JP2002030115A - Poly(alicyclic acid anhydride) - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a poly(alicyclic acid anhydride) being a precursor in the production of a poly(alicyclic imide). SOLUTION: The poly(alicyclic acid anhydride) composition is a compound represented by formula I (wherein l is an integer of 1 or 2; m is an integer of 3-30,000; R1 to R4, which may be the same as or different from each other, are each H, F, CF3, a 1-10C alkyl, or a 6-20C aryl; and R5 and R6 are each H or a 1-10C alkyl).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a polyalicyclic anhydride which is a precursor suitable for producing a polyalicyclic imide composition useful for a low dielectric constant insulating material.

[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, so that not only power consumption increases, but also signal propagation and delay time increase. This is a major factor in reducing the signal speed of the device. 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. A fluorine resin such as polytetrafluoroethylene is known as a typical low dielectric organic material, but in the case of this resin, heat resistance is insufficient. Also, heat-resistant organic materials are known, but conventional polyimides, epoxy resins,
The relative dielectric constant of a silicone resin or the like is about 3.0 to 4.0, which is not satisfactory in terms of low dielectric properties. In addition, the conventional polyimide has a large anisotropy of the dielectric constant, and has a problem that the relative dielectric constant is different between the direction between the wirings and the direction between the wiring layers. On the other hand, a polyalicyclic imide composition is effective as an insulating material having both low dielectric properties, heat resistance, low refractive index, and isotropic dielectric constant (low birefringence). The imide composition is obtained by vinyl addition polymerization of one or several corresponding unsaturated group-containing alicyclic imide compounds in the presence of a metal catalyst. However, copolymers using several kinds of unsaturated group-containing alicyclic imide compounds have to synthesize unsaturated monomer-containing alicyclic imide compounds, which are monomers, respectively. In terms of application to the formula imide composition, there is a problem that the synthesis takes time and the like.

[0003]

SUMMARY OF THE INVENTION The present invention is useful for producing a polyalicyclic imide composition excellent in low dielectric property, heat resistance, low refractive index and isotropic dielectric constant (low birefringence). It is an object of the present invention to provide a polyalicyclic acid anhydride which is a suitable precursor.

[0004]

According to the present invention, there is provided a compound represented by the general formula (1):
It is a polyalicyclic acid anhydride characterized by being represented by these.

[0005]

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(In the general formula (1), l is 1-2, m
Represents an integer of 3 to 30,000. R ^{1 to} R ⁴ are H, F, C
F ₃ represents any one of an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 20 carbon atoms, which may be the same or different. R ^5, R ⁶ represents H, or an alkyl group having 1 to 10 carbon atoms. )

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The polyalicyclic acid anhydride represented by the general formula (1) in the present invention is obtained by converting the alicyclic acid anhydride compound having an unsaturated group represented by the general formula (2) into It is obtained by vinyl addition polymerization in a polymerization solvent under a metal catalyst.

[0008]

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In the general formula (2), 1 represents an integer of 1 to 2. R ^{1 to} R ⁴ represent any of H, F, CF ₃ , an alkyl group having 1 to 10 carbon atoms, and an aryl group having 6 to 20 carbon atoms, and may be the same or different. R ^5, R ⁶ represents H, or an alkyl group having 1 to 10 carbon atoms.

