoxydiphenylmethane.

In the compound represented by the formula (5), the diisocyanates in which the functional group Y is an isocyanate group are the above-mentioned diamines in which "amino" is replaced with "isocyanate". Can be mentioned.

In the siloxane compound represented by the formula (6) 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 ( 10
-Aminodecamethylene) tetramethyldisiloxane, aminopropyl-terminated dimethylsiloxane tetramers, octamers, bis (3-aminophenoxymethyl) tetramethyldisiloxane, and the like, and these can be used in combination. .

Further, in the compound represented by the formula (6), as the diisocyanates in which the functional group Y is an isocyanate group, in the diamines exemplified above, "amino" is replaced with "isocyanate". I can list things.

In the compounds represented by the above formulas (5) and (6), the diisocyanates whose functional group Y is an isocyanate group are prepared by reacting the corresponding diamines exemplified above with phosgene according to a conventional method. Therefore, it can be easily manufactured.

When tetracarboxylic acid dianhydride and diamine are used as raw materials in the production of the above-mentioned polyimide used in the present invention, these are added in an organic solvent, if necessary, with tributylamine, triethylamine or phosphorus. In the presence of a catalyst such as triphenyl acid (20 parts by weight or less of the reaction product), heating to 100 ° C. or higher, preferably 180 ° C. or higher to directly obtain a polyimide, tetracarboxylic dianhydride and diamine as an organic solvent After reacting at 100 ° C. or lower in a medium to obtain a polyamic acid that is a precursor of polyimide,
A method for obtaining a polyimide by adding a dehydration catalyst (1 to 5 times by mole of tetracarboxylic acid dianhydride) such as p-toluenesulfonic acid if necessary, and imidizing by heating.
Alternatively, this polyamic acid is used as an acid anhydride such as acetic anhydride, propionic anhydride, or benzoic anhydride, a dehydrating ring-closing agent such as a carbodiimide compound such as dicyclohexylcarbodiimide, and if necessary, a ring-closing catalyst such as pyridine, isoquinoline, imidazole, or triethylamine. (The dehydration ring-closing agent and the ring-closing catalyst are 2 to 10 times mol of tetracarboxylic dianhydride)
And a chemical ring closure at a relatively low temperature (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, dimethyl sulfoxide, sulfolane, hexamethylphosphoric triamide,
Aprotic polar solvent such as 1,3-dimethyl-2-imidazolidone, phenol, cresol, xylenol,
Examples thereof include phenolic solvents such as p-chlorophenol. In addition, 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 or the like as the above solvent. It is also possible to mix and use.

When tetracarboxylic dianhydride and diisocyanate are used as the raw materials, it is possible to produce them according to the method for directly obtaining the above-mentioned polyimide, and the reaction temperature at this time is Above room temperature, especially 60 ° C
The above is preferable. In the reaction of tetracarboxylic dianhydride and diamine or diisocyanate, by reacting them in an equimolar amount, it is possible to obtain a polyimide having a high degree of polymerization, either one of them as necessary. It is also possible to produce a polyimide by using an excess amount in the range of 10 mol% or less.

The molecular weight of the polyimide used in the present invention is different depending on the type of repeating units constituting the polyimide, and thus the film-forming property varies. Therefore, it is preferable to appropriately set the molecular weight according to the film-forming property. When it is used in the adhesive tape for electronic parts of the present invention, the adhesive layer needs to have a certain degree of film-forming property, and also has low heat resistance. Therefore, a low molecular weight one is not preferable. In the present invention, it is generally necessary that the number average molecular weight is 4,000 or more. Further, when it is used as a thermoplastic adhesive, if the viscosity during melting is too high, the adhesiveness is significantly reduced. The molecular weight is one of the factors that regulate the viscosity at the time of melting, but the number average molecular weight of the polyimide used in the present invention is generally 400,000 or less, and above that, the increase in viscosity is large. , It becomes difficult to use as an adhesive. The GPC measurement conditions used for measuring the molecular weight are shown after Table 3.

The bisimide compound that can be contained in the adhesive layer B of the present invention to adjust the temperature at which it can be pressure-bonded or the glass transition temperature of the adhesive layer can be obtained by using a general bisimide production method. That is, it can be produced from a diamine or diisocyanate corresponding to a desired structure and a carboxylic acid anhydride. Specifically, the bisimide compound represented by the formula (4a) is phthalic anhydride, 4-methylphthalic anhydride, 4-ethylphthalic anhydride, 4-methoxyphthalic anhydride, 4-chlorophthalic anhydride. It can be produced by reacting a phthalic anhydride derivative such as 4-bromophthalic anhydride with a compound represented by the above formula (5).

On the other hand, the bisimide compound represented by the formula (4b), that is, the bismaleimide compound, includes maleic anhydride, methylmaleic anhydride, ethylmaleic anhydride, 2,3-dimethylmaleic anhydride and chloro. It can be produced by reacting a maleic anhydride derivative such as maleic anhydride, bromomaleic anhydride or 2,3-dichloromaleic anhydride with a compound represented by the above formula (5). .

More specifically, the bisimide compound represented by the above formula (4a) can be produced as follows. Two or more moles of phthalic anhydride or a phthalic anhydride derivative with respect to the diamine represented by the formula (5) in an organic solvent, if necessary, in the presence of a catalyst such as tributylamine, triethylamine, and triphenylphosphite ( 20 parts by weight or less of the reaction product), 100 ° C or higher, preferably 180
A method of directly obtaining a bisimide compound by heating to ℃ or more, phthalic anhydride and a diamine are reacted in an organic solvent at 100 ℃ or less to obtain a bisamic acid which is a precursor of bisimide, and then p-toluene, if necessary. A method in which a dehydration catalyst such as sulfonic acid (1-5 times the molar amount of phthalic anhydride or a phthalic anhydride derivative) is added, and imidization is performed by heating, and the above-mentioned bisamidic acid is converted into acetic anhydride, propionic anhydride, benzoic anhydride, etc. Acid anhydrides, dehydration ring-closing agents such as carbodiimide compounds such as dicyclohexylcarbodiimide, and, if necessary, ring-closing catalysts such as pyridine, isoquinoline, imidazole, triethylamine (dehydration ring-closing agents and ring-closing catalysts are phthalic anhydride or phthalic anhydride derivatives). 2 to 10 times mol)
And a chemical ring closure at a relatively low temperature (room temperature to about 100 ° C.). In any of these cases of ring closure, after the completion of the ring closure reaction, the reaction solution can be poured into about 10 times the amount of methanol to precipitate the product, which can be washed with methanol and dried to obtain a bisimide compound.

When phthalic anhydride or a phthalic anhydride derivative and diisocyanate are used as the raw materials, the bisimide compound can be produced directly according to the above-mentioned method. The reaction temperature is preferably room temperature or higher, particularly preferably 60 ° C. or higher.

The bisimide compound represented by the above formula (4b), that is, the bismaleimide compound, can be produced as follows. A maleic anhydride or a maleic anhydride derivative in an amount of at least 2 times the molar amount of the diamine represented by the formula (5) is reacted with the diamine in an organic solvent at 100 ° C. or lower to obtain a bismaleamide acid as a bismaleimide precursor. After that, if necessary, a dehydration catalyst such as p-toluenesulfonic acid (1-5 times mole of maleic anhydride or maleic anhydride derivative) is added, and heating is performed at about 150 ° C. for imidization, and the above-mentioned method. Bismaleamic acid is used as an acid anhydride such as acetic anhydride, propionic anhydride, or benzoic anhydride, a dehydration ring-closing agent such as carbodiimide compound such as dicyclohexylcarbodiimide, and a ring-closing catalyst such as pyridine, isoquinoline, imidazole, or triethylamine (dehydration if necessary). The ring-closing agent and the ring-closing catalyst are 2 to 10 times mol of maleic anhydride or a maleic anhydride derivative). Pressurized to, and a method for chemical cyclization at a relatively low temperature (about room temperature to 100 ° C.). In either method, the imidization reaction (dehydration ring closure reaction) is preferably carried out at a low temperature of 150 ° C. or lower because the double bond of the maleimide group portion is highly reactive. In any of these cases of ring closure, after completion of the ring closure reaction, the reaction solution can be poured into about 10 times the amount of methanol to precipitate the product, which can be washed with methanol and dried to obtain a bismaleimide compound.

As the organic solvent used in the synthesis reaction of the above bisimide compound, N-methyl-2-pyrrolidone,
Aprotic polar solvents such as N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, sulfolane, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidone, phenol, cresol, xylenol, p- Examples thereof include phenol solvents such as chlorophenol. Also, if necessary,
Benzene, toluene, xylene, methyl ethyl ketone,
Acetone, tetrahydrofuran, dioxane, monoglyme, diglyme, methyl cellosolve, cellosolve acetate, methanol, ethanol, isopropanol,
It is also possible to mix and use methylene chloride, chloroform, trichlene, nitrobenzene or the like in the above solvent.

