JPH0977975A - Polyimide resin composition and adhesive prepared using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyimide resin compsn. excellent in adhesive and mechanical properties by adding a fibrous reinforcement to a polyimide obtd. by reacting a specific diamine mixture with a tetracarboxylic dianhydride. SOLUTION: This resin compsn. is prepd. by incorporating 5-100 pts.wt. at least one fibrous reinforcement selected from among carbon fibers, glass fibers, arom. polyamide fibers, and potassium titanate fibers into 100 pts.wt. polyimide obtd. by reacting a diamine mixture comprising 1mol of an arom. diamine represented by formula I (wherein R is a group represented by formula II or III) and 0.10-0.005mol of a diaminosiloxane compd. represented by formula IV (wherein (n) is 0-7) with at least one tetracarboxylic dianhydride selected from among pyromellitic dianhydride, biphenyltetracarboxylic dianhydride, and benzophenonetetrcarboxylic dianhydride. The incorporation of the reinforcement imparts excellent adhesive and mechanical properties to the compsn., from which a polyimide film and an adhesive are obtd.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyimide resin composition having excellent adhesiveness. Furthermore, the present invention relates to a polyimide film made of this resin composition and an adhesive using the same.

[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, they require high-temperature and high-pressure adhesion conditions in order to obtain a good adhesion state.

On the other hand, many techniques 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.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polyimide resin composition having excellent adhesiveness, a polyimide film made of this resin composition, and an adhesive using the same.

[0005]

Means for Solving the Problems As a result of intensive studies for solving the above-mentioned problems, the present inventors have found that by adding a fiber reinforcing material to a polyimide having a specific structure, excellent adhesion and mechanical properties can be obtained. The present invention has been accomplished by finding a polyimide resin composition having physical properties, and further finding a polyimide film made of this resin composition and an adhesive using the same.

That is, the present invention includes: 1) General formula (1)

[0007]

Embedded image General formula (2) per mol of the aromatic diamine represented by
(Formula 5)

[0008]

Embedded image (In the formula, n is an integer of 0 to 7), a diamine mixture containing 0.10 to 0.005 mol of a diaminosiloxane compound, pyromellitic dianhydride, biphenyltetracarboxylic dianhydride, and benzophenonetetra. Polyimide 10 obtained by reacting with one or more tetracarboxylic dianhydrides selected from carboxylic dianhydrides
A polyimide resin excellent in adhesiveness and mechanical properties, containing 5 to 100 parts by weight of carbon fiber, glass fiber, aromatic polyamide fiber, and potassium titanate fiber, relative to 0 part by weight. Composition, 2) General formula (3) (Chemical Formula 6) in producing the polyimide resin composition described in 1) above.

[0009]

[Chemical 6] (Wherein, Z has 6 to 15 carbon atoms and is a monocyclic aromatic group,
An aromatic dicarboxylic acid anhydride represented by a condensed polycyclic aromatic group or a divalent group that is a non-condensed polycyclic aromatic group in which aromatic groups are directly or cross-linked with each other by a bridge member) / Or general formula (4) V-NH2 (4) (In the formula, V has 6 to 15 carbon atoms, a monocyclic aromatic group,
A condensed monocyclic aromatic group or a monovalent group which is a non-condensed polycyclic aromatic group in which aromatic groups are connected to each other directly or by a cross-linking member) Polyimide resin composition obtained by sealing the molecular end of the polymer described in 1) above, 3) Polyimide film obtained from the polyimide resin composition described in 1) or 2) above, 4) Polyimide film according to 3) above. Is an adhesive W using.

The polyimide used in the present application has a skeleton
The structural unit represented by the following general formula (5) (Chemical formula 7) is based on 1 mol of the structural unit represented by the following general formula (6) (Chemical formula 8),
It is contained in a proportion of 0.10 to 0.005 mol.