Specific examples of the unsaturated group-containing alicyclic acid anhydride used include bicyclo [2,2,1] hept-5-
Ene-2,3-dicarboxylic anhydride, 2,3-dimethyl-bicyclo [2,2,1] hept-5-ene-2,3-
Dicarboxylic anhydride, 7-fluoro-bicyclo [2,
2,1] hept-5-ene-2,3-dicarboxylic anhydride, 7,7-difluoro-bicyclo [2,2,1] hept-5-ene-2,3-dicarboxylic anhydride, 5, 6-
Difluoro-bicyclo [2,2,1] hept-5-ene-2,3-dicarboxylic anhydride, 5,6,7,7, -tetrafluoro-bicyclo [2,2,1] hept-5-ene -2,3-dicarboxylic anhydride, 7-trifluoromethyl-bicyclo [2,2,1] hept-5-ene-2,
3-dicarboxylic anhydride, 7,7-bis (trifluoromethyl) -bicyclo [2,2,1] hept-5-ene-
2,3-dicarboxylic anhydride, 5,6-bis (trifluoromethyl) -bicyclo [2,2,1] hept-5-ene-2,3-dicarboxylic anhydride, 5,6,7,7 , −
Tetrakis (trifluoromethyl) -bicyclo [2,
2,1] hept-5-ene-2,3-dicarboxylic anhydride, 7-methyl-bicyclo [2,2,1] hept-5-
Ene-2,3-dicarboxylic anhydride, 7,7-dimethyl-bicyclo [2,2,1] hept-5-ene-2,3-
Dicarboxylic anhydride, 5,6-dimethyl-bicyclo [2,2,1] hept-5-ene-2,3-dicarboxylic anhydride, 5,6,7,7-tetramethyl-bicyclo [2,2 , 1] Hept-5-ene-2,3-dicarboxylic anhydride, 7-ethyl-bicyclo [2,2,1] hept-5-ene-2,3-dicarboxylic anhydride, 7,7-diethyl -Bicyclo [2,2,1] hept-5-ene-
2,3-dicarboxylic anhydride, 5,6-diethyl-bicyclo [2,2,1] hept-5-ene-2,3-dicarboxylic anhydride, 5,6,7,7-tetraethyl-bicyclo [ 2,2,1] hept-5-ene-2,3-dicarboxylic anhydride, 7-cyclohexyl-bicyclo [2,2,
1] hept-5-ene-2,3-dicarboxylic anhydride,
7,7-dicyclohexyl-bicyclo [2,2,1] hept-5-ene-2,3-dicarboxylic anhydride, 7-phenyl-bicyclo [2,2,1] hept-5-ene-
2,3-dicarboxylic anhydride, 7,7-diphenyl-bicyclo [2,2,1] hept-5-ene-2,3-dicarboxylic anhydride, 7-methyl-7-phenyl-bicyclo [2, 2,1] hept-5-ene-2,3-dicarboxylic anhydride, 5,6-difluoro-7,7-diphenyl-
Bicyclo [2,2,1] hept-5-ene-2,3-dicarboxylic anhydride, 5,6-dimethyl-7,7-diphenyl-bicyclo [2,2,1] hept-5-ene-2 ,
3-dicarboxylic anhydride, 5,6-bis (trifluoromethyl) -7,7-diphenyl-bicyclo [2,2
1] hept-5-ene-2,3-dicarboxylic anhydride,
Bicyclo [2,2,2] oct-5-ene-2,3-dicarboxylic anhydride, bicyclo [2,2,2] oct-5
-Ene-2,3-dicarboxylic anhydride, 7,8-difluoro-bicyclo [2,2,2] oct-5-ene-2,
3-dicarboxylic anhydride, 7,7,8,8-tetrafluoro-bicyclo [2,2,2] oct-5-ene-2,
3-dicarboxylic anhydride, 5,6-difluoro-bicyclo [2,2,2] oct-5-ene-2,3-dicarboxylic anhydride, 5,6,7,7,8,8-hexafluoro -Bicyclo [2,2,2] oct-5-ene-2,3-
Dicarboxylic anhydride, 7,8-bis (trifluoromethyl) -bicyclo [2,2,2] oct-5-ene-2,
3-dicarboxylic anhydride, 7,7,8,8-tetrakis (trifluoromethyl) -bicyclo [2,2,2] oct-5-ene-2,3-dicarboxylic anhydride, 5,6-
Bis (trifluoromethyl) -bicyclo [2,2,2]
Oct-5-ene-2,3-dicarboxylic anhydride, 5,
6,7,7,8,8-hexakis (trifluoromethyl) -bicyclo [2,2,2] oct-5-ene-2,
3-dicarboxylic anhydride, 7,8-dimethyl-bicyclo [2,2,2] oct-5-ene-2,3-dicarboxylic anhydride, 7,7,8,8-tetramethyl-bicyclo [2 , 2,2] oct-5-ene-2,3-dicarboxylic anhydride, 5,6-dimethyl-bicyclo [2,2,2]
Oct-5-ene-2,3-dicarboxylic anhydride, 5,
6,7,7,8,8-Hexamethyl-bicyclo [2,
2,2] oct-5-ene-2,3-dicarboxylic anhydride, 7,8-diethyl-bicyclo [2,2,2] oct-5-ene-2,3-dicarboxylic anhydride, 7, 7,
8,8-tetraethyl-bicyclo [2,2,2] oct-5-ene-2,3-dicarboxylic anhydride, 5,6-diethyl-bicyclo [2,2,2] oct-5-ene-
2,3-dicarboxylic anhydride, 5,6,7,7,8,8
-Hexaethyl-bicyclo [2,2,2] oct-5-
Ene-2,3-dicarboxylic anhydride, 7,8-dicyclohexyl-bicyclo [2,2,2] oct-5-ene-
2,3-dicarboxylic anhydride, 7,8-diphenyl-bicyclo [2,2,2] oct-5-ene-2,3-dicarboxylic anhydride, 5,6-difluoro-7,8-diphenyl- Bicyclo [2,2,2] oct-5-ene-2,
3-dicarboxylic anhydride, 5,6-dimethyl-7,8-
Diphenyl-bicyclo [2,2,2] oct-5-ene-2,3-dicarboxylic anhydride, 5,6-bis (trifluoromethyl) -7,8-diphenyl-bicyclo [2
2,2] oct-5-ene-2,3-dicarboxylic anhydride, and the like, but are not limited thereto. As the unsaturated group-containing alicyclic acid anhydride to be used, the exo-form of the configuration of the acid anhydride part is an endo-form, so that the polymerization of the unsaturated group-containing alicyclic acid anhydride is performed. It is preferable in that it has high reactivity.