In the present invention, the adhesive layer A and the adhesive layer B may contain one kind of polyimide selected from the above-mentioned polyimides alone, but two kinds of the polyimides may be contained in order to adjust the glass transition temperature. The above can be appropriately mixed and contained. In addition, the adhesive layer B has the above formula (4
The bisimide compound represented by a) to (4b) may be added in an amount of 1 to 100 parts by weight based on 100 parts by weight of the polyimide. Usually, the pressure bonding is performed at a temperature higher than the glass transition temperature of the polyimide constituting the adhesive layer B by 50 ° C. or more. In order to press-bond in a short time, the temperature is higher than the glass transition temperature of the polyimide by 100 ° C. or more. Therefore, when a bisimide compound having a melting point lower than the glass transition temperature (Tg) + 40 ° C. of the polyimide constituting the adhesive layer B is contained, the temperature at which the adhesive layer can be pressure-bonded is lowered to around the melting point of the bisimide compound contained. Can be made.

On the other hand, the T of the polyimide forming the adhesive layer B
When a bisimide compound having a melting point higher than g + 40 ° C is included, the temperature at which the adhesive layer can be pressure-bonded is determined by the glass transition temperature of the polyimide and is not affected. Will not decrease. Therefore, it is possible to use a low Tg (about 100 to 200 ° C.) resin which is usually difficult to use.

Adhesive layer A constituting the adhesive tape of the present invention,
When the adhesive layer B and the adhesive layer C are composed of the above-mentioned polyimides, since the polyimides have similar structures, the adhesive layers have almost the same thermal expansion coefficient. Therefore, the adhesive tape of the present invention has little distortion from normal temperature to the time of heating and has good workability. In the adhesive sheet of the present invention, the glass transition temperature of the adhesive layer A provided in contact with the metal plate needs to be higher than the glass transition temperature of the adhesive layer B, and the glass transition temperature of the adhesive layer B is It is necessary that the temperature is higher than the glass transition temperature of the adhesive layer C. Further, from the relationship of the bonding time / pressure / temperature to the electronic component, the glass transition temperature of the adhesive layer A is preferably 40 ° C. or more higher than the glass transition temperature of the adhesive layer B.

The adhesive tape for electronic parts of the present invention can be produced by laminating the above-mentioned resin layer containing polyimide on a metal plate. Various methods can be adopted as the laminating method. For example, a high Tg polyimide solution is applied and dried on a metal plate, a low Tg polyimide solution is applied and dried on the polyimide layer, and a polyimide solution having a lower glass transition temperature is further applied on the polyimide layer. It can be obtained by a method of coating and drying. Also, for example, 3
On one surface of each of the two peelable films, a coating solution comprising the above polyimide is applied and dried to obtain polyimide films having different glass transition temperatures, and then thermocompression bonding is sequentially performed on the metal plate from the polyimide film having a high glass transition temperature. It can also be obtained by the method. In addition, three polyimide films having different glass transition temperatures were thermocompression-bonded in advance, and then the resulting laminated film was thermocompression-bonded so that the high Tg side thereof was bonded to a metal plate. One polyimide was formed into a film. Later, a laminate obtained by a method in which two polyimide solutions having different glass transition temperatures from those of the polyimide are sequentially applied and dried, or a method in which three polyimide solutions having different glass transition temperatures are simultaneously coated is applied. It is also possible to adopt a method such as thermocompression bonding so that the high Tg side of the film adheres to the metal plate.

In the adhesive tape of the present invention, the adhesive layer A, the adhesive layer B and the adhesive layer C can be formed on both sides of the metal plate by the above method, and the adhesive layer A, the adhesive layer B and the adhesive layer B can be formed. It is also possible to further laminate an adhesive layer on the adhesive layer C.

The thickness of each adhesive layer of the adhesive tape for electronic parts in the present invention is appropriately selected, but is usually 10 to 250.
It is preferably in the range of μm. Further, since the uppermost adhesive layer C is required to be capable of temporary pressure bonding at low temperature, it is usually 1
˜20 μm, more preferably in the range of about 2 to 10 μm.

In the present invention, in order to form the adhesive layer by coating, a coating varnish obtained by dissolving the polyimide or the polyimide and the bisimide compound in an appropriate solvent is used. As a solvent for dissolving the polyimide and bisimide used in the present invention, N-methyl-2
-Pyrrolidone, N, N-dimethylacetamide, N, N
An aprotic polar solvent such as dimethylformamide, dimethylsulfoxide, sulfolane, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidone,
Examples thereof include phenolic solvents such as phenol, cresol, xylenol and p-chlorophenol, and a wide range of organic solvents such as isophorone, cyclohexanone, carbitol acetate, diglyme, dioxane and tetrahydrofuran. Further to this, alcohol solvents such as methanol, ethanol and isopropanol, ester solvents such as methyl acetate, ethyl acetate and butyl acetate, nitrile solvents such as acetonitrile and benzonitrile, aromatic solvents such as benzene, toluene and xylene. Alternatively, a halogen-based solvent such as chloroform or dichloromethane may be mixed and used to such an extent that the polyimide or bisimide compound does not precipitate. It is preferable to appropriately change the concentration and viscosity of the polyimide solution according to the coating conditions.

In the present invention, the adhesive layer A and the adhesive layer B provided on the metal plate have the following characteristics in order to control the characteristics at the time of adhesion.
A filler having a particle size of 1 μm or less may be included.
When the filler is mixed, the content is 0.
It is preferably in the range of 1 to 50% by weight, more preferably 0.
It is 4 to 25% by weight. If the amount of filler is more than 50% by weight, the adhesive strength will be significantly reduced, while 0.1% by weight
If the amount is less than the above, 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 thickness of 1 is formed on the adhesive layer C.
It is also possible to provide a peelable film of ˜200 μm as a protective layer. Specifically, polyethylene, polypropylene, fluorine resin, polyethylene terephthalate,
A resin film of polyimide or the like, or a film or a paper of which the surface is subjected to a release treatment using a silicone-based release agent or the like, or a weak adhesive treatment is used.

[0052]

The present invention will be described in detail below with reference to examples. First, the production of the polyimide used for the adhesive layer A and the coating varnish containing the same will be described. Synthesis Example 1 In a flask equipped with a stirrer, 4,4'-diamino-3,
3 ', 5,5'-tetraethyldiphenylmethane 31.
04 g (100 mmol) and 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride 8.96 g
(25 mmol) and 16.36 g of pyromellitic anhydride
(75 mmol) and 300 ml of N-methyl-2-pyrrolidone (hereinafter referred to as “NMP”) were introduced under ice temperature, and stirring was continued for 1 hour. This solution is then added at room temperature to 2
Polyamic acid was synthesized by reacting for a time. To the obtained polyamic acid, 50 ml of toluene and 1.0 g of p-toluenesulfonic acid were added, heated to 160 ° C., and the water which was azeotropically distilled with toluene as the reaction proceeded was separated for 3 hours. The reaction was carried out. Then toluene was distilled off, the obtained polyimide varnish was poured into methanol, separating the resulting precipitate, crushing, washing, by going through the step of drying, the structural units that are represented by the formula described above 50.0 g (yield 95%) of polyimide having a molar ratio of (1a) :( 1b) = 25: 75 was obtained.

The infrared absorption spectrum of the obtained polyimide was measured and found to be 1718 cm ^-1 and 1783 cm ^-1.
A typical imide absorption was observed. Moreover, the number average molecular weight, the glass transition temperature (Tg), and the thermal decomposition start temperature were measured. The results are shown in Table 1. This polyimide was dissolved in N, N-dimethylformamide (hereinafter referred to as "DMF") at a concentration of 25% by weight to prepare a coating varnish.

Synthesis Example 2 4,4'-diamino-3,3 ', 5,5'-tetraethyldiphenylmethane 31.04 g (100 mmol) and 3,3', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride 17.92 g (50 mmol), pyromellitic anhydride 10.91 g (50 mmol) and NMP3
The same procedure as in Synthesis Example 1 was carried out using 00 ml to obtain 53.5 g (yield 95%) of a polyimide in which the molar ratio of each structural unit was (1a) :( 1b) = 50: 50. When the infrared absorption spectrum of the obtained polyimide was measured,
Typical imide absorptions were observed at 1718 cm ^-1 and 1783 cm ^-1 . Moreover, the number average molecular weight, Tg, and thermal decomposition start temperature were measured. The results are shown in Table 1. This polyimide was dissolved in DMF at a concentration of 25% by weight to prepare a coating varnish.

Synthesis example 3 4,4'-diamino-3,3 ', 5,5'-tetraethyldiphenylmethane 31.04 g (100 mmol) and 3,3', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride 26.88 g (75 mmol), pyromellitic anhydride 5.46 g (25 mmol) and NMP30
In the same manner as in Synthesis Example 1 using 0 ml, 57.4 g (yield 97%) of polyimide having a molar ratio of each structural unit of (1a) :( 1b) = 75: 25 was obtained. When the infrared absorption spectrum of the obtained polyimide was measured, it was 1
Typical imide absorptions were observed at 718 cm ^-1 and 1783 cm ^-1 . Moreover, the number average molecular weight, Tg, and thermal decomposition start temperature were measured. The results are shown in Table 1. This polyimide was dissolved in DMF at a concentration of 25% by weight to prepare a coating varnish.

