JPH08134213A - Polyimide and heat-resistant adhesive made therefrom - Google Patents

Abstract

PURPOSE: To obtain a polyimide which gives a heat-resistant adhesive that enables bonding with a high bond strength at a low temperature and low pressure by reacting a mixture of a specified aromatic diamine and a specified diaminosiloxane with a tetracarboxylic acid dianhydride. CONSTITUTION: 1mol of an aromatic diamine represented by formula I (wherein X1 is -O-, -CO-, -S-, -SO2 -, -CH2 -, etc.) [e.g. 4,4'-bis(4-aminophenoxy)diphenyl ether] is mixed with 0.1-0.005mol of an ω, ω'-bis(3-aminopropyl) polydimethylsiloxane compound represented by formula II (wherein n is 0 to 7). The obtained diamine mixture is reacted by heating with a tetracarboxylic acid dianhydride represented by formula III (wherein Ar is a group of formula IV, V or VI; and Ar' is a direct bond, -O-, -CO-, -SO2 -, -CH2 -, etc.) (e.g. pyromellitic dianhydride) to produce a polyimide. A heat-resistant adhesive is produced by using the obtained polyimide as the effective constituent.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to heat resistant adhesives. Specifically, it relates to a solution of a heat-resistant adhesive capable of adhering at low temperature and low pressure.

[0002]

2. Description of the Related Art As adhesives for various high-performance materials used in the fields of electronics, aerospace equipment, transportation equipment, etc., heat-resistant adhesives made of organic synthetic polymers have been known more than ever before. Among them, polybenzimidazole-based and polyimide-based adhesives have been developed as those having excellent heat resistance. Particularly, as a polyimide-based heat-resistant adhesive having excellent heat resistance and adhesive strength, U.S. Pat. No. 4,065,345 and JP-A-61-61
The adhesive disclosed in Japanese Patent Publication No. 143477 or the like is known. Although these heat-resistant adhesives have excellent heat resistance and adhesiveness, high-temperature and high-pressure bonding conditions are required to obtain a good bonded state.

In these, a solution of a polyamic acid as a precursor thereof is applied to an adherend, subjected to solvent removal and imidization, and then dried, which is then applied to another adherend under conditions of high temperature and high pressure. It was a method of adhering. In this method, after imidization, it is necessary to provide for adhesion, not only the operation is complicated, but because the imidization reaction proceeds simultaneously with the removal of the solvent,
It is difficult to constantly control the imidization reaction,
There is a problem that the reproducibility such as the adhesive strength is poor. On the other hand, a method of controlling the imidization reaction in a solution and using it as a polyimide solution is disclosed in Japanese Patent Application No. 5-12901.
No. 2 and Japanese Patent Application No. 5-201313.

On the other hand, many methods for improving the adhesiveness by using a diaminosiloxane compound together have been reported (Japanese Patent Laid-Open Nos. 5-74245, 5-98233,
5-98234, 5-98235, 5-98236, 5
-98237, 5-112760, etc.), the heat resistance inherent to the aromatic polyimide is impaired due to the large amount of the diaminosiloxane compound used in combination, and an organic solvent solution of a polyamic acid, which is a precursor of the polyimide, forms a layer. There was also a problem with storage stability such as separation.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a polyimide obtained by a specific method and its precursor polyamic acid organic solvent solution have excellent heat resistance. They have found that they can be used as adhesives and have reached the present invention. That is, the present invention includes: 1) General formula (1)

[0006]

[Chemical 4] (In the formula, X1 is -O-, -CO-, -S-, -SO2-,
--CH2-, --C (CH3) 2 --or --C (CF3)
Represents 2-. ) With respect to 1 mol of the aromatic diamine represented by the general formula (2)

[0007]

Embedded image (In the formula, n is 0 to 7), and the diaminosiloxane compound has a molar ratio of 0.10 to 0.005, and the aromatic tetracarboxylic acid dicarboxylic acid represented by the general formula (3). A polyimide obtained by reacting an anhydride component with heating in the presence or absence of a dicarboxylic acid anhydride and / or a monoamine compound, 2) to a total amount of 1 mol of the aromatic tetracarboxylic acid dianhydride. On the other hand, 0.8 to 1.2 mol of a diamine component is used, and 3) 0.001 with respect to 1 mol of the total amount of the aromatic tetracarboxylic dianhydride as described above. To 0.20 mol of dicarboxylic acid anhydride and / or monoamine are used, and 4) the polyimide according to 1) to 3) above or the polyimide thereof. Heat-resistant adhesive containing a polyamic acid which is a precursor of the imide or its solution.

