JP2001311055A - Adhesive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive composition excellent in soldering heat resistance, heat resistance and adhesion, in particular capable of bonding at low temperatures of <=250 deg.C. SOLUTION: This adhesive composition essentially comprises 100 pts.wt. of a soluble polyimide of general formula (1) (wherein, R1 is a tetravalent organic group; R2 is a trivalent organic group; R3 is a univalent organic group; R4 is a bivalent organic group; p is an integer of 1-4; m is an integer of >=1; and n is an integer of >=0) and 1-150 pts.wt. of a compound having at least two unsaturated double bonds.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an adhesive composition which can be adhesively cured at a relatively low temperature, is soluble in a solvent, and is excellent in heat resistance and adhesiveness. The adhesive composition of the present invention can be used for a flexible printed circuit board, TAB (Tape Automat).
It is useful as an adhesive having excellent heat-resistant adhesiveness used for tapes for ed bonding, composite lead frames, laminated materials and the like.

[0002]

2. Description of the Related Art In recent years, electronic devices have become more sophisticated and more sophisticated.
With miniaturization progressing, there has been a demand for miniaturization and weight reduction of electronic components used accordingly. Therefore, a semiconductor element packaging method and a wiring material or a wiring component for mounting the same have been required to have higher density, higher function and higher performance. In particular, semiconductor packages, COL and LOC packages, MCM
(Multi ChipModule) and other high-density packaging materials and multilayer FPC
There is a demand for a material exhibiting good adhesiveness, which can be suitably used as a printed wiring board material such as described above, and further as an aerospace material.

Conventionally, acrylic, phenolic, epoxy and polyimide adhesives have been known as adhesive materials showing good mechanical properties, heat resistance and insulating properties in semiconductor packages and other mounting materials. .

However, phenol-based and epoxy-based adhesives have excellent adhesiveness, but are inferior in flexibility. A problem arises in that a flexible acrylic adhesive has low heat resistance. To solve this, polyimide is used. Since polyimide has excellent heat resistance among various organic polymers, it is widely used in the fields of space and aviation, and is also used as an adhesive material. However, polyimide adhesives having high heat resistance require 300
It requires a high temperature of around ° C and a high pressure, and its adhesive strength is not so high. Further, the conventional polyimide-based adhesive has a high water absorption rate. For example, when a lead frame using the polyimide-based adhesive is immersed in a solder bath, it has a problem that blisters and the like are easily generated.

[0005]

SUMMARY OF THE INVENTION Accordingly, the present inventors
In order to solve the above problems, solder heat resistance, excellent heat resistance and adhesiveness, with the aim of providing an adhesive composition that can be bonded at a low temperature of 250 ° C. or less, as a result of extensive research,
The present invention has been completed.

[0006]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a specific object can be achieved with a specific adhesive composition, and have completed the present invention. The first aspect of the present invention is that (A) 100 parts by weight of a soluble polyimide represented by the general formula (1), (B) a compound having two or more unsaturated double bonds, and 1 to 150 parts by weight as essential components. (Wherein R ¹ is a tetravalent organic group,
R ² is a trivalent organic group, R ³ is a monovalent organic group, R ⁴ is a divalent organic group, p is an integer of 1 to 4, m is an integer of 1 or more, and n is 0
Integer greater than or equal to. )

[0007]

Embedded image The second aspect of the present invention is the Tg of the adhesive composition in the B-stage state.
Is 10 ° C. to 110 ° C., and in the third aspect of the present invention, Tg after curing of the adhesive composition is:
4. The adhesive composition according to claim 1, wherein the temperature is 70 ° C. to 300 ° C. 4.
The adhesive composition according to any one of claims 1 to 3, wherein the temperature is 100C to 300C. The fifth aspect of the present invention is that the thermogravimetric reduction start temperature of the adhesive composition is 200C or more. The adhesive composition according to any one of claims 1 to 4, wherein the adhesive composition has a thermal expansion coefficient of 2 after curing.
The adhesive composition according to any one of claims 1 to 5, wherein the content of the adhesive composition is 0 ppm to 500 ppm. The adhesive composition according to any one of claims 1 to 6, wherein the product is a polyimide obtained using an alicyclic acid dianhydride as a raw material.
A soluble polyimide is a diamine having 1 to 5 aromatic rings or a diamine having a siloxane bond in all diamines,
The adhesive composition according to any one of claims 1 to 7, wherein the polyimide is a polyimide used as a raw material in an amount of 5 to 100 mol%. The acid dianhydride in the total acid dianhydride is 10 to 1
00 mol% is used that the adhesive composition according to any one of claims 1 to 8, wherein, (wherein, R ⁵ is
-, - CO -, - O -, - C (CF 3) 2 -, - C (CH
₃ ) _2- and R ⁶ represent a divalent organic group. )

[0008]

Embedded imageA tenth aspect of the present invention is that the soluble polyimide is selected from
Diamine is used in an amount of 10 to 100 mol% based on all diamines.
The contact according to any one of claims 1 to 9, wherein
The adhesive composition is represented by the formula:⁷Is-, -CO-, -O
−, −C (CF_Three) _Two-, -C (CH_Three)_Two-, -COO-
And R⁸Is hydrogen, halogen, methoxy, C1-C5
M is 0, 1, 2, 3 and n is 0,
1, 2, 3, and 4 are shown. )

[0009]

Embedded image An eleventh aspect of the present invention is the composition wherein the component (B) is a (meth) acrylic acid-based compound having two or more (meth) acryloyl groups and / or a compound having two or more allyl groups. 10. The adhesive composition according to any one of 10 above.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION 100 parts of a soluble polyimide represented by the general formula (1) and 2 parts or more of a (meth) acrylic compound having at least two (meth) acryloyl groups
This is for an adhesive composition containing 0 part as an essential component. Wherein R ¹ is a tetravalent organic group, R ² is a trivalent organic group, and R ³
Is a monovalent organic group, R ⁴ is a divalent organic group, p is an integer of 1 to 4, m is an integer of 1 or more, and n is an integer of 0 or more. )

[0011]

