JP2002356553A - Polyimide and polyamido acid - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyamide and a polyamic acid, excellent in solubility and in photosensitivity, low perimtability. SOLUTION: The polyimide has a unit of the formula (I) and the polyamic acid has a unit of the formula (II) [R1 and R2 are H or an alkyl group C1-C12, Z is a condensed polycyclic aromatic group or a group of (A) as shown below ((X= -CO-, -C(=N2 )-; Y; -CH2 -, -O-, -SO2 -, -S-, -CO-, -C(=N2 )-, W; -CH2 -, -C(CH3 )2 -, -C(CF3 )2 -, -S-, -SO-, -SO2 -, -O-; b, m, n=0 or 1; r=a alkyl of C1-C4, a halogen, or a phenyl group; a=0 or 1-3)].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to novel polyimides and polyamic acids. More specifically, the present invention relates to novel polyimides and polyamic acids which exhibit excellent heat resistance, mechanical properties, and adhesive properties, and exhibit high solvent solubility, low dielectric properties, or high sensitivity and high resolution photosensitivity. These polyimides and polyamic acids are very useful for photoresist applications, and are also very useful as insulating films, especially as insulating films used for surface protection films and interlayer insulating films of highly integrated semiconductor devices and highly integrated multilayer wiring boards. It is.

[0002]

2. Description of the Related Art Conventionally, a polyimide obtained by reacting a tetracarboxylic dianhydride with a diamine has excellent mechanical strength and dimensional stability in addition to its high heat resistance, and has excellent flame retardancy and electrical insulation properties. Electric and electronic equipment,
It is used in fields such as aerospace equipment and transportation equipment, and is expected to be widely used in fields requiring heat resistance in the future. In recent years, due to the remarkable expansion of electrical and electronic equipment represented by computers and the like, polyimide has excellent heat resistance, electrical properties, and mechanical strength. It has been expected as a high-performance material in various fields such as an interlayer insulating film, a film-like base material for printed wiring, and a protective film for solar cells. In particular, polyimide resin has excellent heat resistance and mechanical properties, as well as flattening ability, processability, low dielectric properties, and photosensitivity. It is also superior in terms of its ability to form.

[0003] As a conventional technique corresponding to the photosensitive polyimide of the present invention, Japanese Patent No. 21
No. 25907 and Japanese Patent No. 1976781. These are the papers of Pfeifer et al. (Pfeifer, J. and Ro
hde, O., Polyimides: Synthesis, Characterization, and A
pplication, Proc.2nd.Intl.Conf.Polyimides, 130 ~ pages,
(1985)) is a negative photosensitive polyimide having a curing mechanism by a photocrosslinking reaction between a benzophenone structure in a skeleton and an alkyl group (hereinafter abbreviated as the present mechanism).

The prior art specifically includes 4,4'-diamino-3,3 ', 5,5'-tetramethyldiphenylmethane and 2,3,5,6-tetramethyl-1,4-phenylene Polyimides of various diamines such as diamine and benzophenonetetracarboxylic dianhydride are disclosed. These photosensitive polyimides tend to have higher photosensitivity due to an increase in the content of alkyl groups in the molecule (POLYMER ENGINEERING AND SCIENCE, MID-NOVEMBER 199).
2, Vol. 32, No. 21, 1623). This prior art also shows a photosensitive polyimide having a high intramolecular alkyl group content and a high sensitivity, but as the sensitivity is increased, a diamine unit having a high alkyl group content must be designed. At present, the manufacturing cost has to be high.

Further, the claims of Japanese Patent No. 2125907 include a description which includes a polyimide using diaminoindane as a diamine unit. This corresponds to the structure of the polyimide of the present invention (1,1- as a diamine unit).
Polyimide using dimethyldiaminoindane). However, this diaminoindane does not have any literature which shows a specific and consistent production method. As a production route, first, indene is produced as a raw material, and the indene is nitrated and reduced to introduce an amino group, and an aromatic ring is reduced by a technique shown in U.S. Pat. No. 3,875,228. As shown in the production example of Japanese Patent Application Laid-Open No. 9-504794, a method of protecting, nitrating, deprotecting and reducing an amino group may be added to introduce a second amino group. As described above, production of diaminoindane must be performed through many steps by combining various techniques, and it is presumed that it is not easy.