The most important point in the present invention is to add the following formula (4) to a heat-resistant adhesive solution containing a polyimide in the present application and / or a heat-resistant adhesive solution containing a polyamic acid which is a precursor of the polyimide. The structural unit represented by (Chemical Formula 6) is a structural unit 1 represented by the following formula (5) (Chemical Formula 7).
On the other hand, the content is 0.10 to 0.005.

[0009]

[Chemical 6] (In the formula, n is 0 to 7)

[0010]

[Chemical 7] (In the formula, X1 is -O-, -CO-, -S-, -SO2-,
--CH2-, --C (CH3) 2 --or --C (CF3)
Represents 2-. ) The content ratio of the structural unit represented by the above formula (4) is 0.005.
In the following cases, the effect of improving the adhesiveness is insufficient, and O. When it is 10 or more, the heat resistance of the adhesive itself is impaired. Furthermore, in the case of a heat-resistant adhesive containing a polyamic acid that is a precursor of polyimide, if it is 0.10 or more, the layers are severely separated and it cannot be stably stored. The ratio of the structural unit represented by the above formula (4) to the structural unit 1 represented by the above formula (5) is preferably 0.01 to 0.0.
5, more preferably 0.01 to 0.03, and most preferably 0.01 to 0.02.

In the present invention, the aromatic diamine represented by the general formula (1) is specifically 4,4'-bis (4-aminophenoxy) diphenyl ether 4,4'-bis (3- Aminophenoxy) diphenyl ether 3,3′-bis (4-aminophenoxy) diphenyl ether 3,3′-bis (3-aminophenoxy) diphenyl ether bis [4- (4-aminophenoxy) phenyl ] Ketone Bis [4- (3-aminophenoxy) phenyl] ketone Bis [3- (4-aminophenoxy) phenyl] ketone Bis [3- (3-aminophenoxy) phenyl] ketone Bis [4- (4-aminophenoxy) ) Phenyl] sulfide Bis [4- (3-aminophenoxy) phenyl] sulfide Bis [3- (4-aminophenoxy) phenyl] sulf Debis [3- (3-aminophenoxy) phenyl] sulfide Bis [4- (4-aminophenoxy) phenyl] sulfone Bis [4- (3-aminophenoxy) phenyl] sulfone Bis [3- (4-aminophenoxy) Phenyl] sulfone Bis [3- (3-aminophenoxy) phenyl] sulfone Bis [4- (4-aminophenoxy) phenyl] methane Bis [4- (3-aminophenoxy) phenyl] methane Bis [3- (4-amino) Phenoxy) phenyl] methane bis [3- (3-aminophenoxy) phenyl] methane 2,2-bis [4- (4-aminophenoxy) phenyl] propane 2,2-bis [4- (3-aminophenoxy) phenyl ] Propane 2,2-bis [3- (4-aminophenoxy) phenyl] propane 2,2-bis 3- (3-Aminophenoxy) phenyl] propane 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane 2,2-bis [4 -(3-Aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane 2,2-bis [3- (4-aminophenoxy) phenyl] -1,1,1,3,3 3,3-hexafluoropropane 2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane and the like can be mentioned. It is not limited. The diaminosiloxane has the general formula (2)

[0012]

Embedded image A ω, ω′-bis (3-aminopropyl) polydimethylsiloxane compound represented by the following formula where n is 0 to 7 is used.