Embedded image The details of the present invention will be described. The polyamic acid used in the present invention is obtained by reacting a diamine and an acid dianhydride in an organic solvent. In an inert atmosphere such as argon or nitrogen, diamine is dissolved in an organic solvent or dispersed in a slurry state, and acid dianhydride is dissolved in an organic solvent and added in a slurry state or a solid state. I do. At least one of the diamines used in the present invention uses a diamine having a hydroxyl group or a carboxylic acid. In this case, if the diamine and the acid dianhydride are substantially equimolar, a polyamic acid having one kind of acid component and one kind of diamine component is obtained. The polyamic acid copolymer can be arbitrarily obtained by adjusting the molar ratio of the acid dianhydride component and the diamine component. For example, the diamine component-1 and the diamine component-2 may be added first to the organic polar solvent, and then the acid dianhydride component may be added to form a solution of the polyamic acid polymer. Alternatively, the diamine component-1 may be added first to the organic polar solvent, the acid dianhydride component may be added, and then the diamine component-2 may be added to form a polyamic acid polymer solution. The diamine component-1 may be added first to the organic polar solvent, then the acid dianhydride component-1 may be added, and then the acid dianhydride-2 may be added to form a polyamic acid polymer solution. The diamine component-1 and the diamine component-2 are added to the organic polar solvent first, and the acid dianhydride component-1 is added.
, Followed by the addition of acid dianhydride-2 to form a solution of a polyamic acid polymer.

The same is true even if the above addition method is reversed so that the acid dianhydride is added first and the diamine component is added later.

The reaction temperature at this time is preferably from -20 ° C to 90 ° C. The reaction time is about 30 minutes to 24 hours.
The average molecular weight of the polyamic acid is 5,000 to 1,000,000
It is desirable that If the average molecular weight is less than 5,000, the molecular weight of the resulting polyimide composition also becomes low, and the resin becomes brittle even if the polyimide composition is used as it is. On the other hand, if it exceeds 1,000,000, the viscosity of the polyamic acid varnish becomes too high. Is difficult and not preferable.

It is also possible to compound various organic additives, inorganic fillers, or various reinforcing materials with the polyimide composition. Here, examples of the organic polar solvent used for the polyamic acid formation reaction include sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, N, N-dimethylformamide, N, N
-Formamide solvents such as diethylformamide,
Acetamide solvents such as N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-2-
Pyrrolidone, pyrrolidone solvents such as N-vinyl-2-pyrrolidone, phenols, o-, m-, or p-cresol, xylenol, halogenated phenols, phenolic solvents such as catechol, ether solvents such as tetrahydrofuran, dioxane, Methanol, ethanol, alcohol solvents such as butanol and the like, cellosolves such as butyl cellosolve or hexamethylphosphoramide, γ-butyrolactone, and the like can be mentioned, and it is desirable to use these alone or as a mixture, and furthermore, xylene, toluene Aromatic hydrocarbons such as are also usable. The solvent is not particularly limited as long as it dissolves the polyamic acid. Since the polyamic acid is synthesized and then heated and decompressed to remove the solvent and imidize at the same time, it is advantageous in terms of the process to dissolve the polyamic acid and select one having a boiling point as low as possible. Next, the step of imidizing the polyamic acid will be described.

When the polyamic acid is imidized, it generates water. The generated water easily hydrolyzes the polyamic acid and causes a decrease in molecular weight. As a method of imidizing while removing water, usually, 1) a method of adding an azeotropic solvent such as toluene and xylene and removing by azeotropic distillation, 2).
There is a chemical imidation method in which an aliphatic acid dianhydride such as acetic anhydride and a tertiary amine such as triethylamine, pyridine, picoline and isoquinoline are added. The removal of water by the azeotropic method 1) cannot be avoided because water exists in the solution system and hydrolysis by water is inevitable. The chemical imidation method of 2) is more advantageous than the system of 1) in terms of hydrolysis because the generated water is chemically removed by converting the aliphatic acid dianhydride into an aliphatic acid. is there. However, aliphatic acid dianhydride
Since tertiary amines are present, a step of removing them is required.

According to the present invention, the water produced by imidization is heated and decompressed and positively removed from the system to suppress hydrolysis and avoid a decrease in molecular weight. In addition, when the acid dianhydride used as a raw material is mixed with a tetracarboxylic acid that has been opened by hydrolysis or one in which one of the acid dianhydrides has been hydrolyzed, and the polymerization reaction of the polyamic acid is stopped. By decompression and heating during imidization, the ring-opened acid dianhydride is closed again to form an acid dianhydride, and reacts with the amine remaining in the system during imidization, and an improvement in molecular weight is expected. it can. The heating conditions for imidization are 80 to 400 ° C. The temperature is 100 ° C. or higher, preferably 120 ° C. or higher, at which imidization is efficiently performed and water is efficiently removed.
The maximum temperature is desirably set to a temperature equal to or lower than the thermal decomposition temperature of the polyimide used. Usually, imidization is almost completed at about 250 to 350 ° C., so the maximum temperature can be set to this level. The pressure is preferably reduced as long as the pressure is such that water generated during imidization can be efficiently removed under the above heating conditions. Specifically, the pressure for heating under reduced pressure is 0.9 to 0.001 atm, preferably 0.8 to 0.001 atm, and more preferably 0.7 to 0.01 atm. The acid dianhydride used in this polyimide composition is not particularly limited as long as it is an acid dianhydride. For example, butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-
Cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 3,5,6
-Tricarboxynorbonane-2-acetic acid dianhydride, 2,
3,4,5-tetrahydrofurantetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofural)-
Fats such as 3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride and bicyclo [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride Aromatic or alicyclic tetracarboxylic dianhydride; pyromellitic acid, dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenyl sulfone Tetracarboxylic dianhydride, 1,4
5,8-naphthalenetetracarboxylic dianhydride, 2,
3,6,7-naphthalenetetracarboxylic dianhydride,
3,3 ′, 4,4′-biphenylethertetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3 ′, 4
4′-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ′,
4,4'-perfluoroisopropylidene diphthalic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene- Bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, bis (triphenylphthalic acid) ) Aromatic tetracarboxylic dianhydrides such as -4,4'-diphenylmethane dianhydride;
3,3a, 4,5,9b-Hexahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-
1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan- 1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-
Dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione represented by the following general formula (2)

[0017]

Embedded image (Wherein R ⁹ represents a divalent organic group having an aromatic ring, R ¹⁰
And R ¹¹ each represent a hydrogen atom or an alkyl group. ) The following general formula (3)

[0018]

Embedded image (Wherein R ¹² represents a divalent organic group having an aromatic ring, R ¹³
And R ¹⁴ each represent a hydrogen atom or an alkyl group. And the like. Aliphatic tetracarboxylic dianhydrides having an aromatic ring such as the compounds represented by These tetracarboxylic dianhydrides can be used alone or in combination of two or more.