The vinyl addition polymerization of the unsaturated group-containing alicyclic acid anhydride is carried out using a metal catalyst. The reaction temperature is preferably from 0 to 250 ° C, more preferably from 20 ° C to
150 ° C. The reaction pressure is not particularly limited, and the reaction can be usually carried out at normal pressure. The reaction time is preferably 0.5 to 120 hours, more preferably 0.5 to 120 hours.
~ 48 hours.

Preferred examples of the polymerization solvent include aromatic hydrocarbons such as benzene, toluene and xylene; ketones such as acetone, methyl ethyl ketone, cyclohexanone and heptanone; and halogenated compounds such as 1,2-dichloroethane, chloroform and chlorobenzene. Hydrocarbons, 1,
Ethers such as 2-dimethoxyethane, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, tetrahydrofuran, 1,3-dioxane, and 1,4-dioxane; N, N-dimethylformamide;
N-dimethylacetamide, dimethylsulfoxide, N
And aprotic polar solvents such as -methyl-2-pyrrolidone and sulfolane. These polymerization solvents can be used alone or in combination of two or more.

The metal catalyst preferably used in the present invention is
Usually, it is a Group 4 or Group 10 transition metal catalyst, and specific examples thereof include Cp ₂ ZrCl ₂ / methylaluminoquinosan (MAO), Cp ₂ ZrCl ₂ / methylisobutylaluminoxane, P
dCl ₃ / MAO, Ni (acac) ₂ / MAO, Ni (acac) ₂ / EtAlCl ₂ , Ni (aca
_{c) 2 · 2H 2 O /} EtAlCl 2, Ni (acac) 2 / TiCl 4, Ni (acac) 2 / BF 3 · E
t ₂ O, NiCl ₂ (PPh ₃ ) ₂ / AlCl ₃ , Pd (acac) ₂ / EtAlCl ₂ , PdCl
₂ (C ₆ H ₅ CN) ₂ / EtAlCl ₂ , PdCl ₂ (C ₆ H ₅ CN) ₂ / TiCl ₄ , PdCl ₂ (C _{6
H 5 CN) 2 / BF 3} · Et 2 O in the combined catalyst system, [(η ³ -allyl) P
_{dX] (X = BF 4,} SbF 6, AsF 6, PF 6, CF 3 SO 3 -) allyl Pd represented by
Ion complex, CpTiCl _3, Hafuchitanosen having cyclopentadienyl group an ether group CpTiCl _3, Hafuchitanosen having an ester group to the cyclopentadienyl group of CpTiCl _3, but can be given not limited thereto. The concentration of the catalyst is preferably from 0.01 to 10 mol%, more preferably from 0.1 to 5 mol%, based on the reaction raw materials. The reaction is preferably performed under an inert gas in order to suppress the deactivation of the catalyst. The unsaturated group-containing alicyclic acid anhydride of the present invention may be copolymerized with another norbornene-based compound.

By such a polymerization reaction, a polyalicyclic acid anhydride containing a repeating unit represented by the general formula (1) can be obtained.

The weight average molecular weight of the polyalicyclic acid anhydride of the present invention is preferably from 500 to 5,000,000, and from the viewpoint of mechanical properties, solvent resistance and good coating properties of the polymer film.
More preferably, it is 00 to 1,000,000.

By reacting the polyalicyclic acid anhydride obtained in the present invention with the aromatic amine compound represented by the general formula (3), a polyalicyclic imide useful as a low dielectric constant interlayer insulating material is obtained. Can be obtained.

The reaction between the polyalicyclic acid anhydride and the aromatic amine compound represented by the general formula (3) is carried out in an organic solvent at a reaction temperature of 20 ° C to 200 ° C, preferably 50 ° C to 150 ° C.
For 0.5 to 24 hours.