Furthermore, the following diamines can be used in combination within the range not impairing the various performances of the present invention. Examples of diamines that can be used in combination include m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, m-aminobenzylamine, o-aminobenzylamine, 3-chloro-1,2-phenylenediamine, 4-chloro-1,
2-phenylenediamine, 2,3-diaminotoluene,
2,4-diaminotoluene, 2,5-diaminotoluene, 2,6-diaminotoluene, 3,4-diaminotoluene, 3,5-diaminotoluene, 2-methoxy-1,
4-phenylenediamine, 4-methoxy-1,2-phenylenediamine, 4-methoxy-1,3-phenylenediamine, benzidine, 3,3'-dichlorobenzidine,
3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 3,3'-diaminodiphenyl ether,
3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,
3'-diaminodiphenyl sulfoxide, 3,4'-diaminodiphenyl sulfoxide, 4,4'-diaminodiphenyl sulfoxide, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone,
4,4'-diaminodiphenyl sulfone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone 4,4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4, 4'-diaminodiphenylmethane, 1,
1-bis [4- (4-aminophenoxy) phenyl] ethane, 1,2-bis [4- (4-aminophenoxy) phenyl] ethane, 1,1-bis [4- (4-aminophenoxy) phenyl] Propane, 1,2-bis [4- (4
-Aminophenoxy) phenyl] propane, 1,3-bis [4- (4-aminophenoxy) phenyl] propane, 1,1-bis [4- (4-aminophenoxy) phenyl] butane, 1,3-bis [ 4- (4-aminophenoxy) phenyl] butane, 1,4-bis [4- (4-aminophenoxy) phenyl] butane, 2,2-bis [4
-(4-Aminophenoxy) phenyl] butane, 2,3
-Bis [4- (4-aminophenoxy) phenyl] butane, 2- [4- (4-aminophenoxy) phenyl]-
2- [4- (4-aminophenoxy) -3-methylphenyl] propane, 2,2-bis [4- (4-aminophenoxy) -3-methylphenyl] propane, 2- [4-
(4-Aminophenoxy) phenyl] -2- [4- (4
-Aminophenoxy) -3,5-dimethylphenyl] propane, 2,2-bis [4- (4-aminophenoxy)
-3,5-Dimethylphenyl] propane, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3
-Aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, 4,4'-bis (3-aminophenoxy) biphenyl, 3,3 '-Bis (4-aminophenoxy) biphenyl, 3,3'-bis (3-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] sulfoxide, 1,3-bis [4
-(4-aminophenoxy) benzoyl] benzene,
1,3-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,4-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,4-bis [4- (4
-Aminophenoxy) benzoyl] benzene, 4,4 '
-Bis (3-aminophenoxy) -3,3'-dimethylbiphenyl, 4,4'-bis (3-aminophenoxy)
-3,3 ', 5,5'-tetramethylbiphenyl, 4,
4'-bis (3-aminophenoxy) -3,3 ', 5
5'-tetrachlorobiphenyl, 4,4'-bis (3-
Aminophenoxy) -3,3 ', 5,5'-tetrabromobiphenyl, bis [4- (3-aminophenoxy)-
3-methoxyphenyl] sulfide, [4- (3-aminophenoxy) phenyl] [4- (3-aminophenoxy) -3,5-dimethoxyphenyl] sulfide, bis [4- (3-aminophenoxy) -3, 5-dimethoxyphenyl] sulfide, 1,1-bis [4- (3-aminophenoxy) phenyl] propane, 1,3-bis [4
-(3-aminophenoxy) phenyl] propane, 1,
3-bis (3-aminophenoxy) benzene, 1,3-
Bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminobenzoyl) biphenyl, 4,4'-bis (3-aminobenzoyl) biphenyl, 3,3'-bis (4-aminobenzoyl) biphenyl , 3,3'-bis (3-aminobenzoyl) biphenyl, 4,4'-bis (4-aminobenzoyl) diphenylether, 4,
4'-bis (3-aminobenzoyl) diphenyl ether, 3,3'-bis (4-aminobenzoyl) diphenyl ether, 3,3'-bis (3-aminobenzoyl)
Diphenyl ether, bis [4- (4-aminobenzoyl) phenyl] ketone, bis [4- (3-aminobenzoyl) phenyl] ketone, bis [3- (4-aminobenzoyl) phenyl] ketone, bis [3 -(3-Aminobenzoyl) phenyl] ketone