Synthesis Example 4 4,4'-diamino-3,3 ', 5,5'-tetramethyldiphenylmethane 25.45 g (100 mmol) and 3,3', 4,4'-diphenylsulfone tetracarboxylic acid diester 17.92 g (50 mmol) of anhydride, 10.91 g (50 mmol) of pyromellitic anhydride and NMP3
The same procedure as in Synthesis Example 1 was carried out using 00 ml to obtain 52.1 g (yield 96%) of polyimide in which the molar ratio of each structural unit was (1a) :( 1b) = 50: 50. When the infrared absorption spectrum of the obtained polyimide was measured,
Typical imide absorptions were observed at 1718 cm ^-1 and 1783 cm ^-1 . Moreover, the number average molecular weight, Tg, and thermal decomposition start temperature were measured. The results are shown in Table 1. This polyimide was dissolved in DMF at a concentration of 25% by weight to prepare a coating varnish.

Synthesis Example 5 41.05 g (100 mmol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane and 3,2,2-bis [4- (4-aminophenoxy) phenyl] propane
17.92 g (50 mmol) of 3 ', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride, 10.91 g (50 mmol) of pyromellitic anhydride and NMP300
Using 3 ml and in the same manner as in Synthesis Example 1, 63.0 g (yield 95%) of polyimide was obtained in which the molar ratio of each structural unit was (1a) :( 1b) = 50: 50. When the infrared absorption spectrum of the obtained polyimide was measured, it was found to be 17
Typical absorption of imide was observed 18cm ^-1 and 1783 cm ^-1. Moreover, the number average molecular weight, Tg, and thermal decomposition start temperature were measured. The results are shown in Table 1. This polyimide was dissolved in DMF at a concentration of 25% by weight to prepare a coating varnish.

Synthesis Example 6 Bis [4- (4-aminophenoxy) phenyl] sulfone 42.77 g (100 mmol) and 3,3 ', 4.
4'-diphenylsulfone tetracarboxylic acid dianhydride 1
7.92 g (50 mmol) and pyromellitic dianhydride 1
Using 0.91 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) = 50: 50 polyimide 67.3 g (yield 94%). When the infrared absorption spectrum of the obtained polyimide was measured, it was 1718 cm.
Typical imide absorptions were observed at ^-1 and 1783 cm ^-1 . Moreover, the number average molecular weight, Tg, and thermal decomposition start temperature were measured. The results are shown in Table 1. This polyimide was dissolved in DMF at a concentration of 25% by weight to prepare a coating varnish.

Synthesis Example 7 4,4'-bis (4-aminophenoxy) biphenyl 3
6.84 g (100 mmol) and 3,3 ', 4,4'-
Diphenyl sulfone tetracarboxylic acid dianhydride 17.9
2 g (50 mmol) and pyromellitic anhydride 10.91
Using g (50 mmol) and 300 ml of NMP, the molar ratio of each structural unit was (1
a): Polyimide 5 represented by (1b) = 50: 50
9.6 g (96% yield) was obtained. The infrared absorption spectrum of the obtained polyimide was measured to be 1718 cm ^-1.
And a typical imide absorption at 1783 cm ^-1 was observed. Moreover, the number average molecular weight, Tg, and thermal decomposition start temperature were measured. The results are shown in Table 1. This polyimide was dissolved in DMF at a concentration of 25% by weight to prepare a coating varnish.

Synthesis Example 8 1,3-bis (4-aminophenoxy) benzene 29.
23 g (100 mmol) and 17.92 g of 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride
(50 mmol) and pyromellitic anhydride 10.91 g
(50 mmol) and 300 ml of NMP were used in the same manner as in Synthesis Example 1 so that the molar ratio of each structural unit was (1a):
(1b) = 52.8 g of polyimide represented by 50:50
(Yield 97%) was obtained. The infrared absorption spectrum of the obtained polyimide was measured to be 1718 cm ⁻¹ and 17
Typical imide absorption was observed at 83 cm ^-1 . Moreover, the number average molecular weight, Tg, and thermal decomposition start temperature were measured. The results are shown in Table 1. DM this polyimide
It was dissolved in F at a concentration of 25% by weight to prepare a coating varnish.

Synthesis Example 9 1,4-bis (4-aminophenoxy) benzene 29.
23 g (100 mmol) and 17.92 g of 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride
(50 mmol) and pyromellitic anhydride 10.91 g
(50 mmol) and 300 ml of NMP were used in the same manner as in Synthesis Example 1 so that the molar ratio of each structural unit was (1a):
(1b) = 50: 50 Polyimide 52.3 g
(Yield 96%) was obtained. The infrared absorption spectrum of the obtained polyimide was measured to be 1718 cm ⁻¹ and 17
Typical imide absorption was observed at 83 cm ^-1 . Moreover, the number average molecular weight, Tg, and thermal decomposition start temperature were measured. The results are shown in Table 1. DM this polyimide
It was dissolved in F at a concentration of 25% by weight to prepare a coating varnish.

Next, the production of the polyimide used for the adhesive layer B and the coating varnish containing the same will be described. Synthesis Example 10 1,4-bis (4-aminophenoxy) benzene 19.
58 g (67 mmol) and 1,3-bis (3-aminopropyl) -1,1,3,3, -tetramethyldisiloxane 8.20 g (33 mmol) and 3,3 ', 4,4'-
Diphenyl sulfone tetracarboxylic dianhydride 35.8
Polyimide 5 having a molar ratio of each structural unit of (1a) :( 2) = 67: 33 was prepared in the same manner as in Synthesis Example 1 using 3 g (100 mmol) and 300 ml of NMP.
8.0 g (yield 97%) was obtained. The infrared absorption spectrum of the obtained polyimide was measured to be 1718 cm ^-1.
And a typical imide absorption at 1783 cm ^-1 was observed. Moreover, the number average molecular weight, Tg, and thermal decomposition start temperature were measured. The results are shown in Table 2. This polyimide was added to tetrahydrofuran (hereinafter referred to as "THF") 2
It melt | dissolved in the density | concentration of 5 weight%, and prepared the coating varnish.

Synthesis Example 11 1,3-bis (4-aminophenoxy) benzene 19.
58 g (67 mmol) and 1,3-bis (3-aminopropyl) -1,1,3,3, -tetramethyldisiloxane 8.20 g (33 mmol) and 3,3 ', 4,4'-
Diphenyl sulfone tetracarboxylic dianhydride 35.8
Polyimide 5 having a molar ratio of each structural unit of (1a) :( 2) = 67: 33 was prepared in the same manner as in Synthesis Example 1 using 3 g (100 mmol) and 300 ml of NMP.
8.0 g (yield 97%) was obtained. The infrared absorption spectrum of the obtained polyimide was measured to be 1718 cm ^-1.
And a typical imide absorption at 1783 cm ^-1 was observed. Moreover, the number average molecular weight, Tg, and thermal decomposition start temperature were measured. The results are shown in Table 2. This polyimide was dissolved in THF at a concentration of 25% by weight to prepare a coating varnish.

Synthesis Example 12 23.08 g (67 mmol) of 1,3-bis [1- (4-aminophenyl) -1-methylethyl] benzene and 1,3-bis (3-aminopropyl) -1,1 , 3,
8.20 g (33 mmol) of 3, -tetramethyldisiloxane and 35.83 g (100 mmol) of 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride
And 300 ml of NMP in the same manner as in Synthesis Example 1 and the molar ratio of each structural unit was (1a) :( 2) = 67: 3.
62.5 g (yield 98%) of polyimide shown by 3 was obtained. 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, the number average molecular weight, T
g and thermal decomposition start temperature were measured. The results are shown in Table 2.
Shown in. This polyimide was dissolved in THF at a concentration of 25% by weight to prepare a coating varnish.

Synthesis Example 13 4,4'-bis (4-aminophenoxy) biphenyl 2
4.68 g (67 mmol), 1,3-bis (3-aminopropyl) -1,1,3,3, -tetramethyldisiloxane 8.20 g (33 mmol), 3,3 ',
35.83 g (100 mmol) of 4,4'-diphenylsulfone tetracarboxylic dianhydride and 300 m of NMP
Using 1 in the same manner as in Synthesis Example 1, 64.0 g (yield 98%) of polyimide having a molar ratio of each structural unit of (1a) :( 2) = 67: 33 was obtained. When the infrared absorption spectrum of the obtained polyimide was measured, it was found to be 1718.
typical absorption of imide was observed cm ^-1 and 1783 cm ^-1. Moreover, the number average molecular weight, Tg, and thermal decomposition start temperature were measured. The results are shown in Table 2. This polyimide was dissolved in THF at a concentration of 25% by weight to prepare a coating varnish.

