JPH10152559A - Aromatic diamine compound, and polyamic acid and polyimide using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject compound capable of giving polyimide excellent both in resistance to heat and low dielectric constant, and useful as an electrical insulator. SOLUTION: This aromatic diamine compound is shown by the formula (R<1> and R<2> are each independently a 1-6C alkyl, 1-6C alkyl halide, or 6-14C monovalent monocyclic or condensed polycyclic aromatic group; and (a) and (b) are each independently an integer of 0 to 4). This aromatic diamine compound can be subjected to polycondensation with a tetracarboxylic acid dianhydride in an organic solvent, to produce the 2nd objective polyamic acid. Furthermore, the polyamic acid can be subjected to dehydrocyclization into the 3rd objective polyimide. The polyimide thus produced is very suitable for, especially, interlayer insulating films for LSI's.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel aromatic diamine compound, and to a polyamic acid and a polyimide obtained from the aromatic diamine compound.

[0002]

2. Description of the Related Art Large-scale integrated circuits (LSIs) are steadily becoming more highly integrated, multifunctional, and more sophisticated, reflecting advances in microfabrication technology. As a result, the circuit resistance and the capacitance between the wirings (hereinafter referred to as “parasitic resistance” and “parasitic capacitance”, respectively) increase, which not only increases the power consumption, but also increases the delay time, and This is a major factor in reducing the signal speed. Therefore, it is required to reduce the parasitic resistance and the parasitic capacitance. One of the solutions is to reduce the parasitic capacitance by covering the periphery of the wiring with an interlayer insulating film having a low dielectric constant, thereby increasing the speed of the device. Is trying to respond to the change. Specifically, attempts have been made to replace a silicon oxide film used as a conventional interlayer insulating film with an organic film having a lower dielectric constant. However, the interlayer insulating film needs to have not only low dielectric properties but also excellent heat resistance that can withstand a thin film forming step in manufacturing a mounting substrate and post-processes such as chip connection and pinning. As a typical low dielectric organic material, a fluorine resin such as polytetrafluoroethylene is known, but in the case of this resin, heat resistance is insufficient. Polyimide is known as an organic material having high heat resistance, but the relative permittivity of conventional polyimide is about 2.95 to 3.5, which is not satisfactory in terms of low dielectric property. That is, an insulating material having both high heat resistance and low dielectric properties at the same time has not been found yet.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polyimide useful as an insulating material having both excellent heat resistance and low dielectric properties, and an aromatic diamine and a polyamic acid capable of producing the polyimide. Is to do.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, a polyimide synthesized using a specific aromatic diamine compound has high heat resistance and low dielectric properties. The present inventors have found that the present invention is excellent in both aspects, and have completed the present invention. That is, the gist of the present invention is as follows: first, the general formula (1)

[0005]

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[In the general formula (1), R ¹ and R ²
Are each independently an alkyl group having 1 to 6 carbon atoms,
To 6 halogenated alkyl groups or 1 to 6 carbon atoms
A represents a monovalent or condensed polycyclic aromatic group; a and b each independently represent an integer of 0 to 4; (Hereinafter referred to as "first invention").

The gist of the present invention is that, secondly, the general formula (2)

[0008]

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[In the general formula (2), R ¹ and R ²
Are each independently an alkyl group having 1 to 6 carbon atoms,
Represents a halogenated alkyl group of 6 to 6 or a monocyclic or condensed polycyclic aromatic group having 6 to 14 carbon atoms, and Ar represents a monocyclic or condensed polycyclic aromatic group, or A tetravalent aromatic group having 6 to 50 carbon atoms selected from non-fused polycyclic aromatic groups directly or mutually connected by a linking group, and a and b are each independently an integer of 0 to 4 . And a repeating unit represented by the formula:
Logarithmic viscosity [ηinh] (N, N-dimethylformamide solvent, 30 ° C., concentration 0.5 g / dl) is 0.1 to 4 dl / g.
(Hereinafter, referred to as “second invention”).

The gist of the present invention is that, thirdly, the general formula (3)

[0011]

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[In the general formula (3), R ¹ and R ²
Are each independently an alkyl group having 1 to 6 carbon atoms,
Represents a halogenated alkyl group of 6 to 6 or a monocyclic or condensed polycyclic aromatic group having 6 to 14 carbon atoms, and Ar represents a monocyclic or condensed polycyclic aromatic group, or A tetravalent aromatic group having 6 to 50 carbon atoms selected from non-fused polycyclic aromatic groups directly or mutually connected by a linking group, and a and b are each independently an integer of 0 to 4 . And a repeating unit represented by the formula:
Polyimide having a logarithmic viscosity [ηinh] (N, N-dimethylformamide solvent, 30 ° C., concentration 0.5 g / dl) of 0.1 to 4 dl / g (hereinafter referred to as “third invention”).