Bis [4- (4-aminobenzoyl) phenyl] sulfide, bis [4- (3-aminobenzoyl) phenyl] sulfide, bis [3- (4-aminobenzoyl) phenyl] sulfide, bis [3- ( 3-Aminobenzoyl) phenyl] sulfide, bis [4-
(4-aminobenzoyl) phenyl] sulfone, bis [4- (3-aminobenzoyl) phenyl] sulfone,
Bis [3- (4-aminobenzoyl) phenyl] sulfone, Bis [3- (3-aminobenzoyl) phenyl] sulfone, Bis [4- (4-aminobenzoyl) phenyl] methane, Bis [4- (3-amino) Benzoyl) phenyl] methane, bis [3- (4-aminobenzoyl) phenyl] methane, bis [3- (3-aminobenzoyl)
Phenyl] methane, 2,2-bis [4- (4-aminobenzoyl) phenyl] propane, 2,2-bis [4-
(3-Aminobenzoyl) phenyl] propane, 2,2
-Bis [3- (4-aminobenzoyl) phenyl] propane, 2,2-bis [3- (3-aminobenzoyl) phenyl] propane, 2,2-bis [4- (4-aminobenzoyl) phenyl]- 1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (3-aminobenzoyl) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2 , 2-bis [3- (4-aminobenzoyl) phenyl] -1,1,1,3,3,3-
Hexafluoropropane, 2,2-bis [3- (3-aminobenzoyl) phenyl] -1,1,1,3,3,3
-Hexafluoropropane, 4,4'-bis [4- (4
-Aminophenoxy) phenoxy] diphenyl sulfone, 4,4'-bis [4- (3-aminophenoxy) phenoxy] diphenyl sulfone, 3,3'-bis [4-
(4-Aminophenoxy) phenoxy] diphenyl sulfone, 3,3′-bis [4- (3-aminophenoxy)
Phenoxy] diphenyl sulfone, 4,4'-bis [4
-(4-Aminocumyl) phenoxy] diphenylsulfone, 4,4'-bis [4- (3-aminocumyl) phenoxy] diphenylsulfone, 3,3'-bis [4- (4
-Aminocumyl) phenoxy] diphenyl sulfone,
3,3'-bis [4- (3-aminocumyl) phenoxy] diphenylsulfone, 4,4'-bis [4- (4-
Aminophenoxy) benzoyl] diphenyl ether,
4,4'-bis [4- (3-aminophenoxy) benzoyl] diphenyl ether, 3,3'-bis [4- (4
-Aminophenoxy) benzoyl] diphenyl ether, 3,3'-bis [4- (3-aminophenoxy) benzoyl] diphenyl ether, 4,4'-bis [4-
(4-aminophenoxy) phenoxy] biphenyl,
4,4'-bis [4- (3-aminophenoxy) phenoxy] biphenyl, 3,3'-bis [4- (4-aminophenoxy) phenoxy] biphenyl, 3,3'-bis [4- (3- Aminophenoxy) phenoxy] biphenyl, 4,4'-bis [4- (4-aminocumyl) phenoxy] biphenyl, 4,4'-bis [4- (3-aminocumyl) phenoxy] biphenyl

3,3'-bis [4- (4-aminocumyl) phenoxy] biphenyl, 3,3'-bis [4-
(3-aminocumyl) phenoxy] biphenyl, 4,
4'-bis [4- (4-aminophenoxy) benzoyl] biphenyl, 4,4'-bis [4- (3-aminophenoxy) benzoyl] biphenyl, 3,3'-bis [4- (4-aminophenoxy) ) Benzoyl] biphenyl, 3,3'-bis [4- (3-aminophenoxy) benzoyl] biphenyl and the like.