Also, Yamashita et al. Suggested that the photosensitivity of the obtained polyimide could be improved by controlling the intramolecular conformation in the photocrosslinking reaction by this mechanism (Shun Yamashita) , "Recent Advances in Polyimide", 1992, 2
9-page, 1993). This means that there is a possibility of improving sensitivity other than the method of increasing the intramolecular methyl group content, that is, there is a possibility that a photosensitive polyimide with high sensitivity can be produced while suppressing the cost of introducing an alkyl group. As a suggestion, in the photosensitive polyimide according to the present mechanism shown in the above-mentioned prior art, it was not possible to realize low-cost production by maximizing the photosensitive sensitivity in a conformational manner. .

[0007] In general, it is not satisfactory to supply high-sensitivity and high-resolution photosensitive polyimide by the present mechanism at low cost, and development of this inexpensive, high-sensitivity and high-resolution negative-type photosensitive polyimide is required. Had been

On the other hand, according to Japanese Patent Publication No. Hei 7-116112,
Diaminoindane derivatives have been reported along with their preparation. It has been reported that this diaminoindan derivative is used as a raw material such as isocyanate, epoxy resin and bismaleimide, as a curing agent for isocyanates, and as a modifier for various resins and rubbers. However, this diaminoindane derivative is useful as a monomer for polyimide, and the obtained various polyimides have excellent photosensitivity and exhibit remarkably high solvent solubility.
It was not known at all.

[0009]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a novel compound which is excellent in heat resistance, mechanical properties and adhesive properties, and exhibits high solvent solubility, low dielectric property, or high sensitivity and high resolution photosensitivity. Another object of the present invention is to provide a polyimide and a polyamic acid which are useful for applications such as a photoresist and an insulating film.

[0010]

Means for Solving the Problems As a result of intensive studies, the present inventors have synthesized a novel polyimide and a novel polyamic acid having a 1,1-dimethylindane skeleton in a repeating structure, and obtained the polyimide and the polyamide. The inventors have found that an acid has excellent photosensitivity, low dielectric constant and remarkably high solvent solubility, and have completed the present invention.

That is, the present invention is a polyimide having a repeating unit represented by the following general formula (I).

[0012]

Embedded image (Wherein, R ₁ and R ₂ each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and Z represents a condensed polycyclic aromatic group or the following formula:

[0013]

Embedded image At least one group selected from the group consisting of However, X is -CO- or -C (= N ₂₎ - indicates, Y is a direct _{bond, -CH 2 -, - O -} , - SO 2 -, - S -, - CO- or -C
(= N ₂ )-, W is a direct bond, -CH _2- , -C (CH
₃ ) _2- , -C (CF ₃ ) _2- , -S-, -SO-, -SO ₂ -or-
Indicates O-. b represents an integer of 0 or 1, m and n each independently represent an integer of 0 or 1, r represents each independently an alkyl group having 1 to 4 carbon atoms, a halogen group or a phenyl group. And a represents 0 or an integer of 1 to 3. Further, the present invention is characterized in that a diaminoindane derivative represented by the following general formula (II) and an aromatic tetracarboxylic dianhydride represented by the following general formula (III) are used as monomers. A method for producing a polyimide having a repeating unit represented by the general formula (I).

[0014]

Embedded image Further, the present invention is a polyamic acid having a repeating unit represented by the following general formula (IV).