Hereinafter, the present invention will be described in detail. Aromatic diamine compound In the general formula (1) representing the aromatic diamine compound of the first invention, examples of the alkyl group having 1 to 6 carbon atoms for R ¹ and R ² include a methyl group, an ethyl group, and n-propyl. Group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group and the like.
Examples of the halogenated alkyl group 6 include a fluoromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a pentafluoroethyl group, a 3,3,3
-Trifluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, heptafluoropropyl group, chloromethyl group, bromomethyl group and the like,
Examples of the monovalent monocyclic or condensed polycyclic aromatic group having 6 to 14 carbon atoms include a phenyl group, an o-toluyl group,
m-toluyl group, p-toluyl group, 1-naphthyl group, 2
-Naphthyl group, 1-anthranyl group, 2-anthranyl group, 9-anthranyl group and the like. Among these groups, a methyl group, an ethyl group, an i-propyl group,
A t-butyl group, a trifluoromethyl group, a phenyl group and the like are preferable.

Preferred specific examples of the aromatic diamine compound of the first invention include 9,9-bis [4- (4-aminophenoxy) -3-phenylphenyl] fluorene,
9-bis [4- (3-aminophenoxy) -3-phenylphenyl] fluorene, 9,9-bis [4- (2-aminophenoxy) -3-phenylphenyl] fluorene, 9,9-bis [4- (4-amino-3-methylphenoxy) -3-phenylphenyl] fluorene, 9,9
-Bis [4- (4-amino-2-methylphenoxy)-
3-phenylphenyl] fluorene, 9,9-bis [4
-(4-amino-3-ethylphenoxy) -3-phenylphenyl] fluorene, 9,9-bis [4- (4-amino-2-ethylphenoxy) -3-phenylphenyl] fluorene, 9,9-bis [4- (4-amino-3
-I-propylphenoxy) -3-phenylphenyl]
Fluorene, 9,9-bis [4- (4-amino-2-i
-Propylphenoxy) -3-phenylphenyl] fluorene, 9,9-bis [4- (4-amino-3-t-butylphenoxy) -3-phenylphenyl] fluorene, 9,9-bis [4- (4 -Amino-2-t-butylphenoxy) -3-phenylphenyl] fluorene,
9,9-bis [4- (4-amino-3-trifluoromethylphenoxy) -3-phenylphenyl] fluorene, 9,9-bis [4- (4-amino-2-trifluoromethylphenoxy) -3-phenylphenyl] fluorene, 9,9-bis [4- (3-amino-2-methylphenoxy) -3-phenylphenyl] fluorene, 9,
9-bis [4- (3-amino-4-methylphenoxy)
-3-phenylphenyl] fluorene, 9,9-bis [4- (3-amino-5-methylphenoxy) -3-phenylphenyl] fluorene, 9,9-bis [4- (3
-Amino-6-methylphenoxy) -3-phenylphenyl] fluorene, 9,9-bis [4- (3-amino-
2-trifluoromethylphenoxy) -3-phenylphenyl] fluorene, 9,9-bis [4- (3-amino-4-trifluoromethylphenoxy) -3-phenylphenyl] fluorene, 9,9-bis [4- (3-amino-5-trifluoromethylphenoxy) -3-phenylphenyl] fluorene, 9,9-bis [4- (3-amino-6-trifluoromethylphenoxy) -3-phenylphenyl ] Fluorene, 9,9-bis [4- (2-
Amino-3-methylphenoxy) -3-phenylphenyl] fluorene, 9,9-bis [4- (2-amino-4
-Methylphenoxy) -3-phenylphenyl] fluorene, 9,9-bis [4- (2-amino-5-methylphenoxy) -3-phenylphenyl] fluorene, 9,
9-bis [4- (2-amino-6-methylphenoxy)
-3-phenylphenyl] fluorene, 9,9-bis [4- (2-amino-3-trifluoromethylphenoxy) -3-phenylphenyl] fluorene, 9,9-bis [4- (2-amino- 4-trifluoromethylphenoxy) -3-phenylphenyl] fluorene, 9,9-
Bis [4- (2-amino-5-trifluoromethylphenoxy) -3-phenylphenyl] fluorene, 9,9
-Bis [4- (2-amino-6-trifluoromethylphenoxy) -3-phenylphenyl] fluorene. Of these aromatic diamine compounds, 9,9-bis [4- (4-aminophenoxy) -3
-Phenylphenyl] fluorene, 9,9-bis [4-
(4-amino-2-methylphenoxy) -3-phenylphenyl] fluorene, 9,9-bis [4- (4-amino-2-trifluoromethylphenoxy) -3-phenylphenyl] fluorene, 9,9- Bis [4- (2-amino-4-trifluoromethylphenoxy) -3-phenylphenyl] fluorene and the like are preferred.