[0011]

[Chemical 7] (In the formula, n is an integer of 0 to 7)

[0012]

Embedded image If the content ratio of the structural unit represented by the general formula (5) is 0.005 mol or less, the effect of improving the adhesiveness is not sufficient, and if it is 0.1 mol or more, the adhesive itself is not improved. Heat resistance is impaired. Preferably 0.01 to 0.05
And more preferably 0.01 to 0.03, and most preferably 0.01 to 0.02. This polyimide 10
5 to 100 parts by weight, preferably 5 to 100 parts by weight
A polyimide resin composition having 60 parts by weight of carbon fiber, glass fiber, aromatic polyamide fiber, and one or more kinds of fiber reinforcing material selected from potassium titanate fiber and having excellent adhesiveness and mechanical properties.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The aromatic diamine used in the present invention is 1,3-bis (3-aminophenoxy) benzene and 4,4'-bis (3-aminophenoxy) biphenyl, which are used as diaminosiloxane compounds. Is an integer of n = 0 to 7 in the general formula (2), ω, ω′-bis (3-
Aminopropyl) polydimethylsiloxane compound. Further, as tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride There are things etc. The diamine component and the tetracarboxylic dianhydride used in the method of the present invention are 0.8 to 1.0 mol of the tetracarboxylic dianhydride per mol of the diamine component, preferably 0.9 to 1.1 mol. Is.

Further, one or more other diamines or tetracarboxylic dianhydrides may be mixed and polymerized within a range that does not impair the properties and physical properties of the polyimide. Examples of diamines that can be mixed and used include, for example, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, m-aminobenzylamine, o-aminobenzylamine, p-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'-dimethoxy Benzidine, 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,

1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene,
1,4-bis (3-aminophenoxy) benzene, 1,4-
Bis (4-aminophenoxy) benzene, 1,3-bis (3-aminobenzoyl) benzene, 1,3-bis (4-
Aminobenzoyl) benzene, 1,4-bis (3-aminobenzoyl) benzene, 1,4-bis (4-aminobenzoyl) benzene, 3,3'-bis (3-aminophenoxy)
Biphenyl, 3,3'-bis (4-aminophenoxy) biphenyl, 4,4'-bis (3-aminophenoxy) biphenyl, 4,4'-bis (4-aminophenoxy) biphenyl,
4,4'-bis (3-aminophenoxy) -3-methylbiphenyl, 4,4'-bis (3-aminophenoxy) -3,3'-
Dimethylbiphenyl, 4,4'-bis (3-aminophenoxy) -3,5-dimethylbiphenyl, 4,4'-bis (3-aminophenoxy) -3,3 ', 5,5'-tetramethylbiphenyl, 4,4'-bis (3-aminophenoxy) -3,3'-dichlorobiphenyl, 4,4'-bis (3-aminophenoxy)
-3,5-dichlorobiphenyl, 4,4'-bis (3-aminophenoxy) -3,3 ', 5,5'-tetrachlorobiphenyl,
4,4'-bis (3-aminophenoxy) -3,3'-dibromobiphenyl, 4,4'-bis (3-aminophenoxy) -3,
5-dibromobiphenyl, 4,4'-bis (3-aminophenoxy) -3,3 ', 5,5'-tetrabromobiphenyl, bis [3- (3-aminophenoxy) phenyl] methane, bis [3- (4-aminophenoxy) phenyl] methane,
Bis [4- (3-aminophenoxy) phenyl] methane, bis [4- (4-aminophenoxy) phenyl] methane,

1,1-bis [4- (3-aminophenoxy) phenyl] ethane, 1,1-bis [4- (4-aminophenoxy) phenyl] ethane, 1,2-bis [4- (3
-Aminophenoxy) phenyl] ethane, 1,2-bis [4- (4-aminophenoxy) phenyl] ethane, 1,
1-bis [4- (3-aminophenoxy) phenyl] propane, 1,1-bis [4- (4-aminophenoxy) phenyl] propane, 1,2-bis [4- (3-aminophenoxy) phenyl] Propane, 1,2-bis [4- (4-
Aminophenoxy) phenyl] propane, 1,3-bis [4- (3-aminophenoxy) phenyl] propane,
1,3-bis [4- (4-aminophenoxy) phenyl]
Propane, 2,2-bis [4- (3-aminophenoxy)
Phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 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-amino Phenoxy) -3,5
-Dimethylphenyl] propane, 2,2-bis [4- (4
-Aminophenoxy) -3,5-dimethylphenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2
-Bis [4- (4-aminophenoxy) phenyl] -1,
1,1,3,3,3-hexafluoropropane, 2,2-bis (3
-(3-Aminophenoxy) phenyl] -1,1,1,3,3,3
-Hexafluoropropane, 2,2-bis [3- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane,