[0018]

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(In the general formula (3), n, o, and p are 0
Is an integer satisfying n + o ≧ 1. X
Is a direct bond, or O, S, CH ₂ , CO, SO, SO ₂
Is shown. R ⁷ and R ⁸ are F, CF ₃ , OCF ₃ , C 1 to C 1
0 represents an alkyl group or an aryl group having 6 to 20 carbon atoms, which may be the same or different. ) Further, the formula of R ^7, R ⁸ is F, CF _3, OCF _3, alkyl group having 1 to 10 carbon atoms, are shown or aryl group having 6 to 20 carbon atoms, R ^7, R It is more preferable that at least one of ⁸ is CF ₃ from the viewpoint of lowering the dielectric constant.

[0020]

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Preferred examples of the solvent used in this reaction include aromatic hydrocarbons such as benzene, toluene and xylene, ketones such as acetone, methyl ethyl ketone, cyclohexanone and heptanone, 1,2-dichloroethane, chloroform and chlorobenzene. Halogenated hydrocarbons, 1,2-dimethoxyethane, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, tetrahydrofuran, 1,3-dioxane, 1,4
Ethers such as dioxane, aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone and sulfolane, and protic polar solvents such as acetic acid. Can be mentioned. Also, these organic solvents,
They can be used alone or in combination of two or more.