The aromatic diamine compound of the first invention is, for example, a bisphenol compound represented by the formula (4) and a nitrohalobenzene compound represented by the formula (5) or a formula (6). After condensation with a dinitrobenzene compound, it can be obtained by reducing the resulting aromatic dinitro compound.

[0016]

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[0017]

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[In the general formulas (5) and (6), R
Represents an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 6 carbon atoms or a monovalent or condensed polycyclic aromatic group having 6 to 14 carbon atoms, and n represents 0 to 4 It is an integer. The bisphenol compound represented by the formula (4) is, for example,
JP-A-6-228035 and Research Disclosure,
378 , P647-P650 (1995).

Preferred specific examples of the nitrohalobenzene compound represented by the general formula (5) include 4-chloronitrobenzene, 3-chloronitrobenzene, 2-chloronitrobenzene, 2-chloro-3-nitrotoluene, and 2-chloro-nitrotoluene. 4-nitrotoluene, 2-chloro-5-nitrotoluene, 2-chloro-6-nitrotoluene, 3-chloro-2-nitrotoluene, 3-chloro-4-nitrotoluene, 3-chloro-5-nitrotoluene, 3-chloro-6
-Nitrotoluene, 4-chloro-2-nitrotoluene,
4-chloro-3-nitrotoluene, 5-chloro-2-nitrotoluene, 2-chloro-3-nitrobenzotrifluoride, 2-chloro-4-nitrobenzotrifluoride, 2-chloro-5-nitrobenzotrifluoride, 2
-Chloro-6-nitrobenzotrifluoride, 3-chloro-2-nitrobenzotrifluoride, 3-chloro-4
-Nitrobenzotrifluoride, 3-chloro-5-nitrobenzotrifluoride, 3-chloro-6-nitrobenzotrifluoride, 4-chloro-2-nitrobenzotrifluoride, 4-chloro-3-nitrobenzotrifluoride, 5-chloro-2-nitrobenzotrifluoride and the like can be mentioned.

Preferred specific examples of the dinitrobenzene compound represented by the general formula (6) include 1,2-dinitrobenzene, 1,3-dinitrobenzene, 1,4-dinitrobenzene, and 4-methyl-1. , 2-Dinitrobenzene, 4-methyl-1,3-dinitrobenzene, 5-methyl-1,3-dinitrobenzene, 6-methyl-1,3-
Dinitrobenzene, 2-methyl-1,4-dinitrobenzene, 4-trifluoromethyl-1,2-dinitrobenzene, 4-trifluoromethyl-1,3-dinitrobenzene, 5-trifluoromethyl-1,3- Examples thereof include dinitrobenzene, 6-trifluoromethyl-1,3-dinitrobenzene, and 2-trifluoromethyl-1,4-dinitrobenzene.

The condensation reaction between the bisphenol compound represented by the formula (4) and the nitrohalobenzene compound represented by the general formula (5) or the dinitrobenzene compound represented by the general formula (6) is carried out by the reaction of the bisphenol compound. Of the nitrohalobenzene compound or the dinitrobenzene compound is twice or more, preferably 2 to 3 times, the molar amount of the reaction raw material in the organic solvent, usually 1 to 80% by weight, preferably 30 to 30% by weight. The reaction is carried out at a temperature of 50 to 250 ° C, preferably 50 to 180 ° C, for 0.5 to 24 hours in the presence of a basic compound.
Preferred specific examples of the organic solvent include aromatic hydrocarbons such as benzene, toluene and xylene; ketones such as acetone and methyl ethyl ketone; halogenated hydrocarbons such as 1,2-dichloroethane and chlorobenzene;
-Dimethoxyethane, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether,
Ethers such as diethylene glycol diethyl ether, tetrahydrofuran, 1,3-dioxane, 1,4-dioxane, N, N-dimethylformamide, N, N-
Aprotic polar solvents such as dimethylacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, and sulfolane can be exemplified. These organic solvents are
They can be used alone or in combination of two or more. Examples of the basic compound include an alkali metal hydroxide, an alkali metal bicarbonate, an alkali metal carbonate, and an alkali metal alkoxide compound. These basic compounds can be used alone or in combination of two or more. The amount of the basic compound used is usually at least 2 moles, preferably 2 to 3 moles, per mole of the bisphenol compound. After the condensation reaction, by-product salts are removed by filtration, and then the reaction solution is added to a poor solvent to coagulate the resulting compound. Thereafter, by filtering or distilling off the organic solvent, a predetermined aromatic dinitro compound can be obtained. The obtained aromatic dinitro compound is used as it is or after further purification by recrystallization,
Used for reduction reaction.