1,1-bis [4- (3-aminophenoxy) phenyl] butane, 1,1-bis [4- (4-aminophenoxy) phenyl] butane, 1,2-bis [4- (3
-Aminophenoxy) phenyl] butane, 1,2-bis [4- (4-aminophenoxy) phenyl] butane, 1,
3-bis [4- (3-aminophenoxy) phenyl] butane, 1,3-bis [4- (4-aminophenoxy) phenyl] butane, 1,4-bis [4- (3-aminophenoxy) phenyl] Butane, 1,4-bis [4- (4-aminophenoxy) phenyl] butane, 2,2-bis [4- (3
-Aminophenoxy) phenyl] butane, 2,2-bis [4- (4-aminophenoxy) phenyl] butane, 2,
3-bis [4- (3-aminophenoxy) phenyl] butane, 2,3-bis [4- (4-aminophenoxy) phenyl] butane, bis [3- (3-aminophenoxy) phenyl] ketone, bis [ 3- (4-aminophenoxy)
Phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] ketone, bis [3- (3-aminophenoxy) phenyl] sulfide, bis [3- (4-Aminophenoxy) phenyl] sulfide, bis [4- (3
-Aminophenoxy) phenyl] sulfide, bis [4
-(4-aminophenoxy) phenyl] sulfide, 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,

Bis [3- (3-aminophenoxy) phenyl] sulfoxide, bis [4- (3-aminophenoxy) phenyl] sulfoxide, bis [4- (4-aminophenoxy) phenyl] sulfoxide, bis [3- ( 3
-Aminophenoxy) phenyl] sulfone, bis [3-
(4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone,
Bis [4- (4-aminophenoxy) phenyl] sulfone, Bis [3- (3-aminophenoxy) phenyl] ether, Bis [3- (4-aminophenoxy) phenyl] ether, Bis [4- (3-amino) Phenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, 1,3-bis [4- (4-aminophenoxy) benzoyl] benzene, 1,3-bis [4
-(3-Aminophenoxy) benzoyl] benzene, 1,
4-bis [4- (4-aminophenoxy) benzoyl]
Benzene, 1,4-bis [4- (3-aminophenoxy)
Benzoyl] benzene, 1,3-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene,
1,3-bis [4- (3-aminophenoxy) -α, α-
Dimethylbenzyl] benzene, 1,4-bis [4- (4-
Aminophenoxy) -α, α-dimethylbenzyl] benzene and the like, which may be used alone or in combination of two or more.

The tetracarboxylic dianhydrides used as a mixture are ethylene tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, pyromellitic dianhydride. ,
2,2 ', 3,3'-benzophenone tetracarboxylic dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic acid Dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3 -Dicarboxyphenyl) propane dianhydride, bis (2,3-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (2,3-dicarboxyphenyl) Sulfone dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 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 (2,3-dicarboxyphenyl) ethane dianhydride, 1,
2-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,3-bis (2,3-dicarboxyphenoxy) benzene dianhydride, 1,3-bis (3,4-dicarboxyphenoxy) Benzene dianhydride, 1,4-bis (2,3-dicarboxyphenoxy) benzene dianhydride, 1,4-bis (3,4
-Dicarboxyphenoxy) benzene dianhydride, 2,3,6,
7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-
Naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,4,9,10-perylenetetra Carboxylic dianhydride, 2,3,6,7-anthracene tetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, etc., and these tetracarboxylic dianhydrides are independent. Alternatively, two or more kinds may be mixed and used.

The polyimide used in the present invention is a polyimide having the above-mentioned repeating structural unit obtained by using these diamine mixture and tetracarboxylic dianhydride as monomer components, and these polyimides have their polymer molecular terminals substituted. Group-free aromatic monoamine and /
Also included are aromatic dicarboxylic acid anhydrides, or polyimides substituted with aromatic monoamines and / or aromatic dicarboxylic acid anhydrides that are not reactive with amines or dicarboxylic acid anhydrides.

The polyimide in which the terminal of the polymer molecule is substituted with an aromatic monoamine and / or an aromatic dicarboxylic acid anhydride has the general formula (2) with respect to 1 mol of the aromatic diamine represented by the general formula (1). A diaminosiloxane compound represented by the following formula, that is, 0.10 to 0.005 mol of ω, ω'-bis (3-aminopropyl) polydimethylsiloxane compound in which n is 0 to 7, is used, and these are pyromellitic dianhydride. , Biphenyltetracarboxylic dianhydride,
One or more types of tetracarboxylic acid dianhydride selected from benzophenone tetracarboxylic acid dianhydride are added to the compound represented by the general formula (3)

[0022]