In particular, in order to obtain a polyimide having high solubility in an organic solvent, 2,2'-hexafluoropropylidene diphthalic dianhydride, an ester dianhydride represented by the following general formula, It is desirable to use a part of the material.

[0020]

Embedded image (Wherein, R ¹⁵ represents a divalent organic group, preferably a divalent organic group selected from Chemical Formula 11, more preferably
2,2-bisphenylpropylidene. Where R ¹⁶
Represents hydrogen, a halogen, a methoxy group, or an alkyl group having 10 or less carbon atoms. )

[0021]

Embedded image The diamine having a hydroxyl group and a carboxylic acid is not particularly limited as long as it has a hydroxyl group and a carboxylic acid, and examples thereof include the following.

For example, diaminophenols such as 2,4-diaminophenol and 3,3'-diamino-4,4 '
-Dihydroxybiphenyl, 4,4'-diamino-3,
3'-dihydroxybiphenyl, 4,4'-diamino-
Hydroxybiphenyl compounds such as 2,2′-dihydroxybiphenyl and 4,4′-diamino-2,2 ′, 5,5′-tetrahydroxybiphenyl, 3,3′-diamino-4,4′-dihydroxydiphenylmethane, 4,
4'-diamino-3,3'-dihydroxydiphenylmethane, 4,4'-diamino-2,2'-dihydroxydiphenylmethane, 2,2-bis [3-amino-4-
Hydroxyphenyl] propane, 2,2-bis [4-amino-3-hydroxyphenyl] propane, 2,2-bis
[3-amino-4-hydroxyphenyl] hexafluoropropane, 4,4′-diamino-2,2 ′, 5,5′-
Hydroxydiphenylalkanes such as hydroxydiphenylmethane such as tetrahydroxydiphenylmethane,
3,3′-diamino-4,4′-dihydroxydiphenyl ether, 4,4′-diamino-3,3′-dihydroxydiphenyl ether, 4,4′-diamino-2,
Hydroxy diphenyl ether compounds such as 2′-dihydroxy diphenyl ether and 4,4′-diamino-2,2 ′, 5,5′-tetrahydroxy diphenyl ether; 3,3′-diamino-4,4′-dihydroxy diphenyl sulfone; 4'-diamino-3,3'-dihydroxydiphenylsulfone, 4,4'-diamino-2,2'-dihydroxydiphenylsulfone, 4,
Diphenylsulfone compounds such as 4'-diamino-2,2 ', 5,5'-tetrahydroxydiphenylsulfone and bis [such as 2,2-bis [4- (4-amino-3-hydroxyphenoxy) phenyl] propane (Hydroxyphenyl) phenyl] alkane compounds, 4,4′-
Bis (hydroxyphenoxy) biphenyl compounds such as bis (4-amino-3-hydroxyphenoxy) biphenyl and bis [such as 2,2-bis [4- (4-amino-3-hydroxyphenoxy) phenyl] sulfone (Hydroxyphenoxy) phenyl] sulfone compound, 3,5-
Diaminobenzoic acids such as diaminobenzoic acid, 3,3′-
Diamino-4,4'-dicarboxybiphenyl, 4,4
'-Diamino-3,3'-dicarboxybiphenyl,
Carboxybiphenyl compounds such as 4,4'-diamino-2,2'-dicarboxybiphenyl and 4,4'-diamino-2,2 ', 5,5'-tetracarboxybiphenyl;3,3'-diamino-4,4'-dicarboxydiphenylmethane,4,4'-diamino-3,3'-dihydroxydiphenylmethane,4,4'-diamino-2,
2'-dihydroxydiphenylmethane, 2,2-bis
[3-amino-4-carboxyphenyl] propane, 2,
2-bis [4-amino-3-carboxyphenyl] propane, 2,2-bis [3-amino-4-carboxyphenyl] hexafluoropropane, 4,4′-diamino-
Carboxydiphenylalkanes such as carboxydiphenylmethane such as 2,2 ', 5,5'-tetracarboxydiphenylmethane, 3,3'-diamino-4,4'-dicarboxydiphenylether, and 4,4'-diamino-
3,3′-dicarboxydiphenyl ether, 4,4
Carboxydiphenyl ether compounds such as'-diamino-2,2'-dicarboxydiphenyl ether and 4,4'-diamino-2,2 ', 5,5'-tetracarboxydiphenyl ether; 3,3'-diamino-4,4' −
Dicarboxydiphenylsulfone, 4,4′-diamino-3,3′-dicarboxydiphenylsulfone,
4,4'-diamino-2,2'-dicarboxydiphenylsulfone, 4,4'-diamino-2,2 ', 5
Diphenylsulfone compounds such as 5′-tetracarboxydiphenylsulfone; bis [(carboxyphenyl) phenyl] alkane compounds such as 2,2-bis [4- (4-amino-3-carboxyphenoxy) phenyl] propane; Bis (hydroxyphenoxy) biphenyl compounds such as 4'-bis (4-amino-3-hydroxyphenoxy) biphenyl, and 2,2-bis [4- (4-amino-3-carboxyphenoxy) phenyl] sulfone Bis [(carboxyphenoxy) phenyl] sulfone compound. In addition, the diamine used in the polyimide composition is not particularly limited as long as it is a diamine, for example, p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminophenylethane,
4,4′-diaminophenyl ether, 4,4′-didiaminophenyl sulfide, 4,4′-didiaminophenyl sulfone, 1,5-diaminonaphthalene, 3,3
-Dimethyl-4,4'-diaminobiphenyl, 5-amino-1- (4'-aminophenyl) -1,3,3-trimethylindane, 6-amino-1- (4'-aminophenyl) -1, 3,3-trimethylindane, 4,4'-
Diaminobenzanilide, 3,5-diamino-3′-trifluoromethylbenzanilide, 3,5-diamino-
4'-trifluoromethylbenzanilide, 3,4'-
Diaminodiphenyl ether, 2,7-diaminofluorene, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4′-methylene-bis (2-chloroaniline), 2,2 ′, 5,5′- Tetrachloro-4,
4'-diaminobiphenyl, 2,2'-dichloro-4,
4'-diamino-5,5'-dimethoxybiphenyl,
3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl ] Propane, 2,2-bis [4
-(4-aminophenoxy) phenyl] hexafluoropropane, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) -biphenyl, 1,3'-bis (4- Aminophenoxy) benzene, 9,9-bis (4-aminophenyl) fluorene, 4,4 ′-(p-phenyleneisopropylidene) bisaniline, 4,4 ′-(m-phenyleneisopropylidene) bisaniline, 2,2 ′ -Bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4'-bis [4- (4-amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl and the like Aromatic diamine; two amino groups bonded to an aromatic ring such as diaminotetraphenylthiophene and the nitrogen of the amino group Aromatic diamine having a heteroatom other than a child; 1,1-methaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4-diaminoheptamethylene Diamine, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-methanoindanylene dimethylenediamine, tricyclo [6,2,1,
0 ^2.7 ] -undecylenedimethyldiamine, 4,4'-
Aliphatic and alicyclic diamines such as methylenebis (cyclohexylamine);