The reduction method is not particularly limited, and for example, a known method for reducing a nitro group to an amino group can be used. In the reduction reaction of the aromatic dinitro compound in the first invention, for example, a hydrogen catalyst such as a metal catalyst such as nickel, palladium, and platinum, a supported catalyst in which these metals are supported on an appropriate carrier, and a Raney catalyst such as nickel and copper are used. In a reaction solvent inert to the reaction in the presence of an oxidation catalyst, at a temperature of 20 to 200 ° C and a pressure of normal pressure to 50 kgf
/ Cm ² and reducing the aromatic dinitro compound to an aromatic diamino compound using hydrogen.
Examples of the reaction solvent include aliphatic alcohols such as methanol, ethanol, and isopropanol; ethylene glycol monoalkyl ethers such as methyl cellosolve and ethyl cellosolve; aromatic hydrocarbons such as toluene, benzene, and xylene; tetrahydrofuran, dioxane; Examples thereof include ethers such as dipropyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, and diethylene glycol diethyl ether. These reaction solvents are
They can be used alone or in combination of two or more. After the reduction reaction, the hydrogenation catalyst is removed from the reaction mixture by filtration or the like, and then the reaction solution is added to a poor solvent to coagulate the resulting compound. Then, an aromatic diamine compound can be obtained by filtration or distilling off the reaction solvent. The obtained aromatic diamine compound is used as it is or after being purified by recrystallization or the like to produce the polyamic acid in the second invention.

The polyamic acid of the second invention polyamic acid, an aromatic diamine compound of the first invention, a tetracarboxylic dianhydride represented by the following general formula (7), to polycondensation in an organic solvent Can be manufactured.

[0024]

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(Where Ar is A in the general formula (2))
Synonymous with r. In producing the polyamic acid of the second invention, the aromatic diamine compound of the first invention can be used alone or in combination of two or more. Preferred specific examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone. Tetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4
4'-biphenyltetracarboxylic dianhydride, 2,
2 ', 3,3'-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane Dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (2,3-dicarboxyphenyl) ether dianhydride, bis (3,4-
Dicarboxyphenyl) sulfone dianhydride, bis (2,
3-dicarboxyphenyl) sulfone dianhydride, 2,2
-Bis (3,4-dicarboxyphenyl) -1,1,
1,3,3,3-hexafluoropropane dianhydride,
2,2-bis (2,3-dicarboxyphenyl) -1,
1,1,3,3,3-hexafluoropropane dianhydride, 9,9-bis [4- (3,4-dicarboxyphenoxy) phenyl] fluorene dianhydride, 9,9-bis [4- ( 2,3-dicarboxyphenoxy) phenyl]
Fluorene dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride An anhydride and the like can be mentioned. These tetracarboxylic dianhydrides can be used alone or in combination of two or more. When producing the polyamic acid of the second invention, a diamine compound other than the aromatic diamine compound of the first invention can be used within a range that does not substantially impair the properties of the polyimide of the third invention. . In this case, the amount of the diamine compound used other than the aromatic diamine compound of the first invention is preferably 50 mol% or less, more preferably 30 mol%, of the wholly aromatic diamine compound used for producing the polyamic acid of the second invention.
Mol% or less.