Synthesis Example 14 4,4'-bis (4-aminophenoxy) diphenyl ether 25.75 g (67 mmol) and 1,3-bis (3-aminopropyl) -1,1,3,3, -tetramethyl Disiloxane 8.20 g (33 mmol) and 3,
35.83 g (100 mmol) of 3 ', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride and NMP3
By the same method as in Synthesis Example 1 using 00 ml, 64.0 g (yield 97%) of polyimide having a molar ratio of each structural unit of (1a) :( 2) = 67: 33 was obtained. When the infrared absorption spectrum of the obtained polyimide was measured, typical imide absorption was observed at 1718 cm ^-1 and 1783 cm ^-1 . Moreover, the number average molecular weight, Tg, and thermal decomposition start temperature were measured. The results are shown in Table 2. This polyimide was dissolved in THF at a concentration of 25% by weight to prepare a coating varnish.

Synthesis Example 15 28.98 g (67 mmol) of bis [4- (4-aminophenoxy) phenyl] sulfone 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'-diphenylsulfone tetracarboxylic dianhydride and 300 m of NMP
Using 1 in the same manner as in Synthesis Example 1, 65.0 g (yield 94%) of polyimide having a molar ratio of each structural unit of (1a) :( 2) = 67: 33 was obtained. When the infrared absorption spectrum of the obtained polyimide was measured, it was found to be 1718.
typical absorption of imide was observed cm ^-1 and 1783 cm ^-1. Moreover, the number average molecular weight, Tg, and thermal decomposition start temperature were measured. The results are shown in Table 2. This polyimide was dissolved in THF at a concentration of 25% by weight to prepare a coating varnish.

Synthesis Example 16 27.50 g (67 mmol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane and 1,3-
Bis (3-aminopropyl) -1,1,3,3, -tetramethyldisiloxane 8.20 g (33 mmol) and 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride 35.83 g (100 mmol) and NM
Using P300 ml and in the same manner as in Synthesis Example 1, 65.0 g (yield 96%) of a polyimide having a molar ratio of each structural unit of (1a) :( 2) = 67: 33 was obtained. When the infrared absorption spectrum of the obtained polyimide was measured, typical imide absorption was observed at 1718 cm ^-1 and 1783 cm ^-1 . Moreover, the number average molecular weight, Tg, and thermal decomposition start temperature were measured. The results are shown in Table 2. This polyimide was dissolved in THF at a concentration of 25% by weight to prepare a coating varnish.

Synthesis Example 17 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane 34.74 g (67 mmol) and 1,3-bis (3-aminopropyl) -1,1,
8.20 g of 3,3, -tetramethyldisiloxane (33
Mmol) and 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride 35.83 g (100 mmol) and 300 ml of NMP in the same manner as in Synthesis Example 1 and the molar ratio of each structural unit was (1a): (2) = 6
74.0 g of polyimide shown by 7:33 (yield 98
%) Was obtained. The infrared absorption spectrum of the obtained polyimide was measured and found to be 1718 cm ⁻¹ and 1783 cm ^−1.
A typical imide absorption was observed. Moreover, the number average molecular weight, Tg, and thermal decomposition start temperature were measured. The results are shown in Table 2. 25% by weight of this polyimide in THF
A varnish for coating was prepared by dissolving at a concentration of.

Synthesis Example 18 9,9-bis (4-aminophenyl) fluorene 23.
35 g (67 mmol) and 1,3-bis (3-aminopropyl) -1,1,3,3, -tetramethyldisiloxane 8.20 g (33 mmol) and 3,3 ', 4,4'-
Diphenyl sulfone tetracarboxylic dianhydride 35.8
Polyimide 6 represented by a molar ratio of each structural unit of (1a) :( 2) = 67: 33 in the same manner as in Synthesis Example 1 using 3 g (100 mmol) and 300 ml of NMP.
0.5 g (yield 95%) was obtained. The infrared absorption spectrum of the obtained polyimide was measured to be 1718 cm ^-1.
And a typical imide absorption at 1783 cm ^-1 was observed. Moreover, the number average molecular weight, Tg, and thermal decomposition start temperature were measured. The results are shown in Table 2. This polyimide was dissolved in THF at a concentration of 25% by weight to prepare a coating varnish.

Synthesis Example 19 2,2-bis [4- (4-aminophenoxy) phenyl] propane 20.53 g (50 mmol) and 1,3-
Bis (3-aminopropyl) -1,1,3,3, -tetramethyldisiloxane 12.43 g (50 mmol) and 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride 35.83 g (100 mmol) and NM
In the same manner as in Synthesis Example 1 using 300 ml of P, 61.0 g (yield 93%) of a polyimide in which the molar ratio of each structural unit was (1a) :( 2) = 50: 50 was obtained. When the infrared absorption spectrum of the obtained polyimide was measured, typical imide absorption was observed at 1718 cm ^-1 and 1783 cm ^-1 . Moreover, the number average molecular weight, Tg, and thermal decomposition start temperature were measured. The results are shown in Table 2. This polyimide was dissolved in THF at a concentration of 25% by weight to prepare a coating varnish.

Synthesis Example 20 30.79 g (75 mmol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane and 1,3-
Bis (3-aminopropyl) -1,1,3,3, -tetramethyldisiloxane 6.21 g (25 mmol) and 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride 35.83 g (100 mmol) and NM
Using P300 ml and in the same manner as in Synthesis Example 1, 65.0 g (yield 94%) of a polyimide in which the molar ratio of each structural unit was (1a) :( 2) = 75: 25 was obtained. When the infrared absorption spectrum of the obtained polyimide was measured, typical imide absorption was observed at 1718 cm ^-1 and 1783 cm ^-1 . Moreover, the number average molecular weight, Tg, and thermal decomposition start temperature were measured. The results are shown in Table 2. This polyimide was dissolved in THF at a concentration of 25% by weight to prepare a coating varnish.

Synthesis Example 21 32.84 g (80 mmol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane and 1,3-
Bis (3-aminopropyl) -1,1,3,3, -tetramethyldisiloxane 4.97 g (20 mmol) and 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride 35.83 g (100 mmol) and NM
Using P300 ml and in the same manner as in Synthesis Example 1, 68.0 g (yield 97%) of a polyimide having a molar ratio of each structural unit of (1a) :( 2) = 80: 20 was obtained. When the infrared absorption spectrum of the obtained polyimide was measured, typical imide absorption was observed at 1718 cm ^-1 and 1783 cm ^-1 . Moreover, the number average molecular weight, Tg, and thermal decomposition start temperature were measured. The results are shown in Table 2. This polyimide was dissolved in THF at a concentration of 25% by weight to prepare a coating varnish.

Synthesis Example 22 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 35.83 g of 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride (100 mmol) and NM
Using P300 ml and in the same manner as in Synthesis Example 1, 68.0 g (yield 97%) of a polyimide in which the molar ratio of each structural unit was (1a) :( 2) = 90: 10 was obtained. When the infrared absorption spectrum of the obtained polyimide was measured, typical imide absorption was observed at 1718 cm ^-1 and 1783 cm ^-1 . Moreover, the number average molecular weight, Tg, and thermal decomposition start temperature were measured. The results are shown in Table 2. This polyimide was dissolved in THF at a concentration of 25% by weight to prepare a coating varnish.

Synthesis Example 23 2,2-bis [4- (4-aminophenoxy) phenyl] propane 30.79 g (75 mmol) and 1,3-
Bis [(aminophenoxy) methyl] -1,1,3
9.42 g (25 mmol) of 3, -tetramethyldisiloxane and 35.83 g (100 mmol) of 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride
And 300 ml of NMP, the molar ratio of each structural unit was (1a) :( 2) = 75: 25 in the same manner as in Synthesis Example 1.
69.0 g (yield 95%) of the polyimide shown by was obtained. 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, the number average molecular weight, T
g and thermal decomposition start temperature were measured. The results are shown in Table 2.
Shown in. This polyimide was dissolved in THF at a concentration of 25% by weight to prepare a coating varnish.

Synthesis Example 24 In the above formula (6), 30.79 g (75 mmol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane and Y = NH ₂ , R = propylene, n =
10.72 g (25 mmol) of an aminopropyl-terminated dimethylsiloxane tetramer represented by 3 and 3,3 ', 4
4'-diphenylsulfone tetracarboxylic acid dianhydride 3
A polyimide 6 in which the molar ratio of each structural unit was (1a) :( 2) = 75: 25 was obtained by the same method as in Synthesis Example 1 using 5.83 g (100 mmol) and 300 ml of NMP.
7.0 g (yield 91%) was obtained. The infrared absorption spectrum of the obtained polyimide was measured and found to be 1712 cm ^-1.
And a typical imide absorption at 1783 cm ^-1 was observed. Moreover, the number average molecular weight, Tg, and thermal decomposition start temperature were measured. The results are shown in Table 2. This polyimide was dissolved in THF at a concentration of 25% by weight to prepare a coating varnish.