[0023]

Embedded imageMonosubstituted phenylenediamines represented by the formula:¹⁷
Is -O-, -COO-, -OCO-, -CONH- and
And a divalent organic group selected from —CO— and ¹⁸Is
It represents a monovalent organic group having a teroid skeleton. );
Formula 13

[0024]

Embedded image (R ¹⁹ represents a hydrocarbon group having 1 to 12 carbon atoms;
And z is an integer of 1 to 20. And the like. These diamine compounds can be used alone or in combination of two or more. A specific method of heating and drying the polyamic acid solution under reduced pressure to directly imidize the polyamic acid solution will be described. Any method can be used as long as it can be dried by heating under reduced pressure, but it can be carried out as a batch-type method, a vacuum oven, or a continuous-type method using, for example, a twin-screw or 3-screw extruder with a decompression device. These methods are selected according to the production amount.
The twin-screw or triple-screw extruder with a decompression device referred to here is a general melt extruder that heat-melts and extrudes a thermoplastic resin, and is provided with a device that removes the solvent by reducing the pressure to a general melt extruder. . The polyamic acid solution is kneaded by the extruder with a biaxial or triaxial extruder to remove the solvent and water generated at the time of imidation, thereby obtaining a polyimide having a hydroxyl group or a carboxylic acid. Next, a manufacturing process of the epoxy-modified polyimide will be described. Epoxy modification by dissolving the above-mentioned thermoplastic polyimide having a hydroxyl group or carboxylic acid in an organic solvent and reacting with an epoxy resin having two or more epoxy groups or a compound having an epoxy group and a double bond or an epoxy group and a triple bond. A polyimide is obtained. The solvent used in the reaction is not particularly limited as long as it does not react with the epoxy group and dissolves the polyimide having a hydroxyl group or a carboxylic acid. For example, sulfoxide solvents such as dimethylsulfoxide and diethylsulfoxide, N, N-dimethylformamide, N, N
A formamide solvent such as N-diethylformamide,
Acetamide solvents such as N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-2-
Pyrrolidone solvents such as pyrrolidone and N-vinyl-2-pyrrolidone; ether solvents such as tetrahydrofuran and dioxane; alcohol solvents such as methanol, ethanol and butanol; cellosolves such as butyl cellosolve and hexamethylphosphoramide; γ-butyrolactone And aromatic hydrocarbons such as xylene and toluene. These can be used alone or as a mixture. The solvent is not particularly limited as long as it dissolves a thermoplastic polyimide having a hydroxyl group or a carboxylic acid. After that, since the solvent is removed,
It is advantageous in the process to dissolve a thermoplastic polyimide having a hydroxyl group or a carboxylic acid and to select one having a boiling point as low as possible. The reaction is preferably performed at a temperature of 40 ° C. to 130 ° C. at which the epoxy group reacts with the hydroxyl group / carboxyl group. Particularly, for a compound having an epoxy group and a double bond or an epoxy group and a triple bond,
It is desirable that the reaction be performed at a temperature at which the double bond / triple bond is not decomposed or crosslinked by heat. Specifically, 4
It is 0 degrees or more and 100 degrees or less, and more desirably 50 degrees or more and 90 degrees or less. The reaction time is about several minutes to about eight hours. The epoxy resin having two or more epoxy groups is not particularly limited as long as it has two or more epoxy groups in a molecule, and examples thereof are as follows.

For example, a bisphenol resin such as Epicoat 828 (manufactured by Yuka Shell) or an orthocresol novolak resin such as 180S65 (manufactured by Yuka Shell) 157
Bisphenol A novolak resin such as S70 (manufactured by Yuka Shell), trishydroxyphenylmethane novolak resin such as 1032H60 (manufactured by Yuka Shell), ESN3
Naphthalene aralkyl novolak resin such as 75, tetraphenylolethane 1031S (manufactured by Yuka Shell), Y
GD414S (Toto Kasei), Trishydroxyphenylmethane EPPN502H (Nippon Kayaku), Special bisphenol VG3101L (Mitsui Chemicals), Special naphthol NC
7000 (Nippon Kayaku), TETRAD-X, TETRA
Glycidylamine type resins such as DC (manufactured by Mitsubishi Gas Chemical Company) and the like. The compound having an epoxy group and a double bond is not particularly limited as long as it has an epoxy group and a double bond in a molecule, and examples thereof are as follows.

Examples include allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, and glycidyl vinyl ether. Epoxy group and 3
The compound having a heavy bond is not particularly limited as long as it has an epoxy group and a triple bond in the molecule, and examples thereof include the following. Propagyl glycidyl ether / glycidyl propiolate / ethynyl glycidyl ether can be exemplified.