[0015]

Embedded image (Wherein, R ₁ and R ₂ each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and Z represents a condensed polycyclic aromatic group or the following formula:

[0016]

Embedded image At least one group selected from the group consisting of However, X is -CO- or -C (= N ₂₎ - indicates, Y is a direct _{bond, -CH 2 -, - O -} , - SO 2 -, - S -, - CO- or -C
(= N ₂ )-, W is a direct bond, -CH _2- , -C (CH
₃ ) _2- , -C (CF ₃ ) _2- , -S-, -SO-, -SO ₂ -or-
Indicates O-. b represents an integer of 0 or 1, m and n each independently represent an integer of 0 or 1, r represents each independently an alkyl group having 1 to 4 carbon atoms, a halogen group or a phenyl group. And a represents 0 or an integer of 1 to 3. Further, the present invention is characterized in that a diaminoindane derivative represented by the general formula (II) and an aromatic tetracarboxylic dianhydride represented by the general formula (III) are used as monomers. A method for producing a polyamic acid having a repeating unit represented by the general formula (IV).

Furthermore, according to the present invention, when the optimum stabilizing structure is calculated based on theoretical calculation, the absolute value | α | of the dihedral angle α is 82 ° or more in the repeating unit structure contained in the molecule.
8 ° or less (where α is four adjacent atoms C)
It is defined as the dihedral angle formed by (carbonyl carbonyl of imide) -N (nitrogen of imide) -CC, and is defined in the range of -180 ° or more and 180 ° or less. ) Is a polyimide.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION R ₁ in the general formulas (I) and (IV)
And R ₂ are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. Among them, an alkyl group having 1 to 20 carbon atoms is preferable, and an alkyl group having 1 to 10 carbon atoms is preferable.
Is more preferable, and an alkyl group having 1 to 5 carbon atoms is particularly preferable. Specifically, a methyl group, an isopropyl group and the like are preferable. The site of R ₁ and R _{2 on} the 1,1-dimethylindane skeleton is not particularly limited. However, in particular, in the general formula (I), a polyimide in which both R ₁ and R ₂ are bonded to any of the 4-, 5-, or 6-positions on the 1,1-dimethylindane skeleton has high solvent solubility. It is preferable because it has.

Further, in the general formula (I), R ₁ and R ₂ are both 4-position, 5-position on the 1,1-dimethylindane skeleton.
Polyimides having a benzophenone structure in which Z is bonded to either the 6-position or the 6-position are preferable because they have high solvent solubility and can obtain high-sensitivity photosensitivity.

Further, in the general formula (I), R ₁ and R ₂ are both methyl groups, and these methyl groups are 1,1-
A polyimide bonded to the 4- and 6-positions on the dimethylindane skeleton and having Z as a benzophenone structure, that is, a polyimide having a repeating unit structure represented by the following formula (V), has high solvent solubility and high sensitivity. It is preferable because photosensitivity can be obtained.

[0021]

Embedded image X in the formula in the definition of Z in the general formulas (I) and (IV)
Is -CO- or -C (= N ₂ )-, Y is a direct bond, -CH _2- , -O-, -SO _2- , -S-, -CO- or -C
(= N ₂ )-, and other groups are not particularly limited as long as they are groups corresponding thereto.

Further, in the general formula (I), R ₁ and R ₂ are both 4-position, 5-position on the 1,1-dimethylindane skeleton.
Polyimide bonded to either the 6-position or the 6-position and X is —CO— or C (＝ N ₂ ) — at the same time has high solvent solubility, and is preferred because high sensitivity photosensitivity is obtained.

Further, in the general formula (I), R ₁ and R ₂
Are bonded to any of the 4-, 5- and 6-positions on the 1,1-dimethylindane skeleton, and X in the general formula (I) is -CO- or C (= N ₂ )- , And Y is —CO— or C (＝ N ₂ ) — or S—, which is preferable since it has high solvent solubility and high photosensitivity.

Particularly, in the general formula (I), R ₁ and R ₂ are both methyl groups, and these methyl groups are 1,1
-Bonding to the 4- and 6-positions on the dimethylindane skeleton,
Is 2,2-bis (3,4-dicarboxyphenyl) -1,
A polyimide having a structure formed from 1,1,3,3,3-hexafluoropropane dianhydride, that is, a polyimide having a repeating unit structure represented by the following formula (VI), exhibits high solvent solubility and low dielectric constant. It is preferable because of its properties.