Specific examples of the aromatic amine compound used include 2-trifluoromethylaniline, 3-trifluoromethylaniline, 4-trifluoromethylaniline, 2,3-bis (trifluoromethyl) aniline,
2,4-bis (trifluoromethyl) aniline, 2,5
-Bis (trifluoromethyl) aniline, 2,6-bis (trifluoromethyl) aniline, 3,4-bis (trifluoromethyl) aniline, 3,5-bis (trifluoromethyl) aniline, 2,4,6 -Tris (trifluoromethyl) aniline, 2,3,4,5,6-pentakis (trifluoromethyl) aniline, 2-fluoro-3-
Trifluoroaniline, 2-fluoro-4-trifluoroaniline, 2-fluoro-5-trifluoroaniline, 3-fluoro-4-trifluoroaniline, 3-fluoro-5-trifluoroaniline, 2-methyl-3-
Trifluoroaniline, 2-methyl-4-trifluoroaniline, 2-methyl-5-trifluoroaniline, 3
-Methyl-4-trifluoroaniline, 3-methyl-5
-Trifluoroaniline, 2-phenyl-3-trifluoroaniline, 2-phenyl-4-trifluoroaniline, 2-phenyl-5-trifluoroaniline, 3-phenyl-4-trifluoroaniline, 3-phenyl-5
-Trifluoroaniline, 2- (3-trifluoromethylphenyl) aniline, 3- (3-trifluoromethylphenyl) aniline, 4- (3-trifluoromethylphenyl) aniline, 2- [3,4- Bis (trifluoromethyl) phenyl] aniline, 3- [3,4-bis (trifluoromethyl) phenyl] aniline, 4- [3,4-bis (trifluoromethyl) phenyl] aniline, 2-
[2,4-bis (trifluoromethyl) phenoxy] aniline, 3- [2,4-bis (trifluoromethyl) phenoxy] aniline, 4- [2,4-bis (trifluoromethyl) phenoxy] aniline, -[3,4-bis (trifluoromethyl) phenoxy] aniline, 3- [3,4-
Bis (trifluoromethyl) phenoxy] aniline, 4
-[3,4-bis (trifluoromethyl) phenoxy] aniline, 2- [3,5-bis (trifluoromethyl) phenoxy] aniline, 3- [3,5-bis (trifluoromethyl) phenoxy] aniline, 4- [3,5-bis (trifluoromethyl) phenoxy] aniline, 2,4-bis [3,5-bis (trifluoromethyl) phenoxy] aniline, 2,3-bis [3,5-bis (tri Fluoromethyl) phenoxy] aniline, 2,6-bis [3,5-bis (trifluoromethyl) phenoxy] aniline, 3,
4-bis [3,5-bis (trifluoromethyl) phenoxy] aniline, 3,5-bis [3,5-bis (trifluoromethyl) phenoxy] aniline, 2,4,6-tris [3,5- Bis (trifluoromethyl) phenoxy] aniline, 2-fluoro-4- [3,5-bis (trifluoromethyl) phenoxy] aniline, 3-fluoro-4
-[3,5-bis (trifluoromethyl) phenoxy] aniline, 2,5-difluoro-4- [3,5-bis (trifluoromethyl) phenoxy] aniline, 2,6-difluoro-4- [3, 5-bis (trifluoromethyl)
Phenoxy] aniline, 3,5-difluoro-4- [3,
5-bis (trifluoromethyl) phenoxy] aniline, 2-trifluoromethyl-4- [3,5-bis (trifluoromethyl) phenoxy] aniline, 3-trifluoromethyl-4- [3,5-bis ( [Trifluoromethyl) phenoxy] aniline, 2,5-bis (trifluoromethyl) -4- [3,5-bis (trifluoromethyl) phenoxy] aniline, 2,6-bis (trifluoromethyl) -4- [ 3,5-bis (trifluoromethyl) phenoxy] aniline, 3,5-bis (trifluoromethyl) -4- [3,5-bis (trifluoromethyl) phenoxy] aniline, 2- [3,5-bis (Trifluoromethyl) benzyl] aniline, 3- [3,5-bis (trifluoromethyl) benzyl] aniline, 4- [3
5-bis (trifluoromethyl) benzyl] aniline,
2,4-bis [3,5-bis (trifluoromethyl) benzyl] aniline, 2,6-bis [3,5-bis (trifluoromethyl) benzyl] aniline, 3,5-bis [3
5-bis (trifluoromethyl) benzyl] aniline,
2,4,6-tris [3,5-bis (trifluoromethyl) benzyl] aniline, 2-fluoro-4- [3,5-
Bis (trifluoromethyl) benzyl] aniline, 3-
Fluoro-4- [3,5-bis (trifluoromethyl)
Benzyl] aniline, 2,5-difluoro-4- [3,5
-Bis (trifluoromethyl) benzyl] aniline,
2,6-difluoro-4- [3,5-bis (trifluoromethyl) benzyl] aniline, 3,5-difluoro-
4- [3,5-bis (trifluoromethyl) benzyl] aniline, 2-trifluoromethyl-4- [3,5-bis (trifluoromethyl) benzyl] aniline, 3-trifluoromethyl-4- [3 , 5-Bis (trifluoromethyl) benzyl] aniline, 2,5-bis (trifluoromethyl) -4- [3,5-bis (trifluoromethyl) benzyl] aniline, 2,6-bis (trifluoromethyl ) -4- [3,5-Bis (trifluoromethyl)
Benzyl] aniline, 3,5-bis (trifluoromethyl) -4- [3,5-bis (trifluoromethyl) benzyl] aniline, 2- [3,5-bis (trifluoromethyl) benzoyl] aniline, -[3,5-bis (trifluoromethyl) benzoyl] aniline, 4- [3,5-bis (trifluoromethyl) benzoyl] aniline, 2,
4-bis [3,5-bis (trifluoromethyl) benzoyl] aniline, 2,6-bis [3,5-bis (trifluoromethyl) benzoyl] aniline, 3,5-bis [3
5-bis (trifluoromethyl) benzoyl] aniline, 2,4,6-tris [3,5-bis (trifluoromethyl) benzoyl] aniline, 2-fluoro-4-