Embedded image (In the formula, Z is a monocyclic aromatic group having 6 to 15 carbon atoms, a condensed polycyclic aromatic group or a non-condensed polycyclic aromatic group in which aromatic groups are directly or cross-linked to each other. An aromatic dicarboxylic acid anhydride represented by a certain divalent group) and / or the general formula (4) V—NH ₂ (4) (in the formula, V is a monocyclic aromatic group having 6 to 15 carbon atoms) Group, a condensed polycyclic aromatic group or an aromatic monoamine represented by a monovalent group which is a non-condensed polycyclic aromatic group in which aromatic groups are connected to each other directly or by a crosslinking member) It can be reacted below.

The aromatic dicarboxylic acid anhydride represented by the general formula (3) includes phthalic anhydride, 2,3-benzophenone dicarboxylic acid anhydride, 3,4-benzophenone dicarboxylic acid anhydride and 2,3-dicarboxylic acid anhydride. Carboxyphenyl 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-dicarboxy Phenylphenyl sulfide anhydride, 1,2-naphthalenedicarboxylic acid anhydride, 2,3-naphthalenedicarboxylic acid anhydride, 1,8-naphthalenedicarboxylic acid anhydride, 1,2
-Anthracene dicarboxylic acid anhydride, 2,3-anthracene dicarboxylic acid anhydride, 1,9-anthracene dicarboxylic acid anhydride and the like can be mentioned. These aromatic dicarboxylic acid anhydrides may be substituted with a group having no reactivity with the amine or the dicarboxylic acid anhydride, and may be used alone or in combination of two or more kinds.

Among these aromatic dicarboxylic acid anhydrides, phthalic anhydride is most preferable from the viewpoint of performance and practical use of the obtained polyimide. When an aromatic dicarboxylic acid anhydride is used, the amount used is 0.10 to 1 mol per 1 mol of the total amount of the aromatic diamine represented by the general formula (1) and the diaminosiloxane compound represented by the general formula (2). 0.005
Is a mole.

The aromatic monoamine represented by the general formula (4) includes, 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, p-nitroaniline, o-aminophenol, m-aminophenol, p-aminophenol,
o-anisidine, m-anisidine, p-anisidine, o
-Phenedine, m-phenenedi, p-phenenedi, o-
Aminobenzaldehyde, m-aminobenzaldehyde, p-aminobenzaldehyde, o-aminobenzonitrile, m-aminobenzonitrile, p-aminobenzonitrile,

2-aminobiphenyl, 3-aminobiphenyl, 4-aminobiphenyl, 2-aminophenylphenyl ether, 3-aminophenylphenyl ether,
4-aminophenyl phenyl ether, 2-aminobezophenone, 3-aminobezophenone, 4-aminobezophenone, 2-aminophenylphenyl sulfide, 3-
Aminophenylphenyl sulfide, 4-aminophenylphenyl sulfide, 2-aminophenylphenyl sulfone, 3-aminophenylphenyl sulfone, 4-aminophenylphenyl sulfone, α-naphthylamine,
β-naphthylamine, 1-amino-2-naphthol, 2
-Amino-1-naphthol, 4-amino-1-naphthol, 5-amino-1-naphthol, 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 can be mentioned. These aromatic monoamines may be substituted with a group having no reactivity with the amine or the dicarboxylic acid anhydride, and may be used alone or in combination of two or more kinds.

Of these aromatic monoamines, aniline is most preferable from the viewpoint of performance and practical use of the obtained polyimide. When using an aromatic monoamine, the amount used is one selected from the tetracarboxylic dianhydrides used, that is, pyromellitic dianhydride, biphenyltetracarboxylic dianhydride, and benzophenonetetracarboxylic dianhydride. It is 0.10 to 0.005 mol per 1 mol of the above tetracarboxylic dianhydride.

The polyimide used in the present invention can be produced by any known method. For example, 1) synthesize a polyamic acid in an organic solvent, remove the solvent by decompression, or isolate the polyamic acid from the obtained polyamic acid solution by using a poor solvent, and then heat the polyamic acid. Then, a polyamic acid solution is obtained in the same manner as in 2) 1), and a dehydrating agent typified by acetic anhydride is added, and if necessary, a catalyst is added to chemically react with the imide. After the polymerization is performed, the polyimide is isolated by a known method, and if necessary, washed and dried, 3) a polyamic acid solution is obtained in the same manner as 1), and then the solvent is removed by decompression or heating. Method of performing thermal imidization at the same time, 4) After charging raw materials in an organic solvent, heating is performed to simultaneously perform synthesis of polyamic acid and imidization reaction, and if necessary, catalyst, azeotropic agent, dehydrating agent, etc. Coexist Method, etc.