The polycondensation reaction between the aromatic diamine compound of the first invention and the tetracarboxylic dianhydride represented by the general formula (7) is usually carried out in an organic solvent. Examples of the organic solvent include N, N-dimethylformamide,
N, N-dimethylmethoxyacetamide, N, N-diethylmethoxyacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 1,2-dimethoxyethane, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, tetrahydrofuran, 1,3
-Dioxane, 1,4-dioxane, pyridine, picoline, dimethyl sulfoxide, dimethyl sulfone, tetramethyl urea and the like. These organic solvents can be used alone or in combination of two or more. The concentration of the reaction raw material in the polycondensation reaction is usually 2 to 50% by weight, preferably 5 to 30% by weight, and the reaction temperature is usually 60 ° C or lower, preferably 50 ° C.
It is as follows. The reaction pressure is not particularly limited, and the reaction can be usually carried out at normal pressure. In addition, the reaction time is usually 0.1.
5 to 24 hours. By such a polycondensation reaction, a polyamic acid containing a repeating unit represented by the general formula (2) can be obtained. The polyamic acid of the second invention contains the repeating unit represented by the general formula (2). In the polyamic acid, the polyamic acid has the general formula (2)
And at least ^one of R ¹ , R ² , a, b or Ar may contain two or more kinds of repeating units,
In this case, two or more kinds of repeating units can be bonded to the molecular chain of the polyamic acid in a random or block manner. Logarithmic viscosity of the polyamic acid of the second invention [ηin
h] (N, N-dimethylformamide solvent, 30 ° C., concentration 0.5 g / dl) is 0.1 to 4 dl / g, preferably 0.3 to 2 dl / g. The polyamic acid of the second invention may be partially imidized as long as the imidation ratio does not exceed 50%.

Polyimide The polyimide of the third invention can be produced by dehydrating and cyclizing a polyamic acid containing a repeating unit represented by the above general formula (2). At the time of the imidization, a heat imidation method or a chemical imidization method can be employed. As the thermal imidization method, for example, a method in which a polyamic acid solution is cast on a substrate having a smooth surface such as glass or metal and heated, or a method in which the polyamic acid solution is directly heated is applied. As the solvent for the polyamic acid solution in these methods, for example, the same organic solvents as those used for producing polyamic acid can be mentioned. In the above-mentioned heat imidization method, a film-like polyimide can be obtained by heating a thin film formed by casting a polyamic acid solution on a substrate under normal pressure or reduced pressure. The heating temperature in this case is usually 100 to 400.
° C, preferably 150 to 350 ° C, and it is preferable to gradually increase the temperature during the reaction. In the above-mentioned heat imidization method, the polyimide is obtained as a powder or a solution by heating the polyamic acid solution. The heating temperature in this case is usually 80 to 300 ° C, preferably 100 to 250 ° C. In the heat imidization method, a component which azeotropes with water and which can be easily separated from water especially outside the reaction system, for example, benzene, toluene, xylene, etc. May be present as a dehydrating agent. Further, in the heating imidization method, in order to promote dehydration ring closure,
Tertiary amines, for example, aliphatic tertiary amines such as trimethylamine, triethylamine, tri-n-propylamine, tri-i-propylamine, tri-n-butylamine; N, N-dimethylaniline, N, N A catalyst such as aromatic tertiary amines such as diethylaniline; heterocyclic tertiary amines such as pyridine, quinoline and isoquinoline, for example, 10 to 10 parts by weight of polyamic acid;
400 parts by weight can also be used.

Next, as the chemical imidization method, for example, a method in which a ring closing agent for dehydrating and cyclizing a polyamic acid is used to form a polyimide in a solution state is employed, and the polyimide is obtained as a powder or a solution. Examples of the solvent used in this method include, for example, the same organic solvents as those used in the production of polyamic acid.
Examples of the ring closing agent used in the chemical imidization method include acid anhydrides such as acetic anhydride, propionic anhydride, and butyric anhydride. These ring-closing agents can be used alone or as a mixture of two or more kinds. The amount of the ring-closing agent is usually 2 to 100 mol per mol of the repeating unit represented by the general formula (2), Preferably 2 to 50
Is a mole. The reaction temperature in the chemical imidation method of
Usually, it is 0 to 200 ° C. In the chemical imidization method, a tertiary amine can be used as a catalyst as in the case of the thermal imidization method. When the polyimide is obtained as a powder by the heat imidization method or the chemical imidization method, the polyimide powder can be separated and recovered from the medium by an appropriate method such as filtration, spray drying, or steam distillation. The imidation ratio of the polyimide of the third invention is
It is 50% or more, preferably 90% or more.