[3,5-bis (trifluoromethyl) benzoyl] aniline, 3-fluoro-4- [3,5-bis (trifluoromethyl) benzoyl] aniline, 2,5-difluoro-4- [3,5-bis (Trifluoromethyl) benzoyl] aniline, 2,6-difluoro-4- [3,5-bis (trifluoromethyl) benzoyl] aniline, 3,5
-Difluoro-4- [3,5-bis (trifluoromethyl) benzoyl] aniline, 2-trifluoromethyl-
4- [3,5-bis (trifluoromethyl) benzoyl]
Aniline, 3-trifluoromethyl-4- [3,5-bis (trifluoromethyl) benzoyl] aniline,
5-bis (trifluoromethyl) -4- [3,5-bis (trifluoromethyl) benzoyl] aniline, 2,6
-Bis (trifluoromethyl) -4- [3,5-bis (trifluoromethyl) benzoyl] aniline, 3,5
-Bis (trifluoromethyl) -4- [3,5-bis (trifluoromethyl) benzoyl] aniline, 2-
[3,5-bis (trifluoromethyl) phenylthio] aniline, 3- [3,5-bis (trifluoromethyl) phenylthio] aniline, 4- [3,5-bis (trifluoromethyl) phenylthio] aniline, 2 , 4-bis [3,
5-bis (trifluoromethyl) phenylthio] aniline, 2,6-bis [3,5-bis (trifluoromethyl) phenylthio] aniline, 3,5-bis [3,5-bis (trifluoromethyl) phenylthio] Aniline,
2,4,6-tris [3,5-bis (trifluoromethyl) phenylthio] aniline, 2-fluoro-4- [3
5-bis (trifluoromethyl) phenylthio] aniline, 3-fluoro-4- [3,5-bis (trifluoromethyl) phenylthio] aniline, 2,5-difluoro-4- [3,5-bis (trifluoro Methyl) phenylthio] aniline, 2,6-difluoro-4- [3,5-bis (trifluoromethyl) phenylthio] aniline,
3,5-difluoro-4- [3,5-bis (trifluoromethyl) phenylthio] aniline, 2-trifluoromethyl-4- [3,5-bis (trifluoromethyl) phenylthio] aniline, 3-trifluoro Methyl-4-
[3,5-bis (trifluoromethyl) phenylthio] aniline, 2,5-bis (trifluoromethyl) -4-
[3,5-bis (trifluoromethyl) phenylthio] aniline, 2,6-bis (trifluoromethyl) -4-
[3,5-bis (trifluoromethyl) phenylthio] aniline, 3,5-bis (trifluoromethyl) -4-
[3,5-bis (trifluoromethyl) phenylthio] aniline, 2- [3,5-bis (trifluoromethyl) phenylsulfinyl] aniline, 3- [3,5-bis (trifluoromethyl) phenylsulfinyl] aniline ,
4- [3,5-bis (trifluoromethyl) phenylsulfinyl] aniline, 2,4-bis [3,5-bis (trifluoromethyl) phenylsulfinyl] aniline,
2,6-bis [3,5-bis (trifluoromethyl) phenylsulfinyl] aniline, 3,5-bis [3,5-
Bis (trifluoromethyl) phenylsulfinyl] aniline, 2,4,6-tris [3,5-bis (trifluoromethyl) phenylsulfinyl] aniline, 2-fluoro-4- [3,5-bis (trifluoromethyl ) Phenylsulfinyl] aniline, 3-fluoro-4-
[3,5-bis (trifluoromethyl) phenylsulfinyl] aniline, 2,5-difluoro-4- [3,5-
Bis (trifluoromethyl) phenylsulfinyl] aniline, 2,6-difluoro-4- [3,5-bis (trifluoromethyl) phenylsulfinyl] aniline,
3,5-difluoro-4- [3,5-bis (trifluoromethyl) phenylsulfinyl] aniline, 2-trifluoromethyl-4- [3,5-bis (trifluoromethyl) phenylsulfinyl] aniline, 3- Trifluoromethyl-4- [3,5-bis (trifluoromethyl) phenylsulfinyl] aniline, 2,5-bis (trifluoromethyl) -4- [3,5-bis (trifluoromethyl) phenylsulfinyl] aniline , 2,
6-bis (trifluoromethyl) -4- [3,5-bis (trifluoromethyl) phenylsulfinyl] aniline, 3,5-bis (trifluoromethyl) -4- [3
5-bis (trifluoromethyl) phenylsulfinyl] aniline, 2- [3,5-bis (trifluoromethyl) phenylsulfonyl] aniline, 3- [3,5-bis (trifluoromethyl) phenylsulfonyl] aniline, -[3,5-bis (trifluoromethyl) phenylsulfonyl] aniline, 2,4-bis [3,5-bis (trifluoromethyl) phenylsulfonyl] aniline, 2,6-bis [3,5-bis ( Trifluoromethyl) phenylsulfonyl] aniline, 3,5-bis [3
5-bis (trifluoromethyl) phenylsulfonyl]
Aniline, 2,4,6-tris [3,5-bis (trifluoromethyl) phenylsulfonyl] aniline, 2-fluoro-4- [3,5-bis (trifluoromethyl) phenylsulfonyl] aniline, 3-fluoro -4- [3,
5-bis (trifluoromethyl) phenylsulfonyl]
Aniline, 2,5-difluoro-4- [3,5-bis (trifluoromethyl) phenylsulfonyl] aniline, 2,6-difluoro-4- [3,5-bis (trifluoromethyl) phenylsulfonyl] aniline, 3,5
-Difluoro-4- [3,5-bis (trifluoromethyl) phenylsulfonyl] aniline, 2-trifluoromethyl-4- [3,5-bis (trifluoromethyl) phenylsulfonyl] aniline, 3-trifluoromethyl -4- [3,5-bis (trifluoromethyl) phenylsulfonyl] aniline, 2,5-bis (trifluoromethyl) -4- [3,5-bis (trifluoromethyl) phenylsulfonyl] aniline, 6-bis (trifluoromethyl) -4- [3,5-bis (trifluoromethyl) phenylsulfonyl] aniline, 3,5-bis (trifluoromethyl) -4- [3,5-bis (trifluoromethyl ) Phenylsulfonyl] aniline and the like. Also, these aromatic amine compounds,
They can be used alone or in combination of two or more.