Thus, a solution of the epoxy-modified polyimide can be obtained. A thermosetting resin such as an epoxy resin or an acrylic resin, or a thermoplastic resin such as polyester, polyamide, polyurethane, or polycarbonate may be appropriately mixed with the epoxy-modified polyimide solution.

Further, even when mixed with a thermosetting resin other than the epoxy resin, good physical properties can be obtained, so that it is preferable. The thermosetting resin used here is bismaleimide
Bisallylnadiimide, phenolic resin, cyanate resin and the like can be mentioned. The epoxy-modified polyimide solution may be directly applied and dried on the joining portion, or may be applied and dried to form a sheet. These drying conditions are based on the remaining epoxy group, double bond, 3
It is desirable to perform the bonding under such a condition that the bonding is not decomposed or crosslinked by heat. It is desirable to mix the epoxy-modified polyimide of the present invention with a curing agent for an epoxy resin, since a cured product having good physical properties can be obtained. Any type of amine-based, imidazole-based, acid anhydride-based, or acid-based curing agent may be used as long as it is a curing agent for epoxy resin. Further, various coupling agents may be mixed. The compound is not particularly limited as long as it is a (meth) acrylic acid compound having two or more (meth) acryloyl groups or a compound having two or more allyl groups, and examples thereof include the following compounds. For example, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, ethylene glycol diacrylate, pentaerythritol diacrylate,
Trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, tetramethylolpropane tetraacrylate, tetraethylene glycol diacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, ethylene glycol dimethacrylate, penta Erythritol dimethacrylate, trimethylolpropane trimethacrylate,
Pentaerythritol trimethacrylate, dipentaerythritol hexamethacrylate, tetramethylolpropane tetramethacrylate, tetraethylene glycol dimethacrylate, methoxydiethylene glycol methacrylate, methoxypolyethylene glycol methacrylate, β-methacryloyloxyethyl hydrogen phthalate, β-methacryloyloxyethyl hydrogen Succinate, 3-chloro-2-hydroxypropyl methacrylate, stearyl methacrylate, phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, phenoxypolyethylene glycol acrylate, β-acryloyloxyethyl hydrogen succinate, lauryl acrylate, ethylene glycol dimethacrylate Rate, diethylene glycol methacrylate, triethylene glycol methacrylate, polyethylene glycol di methacrylate, 1,3
Butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2-hydroxy-1,3 dimethacryloxypropane,
2,2-bis [4- (methacryloxyethoxy) phenyl]
Propane, 2,2-bis [4- (methacryloxydiethoxy) phenyl] propane, 2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane, polyethylene glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol di Acrylate, 2,2-bis [4- (acryloxydiethoxy) phenyl] propane, 2,2-bis [4- (acryloxypolyethoxy) phenyl] propane, 2-hydroxy1-acryloxy-3-methacryloxypropane, trimethylol Propane trimethacrylate, tetramethylol methane triacrylate, tetramethylol methane tetraacrylate, methoxydipropylene glycol methacrylate, methoxytriethylene glycol acrylate, nonylphenoxy Polyethylene glycol acrylate, nonylphenoxy polypropylene glycol acrylate, 1-acryloyloxypropyl-2-phthalate, isostearyl acrylate, polyoxyethylene alkyl ether acrylate, nonylphenoxyethylene glycol acrylate, polypropylene glycol dimethacrylate, 1,4-butanediol di Methacrylate, 3-methyl-1,5-pentanediol dimethacrylate, 1,6-mexanediol dimethacrylate, 1,9-nonanediol methacrylate, 2,4-diethyl-1,5-pentanediol dimethacrylate Methacrylate,
1,4-cyclohexanedimethanol dimethacrylate,
Dipropylene glycol diacrylate, tricyclodecane dimethanol diacrylate, 2,2-hydrogenated bis
[4- (acryloxy-polyethoxy) phenyl] propane, 2,2-bis [4- (acryloxy-polypropoxy) phenyl] propane, 2,4-diethyl-1,5-
Pentanediol diacrylate, ethoxylated thimethylolpropane triacrylate, propoxylated thymethylolpropane triacrylate, isocyanuric acid tri (ethane acrylate), pentathritol tetraacrylate, ethoxylated pentathritol tetraacrylate, propoxylated pentathritol tetraacrylate , Ditrimethylolpropane tetraacrylate,
Dipentaerythritol polyacrylate, triallyl isocyanurate, glycidyl methacrylate, glycidyl allyl ether, 1,3,5-triacryloylhexahydro-s-triazine, triallyl 1,3,5-benzenecarboxylate, triallylamine, triallylcitrate Rate, triallyl phosphate, allobarbital, diallylamine, diallyldimethylsilane, diallyl disulfide, diallyl ether, zalyl sialate, diallyl isophthalate, diallyl terephthalate, 1,3-diaryloxy-2-propanol, diallyl sulfide diallyl maleate, 4, 4'-isopropylidene diphenol dimethacrylate, 4,4'-isopropylidene diphenol diacrylate, trimesic acid triallyl Although ester are preferred, but are not limited to. The (meth) acrylic acid-based compound or the compound having an allyl group is preferably blended in an amount of 1 to 150 parts by weight, more preferably 3 to 140 parts by weight, and most preferably 20 to 100 parts by weight of the soluble compound of the present invention. It is in the range of 120 parts by weight. If the amount is outside the range of 1 to 200 parts by weight, the desired effect may not be obtained or the physical properties may be unfavorably affected. In addition, as the (meth) acrylic acid-based compound or the compound having two or more allyl groups, one compound may be used, or a mixture of several compounds may be used. In particular, from the viewpoint of compatibility with the soluble polyimide, triazine, isocyanurate, a (meth) acrylic acid-based compound having a cyanurate skeleton, or a compound having two or more allyl groups is preferable. Specifically, triallyl isocyanurate , Isocyanuric acid diallyl propyl ester, triallyl cyanurate, 1,3,5-triacroyl-hexahydro-s-triazine, trimetaallyl isocyanurate and the compound of formula 14 can be exemplified. (Where p is an integer of 1 to 10, R ²⁰ is CH ₂ ＣC (CH ₃ ))
COO-, represents a CH ₂ = CHCOO-. )