Synthesis Example 25 4,4'-diamino-3,3 ', 5,5'-tetraethyldiphenylmethane 31.04 g (100 mmol) and 3,3', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride 35.83 g (100 mmol) and NM
Using 300 ml of P, 58.8 g (yield 93%) of a polyimide in which the molar ratio of each structural unit was (1a) :( 2) = 100: 0 was obtained in the same manner as in Synthesis Example 1. When the infrared absorption spectrum of the obtained polyimide was measured,
Typical imide absorptions were observed at 1720 cm ^-1 and 1780 cm ^-1 . Moreover, the number average molecular weight, Tg, and thermal decomposition start temperature were measured. The results are shown in Table 2. This polyimide was dissolved in THF at a concentration of 25% by weight to prepare a coating varnish.

Synthesis Example 26 4,4'-diamino-3,3 ', 5,5'-tetraethyldiphenylmethane 7.76 g (25 mmol) and 1,
16.21 g (25 mmol) of 3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane and 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride 17. 91 g (50 mmol) and NMP
Using 150 ml, in the same manner as in Synthesis Example 1, 27.4 g (yield 91%) of a polyimide having a molar ratio of each structural unit of (1a) :( 2) = 50: 50 was obtained. When the infrared absorption spectrum of the obtained polyimide was measured, it was 1
Typical imide absorptions were observed at 720 cm ^-1 and 1780 cm ^-1 . Moreover, the number average molecular weight, Tg, and thermal decomposition start temperature were measured. The results are shown in Table 2. This polyimide was dissolved in THF at a concentration of 25% by weight to prepare a coating varnish.

Synthesis Example 27 4,4'-diamino-3,3 ', 5,5'-tetraethyldiphenylmethane 11.64 g (37.5 mmol)
And 1,3-bis (3-aminopropyl) -1,1,3,
3.11 g (12.5 mmol) of 3-tetramethyldisiloxane and 17.91 g (50 mmol) of 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride
And 150 ml of NMP, the molar ratio of each structural unit was (1a) :( 2) = 75: 25 in the same manner as in Synthesis Example 1.
29.6 g of polyimide (yield 92%) 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 . Also, the number average molecular weight, T
g and thermal decomposition start temperature were measured. The results are shown in Table 2.
Shown in. This polyimide was dissolved in THF at a concentration of 25% by weight to prepare a coating varnish.

Next, the production of the polyimide used for the adhesive layer C and the coating varnish containing the same will be described. Synthetic Example 28 29.42 g (72 mmol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane and Y = NH ₂ , R = propyl, and n = 8 in the above formula (6) are represented. A method similar to that of Synthesis Example 1 using 21.75 g (28 mmol) of dimethylsiloxane polymer, 35.83 g (100 mmol) of 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic acid dianhydride and 300 ml of NMP. And the molar ratio of each structural unit is (3a) :( 3b) = 7
2:28 Polyimide 78.4 g (yield 94
%) Was obtained. The infrared absorption spectrum of the obtained polyimide was measured and found to be 1718 cm ⁻¹ and 1783 cm ^−1.
A typical imide absorption was observed. Moreover, the number average molecular weight, Tg, and thermal decomposition start temperature were measured. The results are shown in Table 3. 25% by weight of this polyimide in THF
A varnish for coating was prepared by dissolving at a concentration of.

Synthesis Example 29 2,2-bis [4- (4-aminophenoxy) phenyl] propane (30.39 g, 74 mmol) and Y = NH ₂ , R = propyl and n = 8 in the above formula (6). 19.94 g (26 mmol) of the dimethyl siloxane polymer represented, 29.42 g (100 mmol) of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and N
In the same manner as in Synthesis Example 1 using 300 ml of MP, 72.3 g (yield 95%) of polyimide having a molar ratio of each structural unit of (3a) :( 3b) = 74: 26 was obtained.
When the infrared absorption spectrum of the obtained polyimide was measured, typical imide absorption was observed at 1718 cm ^-1 and 1783 cm ^-1 . Moreover, the number average molecular weight, Tg, and thermal decomposition start temperature were measured. The results are shown in Table 3. This polyimide was dissolved in THF at a concentration of 25% by weight to prepare a coating varnish.

Synthesis Example 30 32.74 g (80 mmol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane and Y = NH ₂ , R = propyl and n = 8 in the above formula (6). 15.54 g (20 mmol) of the dimethylsiloxane polymer represented, 29.42 g (100 mmol) of 2,3 ', 3,4'-biphenyltetracarboxylic dianhydride and N
In the same manner as in Synthesis Example 1 using 300 ml of MP, 69.7 g (yield 94%) of polyimide having a molar ratio of each structural unit of (3a) :( 3b) = 80: 20 was obtained.
When the infrared absorption spectrum of the obtained polyimide was measured, typical imide absorption was observed at 1718 cm ^-1 and 1783 cm ^-1 . Moreover, the number average molecular weight, Tg, and thermal decomposition start temperature were measured. The results are shown in Table 3. This polyimide was dissolved in THF at a concentration of 25% by weight to prepare a coating varnish.

Synthesis Example 31 1,3-bis (3-aminophenoxy) benzene 23.
24 g (80 mmol) and Y = N in the above formula (6).
15.2 g (20 mmol) of dimethylsiloxane polymer represented by H ₂ , R = propyl, and n = 8, 2,3 ′,
3,4'-biphenyltetracarboxylic dianhydride 29.
42 g (100 mmol) and 300 ml of NMP were used in the same manner as in Synthesis Example 1 to give 60.1 g of a polyimide having a molar ratio of each structural unit of (3a) :( 3b) = 80: 20 (yield: 93%). ) Got. When the infrared absorption spectrum of the obtained polyimide was measured, it was 1718 cm.
Typical imide absorptions were observed at ^-1 and 1783 cm ^-1 . Moreover, the number average molecular weight, Tg, and thermal decomposition start temperature were measured. The results are shown in Table 3. This polyimide was dissolved in THF at a concentration of 25% by weight to prepare a coating varnish.

Synthesis Example 32 27.14 g (76 mmol) of 1,3-bis [1- (3-aminophenyl) -1-methylethyl] benzene and Y = NH ₂ , R = propyl in the above formula (6), n = 8
18.52 g (2
4 mmol), 2,3 ′, 3,4′-biphenyltetracarboxylic dianhydride 29.42 g (100 mmol) and 300 ml of NMP in the same manner as in Synthesis Example 1 and the molar ratio of each structural unit was (3a) :( 3b) = 76:
60.1 g (yield 93%) of polyimide 24 was obtained. 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, the number average molecular weight,
The Tg and the thermal decomposition start temperature were measured. The results are shown in Table 3. This polyimide was dissolved in THF at a concentration of 25% by weight to prepare a coating varnish.

[0085]

[Table 1]

[0086]

[Table 2]

[0087]

[Table 3]

The molecular weights of the polyimides shown in Tables 1 to 3 were measured by GPC. THF was used as an eluent, and a column used was Shodex 80M × 2. Polystyrene was used as the standard substance of the number average molecular weight. The glass transition temperature was measured by differential thermal analysis (heating in nitrogen at 10 ° C./min). In addition, the thermal decomposition start temperature was determined by thermogravimetric analysis (in nitrogen,
The temperature was raised at 10 ° C./min).

Next, the production of the bisimide compound used for the adhesive layer B will be described. Synthesis Example 33 In a flask equipped with a stirrer, 36.8 g (100 mmol) of 4,4'-bis (3-aminophenoxy) biphenyl, 31.1 g (210 mmol) of phthalic anhydride and N were added.
MP500 ml and ice temperature were introduced, and stirring was continued for 1 hour. Then, this solution was reacted at room temperature for 2 hours to synthesize an amic acid. Triethylamine 4 was added to the obtained amic acid.
0.4 g (400 mmol) and acetic anhydride 30.6 g (3
(00 mmol) was slowly added dropwise, and stirring was continued at room temperature for 2 hours. The solution obtained is poured into methanol and the precipitate is filtered. The precipitate is washed with methanol, 150
After drying at 0 ° C. for 2 hours, 47.5 g (yield of 76% based on diamine) of the bisimide compound represented by the above formula (4a) was obtained. When the infrared absorption spectrum was measured, it was found to be 172
Typical imide absorptions at 0 and 1780 cm ^-1 are 12
Absorption of ether was observed at 40 cm ^-1 . The melting points and the results of elemental analysis are shown in Table 4.

Synthesis Example 34 4,2-bis (4- (3-aminophenoxy) phenyl) propane 41.1 g (100 mmol), phthalic anhydride 31.1 g (210 mmol) and NMP 500 ml.
Was used in the same manner as in Synthesis Example 33 to obtain 53.5 g (yield 80% based on diamine) of the bisimide compound represented by the above formula (4a). Was measured infrared absorption spectrum, the 1720 and 1780 cm ^-1 typical absorption of an imide, absorption of ether was observed at 1240 cm ^-1. The melting points and the results of elemental analysis are shown in Table 4.