In the present invention, as the aromatic tetracarboxylic dianhydride component represented by the general formula (3), pyromellitic dianhydride, biphenyltetracarboxylic dianhydride, benzophenonetetracarboxylic dianhydride, Diphenyl ether tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, bis (dicarboxphenyl)
Sulfone dianhydride, bis (dicarboxyphenyl) propane dianhydride, bis [(dicarboxyphenoxy) phenyl] propane dianhydride, bis (dicarboxyphenoxy) benzene dianhydride, bis (dicarboxyphenyl)
Hexafluoropropane dianhydride is used, but other tetracarboxylic acid dianhydrides may be mixed and used within a range not impairing the heat-resistant adhesive property. Examples of the tetracarboxylic dianhydride that can be mixed and used include ethylene tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, and bis (2,3-dicarboxyphenyl). ) Methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4- Dicarboxyphenyl) ethane dianhydride, 1,2-bis (3,4-dicarboxyphenyl) ethane dianhydride,
1,3-bis (2,3-dicarboxyphenoxy) benzene dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride 2,3,6,7-anthracene tetracarboxylic acid dianhydride, 1,2,7,8-phenanthrene tetracarboxylic acid dianhydride, and the like.

In the present invention, the molecular weight is controlled by adjusting the molar ratio of the monomer components, as in the case of ordinary polycondensation polymers. That is, 0.8 to 1.2 mol of a diamine mixture is used with respect to 1 mol of tetracarboxylic dianhydride. This molar ratio is 0.8 or less and 1.
When it is 2 or more, only a low molecular weight compound is obtained, and it does not sufficiently act as a heat resistant adhesive. Preferably, the diamine compound is 0.9 to 1 mol with respect to 1 mol of tetracarboxylic dianhydride.
1.1 molar ratio, more preferably 0.95 to 1.0
It is a 5 molar ratio.

In producing the heat-resistant adhesive of the present invention, a dicarboxylic acid anhydride or a monoamine may be used for the purpose of sealing the ends of polymer molecules. Specific examples of these compounds include phthalic anhydride, 2,3
-Benzophenone dicarboxylic acid anhydride, 3,4-benzophenone dicarboxylic acid anhydride, 2,3-dicarboxyphenyl phenyl ether anhydride, 3,4-dicarboxyphenyl phenyl ether anhydride, 2,3-biphenyl dicarboxylic acid anhydride 3,4-biphenyldicarboxylic acid anhydride, 2,3-dicarboxyphenylphenyl sulfone anhydride, 3,4-dicarboxyphenylphenyl sulfone anhydride, 2,3-dicarboxyphenylphenyl sulfide anhydride, 3,4 -Dicarboxyphenyl phenyl sulfide anhydride, 1,2-naphthalenedicarboxylic acid anhydride, 2,3-naphthalenedicarboxylic acid anhydride, 1,
Examples thereof include 8-naphthalenedicarboxylic acid anhydride, 1,2-anthracene dicarboxylic acid anhydride, 2,3-anthracene dicarboxylic acid anhydride, and 1,9-anthracene dicarboxylic acid anhydride. These dicarboxylic acid anhydrides may be substituted with a group having no reactivity with amines or dicarboxylic acid anhydrides. These may be used alone or in combination of two or more. Of these aromatic dicarboxylic acid anhydrides, phthalic anhydride is preferably used. Further, examples of the monoamine include the following. For example, aniline, o-toluidine, m-toluidine, p-toluidine, 2,3-xylidine, 2,6
-Xylidine, 3,4-xylidine, 3,5-xylidine, o-chloroaniline, m-chloroaniline, p-chloroaniline, o-bromoaniline, m-bromoaniline, p-bromoaniline, o-nitroaniline, p-nitroaniline, m-nitroaniline, o-aminophenol, p-aminophenol, m-aminophenol,
o-anisidine, m-anisidine, p-anisidine, o
-Phenetidine, m-phenetidine, p-phenetidine, o-aminobenzaldehyde, p-aminobenzaldehyde, m-aminobenzaldehyde, o-aminobenznitrile, p-aminobenznitrile, m-aminobenznitrile, 2-aminobiphenyl, 3 -Aminobiphenyl, 4-aminobiphenyl, 2-aminophenylphenyl ether, 3-aminophenylphenyl ether, 4-aminophenylphenyl ether, 2-aminobenzophenone, 3-aminobenzophenone, 4-aminobenzophenone, 2-aminophenylphenyl Sulfide, 3-aminophenylphenyl sulfide, 4-aminophenylphenyl sulfide, 2-aminophenylphenyl sulfone, 3-aminophenylphenyl sulfone, 4-aminophen Le phenyl sulfone, alpha-naphthylamine, beta-naphthylamine, 1-amino-2-naphthol, 5-amino-1-naphthol, 2-amino-1
-Naphthol, 4-amino-1-nafrole, 5-amino-2-naphthol, 7-amino-2-naphthol, 8
-Amino-1-naphthol, 8-amino-2-naphthol, 1-aminoanthracene, 2-aminoanthracene, 9-aminoanthracene and the like. Usually, of these aromatic monoamines, derivatives of aniline are preferably used. These may be used alone or in combination of two or more.