[0029]

Embedded image The adhesive composition used in the present invention may contain a suitable organic solvent. If it is dissolved in an appropriate organic solvent, it can be used in a solution (varnish) state, which is convenient when forming a film. Specifically, N-methyl-2
-Pyrrolidone, N-acetyl-2-pyrrolidone, N-benzyl-2-pyrrolidone, N, N-dimethylformamide,
N, N-dimethylacetamide, dimethylsulfoxide,
Hexamethylphosphortriamide, N-acetyl-ε-
Preferred examples include caprolactam, dimethylimidazolidinone, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, γ-butyrolactone, dioxane, dioxolan, and tetrahydrofuran. These may be used alone or as a mixed system. This organic solvent may be a solvent in which the solvent used in the synthesis reaction of the polyimide is left as it is, or may be a newly added solvent to the isolated polyimide precursor. Further, in order to improve coatability, a solvent such as toluene, xylene, diethyl ketone, methoxybenzene, or cyclopentanone may be mixed within a range that does not adversely affect the solubility of the polymer.

The solution of the adhesive composition may be directly applied and dried on the portion to be joined, or may be applied and dried to form a sheet. These drying conditions are desirably performed under such a condition that the remaining epoxy group / (meth) acryloyl group is not decomposed or crosslinked by heat, and specifically, 180 ° C. or lower, preferably 150 ° C. or lower. When used as a sheet, the object is adhered to the object by heat lamination, hot press or hot vacuum lamination. The temperature at this time is epoxy or 2
It is desirable that the heat treatment be performed at a temperature at which the heavy bond is not broken, and specifically, it is 180 ° C. or lower, preferably 150 ° C. or lower. In addition, besides these, allyl glycidyl ether / glycidyl acrylate / glycidyl methacrylate /
It is preferable because an adhesive property may be obtained by mixing a compound having two bonds with an epoxy group such as glycidyl vinyl ether.

[0031]

EXAMPLES The present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples.

In the examples, ESDA was 2,2-bis (4
-Hydroxyphenyl) propanedibenzoate-3,
3 ', 4,4'-tetracarboxylic dianhydride, 6FDA
Is 2,2'-hexafluoropropylidene diphthalic dianhydride, BAPS-M is bis [4- (3-aminophenoxy) phenyl] sulfone, DMAc is N, N
-Dimethylacetamide, DMF represents N, N-dimethylformamide.

The weight average molecular weight was measured by GPC manufactured by Waters.
Was measured under the following conditions. (Column: Shodex
KD-806M two, temperature 60 ° C, detector: R
I, flow rate: 1 ml / min, developing solution: DMF (lithium bromide 0.03 M, phosphoric acid 0.03 M), sample concentration: 0.2 w
t%, injection volume: 20 μl, reference substance: polyethylene oxide) Measurement of imidation ratio: Polyamic acid solution (DMF solution) was cast on a PET film, and
After heating at 0 ° C for 10 minutes and at 130 ° C for 10 minutes, peel off the PET film, fix it on a pin frame,
Heat at 250 ° C. for 60 minutes for 60 minutes to obtain a 5 μm thick polyimide film. The polyimide prepared in the example or the comparative example was dissolved in DMF, cast on a PET film, heated at 100 ° C. for 30 minutes, peeled off from the PET film, fixed on a pin frame, and heated at 80 ° C. 5 mm in a vacuum oven.
Heating and drying was performed under Hg conditions for 12 hours to obtain a polyimide film having a thickness of 5 μm. The IR of each film is measured, and the ratio of imide absorption / benzene ring absorption is determined.
The ratio of the absorption of the imide obtained in the above to the ratio of the benzene ring was 10
The percentage of the imide absorption / benzene ring ratio at 0% is determined. This is defined as the imidation ratio. a) Method for measuring adhesive strength: A solution of the adhesive composition was applied to a polyimide film (Apical 25NPI manufactured by Kaneka Chemical Co., Ltd.), and then 45 ° C. for 5 minutes, 60 ° C. for 5 minutes, 80 ° C. for 30 minutes, 120 ° C.
After drying for a minute, a laminated sheet of the polyimide / adhesive composition is obtained. The adhesive composition of this laminated sheet and a copper foil (electrolytic copper foil 3EC-VLP made by Mitsui Metals) are combined, and the temperature is 120 ° C./1 kg.
Weight / cm, polyimide / adhesive composition /
A laminate of copper foil was obtained. This is heated at 100 ° C. for 1 hour for 120 hours.
℃ 1 hour, 140 ℃ 1 hour, 160 ℃ 1 hour, 170 ℃ 3
Heated for hours. This laminate is referred to as JIS-6472-195.
5 was measured. b) Method for measuring Tg of soluble polyimide: apply the obtained soluble polyimide solution on a PET film,
Dry for 5 minutes, 70 ° C for 5 minutes, and 90 ° C for 5 minutes, and peel off from the PET film. This film is fixed with a pin frame, and 80
C. in a vacuum oven for 12 hours to obtain a soluble polyimide film. This is measured with a thermal analyzer TMA-120C manufactured by Seiko Denshi Kogyo KK, and the temperature at the inflection point is defined as Tg of the soluble polyimide. c) Tg measurement method in B-stage state: A solution of the adhesive composition is applied on PET and dried to form a film. Peel this off and make a thermal analyzer DSC2 manufactured by Seiko Denshi Kogyo KK
It measured at 20 and obtained Tg. d) Method for measuring Tg after curing and coefficient of thermal expansion after curing:
Apply on aluminum foil, 50 ° C for 5 minutes, 70 ° C for 5 minutes, 90 ° C
After drying for 5 minutes, the temperature is raised from 100 to 170 ° C. at a rate of about 10 ° C./minute, and the mixture is heated at 170 ° C. for 2 hours. The aluminum foil is removed by etching to obtain a cured film. This film,
Seiko Denshi Kogyo Co., Ltd. thermal analyzer TMA-120
C, and measured the temperature at the inflection point after curing, Tg, 30 ° C.
The average thermal expansion coefficient at 100 ° C. is defined as the thermal expansion coefficient after curing. e) Measuring method of thermogravimetric reduction start temperature: The thermogravimetric loss of the cured film obtained by the Tg measuring method after curing was measured in the air with a thermal analyzer TG / DTA220 manufactured by Seiko Denshi Kogyo Co., Ltd. The temperature at which the weight loss reaches 5% is defined as the thermogravimetric reduction start temperature.