[0025]

Embedded image As shown in the aforementioned Yamashita et al. Document (Shun Yamashita, "Recent Progress of Polyimide", 1992, pp. 29-1993 (1993)
)), In a photosensitive polyimide that exhibits a curing mechanism by a photocrosslinking reaction between a benzophenone structure in the skeleton and an alkyl group, intramolecular charge transfer leads to deactivation of the photocrosslinking reaction. Therefore, in order to increase the sensitivity of the photosensitive polyimide,
It is extremely important to suppress this intramolecular charge transfer.

In order to suppress the above-mentioned intramolecular charge transfer, the present inventors set the angle formed by the plane of the imide ring and the plane of the aromatic ring bonded to the nitrogen atom of the imide ring to a specific range [right angle ( 90 [deg.]) Is found to be very effective. That is, when the polyimide of the present invention calculates the optimal stabilized structure based on theoretical calculation, the angle formed by the plane of the imide ring and the plane of the aromatic ring bonded to the nitrogen atom of the imide ring (hereinafter, dihedral angle and Abbreviation) Absolute value of α | α |
特 徴 It is characterized by being in the following range. As one of the techniques for suppressing the intramolecular charge transfer of the polyimide, there is a method of introducing a bulky substituent into the diamine to control the conformation of the CN bond of the imide. And the polyimide having the repeating unit represented by the general formula (I) is:
It is a very suitable polymer that satisfies such absolute value of dihedral angle | α | This suppresses movement and achieves high sensitivity of the photosensitive performance.

Examples of the method of theoretical calculation include a quantum mechanics method and a molecular mechanics method. Examples of quantum mechanics methods include AM1, PM3, extended Huckel, and MINDO.
/ 3, MNDO, semi-empirical calculation method including MNDO-d, and ab initio method. MM2 is an example of the molecular mechanics method. Further, two or more calculation methods may be used in combination for the purpose of improving the efficiency of the calculation. Specifically, for example, a structure obtained by optimizing a molecular model by a molecular mechanics method may be further optimized by using a quantum mechanics method. For example, a method of producing a molecular model as used in the examples described below is effective.

Here, the dihedral angle is an angle formed by two planes formed by an array of four atoms. Of these four atoms, the second and third atoms are arranged on the Z axis, and the first atom is arranged on the ZX plane.
And the fourth atom are projected onto the XY plane, and the angle is measured. The method of attaching the dihedral angle code is not limited in the present invention.

The chemical structure of the polyimide of the present invention is not limited as long as the absolute value | α | of the dihedral angle α is in the range of 82 ° to 98 °. Furthermore, the absolute value of the dihedral angle α | α |
Is preferably 84 ° or more and 96 ° or less,
It is more preferably at least 90 ° and at most 95 °, particularly preferably at least 89 ° and at most 91 °.

The logarithmic viscosity of the polyimide of the present invention is not particularly limited, but is generally 0.1 to 2.0, preferably 0.2 to 1.9, and more preferably 0.3 to 1.0. 8 is more preferred, 0.4 to 1.7 is particularly preferred, and 0.5 to 1.6 is optimal. If the logarithmic viscosity of the polyimide is too low, the strength and toughness of the processed product generally decrease, which is not preferable. If the logarithmic viscosity of the polyimide is too high, the processability in commercialization generally deteriorates, which is not preferable. The method for evaluating the logarithmic viscosity of the polyimide is not particularly limited. For example, 0.50 g of the polyimide powder is mixed with N-methyl-2.
Can be measured at 35 ° C. after dissolving in 100 ml of pyrrolidone.

The polyimide of the present invention is prepared by adding various diamines and tetracarboxylic dianhydrides in addition to the repeating unit component having the structure represented by the general formula (I) to various physical properties such as heat resistance, hygroscopicity and thermal expansion coefficient. For the purpose of controlling the dielectric constant, the refractive index, the birefringence, and the like, it may be obtained by copolymerization as required.