The logarithmic viscosity of the polyimide of the third invention [ηinh
] (N, N-dimethylformamide solvent, 30 ° C, concentration 0.5 g / dl) is 0.1 to 4 dl / g, preferably 0.3 to 2 dl / g. The polyimide of the third invention has a low dielectric constant and excellent heat resistance, and its relative dielectric constant (1 MHz)
Is usually 3.0 or less, preferably 2.9 or less,
The 5% weight loss temperature (in a nitrogen atmosphere) is usually 400 ° C.
The temperature is preferably at least 500 ° C. Moreover, the polyimide of the third invention has excellent solubility in various solvents. Therefore, the polyimide of the third invention is particularly LS
It can be used very suitably as an interlayer insulating film in I, and is also useful as a general insulating material, a heat-resistant material, and the like. When forming the interlayer insulating film from the polyimide of the third invention, a varnish or paste of the polyamic acid, which is a precursor thereof, a film of the polyimide, and the like are used. To illustrate the method of forming the interlayer insulating film,
It is as follows. (A) A varnish of a polyamic acid is cast between layers of the device, and an excess solvent in the varnish is removed under heating and / or reduced pressure to form a thin film of the polyamic acid. A method in which the polyamic acid is dehydrated and ring-closed under a normal pressure or under pressure to imidize the polyamic acid. (B) A film-like polyimide is disposed between layers of the device, for example, at 100 to 400 ° C under normal pressure or under pressure. How to crimp. As a method for obtaining polyimide in the form of a film, for example, (c) casting a varnish of polyamic acid on a substrate that has been subjected to a release treatment in advance, for example, a substrate of glass, Teflon, polyester, etc., and gradually heating (D) polyimide powder is formed into a film by an appropriate method such as press molding, injection molding, or the like. Specific examples when the polyimide of the third invention is used as an interlayer insulating film include interlayer insulating films for semiconductor multilayer wiring, interlayer insulating films for rigid boards and flexographic printing plates of multilayer printed boards, packages and MCM boards, and the like. An interlayer insulating film or the like can be given. Further, a varnish of the polyamic acid of the second invention or the varnish of the polyimide of the third invention is cast on a substrate, and then heated and dried to obtain a polyimide dry film having a thickness of several tens to several hundreds of μm. it can. Such a dry film can be used for other purposes, for example, as a passivation film (stress buffer film) for semiconductors, an α-ray blocking film, a coverlay film for a flexographic printing plate, an overcoat for a flexographic printing plate, and the like. Other applications of the polyimide of the third invention other than those described above include an adhesive for die bonding, an adhesive tape for lead-on-chip (LOC), a tape for fixing a lead frame, an adhesive film for a multilayer lead frame, and the like. .

[0030]

BEST MODE FOR CARRYING OUT THE INVENTION

The embodiments of the present invention will be described below more specifically with reference to examples of the present invention. However, the present invention
It is not limited to these examples. Example 1 Production of Aromatic Diamine Compound In a vessel equipped with a stirrer and a reflux condenser, 9,9-bis (4
-Hydroxy-3-phenylphenyl] fluorene 3
0.16 g (0.06 mol), 22.06 g (0.14 mol) of p-chloronitrobenzene, anhydrous potassium carbonate 2
3.22 g (0.168 mol) and 120 ml of N, N-dimethylformamide were charged and refluxed at 160 ° C. for 6 hours. Thereafter, the reaction solution was cooled, and the obtained reaction solution was added to 240 ml of a mixed solution of water and ethanol 1: 1 (volume ratio) to precipitate crystals, followed by filtration. The obtained crude crystals were recrystallized using N, N-dimethylformamide, filtered, dried and purified 9,9-bis [4- (4-nitrophenoxy) -3-.
27.75 g of [phenylphenyl] fluorene were obtained. Next, in a vessel equipped with a stirrer, 22.34 g (0.03 mol) of purified 9,9-bis [4- (4-nitrophenoxy) -3-phenylphenyl] fluorene, a palladium catalyst supported on carbon black (Palladium content 5% by weight) 0.2 g of Nippon Engelhardt Co., Ltd. and 180 ml of diethylene glycol ethyl methyl ether were charged and reacted at 70 ° C. for 16 hours with vigorous stirring. After cooling, the reaction solution was filtered to remove the catalyst, added to 200 ml of a 1: 1 (volume ratio) mixed solution of water and ethanol, and the precipitated crystals were separated by filtration, dried, and dried. , 9-Bis [4- (4-aminophenoxy) -3-phenylphenyl] fluorene 17.
2 g were obtained. Infrared absorption spectrum of the aromatic diamine compound (IR), as shown in FIG. 1, and absorption at a wavenumber of 3448cm ^-1 and a wavenumber of 3,365 cm ^-1 corresponding to the N-H bond, corresponding to the C-O-C bond Wave number 1230 cm ^-1
And showed absorption.