[0034]

Example 1 BAPS-M (43.05 g, 0.1 mol) and DMF (300 g) were placed in a 2,000 ml separable flask equipped with a stirrer, and ESDA (115.3 g).
(0.20 mol) was added at once with vigorous stirring, and stirring was continued for 30 minutes. Next, 15.2 g (0.1 mol) of diaminobenzoic acid was dissolved in 150 g of DMF, added to the above solution, and stirred for 30 minutes to obtain a polyamic acid solution. The weight average molecular weight (hereinafter Mw) of this polyamic acid
Was 60,000.

This polyamic acid solution is placed on a Teflon (registered trademark) -coated vat and placed in a vacuum oven for 15 minutes.
0 ° C 10 minutes, 160 ° C 10 minutes, 170 ° C 10 minutes, 180
10 minutes at 190 ° C, 30 minutes at 210 ° C, 5 mmHg
Heated under reduced pressure. Remove from vacuum oven, 1
A thermoplastic polyimide having 60 g of carboxylic acid was obtained. Mw of this polyimide is 65,000 and Tg is 190.
C., the imidation ratio was 100%. (Soluble polyimide: synthesis of epoxy-modified polyimide)
33 g of the synthesized thermoplastic polyimide was added to dioxolan 66
g, and then dissolved in 25 g of dioxolane and added with 38.3 g of Epoxy 828 manufactured by Yuka Shell Co., Ltd. The mixture was heated and stirred at 70 ° C. for 2 hours to synthesize an epoxy-modified polyimide.
4,4'-diaminodiphenylsulfone (hereinafter abbreviated as DDS) is added to 100 g of the epoxy-modified polyimide solution.
5 g, tri (isoacrylate) tri (ethane acrylate) 30
g, Yuka Shell Co., Ltd. epoxy 828 3g, and Nippon Oil & Fats Co., Ltd. P-Heseki 25B 1.5g solution was added to Kanefuchi Chemical polyimide film Apical NPI (25
μm thickness), dried at 45 ° C for 5 minutes, peeled off the pet film, fixed with a pin frame, 65 ° C for 5 minutes and 80 ° C
After drying for 0 minutes, the apical NPI / adhesive composition (thickness 2
0 μm). Copper foil (Mitsui Metals VLP electrolytic copper foil) 1
Lamination was performed at 20 ° C. and 1 kg weight / cm. After lamination, 100 ° C for 2 hours, 120 ° C for 2 hours, 140 ° C
Curing was performed at 170 ° C. for 3 hours for 2 hours to obtain a flexible copper-clad board (laminate). Tg of epoxy-modified polyimide
Tg at 195 ° C., B stage is 25 ° C., Tg after curing of the adhesive composition is 230 ° C., coefficient of thermal expansion after curing of the adhesive composition is 58 ppm, and thermogravimetric onset temperature of the adhesive composition is 300 C. or higher, the adhesive strength of this flexible copper-clad board was 1.5 kgf / cm, and the solder heat resistance was good. The copper foil of the flexible copper-clad plate was removed by etching, and the remaining cured adhesive composition was immersed in an NMP solution heated to 50 ° C. for 10 minutes, but did not dissolve at all.

[0036]

Example 2 33 g of the carboxylic acid-containing thermoplastic polyimide synthesized in Example 1 was dissolved in 66 g of dioxolane, and 1.4 g of glycidyl methacrylic ester was added thereto.
2 mmol) dissolved in 10 g of dioxolane and added.
After heating and stirring at 0 ° C. for 30 minutes, 3.4 g (12 mmol) of epoxy Adeka Optomer KRM-2110 manufactured by Asahi Denka Kogyo was added, followed by heating and stirring at 60 ° C. for 60 minutes to synthesize an epoxy-modified polyimide. A solution obtained by adding 0.5 g of 4,4'-diaminodiphenylsulfone (hereinafter abbreviated as DDS), 1.5 g of Perhexa 25B manufactured by NOF Corporation, and 30 g of tri (isoacrylate) tri (ethane acrylate) to 100 g of the epoxy-modified polyimide solution was carried out. A film was formed under the same conditions as in Example 1 to produce a flexible copper-clad board.

The Tg of the epoxy-modified polyimide is 195
° C, the Tg of the B stage is 20 ° C, the Tg of the adhesive composition after curing is 200 ° C, the thermal expansion coefficient of the adhesive composition after curing is 70 ppm, and the thermogravimetric starting temperature of the adhesive composition is , 300 ° C. or higher, the adhesive strength of this flexible copper-clad board was 1.4 kgf / cm, and the solder heat resistance was good.
The copper foil of the flexible copper-clad plate was removed by etching, and the remaining cured adhesive composition was immersed in an NMP solution heated to 50 ° C. for 10 minutes, but did not dissolve at all.

[0038]

Example 3 68.88 g (0.16 mol) of BAPS-M and 300 g of DMF were placed in a 2000 ml separable flask equipped with a stirrer, and 115.3 g of ESDA.
(0.20 mol) was added at once with vigorous stirring, and stirring was continued for 30 minutes. Then, 4.32 g of 3,3'-dihydroxy-4,4'-diaminobiphenyl
(0.02 mol) and stirred for 30 minutes, then
26 g of silicon diamine PCR 66M13 26g (0.0
2 mol) and stirred for 30 minutes to obtain a polyamic acid solution. The weight average molecular weight (hereinafter Mw) of this polyamic acid
Was 58,000. At this time, the reaction was carried out by cooling with ice water.