These aromatic monoamines and / or dicarboxylic acid anhydrides may be used alone or in combination of two or more kinds without any problem. The amount of these compounds used is 1 to several times the difference in the number of moles of the diamine and the tetracarboxylic acid dianhydride used (monocarboxylic acid dianhydride as the excess component) or dicarboxylic acid anhydride (the excess component is Diamine), but at least one component of 0.
It is generally used in an amount of about 01 mol. Specifically, 0.001 to 0.2 mol of dicarboxylic acid anhydride and / or monoamine is used with respect to 1 mol of the total amount of the tetracarboxylic acid dianhydride. Preferably 0.0
It is 05 to 0.05 mol.

The reaction for producing the polymer in the present invention is usually carried out in an organic solvent. As the organic solvent used in this reaction, any solvent can be used as long as it has no problem in producing a polyamic acid and a polyimide which are precursors of polyimide, and can dissolve the generated polyamic acid and polyimide. Specific examples thereof include amide-based solvents, ether-based solvents, and phenol-based solvents. More specifically, N, N-dimethylformamide,
N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylmethoxyacetamide, N
-Methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-methylcaprolactam, 1,2-
Dimethoxyethane-bis (2-methoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane, bis [2- (2-methoxyethoxy) ethyl] ether,
Tetrahydrofuran, 1,3-dioxane, 1,4-dioxane, pyridine, picoline, dimethyl sulfoxide, dimethyl sulfone, tetramethylurea, hexamethylphosphoramide, phenol, o-cresol, m-
Examples thereof include cresol, p-cresol, cresylic acid, o-chlorophenol, m-chlorophenol, p-chlorophenol, and anisole, and these may be used alone or in combination of two or more. Particularly, an amide solvent is preferable from the viewpoint of solution stability and utilization as workability.

In the present invention, it is possible to coexist with an organic base catalyst when producing a heat resistant adhesive containing a polyimide. As the organic base catalyst, tertiary amines such as pyridine, α-picoline, β-picoline, γ-picoline, quinoline, isoquinoline and triethylamine are used, and pyridine and γ-picoline are particularly preferable. The amount of these catalysts used is 0.00 per 1 mol of the total amount of tetracarboxylic dianhydride.
It is 1 to 0.50 mol. Particularly preferably 0.01 to
It is 0.1 mol.

Further, a diamine compound and a diaminosiloxane compound represented by the general formula (1) in an organic solvent,
As a method of reacting by adding tetracarboxylic acid dianhydride, dicarboxylic acid anhydride or monoamine, (a) after reacting a tetracarboxylic acid dianhydride component with a diamine compound represented by the general formula (1), A method in which a diaminosiloxane compound is added, and then a dicarboxylic acid anhydride or a monoamine is added to continue the reaction. (B) After reacting the tetracarboxylic dianhydride component and the diaminosiloxane compound, the diamine compound represented by the general formula (1) is added, and then the dicarboxylic anhydride or monoamine is added to continue the reaction. Method. (C) A dicarboxylic acid anhydride is added to a diamine mixture composed of a diamine compound represented by the general formula (1) and a diaminosiloxane compound to cause a reaction, and then a tetracarboxylic acid dianhydride component is added to continue the reaction. Method. (D) A method in which a monoamine is added to the tetracarboxylic acid dianhydride component to cause a reaction, then a diamine compound represented by the general formula (1) and a diaminosiloxane compound are added, and the reaction is continued. (E) tetracarboxylic dianhydride component, diamine compound represented by general formula (1), diaminosiloxane compound,
Examples thereof include a method in which a dicarboxylic acid anhydride or a monoamine is added and reacted at the same time, and any addition / reaction method may be used.