The polyimide of the present invention may be produced by any method. However, the method for producing a polyimide of the present invention uses the diaminoindane derivative represented by the general formula (II) and the aromatic tetracarboxylic dianhydride represented by the general formula (III) as monomers. It is characterized by the following.

The diaminoindan derivative represented by the general formula (II) is not particularly limited. For example, 5,7-diamino-1,1-dimethylindane, 4,7-diamino-1,1
-Dimethylindane, 5,7-diamino-1,1,4-trimethylindane, 5,7-diamino-1,1,6-trimethylindane, 5,7-diamino-1,1-dimethyl-
4-ethylindane, 5,7-diamino-1,1-dimethyl-6-ethylindane, 5,7-diamino-1,1-dimethyl-4-isopropylindane, 5,7-diamino-1,1-dimethyl -6-isopropylindane, 5,7
-Diamino-1,1-dimethyl-4-n-propylindane, 5,7-diamino-1,1-dimethyl-6-n-propylindane, 5,7-diamino-1,1-dimethyl-
4-sec-butylindane, 5,7-diamino-1,1
-Dimethyl-6-sec-butylindane, 5,7-diamino-1,1-dimethyl-4-n-butylindane,
5,7-diamino-1,1-dimethyl-6-n-butylindane, 5,7-diamino-1,1-dimethyl-4-te
rt-butylindane, 5,7-diamino-1,1-dimethyl-6-tert-butylindane, 5,7-diamino-1,1,4,6-tetramethylindane, 6,7-diamino-1, 1,4,5-tetramethylindane, 4,7-diamino-1,1,5,6-tetramethylindane, 5,7-
Diamino-1,1-dimethyl-4,6-diethylindane, 5,7-diamino-1,1-dimethyl-4,6-diisopropylindane, 5,7-diamino-1,1,4-trimethyl-6 tert-butyl indane and the like. These diaminoindan derivatives can be used alone or in combination as needed.

A method for producing the diaminoindane derivative represented by the general formula (II) is described in JP-A-64-50848 and the like. That is, it is possible to synthesize an indane derivative from the reaction between a benzene derivative and isoprene, and nitrate and reduce the indane derivative to produce a diaminoindan derivative at low cost.

The aromatic tetracarboxylic dianhydride represented by the general formula (III) is not particularly limited. For example, pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic acid Dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfide dianhydride Object, screw (3,4-
Dicarboxyphenyl) sulfone dianhydride, bis (3,
4-dicarboxyphenyl) methane dianhydride, 2,2-
Bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl)-
1,1,1,3,3,3-hexafluoropropane dianhydride, 1,3-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 1,4-bis (3,4-dicarboxy) Phenoxy) benzene dianhydride, 4,4'-bis (3,4-
Dicarboxyphenoxy) biphenyl dianhydride, 2,2
-Bis [(3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride 2,2 ', 3,3'-benzophenonetetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, 2,2-bis (2,3-
Dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) -1,1,1,1,3,3,
3-hexafluoropropane dianhydride, bis (2,3-
Dicarboxyphenyl) ether dianhydride, bis (2,
3-dicarboxyphenyl) sulfide dianhydride, bis (2,3-dicarboxyphenyl) sulfone dianhydride,
1,3-bis (2,3-dicarboxyphenoxy) benzene dianhydride, 1,4-bis (2,3-dicarboxyphenoxy) benzene dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid Dianhydride, 1,3-bis (3,4-dicarboxybenzoyl) benzene dianhydride, 1,4-bis (3,4-dicarboxybenzoyl) benzene dianhydride, 1,3-bis (2, 3-dicarboxybenzoyl) benzene dianhydride, 1,4-bis (2,3-dicarboxybenzoyl) benzene dianhydride, 4,4'-isophthaloyldiphthalic anhydride, diazodiphenylmethane-3,3 ' , 4,4'-tetracarboxylic dianhydride, diazodiphenylmethane-2,2 ', 3,3'-tetracarboxylic dianhydride, 2,3,6,7-thioxanthone tetracarboxylic dianhydride, 2 , 3,6,7-anthra Non tetracarboxylic dianhydride, 2,3,6,7-xanthone dianhydride, and the like. These aromatic tetracarboxylic dianhydrides can be used alone or in combination as needed.