Example 2 Production of Aromatic Diamine Compound In a vessel equipped with a stirrer and a reflux condenser, 9,9-bis (4
-Hydroxy-3-phenylphenyl] fluorene 10
0.52 g (0.2 mol), 99.24 g (0.44 mol) of 2-chloro-5-nitrobenzotrifluoride, 72.97 g (0.528 mol) of anhydrous potassium carbonate and N, N-dimethylformamide 400 Milliliter was charged and refluxed at 160 ° C. for 2 hours. Thereafter, the reaction solution was filtered to remove salts, and then the mixture of water and ethanol was used.
1 (volume ratio) is added to 100 ml of the mixed solution,
The precipitated crystals were separated by filtration, dried and purified 9,9-
Bis [4- (4-nitro-2-trifluoromethylphenoxy) -3-phenylphenyl] fluorene 146.
8 g were obtained. Next, 60.0 g (0.068 mol) of purified 9,9-bis [4- (4-nitro-2-trifluoromethylphenoxy) -3-phenylphenyl] fluorene and carbon dioxide were placed in a vessel equipped with a stirrer. Palladium catalyst supported on black (palladium content 5% by weight)
1.0 g (manufactured by Nippon Engelhardt Co., Ltd.) and 400 ml of diethylene glycol ethyl methyl ether were charged and reacted at 70 ° C. for 16 hours with vigorous stirring.
After cooling and filtering the reaction solution to remove the catalyst, a 1: 1 (volume ratio) mixed solution of water and ethanol 20
Added in 00 ml, and the precipitated crystals were filtered off.
After drying, 9,9-bis [4- (4-amino-2-trifluoromethylphenoxy) -3-phenylphenyl]
53.2 g of fluorene were obtained. As shown in FIG. 2, the infrared absorption spectrum (IR) of this aromatic diamine compound has a wave number of 3364 cm ^-1 and a wave number of 3 corresponding to the NH bond.
Absorption at 406 cm ^-1 and a wave number of 3383 cm ^-1 and C
And absorption at a wavenumber of 1228 cm ^-1 corresponding to the -OC bond.

Example 3 Production of Polyamic Acid Nitrogen gas was flowed into a vessel equipped with a stirrer, a reflux condenser and a nitrogen inlet tube, and N, N-dimethylformamide was 25.58.
g, and 9,9-bis [4- (4-aminophenoxy) -3-phenylphenyl] fluorene 3.4
24 g (5 mmol) were added and dissolved sufficiently. Thereafter, 1.091 g (5 mmol) of pyromellitic dianhydride was added, and the mixture was stirred at room temperature for 5 hours to obtain a polyamic acid solution. Logarithmic viscosity [ηinh] of this polyamic acid (N, N-dimethylformamide solvent, 30
° C, concentration 0.5 g / dl) was 0.92 dl / g. Infrared absorption spectrum (IR) of this polyamic acid
Is shown in FIG. Production of Polyimide (i) The solution of the polyamic acid was applied on a SUS304 substrate by spin coating,
While sequentially heating to 0 ° C., 200 ° C., 250 ° C., and 300 ° C., heating was performed at each temperature for 20 minutes to form a polyimide film. Thereafter, a gold electrode was formed on the polyimide film by mask evaporation to obtain a sample for relative dielectric constant measurement. Using this sample, the relative dielectric constant (ε) was measured as follows. As a result, ε = 2.82, which was a sufficiently low value. <Measurement of relative dielectric constant (ε)> 1 MH of polyimide film
The capacitance at z was measured using an LCR meter 4284A manufactured by Yokogawa Hewlett-Packard Co., Ltd., and the relative dielectric constant (ε) was determined by the following equation. Here, C is the capacitance, d is the thickness of the sample, ε ₀ is the dielectric constant in vacuum, and S is the area of the upper electrode. (Ii) After the solution of the polyamic acid is cast on a glass plate, the temperature is 80 ° C., 140 ° C., 200 ° C., 250 ° C.
While the temperature was sequentially raised to 300 ° C. and 300 ° C., heating was performed at each temperature for 20 minutes to form a polyimide film, and the glass transition temperature (Tg) and the 5% weight loss temperature (Td5) were measured. As a result, Tg was 293 ° C and Td5 was 544 ° C, and it was confirmed that the composition had high heat resistance. FIG. 4 shows the infrared absorption spectrum (IR) of this polyimide. <Measurement of glass transition temperature (Tg)> Differential scanning calorimeter (DS
According to C), the measurement was performed at a heating temperature of 20 ° C./min in a nitrogen atmosphere. <Measurement of 5% Weight Loss Temperature (Td5)> Using a thermobalance, heating was performed in nitrogen at a heating rate of 10 ° C./min, and the temperature at which 5% weight loss was observed was measured.