Synthesis Example 35 34.4 g (100 mmol) of 1,3-bis (4-amino-α, α-dimethylbenzyl) benzene, 31.1 g (210 mmol) of phthalic anhydride and 500 ml of NMP.
Was used in the same manner as in Synthesis Example 33 to obtain 58.0 g (yield 96% based on diamine) of the bisimide compound represented by the above formula (4a). When the infrared absorption spectrum was measured, typical absorption of imide was observed at 1720 and 1780 cm ⁻¹ . Results of melting point and elemental analysis are shown in Table 4.
Shown in.

Synthesis Example 36 4,4'-bis (4-aminophenoxy) biphenyl 3
6.8 g (100 mmol) and phthalic anhydride 31.1 g
(210 mmol) and NMP (500 ml) were obtained in the same manner as in Synthesis Example 33 to obtain 56.5 g (yield 90% based on diamine) of the bisimide compound represented by the above formula (4a). The infrared absorption spectrum was measured and found to be 17
Typical imide absorptions at 20 and 1780 cm ^-1 are 1
Absorption of ether was observed at 240 cm ^-1 . The melting points and the results of elemental analysis are shown in Table 4.

Synthesis Example 37 4,2-bis [4- (4-aminophenoxy) phenyl] propane 41.1 g (100 mmol), phthalic anhydride 31.1 g (210 mmol) and NMP 500 ml.
Was used in the same manner as in Synthesis Example 33 to obtain 62.3 g (yield 93% based on diamine) of the bisimide compound represented by the above formula (4a). Was measured infrared absorption spectrum, the 1720 and 1780 cm ^-1 typical absorption of an imide, absorption of ether was observed at 1240 cm ^-1. The melting points and the results of elemental analysis are shown in Table 4.

Synthesis Example 38 4,4'-Diamino-3,3 ', 5,5'-tetraethyldiphenylmethane 31.0 g (100 mmol), phthalic anhydride 31.1 g (210 mmol) and NMP50.
47.4 g in the same manner as in Synthesis Example 33 using 0 ml.
A bisimide compound represented by the above formula (4a) (yield: 83% based on diamine) was obtained. When the infrared absorption spectrum was measured, typical absorption of imide was observed at 1720 and 1780 cm ⁻¹ . The melting points and the results of elemental analysis are shown in Table 4.

Synthesis Example 39 43.2 g (100 mmol) of bis [4- (3-aminophenoxy) phenyl] sulfone and phthalic anhydride 31.
Using 1 g (210 mmol) and 500 ml NMP,
In the same manner as in Synthesis Example 33, 59.6 g (yield 86% based on diamine) of the bisimide compound represented by the above formula (4a) was obtained. When the infrared absorption spectrum was measured,
Typical imide absorptions were observed at 1720 and 1780 cm ^-1 . The melting points and the results of elemental analysis are shown in Table 4.

Synthesis Example 40 2,2-bis [4- (4-aminophenoxy) phenyl] propane 41.1 g (100 mmol), trimellitic anhydride 40.5 g (210 mmol) and NMP500.
67.7 g in the same manner as in Synthesis Example 33 using ml.
A bisimide compound represented by the above formula (4a) (yield 89% based on diamine) was obtained. When the infrared absorption spectrum was measured, typical absorption of imide was observed at 1720 and 1780 cm ⁻¹ . The melting points and the results of elemental analysis are shown in Table 4.

Synthesis Example 41 2,2-bis [4- (4-aminophenoxy) phenyl] propane 41.1 g (100 mmol), maleic anhydride 20.6 g (210 mmol) and NMP 500 m.
Using l, in the same manner as in Synthesis Example 33, 48.5 g (yield 85% based on diamine) of the bisimide compound represented by the above formula (4b) was obtained. When the infrared absorption spectrum was measured, typical imide absorption was observed at 1720 and 1780 cm ⁻¹ , and absorption due to the maleimide double bond was found at 690 cm ⁻¹ . Results of melting point and elemental analysis are shown in Table 4.
Shown in.

Synthesis Example 42 4,4'-diamino-3,3 ', 5,5'-tetraethyldiphenylmethane 31.0 g (100 mmol), maleic anhydride 20.6 g (210 mmol) and NMP5.
00 ml was used and 38.1 in the same manner as in Synthesis Example 33.
g (yield 81% based on diamine) of the bisimide compound represented by the above formula (4b) was obtained. When the infrared absorption spectrum was measured, typical imide absorption was observed at 1720 and 1780 cm ⁻¹ , and absorption due to the maleimide double bond was found at 690 cm ⁻¹ . The melting points and the results of elemental analysis are shown in Table 4.

[0099]

[Table 4] In Table 4, the melting point of each bisimide compound was measured by DSC at a temperature increase of 3 ° C./min.

Comparative Synthetic Example 1 16.40 g (40 mmol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane and 8.42 g (40 mmol) of trimellitic anhydride monochloride.
And NMP (120 ml) were used to obtain 20.8 g (yield 92%) of polyether amide imide in the same manner as in Synthesis example 1. When the infrared absorption spectrum of the obtained polyether amide imide was measured, it was 1720 and 1780 cm.
^A typical imide absorption at ^-1 and an amide absorption at 1715 cm ^-1 were observed. The number average molecular weight is 21,
000, Tg is 228 ° C., thermal decomposition initiation temperature is 43
It was 0 ° C. This polyether amide imide resin is
It was dissolved in HF at a concentration of 25% by weight to obtain a coating varnish.

Comparative Synthesis Example 2 4,4'-diaminodiphenyl ether 8.01 g (4
0 mmol) and biphenyltetracarboxylic dianhydride 1
Using 0.80 g (40 mmol) and 120 ml of NMP, 16.1 g (yield 93%) of polyimide was obtained in the same manner as in Synthesis Example 1. The infrared absorption spectrum of the obtained polyetherimide was measured and found to be 1715 and 178.
Typical imide absorption was observed at 6 cm ^-1 . Also,
Its number average molecular weight was insoluble in THF, so it could not be measured by this measuring method. The Tg was 290 ° C and the thermal decomposition starting temperature was 560 ° C. This polyimide was dissolved in o-dichlorophenol at a concentration of 20% by weight to prepare a coating varnish.

Comparative Synthesis Example 3 2,2-bis (1,1 ', 2,2'-tetracarboxy) -4-phenoxyphenyl) propane dianhydride 2
0.8 g (40 mmol) and trimellitic anhydride monochloride 8.42 g (40 mmol) were added to NMP120.
Dissolve in ml and add m-phenylenediamine to this solution.
34 g (0.04 mol) was added and stirred at 0 ° C. for 4 hours,
A 20 wt% NMP varnish of polyamic acid was obtained. This was directly used as a coating varnish. The resin obtained by imidization has a Tg of 216 ° C. and a thermal decomposition initiation temperature of 510.
It was ℃. The infrared absorption spectrum of the obtained polyether amide imide was measured and found to be 1715 and 178.
Typical imide absorption was observed at 6 cm ^-1 . Also,
Its number average molecular weight was insoluble in THF, so it could not be measured by this measuring method.

(Adhesive Tape Production Example) Example 1 A coating of the coating varnish of Synthesis Example 1 was applied on one surface of a copper plate having a thickness of 100 μm using a bar coater so that the layer thickness when dried was 20 μm. The adhesive layer A was formed on the copper plate by drying at 150 ° C. for 60 minutes with a hot air circulation dryer.
Next, the coating varnish obtained in Synthesis Example 26 (having a glass transition temperature different from that of the polyimide of Synthesis Example 1) was applied onto the adhesive layer A so that the layer thickness when dried was 20 μm, The adhesive layer B of the adhesive tape was formed by drying at 150 ° C. for 10 minutes with a hot air circulation dryer. Finally, the coating varnish obtained in Synthesis Example 28 (having a glass transition temperature different from that of the polyimides of Synthesis Examples 1 and 26) on the adhesive layer B has a layer thickness of 5 μm when dried. As described above, and dried at 150 ° C. for 10 minutes with a hot air circulation type dryer to form an adhesive layer A, an adhesive layer B composed of polyimide having different glass transition temperatures on a copper plate,
Total thickness 145 μm having a layer structure in which the adhesive layer C is sequentially laminated
An adhesive tape for electronic parts was produced.

Examples 2 to 49 Adhesive tapes of the present invention were prepared in the same manner as in Example 1 except that the polyimide and bisimide compound obtained in Synthesis Examples 1 to 42 were used. The adhesive layer A of Example 26 and the adhesive layer B of Example 27 were mixed with 10% by weight of a silica filler having a particle size of 0.07 μm (manufactured by Arakawa Chemical Co., Ltd.). Further, 10% by weight of an alumina filler (manufactured by Showa Denko) having a particle diameter of 0.05 μm was mixed in the adhesive layer B of Example 28. In addition, the coating varnish for the adhesive layer B of Examples 29 to 49 was prepared by dispersing or dissolving a bisimide compound.