The polyalicyclic acid anhydride of the present invention is useful for producing a polyalicyclic imide composition having excellent low dielectric constant, heat resistance, low refractive index and isotropic dielectric constant (low birefringence). Is useful as a precursor of

[0024]

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

Method for measuring properties Measurement of weight average molecular weight Using gel permeation chromatography (GPC), the weight average molecular weight (Mw) was calculated in terms of polystyrene.
Was measured.

Measurement of Film Thickness A film formed on a silicon wafer was scratched, the depth of the scratch was measured, and the depth was defined as the film thickness.

Measurement of relative permittivity The capacitance of the polyalicyclic imide film at 1 kHz was measured using an LCR meter 4284A manufactured by Yokogawa-Hewlett-Packard Co., and the relative permittivity (ε) was calculated by the following equation. I asked. ε = C · d / ε ⁰ · S (where C is the capacitance (F), d is the sample film thickness (m), ε ⁰ is the dielectric constant in vacuum, and S is the upper electrode area (m ² ). is there.).

Measurement of Refractive Index Using a He-Ne laser wavelength (633 nm), the refractive index was measured at 20 ° C. by the prism coupler method, and the refractive index in the direction parallel to the film surface (TE) and the refractive index in the direction perpendicular to the film surface (TM) were measured. ) And the difference between them was determined.

Infrared absorption spectrum (IR) measurement Unsaturated group-containing alicyclic acid anhydride was measured by the KBr method, and polyalicyclic imide was measured as it was on a silicon wafer. As a measuring device, a Fourier transform infrared spectrophotometer “FT-720” (manufactured by Horiba, Ltd.) was used.

[0030] dissolved in a measurement solvent DMSO or CDCl ₃ nuclear magnetic resonance spectra ⁽¹ H-NMR), 270MHz
Was measured. The measuring device is a superconducting FTNMR “EX-27”
0 "(manufactured by JEOL Datum Co., Ltd.).

Measurement of Glass Transition Temperature (Tg) The glass transition temperature (Tg) was measured by a differential scanning calorimeter (DSC) in a nitrogen atmosphere at a heating rate of 20 ° C./min.

Measurement of Weight Loss Temperatures (Td1, Td5) Using a thermobalance, heating was performed in nitrogen at a heating rate of 10 ° C./min, and the temperatures at which 1% weight loss and 5% weight loss were observed were measured.

Reference Example 1 Preparation of exo-nadic anhydride
Exo-bicyclo [2,2,1] hept-5-ene-
2,3-dicarboxylic anhydride (exo-nadic anhydride)
Endo-bicyclo [2,2,1] hept-5-ene-
2,3-dicarboxylic anhydride (endo-nadic acid free
Water) (100 g, 0.61 mol) under nitrogen at 200 ° C.
For 6 hours for thermal isomerization. Cool the reaction to 120 ° C
And add 100 ml of toluene, then cool to room temperature.
On rejection, pale yellow crystals precipitated. In addition, this crystal
By recrystallizing with toluene, colorless and transparent needle-like crystals were obtained.
Obtained. The crystals were separated by filtration, dried under reduced pressure and dried.
32.83 g of the target compound were obtained. ¹H-NMR (FIG. 1)
And IR (FIG. 2).

Melting point: 143 to 144 ° C. Infrared absorption spectrum: 1860, 1778 cm ^-1 (more than C = O), 1218,913 cm ^-1 (more than C-O) ¹ H-NMR: (CDCl ₃ , ppm): 6 .34 (s,
2H, CH = CH), 3.45 (s, 2H, CH),
3.01 (s, 2H, CH), 1.56 (dd, 2
H, CH _2).

Reference Example 2 Production of palladium complex 2 g (0.011 mol) of palladium (II) chloride was dissolved in 5 ml of hydrochloric acid (36%) while heating, and after cooling, 150 ml of ethanol was added. After the reaction solution was filtered, 2.31 g (0.025 mol) of 2,5-norbornadiene was added to the filtrate, whereby a yellow solid precipitated. The solid was separated by filtration, dried under reduced pressure, and bicyclo [2,2,
1] 3.07 g of heptadiene-palladium chloride was obtained.

2.62 g (0.0097 mol) of this bicyclo [2,2,1] heptadiene-palladium chloride, 0.88 g (0.0083 mol) of sodium carbonate
Was added thereto, and the mixture was stirred and reacted at room temperature under nitrogen for 2 hours. The reaction solution was separated by filtration and dried under reduced pressure to obtain 2.57 g of bicyclo [2,2,1] heptadiene-palladium chloride dimer as a pale yellow powder.

Further, after dissolving this bicyclo [2,2,1] heptadiene-palladium chloride dimer in chlorobenzene, 1.6 equivalents of silver tetrafluoroborate was added, and the mixture was stirred at room temperature for 15 minutes. A solution of the desired palladium complex was obtained. This solution was used as a polymerization catalyst for an unsaturated group-containing alicyclic imide.