The reaction temperature for producing the polyamic acid which is the precursor of the polyimide is -20 to 60 ° C, preferably 0 to 40 ° C. The reaction time varies depending on the type of tetracarboxylic dianhydride used, the type of solvent, the reaction temperature and the like, but as a guide, it is 1 to 48 hours, usually several hours to ten and several hours. In the present application, the organic solvent solution containing the polyamic acid that is the polyimide precursor obtained by such a method is referred to as a heat-resistant adhesive solution that contains the polyamic acid that is the polyimide precursor. The polyamic acid thus obtained then
By heating and dehydrating at 0 to 400 ° C. for imidization,
Used.

The reaction temperature at the time of producing a heat-resistant adhesive solution containing a polyimide is 100 ° C. or higher, preferably 150 to 300 ° C., and it is common to carry out withdrawing water generated by the reaction. Prior to the imidization, it is possible to first synthesize the polyamic acid at a low temperature of 100 ° C. or lower and then raise the temperature to imidize, but simply by mixing the tetracarboxylic dianhydride component and the diamine component by the above method. After that, imidization can also be performed by immediately raising the temperature in the presence of an organic base. The reaction time varies depending on the type of tetracarboxylic dianhydride used, the type of solvent, the type and amount of organic base catalyst, the reaction temperature, etc., but as a guide, the amount of distilled water reaches the theoretical amount (usually Does not recover all, so the reaction rate is up to 70 to 90%. It is usually several hours to 10 hours. In this case, water generated by the imidization reaction is obtained by adding an azeotropic agent such as toluene to the reaction system,
The method of removing water by azeotropic distillation is general and effective. It is also possible to first synthesize a polyamic acid and then chemically imidize it using an imidizing agent such as acetic anhydride to produce a polyimide-containing heat-resistant adhesive solution. Usually, the heat-resistant adhesive solution containing the polyimide consisting of the polyimide copolymer solution thus obtained has good storage stability,
Moreover, when the copper foil is applied to the adhesive surface and then dried and adhered, sufficient 90 ° peel adhesive strength can be obtained even at a relatively low temperature and a low pressure for adhesion of the copper foil to the polyimide film, silicon nitride and glass. The drying temperature here is different depending on the boiling point of the solvent and cannot be specified, but is usually 100 to 300 ° C. The adhesion temperature is usually 150 to 300 ° C., particularly 250 ° C. or lower is sufficient.

[0025]

The present invention will be described below in detail with reference to examples and comparative examples. Example 1 4,4′-bis (3-aminophenoxy) diphenyl ether 37.68 g (0.098 mol) and a diaminosiloxane compound 0.496 g were placed in a container equipped with a stirrer, a reflux condenser and a nitrogen inlet tube. (0.002 mol) [Toray
Product name BY1 manufactured by Dow Corning Silicone Co., Ltd.
6-871], N-methyl-2-pyrrolidone 236.5.
Into a nitrogen atmosphere, 20.94 g (0.096 mol) of pyromellitic dianhydride was added in portions under a nitrogen atmosphere while paying attention to an increase in solution temperature, and the mixture was stirred at room temperature for about 20 hours. After that, 1.18 g of phthalic anhydride (0.008
Mol) was added and heated to continue heating at the reflux temperature of N-methyl-2-pyrrolidone for 6 hours, and about 50 g of N-methyl-2-pyrrolidone was distilled off. The resulting polyimide solution was applied onto a glass plate so as to have a coating thickness of 15 μm, dried by heating at 250 ° C., then a 1 oz copper foil and its mirror-finished surface were overlapped, and 320 ° C., 5 Kg
/ Cm ² was heat-pressed for 15 minutes. Using the obtained test piece, 9 according to IPC-TM-650 method 2, 4, 9
When the 0 ° peeling adhesive strength was measured, it was 2.13 Kg / c
It was m.