Example 50 An adhesive tape of the present invention was produced in the same manner as in Example 2 except that the copper plate having a thickness of 100 μm was replaced with a copper plate having a thickness of 50 μm. Example 51 An adhesive tape of the present invention was produced in exactly the same manner as in Example 2 except that the copper plate having a thickness of 100 μm was replaced with a copper plate having a thickness of 200 μm. The coating varnish of the adhesive layer used in each of Examples 1 to 51, the type and amount of the bisimide compound and the filler, and the adhesive temperature of the formed adhesive layer are shown in Table 5 below.
~ Shown in Table 7.

Comparative Example 1 The same procedure as in Example 1 was carried out except that the coating varnish containing the polyimide obtained in Synthesis Example 26 was used instead of the coating varnish containing the polyimide obtained in Synthesis Example 1. An adhesive tape for comparison was prepared by coating one surface of a copper plate and forming adhesive layers corresponding to adhesive layers A and B made of polyimide having the same glass transition temperature.

Comparative Example 2 The coating varnish containing the polyimide obtained in Synthesis Example 3 was
Using a bar coater, a polyimide film having a thickness of 50 μm (manufactured by Ube Industries, Ltd .: Upilex 50S) is applied to a dry layer thickness of 20 μm, and the hot air circulation dryer is used for 60 minutes at 150 ° C. An adhesive layer corresponding to the adhesive layer A was formed on one surface of the polyimide film by drying. Then, the coating varnish containing the polyimide obtained in Synthesis Example 26 was applied to the other surface of the polyimide film so that the layer thickness when dried was 20 μm, and the temperature was 150 ° C. in a hot-air circulation dryer. It was dried for 10 minutes to form an adhesive layer corresponding to the adhesive layer B, and an adhesive sheet having adhesive layers having different glass transition temperatures on both surfaces of the polyimide film was produced. The surface of the adhesive layer (polyimide adhesive layer obtained in Synthesis Example 3) corresponding to the adhesive layer A of this adhesive sheet was thermocompression-bonded to one surface of the copper plate used in Example 1 under a nitrogen atmosphere to give a comparative adhesive tape. It was made. In addition, thermocompression bonding is 360 ° C, 4 kg
It was performed at f / cm ² for 2 seconds.

Comparative Example 3 Polyimide-based varnish (Lark TP manufactured by Mitsui Toatsu Chemicals, Inc.)
A 20 wt% NMP solution of I) was prepared. It was coated on one surface of the copper plate used in Example 1 so that the layer thickness of the adhesive layer when dried was 20 μm, and dried at 150 ° C. in a hot air circulation dryer at 1 ° C.
It was dried for 20 minutes to form an adhesive layer corresponding to the adhesive layer A. Further, the same solution was applied onto the formed adhesive layer so that the thickness of the adhesive layer when dried was 20 μm, and dried at 150 ° C. for 120 minutes by a hot air circulation dryer, and then further in a nitrogen atmosphere. It was dried at 250 ° C. for 60 minutes to form an adhesive layer (Tg = 288 ° C.) corresponding to the adhesive layer B, and an adhesive tape for comparison was produced.

Comparative Example 4 A 20% by weight NMP solution of a polyimide varnish (Lark TPI, manufactured by Mitsui Toatsu Chemicals, Inc.) was prepared. This solution was applied to one surface of the polyimide film used in Comparative Example 2 so that the layer thickness of the adhesive layer when dried was 20 μm, and dried at 150 ° C. for 120 minutes with a hot air circulation dryer to obtain an adhesive layer (Tg = 288 ° C.), and the same solution is applied to the other surface of the above polyimide film so that the layer thickness of the adhesive layer is 2 when dried.
Coat to 0 μm and dry with a hot air circulation dryer for 15
After drying at 0 ° C for 120 minutes to form an adhesive layer, it was further dried at 250 ° C for 60 minutes to prepare an adhesive sheet.
One side of the obtained adhesive sheet was thermocompression-bonded to one side of the copper plate used in Example 1 under a nitrogen atmosphere to prepare a comparative adhesive tape. The thermocompression bonding is 360 ° C., 4 kgf / cm
^{It took 2} or 2 seconds.

Comparative Example 5 Polyimide varnish (Mitsui Toatsu Chemicals, Inc .: Lark TP)
A 20 wt% NMP solution of I) was prepared. It was coated on one surface of the copper plate used in Example 1 so that the layer thickness of the adhesive layer when dried was 20 μm, and dried at 150 ° C. in a hot air circulation dryer at 1 ° C.
After being dried for 20 minutes and further dried at 250 ° C. for 60 minutes in a nitrogen atmosphere, an adhesive layer (Tg = 288) corresponding to the adhesive layer A was obtained.
C) was formed. Next, the coating varnish of the polyether amide imide obtained in Comparative Synthesis Example 1 was applied to the adhesive layer surface of the copper plate so that the layer thickness of the adhesive layer when dried was 20 μm, and the hot air circulation dryer was used. It was dried at 150 ° C. for 10 minutes to form an adhesive layer corresponding to the adhesive layer B, and a comparative adhesive tape was produced.

Comparative Example 6 The coating varnish containing the polyimide obtained in Comparative Synthesis Example 2 was applied to one surface of the copper plate used in Example 1 so that the dry adhesive layer had a thickness of 20 μm. It was dried at 150 ° C. for 120 minutes with a hot air circulation dryer to form an adhesive layer corresponding to the adhesive layer A. Then, a 20 wt% NMP solution of polyamide imide (Amorco: Torlon 400T) was used as a coating varnish so that the dried adhesive layer had a layer thickness of 20 μm and was coated with hot air. It was dried at 150 ° C. for 120 minutes by a circulation type dryer to form an adhesive layer (Tg = 230 ° C.) corresponding to the adhesive layer B to prepare a comparative adhesive tape.

Comparative Example 7 The coating varnish containing the polyimide obtained in Comparative Synthesis Example 2 was applied to one surface of the copper plate used in Example 1 so that the thickness of the adhesive layer when dried was 20 μm, It was dried at 150 ° C. for 120 minutes with a hot air circulation dryer to form an adhesive layer corresponding to the adhesive layer A. Then, a 20 wt% NMP solution of the polyamic acid obtained in Comparative Synthesis Example 3 was applied as a coating varnish on the formed adhesive layer so that the layer thickness of the adhesive layer when dried was 20 μm, 1 with hot air circulation type dryer
Dry at 50 ° C for 60 minutes, then 250 ° C under nitrogen atmosphere
Was dried for 60 minutes to form an adhesive layer corresponding to the adhesive layer B to prepare a comparative adhesive tape.

Comparative Example 8 An adhesive tape for comparison was prepared in the same manner as in Example 1, except that the adhesive layer C was not provided and the adhesive layer A and the adhesive layer B were sequentially provided on the metal. Comparative Example 9 An adhesive layer C was formed using the polyimide of Synthesis Example 28 on the adhesive layer B of the tape produced in Comparative Example 7 in the same manner as in Example 1 to produce an adhesive tape for comparison. Also in Comparative Examples 1 to 9, Table 8 shows the coating varnish, the amount of filler added, and the adhesive temperature of the adhesive layer, as in the examples.

[0114]

[Table 5]

[0115]

[Table 6]

[0116]

[Table 7]

[0117]

[Table 8]

In order to evaluate the adhesive tapes obtained in each of the above Examples and Comparative Examples, a lead frame was produced by the following procedure and evaluated. (Assembling the lead frame)
The lead frame used for the semiconductor package shown in FIG. 1 was assembled by the steps (a) and (b) shown below. (A) Punching of adhesive tape The adhesive tape was punched out with a die. (B) Lead frame assembly The adhesive tape punched into a predetermined shape is aligned with the lead frame, heated and pressed on a heated hot plate, and the lead frame and the adhesive tape are attached one by one (under a nitrogen atmosphere, 150 ℃ / 2kgf / cm ² /
The lead frame was temporarily press-bonded for 0.5 second. Examples 1-51 with adhesive layer C, Comparative Example 1 and Comparative Example 9
In the case of, after the temporary pressure bonding, a series of lead frames (consisting of 5 pieces) were main pressure bonded at one time (in a nitrogen atmosphere, 4 kg).
f / cm ^2/2 seconds). The adhesion temperature at this time was the temperature shown in Table 5 to Table 8. The reason why the bonding conditions are different when the lead frame is assembled is that the characteristics of each adhesive tape are different. Here, the optimum bonding condition was selected for each adhesive tape, and the bonding was performed based on that. In the case of Comparative Example 2-8 is no adhesive layer C, since the temporary pressure bonding is not possible, were pasted by one piece at a bonding temperature shown in Table 8 (under a nitrogen atmosphere, 4kgf / cm ^2/2 seconds ).