In the production of polyimide, it is particularly preferable to carry out the reaction in an organic solvent. Examples of the organic solvent used include 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,
Examples thereof include tetramethylurea, hexamethylphosphoramide, phenol, o-cresol, m-cresol, p-cresol, m-cresylic acid, p-chlorophenol, and anisole. These organic solvents may be used alone or in combination of two or more.

In the production of polyimide, a method for adding and reacting an aromatic diamine, a diaminosiloxane compound, a tetracarboxylic dianhydride, an aromatic dicarboxylic anhydride or an aromatic monoamine in an organic solvent is as follows. ) A method of reacting an aromatic diamine and a tetracarboxylic dianhydride, then adding a diaminosiloxane compound, and then adding an aromatic dicarboxylic acid anhydride or an aromatic monoamine to continue the reaction, (b) tetra A method of reacting a carboxylic acid dianhydride and a diaminosiloxane compound, then adding an aromatic diamine, and then adding an aromatic dicarboxylic acid anhydride or an aromatic monoamine to continue the reaction, (c) an aromatic diamine Aromatic dicarboxylic acid anhydride was added to the diamine mixture consisting of After reacting, the reaction is continued by adding a tetracarboxylic dianhydride, or, after reaction by adding an aromatic monoamine to a tetracarboxylic dianhydride to continue the reaction with the addition of the diamine mixture method,
Any addition method may be used such as (d) a method in which an aromatic diamine, a tetracarboxylic acid dianhydride, a diaminosiloxane compound and an aromatic dicarboxylic acid anhydride or an aromatic monoamine are simultaneously added to carry out a reaction.

The polymerization / imidization reaction temperature is usually 300 ° C. or lower. The polymerization / imidization reaction pressure is not particularly limited, and can be carried out at normal pressure. The polymerization / imidization reaction time is
Depending on the type of diamine, the type of tetracarboxylic dianhydride, the type of solvent and the reaction temperature, 4 to 24 hours is usually sufficient. For 100 parts by weight of this polyimide,
A polyimide resin composition having excellent adhesiveness, containing 5 to 100 parts by weight, preferably 5 to 60 parts by weight of carbon fiber, glass fiber, aromatic polyamide fiber, potassium titanate fiber and at least one fiber reinforcing material. Is. The following methods are available for obtaining a polyimide film. The polyimide resin composition obtained by the above method is directly or in the form of pellets previously supplied to an extruder, melted by heating, extruded, and cooled to solidify to obtain a film. Here, the melt extrusion temperature is the polymer
Although it depends on the structure, it is usually in the range of 300 to 450 ° C. If the temperature is lower than 300 ° C, the resin is difficult to melt and cannot be extruded in many cases. Further, even if the resin can be extruded, the fluidity of the molten resin is extremely lowered, and thus it is difficult to take it into a sheet shape. Is not preferable. Also, 450
If the temperature exceeds ℃, the decomposition of the resin proceeds and the appearance of the sheet is impaired by bubbles and the like, which is not preferable.

Thus, the polyimide resin composition of the present invention or the polyimide resin composition of the present invention or the polyimide resin composition of the present invention, which is put into practical use, is obtained by inserting the polyimide film obtained from the polyimide resin composition or the polyimide film obtained from the same between the adherends. The polyimide film to be contacted. Then, if necessary, a pressure of 1 to 1000 kg / cm ² , 100 to 400
Adhesion can be performed by applying a temperature of ° C.
Alternatively, the adherend may be brought into contact with the polyimide resin composition of the present invention or the polyimide film obtained therefrom, and then adhered to each other.

In using the polyimide resin composition of the present invention or the polyimide film obtained therefrom, a glass fiber cloth or a carbon fiber cloth is impregnated with the polyimide resin composition by a known method, and a method of adhering the glass fiber cloth or the carbon fiber cloth with the glass fiber cloth or the adhered film is used. A method of inserting the polyimide resin composition of the present invention or the polyimide film obtained from the same between the bodies, and then inserting glass fiber or carbon fiber cloth into the adhesive layer and then adhering the same is also possible. Further, it is also possible to perform the adhesion after the surface of the adherend is chemically or physically treated. Examples of the surface treatment method include chemical etching with acid or alkali, corona treatment, ultraviolet irradiation, radiation irradiation, sandblasting, heat treatment, plasma treatment, kemmer treatment, homing treatment, plating treatment, oxide film treatment, degreasing treatment and the like.
These methods may be a single method or a composite method.