Examples 2 to 11 Same as Example 1 except that 37.68 g of 4,4'-bis (3-aminophenoxy) diphenyl ether in Example 1 was replaced with various diamines shown in Table 1. The peel adhesion strength was measured. The results are shown in Table 1 together with the results of Example 1. Comparative Examples 1 and 2 In Examples 2 and 3, except that diaminosiloxane was not used at all and 0.10 mol of a tetranuclear diamine was used,
A polyimide solution was prepared in exactly the same manner as in Example 1, and the peel adhesion strength was measured. The results are shown in Table 1. It can be seen that when no diaminosiloxane is used, the peel adhesion strength is reduced to half or less as compared with the case where it is used.

[0027]

[Table 1]

[0028]

[Table 2] Note * 1) 3-APDE: 4,4'-bis (3-aminophenoxy) diphenyl ether 4-APDE: 4,4'-bis (4-aminophenoxy) diphenyl ether 3-APPK: bis [ 4- (3-aminophenoxy) phenyl] ketone 4-APPK: bis [4- (4-aminophenoxy) phenyl] ketone 3-APPS: bis [4- (3-aminophenoxy) phenyl] sulfone 4-APPS: bis [4- (4-Aminophenoxy) phenyl] sulfone 3-APS: Bis [4- (3-aminophenoxy) phenyl] sulfide 3-APPM: Bis [4- (3-aminophenoxy) phenyl] methane 3-APPP: 2,2-bis [4- (3-aminophenoxy)
Phenyl] propane 4-APPP: 2,2-bis [4- (4-aminophenoxy)
Phenyl] propane 3-APCF: 2,2-bis [4- (3-aminophenoxy)
Phenyl] -1,1,1,3,3,3-hexafluoropropane 4-APCF: 2,2-bis [4- (4-aminophenoxy)
Phenyl] -1,1,1,3,3,3-hexafluoropropane * 2) PMDA: pyromellitic dianhydride BPDA: biphenyltetracarboxylic dianhydride BTDA: benzophenone tetracarboxylic dianhydride ODPA: diphenyl ether Tetracarboxylic acid dianhydride * 3) Toray Dow Corning Silicone Co., Ltd. product BY16-871 uses n = 0, BY16-853C uses n = 7

[0029]

Industrial Applicability The heat-resistant adhesive made of polyimide according to the present invention can be bonded at low temperature and low pressure, has good adhesive strength, and is extremely valuable in industry.

Claims (5)

[Claims] 1. General formula (1) (Chemical formula 1) (In the formula, X1 is -O-, -CO-, -S-, -SO2-,
--CH2-, --C (CH3) 2 --or --C (CF3)
Represents 2-. ) With respect to 1 mol of the aromatic diamine represented by the general formula (2) (In the formula, n is 0 to 7) and a diamine mixture containing 0.10 to 0.005 mol of a diaminosiloxane compound, and a general formula (3) (Chemical Formula 3) A polyimide obtained by reacting one or more tetracarboxylic acid dianhydrides selected from the above with heating in the presence or absence of a dicarboxylic acid anhydride and / or a monoamine compound. 2. The polyimide according to claim 1, wherein a total amount of the diamine component of 0.8 to 1.2 mol is used with respect to a total amount of 1 mol of the tetracarboxylic dianhydride component. 3. The dicarboxylic acid anhydride and / or monoamine is used in an amount of 0.001 to 0.20 mol per 1 mol of the total amount of the tetracarboxylic dianhydride component. Polyimide. 4.A solution containing the polyimide according to claim 1 and / or a polyamic acid which is a precursor of the polyimide. 5. A heat-resistant adhesive containing the polyimide according to any one of claims 1 to 3 and / or a polyamic acid which is a precursor of the polyimide.