(Assembly of Semiconductor Package) Next, using the lead frame obtained above, a semiconductor package was assembled in the following steps (c) to (f). (C) Die Bonding A semiconductor chip was bonded to a copper plate (metal heat dissipation plate) portion using a die bonding silver paste and cured at 150 ° C. for 2 hours. (D) Wire Bonding A wire bond was used to connect the wire pad on the semiconductor chip and the silver-plated portion at the end of the inner lead wire with a gold wire. (E) Molding A transfer epoxy molding agent was used for transfer molding. (F) Finishing Step The package was finished including steps such as homing, dam cutting, and plating of the outer lead portion.

(Adhesive tape and semiconductor package (n =
Evaluation of 10)) (A) Lead frame assembling time
In the case of 51, Comparative Example 1 and Comparative Example 9, the total time was 9 seconds, which was 5 seconds for temporary pressure bonding and 4 seconds for main pressure bonding, and 2 including the takt time.
On the other hand, in the case of Comparative Examples 2 to 8 in which the adhesive layer C is not provided, it takes 20 seconds only for the main pressure bonding, and when the tact time is included, it becomes 40 seconds / 10 pieces, which is about 2 seconds. It took twice as long.

(B) Adhesive Strength An adhesive tape was attached (taping) to the copper plate under the conditions for assembling the lead frame (when the adhesive layer C is present,
After temporary pressure-bonding, main pressure-bonding was performed, and in the case where there was no adhesive layer C, the main pressure-bonding was directly performed. As a result, the strength of the adhesive tapes of Examples 1 to 51 and Comparative Example 8 was 35 to 5
While it was 0 g / 10 mm, in Comparative Examples 1 and 3, it was 35 to 50 g / 10 mm and there was no problem, but in Comparative Examples 2, 4, 5 to 7, 9 is 10 to 40 g / 10 m.
fluctuation width is bought can large by m. Further, Comparative Examples 2 and 4 were peeled between the base film and the adhesive layer, and Comparative Examples 5 to 7 and 9 were peeled between the adhesive layers.

(C) Lead embedding state The state in which the lead pins were embedded in the adhesive tape when the lead frame was assembled was observed. In the adhesive tapes of Examples 1 to 51, the lead pins remain in the pasted state at the time of assembling the lead frame in the step (b), that is, the adhesive layer A.
However, in Comparative Examples 1, 3 and 6, the lead pins are distorted or moved during bonding of the semiconductor chip during the die bonding in the step (c) to improve the flatness. There was something missing. Specifically, in the case of Comparative Examples 1 and 3, some lead pins were in contact with the metal heat sink, and in Comparative Example 6, the lead pins were buried in the adhesive layer corresponding to the adhesive layer A. Was there. Comparative Examples 2 and 4 were polyimide films, and Comparative Examples 5, 7 and 9 were stopped at the interface between the adhesive layers corresponding to the adhesive layers A and B.

(D) Evaluation of Semiconductor Package A PCB was obtained from the package obtained as described above.
T test (Pressure Cooker Bias)
d Test) was performed. This electrical reliability test
Apply 5V, 121 ℃, 2atm, 100% RH
Was carried out under the conditions of As a result, in the case of Examples 1 to 51, no short circuit occurred even after 1000 hours had passed. On the other hand, in Comparative Example 1, a short circuit occurred due to contact due to the movement of the lead pin in three and four in Comparative Example 3. In Comparative Examples 2 and 4 to 9, no short circuit occurred, but in Comparative Examples 2 and 4, at the interface between the polyimide film and the adhesive layer, in Comparative Examples 5 to 7 and 9, the adhesive layer A and the adhesive layer B were formed. It was confirmed that there were 8 pieces peeled off at the interface of the corresponding adhesive layer.

From the above results, when the adhesive tape of the present invention is used, a semiconductor package can be satisfactorily manufactured, whereas when the adhesive tape of the comparative example is used, the lead frame is assembled. It is not suitable for use in electronic component manufacturing because it takes time, the lead pins are embedded, a short circuit occurs in the electrical reliability test, and the adhesive strength fluctuates significantly. .

[0125]

Industrial Applicability The adhesive tape for electronic parts of the present invention has sufficient heat resistance and adhesiveness as shown in the above test results, and is at a relatively low temperature, that is, 100 to 180.
Since it can be pressure-bonded at ℃ and has excellent workability, for example, for lead frame fixing tape, TAB tape, between lead frame peripheral members constituting a semiconductor device, that is, lead pins, semiconductor chip mounting substrate It can be suitably used for bonding a heat sink, a semiconductor chip itself, and the like. Furthermore, when a semiconductor package is manufactured using the adhesive tape, there is no embedding of lead pins in the adhesive layer, movement of the lead pins, etc., no peeling between the adhesive layers and between the metal plate and the adhesive layer, and high temperature, high humidity, and high pressure. The electrical reliability is high even in the environment.

[Brief description of drawings]

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

FIG. 2 is a sectional view of another example of a resin-sealed semiconductor device using a conventional adhesive tape.

[Explanation of symbols]

1 ... Semiconductor chip, 2 ... Metal plate (metal heat sink), 3 ... Lead pin, 4 ... Bonding wire, 5 ... Resin, 6 ...
Adhesive layer, 6a ... Adhesive layer A, 6b ... Adhesive layer B, 6c ... Adhesive layer C.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-11-35902 (JP, A) JP-A-10-140106 (JP, A) JP-A-9-67559 (JP, A) JP-A-8- 325533 (JP, A) JP-A-3-296582 (JP, A) JP-A-9-272853 (JP, A) JP-A-9-13001 (JP, A) JP-A-6-291236 (JP, A) JP-A-6-128462 (JP, A) JP-A-11-100565 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09J 4/00-201/10

Claims (7)

(57) [Claims] 1. An adhesive tape for electronic parts, comprising an adhesive layer A, an adhesive layer B, and an adhesive layer C sequentially laminated on at least one surface of a metal plate, wherein the adhesive layers are made of polyimide and are made of gold. the glass transition temperature of the adhesive layer a in contact with the genus plate is higher than the glass transition temperature of the adhesive layer B, the glass transition temperature of the adhesive layer B is rather high than the glass transition temperature of the adhesive layer C, and the adhesive layer
The glass transition temperature of C is 150 ° C. or lower, and the adhesive layer A
Is a structural unit represented by the following formula (1a): 100 to 20 mol
%, And a structural unit represented by the following formula (1b): 0 to 80 mol
%, Containing at least one polyimide
Layer B is a structural unit represented by the following formula (1a) 100 to 40
Mol% and the structural unit represented by the following formula (2) 0 to 60 units.
% Of at least one polyimide,
The coating layer C is a structural unit 90-40 represented by the following formula (3a).
Mol% and structural units 10 to 6 represented by the following formula (3b):
Contains 0 mol% of at least one polyimide
Adhesive tape for electronic parts which is characterized in that that. [Chemical 1] (In the formula, Ar is selected from the following structures having an aromatic ring.
A divalent group is shown. ) [Chemical 2] (In the formula, R ₁ , R ₂ , R ₃ and R ₄ are the same or different.
, A hydrogen atom and an alkane having 1 to 4 carbon atoms, respectively.
A alkyl group or an alkoxy group is shown, but all of these groups are the same.
Sometimes it is not a hydrogen atom. ) [Chemical 3] (In the formula, R is an alkylene group having 1 to 10 carbon atoms, or
-CH ₂ OC ₆ H ₄ which styrene groups are attached to the Si - the
It shows and n means the integer of 1-20. ) [Chemical 4] (In the formula, X is 3,3 ′, 4,4′-diphenyl sulfone.
Structure, 3,3 ', 4,4'-biphenyl structure, and 2,
4 having any of 3 ', 3,4'-biphenyl structure
Represents a valent aromatic group, Ar, R and n are each as defined above.
Has the same meaning as the definition of ) 2. The adhesive layer B comprises the following formulas (4a) and (4):
at least selected from bisimide compounds represented by b)
1 to 100 parts by weight for 100 parts by weight of polyimide
The electron according to claim 1, characterized in that the electron is contained therein.
Adhesive tape for parts. [Chemical 5] (In the formula, Ar has the same meaning as defined above, and R ₅ , R
₆ and R ₇ may be the same or different, and
Hydrogen atom, chlorine atom, bromine atom, carboxyl group, carbon
An alkyl group or an alkoxy group of the numbers 1 to 4 is shown. ) 3. The glass transition temperature of the adhesive layer A is that of the adhesive layer B.
A contract characterized by being 40 ° C or more higher than the glass transition temperature
The adhesive tape for electronic parts according to claim 1. 4. A small number of adhesive layers A, B and C.
At least one of the adhesive layers has a particle size of 1 μm or less.
0.1 to 50% by weight of aluminum.
1. The adhesive tape for electronic parts according to 1. 5. A peelable film is provided on the surface of the adhesive layer C.
The adhesive tape for electronic parts according to claim 1, wherein
Oop. 6. The thickness of the metal plate is in the range of 10 to 300 μm.
The contact for electronic parts according to claim 1, wherein
Wearing tape. 7. The metal plate is copper, white copper, silver, iron, 42 alloy and
And one kind selected from stainless steel
The adhesive tape for electronic parts according to claim 1 or 6.