The polyimide adhesive of the present invention may contain other components within the range not impairing the object of the present invention and may be adhered thereto. Other resins to be added include nylons, polyacetal, polyethylene, polypropylene, polycarbonate, polyarylate, polyamide,
Polysulfone, polyether sulfone, polyether ketone, polyphenylene sulfide, polyamide imide,
Examples thereof include polyphenylene oxide, polyimide, polyetherimide, fluororesin, polybismaleimide, and epoxy resin. It is also possible to add one or more solid lubricants such as molybdenum disulfide, graphite, boron nitride, lead monoxide, and lead powder. In addition, antioxidants,
One or more usual additives such as a heat stabilizer, an ultraviolet absorber, a flame retardant, a flame retardant aid, an antistatic agent, and a coloring agent can be added.

[0035]

The present invention will be described below in detail with reference to examples and comparative examples. In the examples, various physical properties were measured by the following methods. Logarithmic viscosity: A value measured by dissolving 0.50 g of polyimide powder in 100 ml of a mixed solvent of p-chlorophenol and phenol (90:10 weight ratio) by heating and then cooling to 35 ° C. Glass transition temperature (Tg): Measured by DSC (Shimadzu DT-40 series, DSC-41M) at a heating rate of 16 ° C./min 5% weight loss temperature: DTA-Tg in air (Shimadzu DT-
40 series, DSC-40M) 10 ° C / min
Measured at the heating rate of

Synthesis Example-1 1,85-g (2.355 mol) of 1,3-bis (3-aminophenoxy) benzene and a diaminosiloxane compound were placed in a container equipped with stirring, a reflux condenser, a water separator and a nitrogen introducing tube.
11.2g (0.045mol) [Toray Dow Corning Silicone]
Product name BY16-871], 3,3 ', 4,4'-
748.5 g (2.323) of benzophenone tetracarboxylic dianhydride
Mol), phthalic anhydride 22.8 g (0.15 mol), γ-picoline
33.5 g (0.36 mol) and 5.79 kg of m-cresol were charged, and the mixture was heated to 145 ° C. with stirring under a nitrogen atmosphere. During this period, it was confirmed that about 80 g of water was distilled. Further, the reaction was carried out at 140 to 150 ° C for 4 hours. Then, the mixture was cooled to room temperature, discharged into 13.5 kg of methyl ethyl ketone, and then filtered. The polyimide powder was further washed with methyl ethyl ketone, pre-dried in a nitrogen atmosphere at 50 ° C. for 24 hours and then at 180 ° C. for 6 hours to obtain 1.31 kg (yield 94.2%) of the polyimide powder. The polyimide powder had an inherent viscosity of 0.49 dl / g, a Tg of 186 ° C., and a 5% weight loss temperature in air of 542 ° C.

Synthesis Examples-2 to 13 Kinds of aromatic diamine or tetracarboxylic dianhydride and diaminosiloxane compound in Synthesis Example-1,
Alternatively, Synthesis Example-1 except that the content was changed as shown in Table 1
A polyimide powder was obtained in the same manner as. The results are shown in Table 1 together with the results of Synthesis Example-1.

Example-1 40 parts by weight of carbon fiber (HTA-C6) manufactured by Toho Rayon Co., Ltd. was added to 100 parts by weight of the polyimide powder obtained in Synthesis Example-1, and a drum blender-mixer ( Kawada Manufacturing Co., Ltd.). The obtained polyimide resin composition was
Inserted in the mirror surface of the copper foil of z, 310 ° C, 5 kg / cm ²
It was heated and pressed for 15 minutes. Using the obtained test piece, IP
90 according to C-TM-650 method 2, 4, 9
° Peel adhesion strength was measured to be 2.15kg / cm
Met. Further, the obtained polyimide resin composition was supplied to a vent type extruder having a diameter of 30 mm under a nitrogen atmosphere,
After heating and melting at 0 ° C., the strand was air-cooled and cut to obtain a polyimide pellet. The obtained polyimide pellets were supplied to a 20 mm plastomill extruder, heated and melted at 360 ° C., extruded from a slit die having a width of 80 mm, and naturally cooled to obtain a polyimide film having a thickness of about 50 μm.
The tensile strength of this polyimide film is 19.2 kg / m
m ² (according to ASTM D-882). This polyimide film was thermocompression bonded to a copper foil mirror surface in the same manner as the above polyimide resin composition, and the peel adhesive strength was measured and found to be 2.16 kg / cm.