Examples 4 to 9 The procedure of Example 3 was repeated except that the aromatic diamine compound and the tetracarboxylic dianhydride were changed as shown in Table 1, and then the synthesis of a polyamic acid and the production of a polyimide film were performed. The logarithmic viscosity [ηinh] of each polyamic acid, the relative dielectric constant (ε), the glass transition temperature (Tg), and the 5% weight loss temperature (Td5) of each polyimide film were measured in the same manner as in Example 3. The results are shown in Table 1, and the infrared absorption spectra (IR) of the polyamic acids and polyimides of Examples 6 to 9 are shown in FIGS.

Comparative Example 1 Instead of 3.424 g (5 mmol) of 9,9-bis [4- (4-aminophenoxy) -3-phenylphenyl] fluorene, 9,9-bis [4- (4-amino) A polyimide film was formed in the same manner as in Example 4 except that 2.663 g (5 mmol) of phenoxy) phenyl] fluorene was used, and the relative dielectric constant (ε), glass transition temperature (Tg), and 5% weight were obtained. The decrease temperature (Td5) was measured.
As a result, ε = 2.95, Tg = 302 ° C., Td5 = 56
The temperature was 7 ° C. and the heat resistance was good, but the relative dielectric constant was high and it was not satisfactory as an interlayer insulating film of LSI.

[0035]

[Table 1]

[0036]

Industrial Applicability The polyimide of the present invention has a low dielectric constant, excellent heat resistance, and excellent solubility in various solvents, and can be extremely suitably used as an interlayer insulating film especially for LSI. Further, the aromatic diamine compound and the polyamic acid of the present invention are useful as starting materials and intermediates for the polyimide.

[Brief description of the drawings]

FIG. 1 is a diagram showing an IR of an aromatic diamine compound obtained in Example 1.

FIG. 2 is a graph showing IR of an aromatic diamine compound obtained in Example 2.

FIG. 3 IR of polyamic acid obtained according to Example 3
FIG.

FIG. 4 is a view showing an IR of the polyimide obtained in Example 3.

FIG. 5 shows IR of polyamic acid obtained in Example 6.
FIG.

FIG. 6 is a view showing an IR of the polyimide obtained in Example 6.

FIG. 7: IR of polyamic acid obtained in Example 7
FIG.

FIG. 8 is a diagram showing an IR of the polyimide obtained in Example 7.

FIG. 9 shows IR of polyamic acid obtained in Example 8.
FIG.

FIG. 10 is a diagram showing an IR of a polyimide obtained in Example 8.

FIG. 11 shows I of the polyamic acid obtained in Example 9.
It is a figure showing R.

FIG. 12 is a diagram showing an IR of the polyimide obtained in Example 9.

Embedded image

Claims (3)

[Claims] 1. A compound of the general formula (1) [In the general formula (1), R ¹ and R ² are each independently an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 6 carbon atoms or a monovalent monocyclic having 6 to 14 carbon atoms or It represents a condensed polycyclic aromatic group, and a and b are each independently an integer of 0 to 4. ] The aromatic diamine compound represented by these. 2. A compound of the general formula (2) [In the general formula (2), R ¹ and R ² are each independently an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 6 carbon atoms or a monocyclic or condensed polycyclic ring having 6 to 14 carbon atoms. Represents an aromatic group represented by the formula: Ar is a carbon selected from a monocyclic or condensed polycyclic aromatic group and a non-condensed polycyclic aromatic group in which these aromatic groups are directly or mutually connected by a linking group; Represents a tetravalent aromatic group of the number 6 to 50,
a and b are each independently an integer of 0 to 4; ] And a logarithmic viscosity [ηin
h] A polyamic acid having a concentration of 0.1 to 4 dl / g (N, N-dimethylformamide solvent, 30 ° C., concentration 0.5 g / dl). 3. A compound of the general formula (3) [In the general formula (3), R ¹ and R ² are each independently an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 6 carbon atoms or a monocyclic or condensed polycyclic ring having 6 to 14 carbon atoms. Represents an aromatic group represented by the formula: Ar is a carbon selected from a monocyclic or condensed polycyclic aromatic group and a non-condensed polycyclic aromatic group in which these aromatic groups are directly or mutually connected by a linking group; Represents a tetravalent aromatic group of the number 6 to 50,
a and b are each independently an integer of 0 to 4; ] And a logarithmic viscosity [ηin
h] Polyimide having a (N, N-dimethylformamide solvent, 30 ° C., concentration 0.5 g / dl) of 0.1 to 4.