Example 1 In 127 ml of a chlorobenzene solution of the palladium complex obtained in Reference Example 2 under nitrogen, exo-
5 g (0.030 mol) of nadic anhydride was added and reacted at room temperature for 36 hours. The reaction solution was filtered, and the solid was washed with hexane and dried under reduced pressure to obtain a polymer. The yield was 2.31 g. Weight average molecular weight (M
w) was 4000. ¹ H-NMR of this polymer
The spectrum (DMSO-d6, ppm) is shown in FIG. 3, and the infrared absorption spectrum is shown in FIG.

Further, the glass transition temperature (Tg) and the weight loss temperature (Td1, Td5) were measured. Tg is 400
C., not detected, Td1 = 324 ° C., Td5 = 393
° C.

Infrared absorption spectrum: 1859, 1774
cm ^-1 (or more C = O), 1226,917cm ^-1 (or ^{C-O) 1 H-NMR} : (DMSO-d6, ppm): 0.55
-3.80 (br.m, 8H, CH).

Example 2 Preparation of polyalicyclic imide Under nitrogen, 1 g (2.4 mmol) of the polymer obtained in Example 1 was dissolved in 10 g of NMP, and 3,5-bis (trifluoromethyl) aniline was dissolved in 2 g of NMP. 7 g (11.7 mmol)
And reacted at 120 ° C. for 7 hours. This reaction solution was filtered, and the obtained solid was washed with NMP, water, and methanol, and then dried under reduced pressure to obtain a polyalicyclic imide. The yield was 1.35 g. Weight average molecular weight (Mw) is 8
500.

1 g of the above-mentioned polyalicyclic imide was dissolved in 3 g of 2-heptanone. This solution is filtered with a filter made of Sumitomo Electric Industries, Ltd. made of tetrafluoroethylene resin (pore size 2 μm).
And filtered. Next, the solution was placed in a 6 × 6 cm A
l Spin coating on substrate and silicon wafer, then hot plate (SKNW manufactured by Dainippon Screen Co., Ltd.)
-636) for 3 minutes at 80 ° C, and further dried for 0.5 hour at 140 ° C and 1 hour at 250 ° C using an oven (an inert oven manufactured by Koyo Lindberg K.K.). A transparent film was obtained. Then, Al
A mask is formed on this polymer film formed on the
Was vacuum-deposited to form an upper electrode, thereby obtaining a relative dielectric constant (ε) measurement sample. As a result of measuring the dielectric constant of the sample, ε =
2.31 was a low value.

Next, the refractive index was measured using the polymer film formed on the glass. As a result, the refractive index is TE =
1.4857, TM = 1.4810, birefringence is 0.0
047, which is a small value for both the refractive index and the birefringence.

The glass transition temperature was not detected up to 400 ° C., the 1% weight loss temperature was 420 ° C., and the 5% weight loss temperature was 468 ° C.

Infrared absorption spectrum: 3105, 307
3,2974,2897cm ^-1 (CH above), 1716
cm ^-1 (C = O (imide)) ¹ H-NMR: (CDCl ₃ , ppm): 1.25-3.
90 (br.m, 8H, CH), 7.60-8.30
(Br.s, 3H, Ar-H)

[0046]

The polyalicyclic acid anhydride composition of the present invention comprises:
It is useful as a precursor for producing a polyalicyclic imide composition having excellent low dielectric properties, heat resistance, low refractive index, and isotropic dielectric constant (low birefringence).

[Brief description of the drawings]

FIG. 1 ¹ H-NMR spectrum of exo-nadic anhydride synthesized in Reference Example 1

FIG. 2 is an IR spectrum of exo-nadic anhydride synthesized in Reference Example 1.

FIG. 3 shows a ¹ H-NMR spectrum of a polymer synthesized in Example 1.

FIG. 4 is an IR spectrum of a polymer synthesized in Example 1.

Claims (3)

[Claims] 1. A polyalicyclic acid anhydride composition represented by the general formula (1). Embedded image (In the general formula (1), 1 is 1 to 2, and m is 3 to 300.
Indicates an integer of 00. R ^{1 to} R ⁴ represent any of H, F, CF ₃ , an alkyl group having 1 to 10 carbon atoms, and an aryl group having 6 to 20 carbon atoms, and may be the same or different. R ⁵ ,
R ⁶ represents H or an alkyl group having 1 to 10 carbon atoms. ) 2. The polyalicyclic acid anhydride composition according to claim 1, wherein the weight average molecular weight represented by the general formula (1) is 1,000 to 1,000,000. 3. A method for producing a polyalicyclic imide composition, comprising reacting a compound represented by the general formula (1) with an aromatic amine compound.