Examples-2, 3 Using the polyimide powder obtained in Synthesis Example-1, Example-1
Carbon fiber (HTA-C6) 4 manufactured by Toho Rayon Co., Ltd.
The peel adhesive strength was measured in the same manner as in Example-1 except that 5 or 90 parts by weight of the same fiber was used instead of 0 part by weight. The results are shown in Table 2 together with the results of Example-1.

Examples -4, 5 Using the polyimide powder obtained in Synthesis Example-1, Example-1
In place of the carbon fiber (HTA-C6) manufactured by Toho Rayon Co., Ltd. used in 1., glass fiber (Microglass RES) manufactured by Nippon Sheet Glass Co., Ltd. or aramid fiber manufactured by DuPont (Kevlar chopped strand K-49) was used. The peel adhesion strength was measured in the same manner as in Example-1. The results are shown in Table 2 together with the results of Example-1.

Examples-6 to 11 The peel adhesion strength was measured in the same manner as in Example-1 except that the polyimide powders obtained in Synthesis Examples-2 to 7 were used. The results are shown in Table 2 together with the results of Example-1. Comparative Examples-1 to 6 The peel adhesion strength was measured in the same manner as in Example-1 except that the polyimide powders obtained in Synthesis Examples-8 to 13 were used. The results are shown in Table 2 together with the results of Example-1. It can be seen that when the diaminosiloxane compound is not used at all, the peel adhesion strength is reduced to half or less as compared with the case where it is used. Further, when the content of diaminosiloxane is less than the range, sufficient adhesive force cannot be obtained. Further, it can be seen that when the content is more than the range, the physical properties of the polyimide itself are poor and the adhesiveness is poor.

Comparative Examples-7 to 9 The peel adhesion strength was measured in the same manner as in Example-1 except that the polyimide powder obtained in Synthesis Example-1 was not used or fibers outside the range were used. . The results are shown in Table 2 together with the results of Example-1. It can be seen that the heat resistance is improved by using the fiber. Further, when the fiber content was above the range, melt extrusion was impossible.

[0043]

[Table 1]

[0044]

[Table 2]

[0045]

According to the present invention, it is possible to provide a polyimide resin composition excellent in adhesiveness and mechanical properties and a polyimide film obtained therefrom.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Akihiro Yamaguchi 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Mitsui Toatsu Chemicals Co., Ltd.

Claims (4)

[Claims] 1. A compound represented by the general formula (1): General formula (2) per mol of the aromatic diamine represented by
(Chemical formula 2) [Chemical formula 2] (In the formula, n is an integer of 0 to 7), a diamine mixture containing 0.10 to 0.005 mol of a diaminosiloxane compound, pyromellitic dianhydride, biphenyltetracarboxylic dianhydride, and benzophenonetetra. Polyimide 10 obtained by reacting with one or more tetracarboxylic dianhydrides selected from carboxylic dianhydrides
A polyimide resin excellent in adhesiveness and mechanical properties, containing 5 to 100 parts by weight of carbon fiber, glass fiber, aromatic polyamide fiber, and potassium titanate fiber, relative to 0 part by weight. Composition. 2. The general formula (3) (Chemical Formula 3) in the production of the above polyimide (Wherein, Z has 6 to 15 carbon atoms and is a monocyclic aromatic group,
An aromatic dicarboxylic acid anhydride represented by a condensed polycyclic aromatic group or a divalent group that is a non-condensed polycyclic aromatic group in which aromatic groups are directly or cross-linked with each other by a bridge member) / Or general formula (4) V-NH2 (4) (In the formula, V has 6 to 15 carbon atoms, a monocyclic aromatic group,
A condensed monocyclic aromatic group or a monovalent group which is a non-condensed polycyclic aromatic group in which aromatic groups are connected to each other directly or by a cross-linking member) The polyimide resin composition according to claim 1, comprising a polymer obtained by sealing the molecular ends. 3. A polyimide film obtained from the polyimide resin composition according to claim 1. 4. An adhesive using the polyimide film according to claim 3.