The polyamic acid solution is placed on a Teflon-coated vat and placed in a vacuum oven at 150 ° C. for 10 minutes.
160 ° C for 10 minutes, 170 ° C for 10 minutes, 180 ° C for 10 minutes, 1
The mixture was heated under reduced pressure at a pressure of 5 mmHg at 90 ° C for 10 minutes and 210 ° C for 30 minutes. It was taken out from the vacuum oven to obtain 202 g of a thermoplastic polyimide having a hydroxyl group. The Mw of this polyimide is 62,000, the Tg is 190 ° C., and the imidization ratio is 10
It was 0%. (Synthesis of Epoxy-Modified Polyimide) 33 g of the synthesized thermoplastic polyimide was dissolved in 66 g of dioxolan, and 0.5 g of triethylamine and 1.0 g (7 mmol) of glycidyl methacrylate were dissolved in 25 g of dioxolan and added. The mixture was heated and stirred at 60 ° C. for 2 hours to synthesize an epoxy-modified polyimide. In 100 g of an epoxy-modified polyimide solution, 0.5 g of DDS, 30 g of tri (ethane acrylate) isocyanurate, and Epoxy 10 manufactured by Yuka Shell Co., Ltd.
32H60 3g, Perbutyl IF manufactured by NOF Corporation
1.5 g of the solution was added to Kanebuchi Chemical's Apical NPI.
(25 μm thickness) and applied in the same manner as in Example 1.
An apical NPI / adhesive composition (20 μm thickness) was obtained. In the same manner as in Example 1, a flexible copper-clad board was obtained. Tg of epoxy-modified polyimide is 200 ° C, B
The Tg of the stage is 40 ° C., and the Tg after curing of the adhesive composition is
g is 245 ° C., the thermal expansion coefficient after curing of the adhesive composition is 65 ppm, and the thermogravimetric starting temperature of the adhesive composition is 3
00 ° C or higher, the adhesive strength of this flexible copper-clad board is
1.2 kgf / cm, the solder heat resistance was good. The copper foil of the flexible copper-clad board is removed by etching, and the remaining cured adhesive composition is added to an NMP solution heated to 50 ° C. for 1 hour.
Immersion for 0 minutes did not dissolve at all.

[0040]

Comparative Example 1 20 g of Platabond M1276 (copolymerized nylon, manufactured by Nippon Rilsan Co.), Epicoat 1032
5 g of H60 and 3 g of 4,4 ′ diaminodiphenylsulfone were dissolved in 83 g of DMF. The obtained varnish was cast on a polyimide film (Apical 25AH, manufactured by Kanegabuchi Chemical Industry Co., Ltd.), dried at 100 ° C. for 10 minutes, and further dried for 1 minute.
After drying at 50 ° C. for 10 minutes, a 30 μm-thick film-like joining member was obtained. The obtained film-like joining member was combined with a polyimide film (Apical 50AH, manufactured by Kaneka Chemical Co., Ltd.)
Sandwiched by 5μm copper foil, temperature 200 ℃, pressure 3MPa
For 20 minutes to obtain a copper-clad flexible laminate.

The Tg of the B stage is 30 ° C., the Tg after curing of the adhesive composition is 110 ° C., the coefficient of thermal expansion is such that the adhesive was brittle and could not be measured. , 230 ° C., the adhesive strength of this flexible copper-clad board was 0.8 kgf / cm, and swelling occurred when immersed in a solder bath. The copper foil of the flexible copper-clad board was etched away, and the remaining cured adhesive composition was heated to 50 ° C.
When immersed in the MP solution for 10 minutes, swelling and deterioration occurred.

[0042]

As described above, it is possible to provide an adhesive composition which is excellent in solder heat resistance, heat resistance and adhesiveness, and which can be bonded particularly at a low temperature of 250 ° C. or lower.

Claims (11)

[Claims] An essential component is (A) 100 parts by weight of a soluble polyimide represented by the general formula (1), (B) a compound having two or more unsaturated double bonds, and 1 to 150 parts by weight. Adhesive composition. (Where R ¹ is a tetravalent organic group, R ² is a trivalent organic group, R ³ is a monovalent organic group, R ⁴ is a divalent organic group, p is an integer of 1-4, m Is an integer of 1 or more, and n is an integer of 0 or more.) 2. The Tg of the adhesive composition in the B-stage state is 1
The adhesive composition according to claim 1, wherein the temperature is 0C to 110C. 3. The Tg after curing of the adhesive composition is from 70 ° C.
The adhesive composition according to claim 1, wherein the temperature is 300 ° C. 4. 4. The Tg of the soluble polyimide is from 100 ° C. to 3 ° C.
The adhesive composition according to any one of claims 1 to 3, which is at 00C. 5. The thermogravimetric reduction start temperature of the adhesive composition is 20.
The adhesive composition according to any one of claims 1 to 4, wherein the temperature is 0C or higher. 6. A cured product having a coefficient of thermal expansion of 20 ppm to 500 ppm.
The adhesive composition according to any one of claims 1 to 5, wherein the content is ppm. 7. The polyimide according to claim 1, wherein the soluble polyimide is an acid dianhydride having 1 to 3 aromatic rings or a polyimide obtained from an alicyclic acid dianhydride as a raw material. The adhesive composition according to claim 1. 8. The polyimide according to claim 1, wherein said soluble polyimide is a diamine having 1 to 5 aromatic rings or a diamine having a siloxane bond as a raw material in an amount of 5 to 100 mol% of the total diamine. The adhesive composition according to any one of the above. 9. The method of claim 1, wherein the soluble polyimide is selected from the group consisting of
The anhydride should be used in an amount of 10 to 100 mol% based on the total acid dianhydride.
The contact according to any one of claims 1 to 8,
Adhesive composition. (Where R^FiveIs-, -CO-, -O-,
−C (CF_Three) _Two-, -C (CH_Three)_Two-Is R⁶Is divalent
Represents an organic group. ) 10. The adhesive composition according to claim 1, wherein the diamine selected from the formula (3) is used as the soluble polyimide in the total diamine in an amount of 10 to 100 mol%. (Wherein, R ⁷ is-, -CO-, -O-,-
C (CF ₃ ) _2- , -C (CH ₃ ) _2- , -COO-
⁸ is hydrogen, halogen, a methoxy group, a C1 to C5 alkyl group, m is 0, 1, 2, 3 and n is 0, 1, 2, 2,
3 and 4 are shown. ) 11. The method according to claim 1, wherein the component (B) is a (meth) acrylic acid compound having two or more (meth) acryloyl groups and / or a compound having two or more allyl groups. The adhesive composition according to claim 1. ,