In a particularly preferred method for producing the polyimide of the present invention, both R ₁ and R _{2 in} the general formula (II) are methyl groups, and these methyl groups are the 4-position on the 1,1-dimethylindane skeleton. And a diaminoindane bonded to the 6-position, that is, 5,7-diamino-1,1,4,6-tetramethylindane represented by the following formula (VII) and an aromatic compound represented by the general formula (III) In this method, benzophenonetetracarboxylic dianhydride is used as the tetracarboxylic dianhydride.

[0037]

Embedded image In producing the polyimide of the present invention, the general formula (II)
In addition to the diaminoindane derivative represented by the general formula (III) and the aromatic tetracarboxylic dianhydride represented by the general formula (III), other various diamines and tetracarboxylic dianhydrides are used in combination as monomers to form a copolymer. It can be polymerized.

The diamine component used in the copolymerization is not particularly restricted but includes, for example, the following compounds.

A) p-Phenylenediamine and m-phenylenediamine having one benzene ring.

B) 3,3'- having two benzene rings
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 sulfone,
3,4′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfone, 3,3′-diaminobenzophenone, 4,4′-diaminobenzophenone, 3,4′-diaminobenzophenone, 3,3′-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2-di (3-aminophenyl) propane, 2,2-di (4-aminophenyl) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 2,2-di (3-aminophenyl) -1,1,1,1,3,3,3-hexafluoropropane,
2,2-di (4-aminophenyl) -1,1,1,3,3,3
-Hexafluoropropane, 2- (3-aminophenyl) -2- (4-aminophenyl) -1,1,1,1,3,3,
3-hexafluoropropane, 1,1-di (3-aminophenyl) -1-phenylethane, 1,1-di (4-aminophenyl) -1-phenylethane, 1- (3-aminophenyl) -1 -(4-aminophenyl) -1-phenylethane.

C) 1,3- having three benzene rings
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, 1,3-bis (3-amino-α, α-dimethylbenzyl) benzene, 1,3-bis (4-amino-α, α
-Dimethylbenzyl) benzene, 1,4-bis (3-amino-α, α-dimethylbenzyl) benzene, 1,4-bis (4-amino-α, α-dimethylbenzyl) benzene, 1,3-bis ( 3-amino-α, α-ditrifluoromethylbenzyl) benzene, 1,3-bis (4-amino-α, α-ditrifluoromethylbenzyl) benzene,
1,4-bis (3-amino-α, α-ditrifluoromethylbenzyl) benzene, 1,4-bis (4-amino-α,
α-ditrifluoromethylbenzyl) benzene, 2,6
-Bis (3-aminophenoxy) benzonitrile, 2,
6-bis (3-aminophenoxy) pyridine.

D) 4,4'- having four benzene rings
Bis (3-aminophenoxy) biphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, bis [4-
(3-aminophenoxy) phenyl] ketone, bis [4
-(4-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl ] Sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, 2,2-bis [4- (3
-Aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,1,3 , 3,3-Hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,1,3,3,3-hexafluoropropane.

E) 1,3- having 5 benzene rings
Bis [4- (3-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (4-aminophenoxy) benzoyl] benzene, 1,4-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,4-bis [4
-(4-aminophenoxy) benzoyl] benzene,
1,3-bis [4- (3-aminophenoxy) -α, α-
Dimethylbenzyl] benzene, 1,3-bis [4- (4
-Aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3-aminophenoxy)
-Α, α-dimethylbenzyl] benzene, 1,4-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene.

F) 4,4'- having 6 benzene rings
Bis [4- (4-aminophenoxy) benzoyl] diphenyl ether, 4,4'-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzophenone, 4,4'-bis [4- (4- Amino-α, α-dimethylbenzyl) phenoxy] diphenylsulfone, 4,4 ′
-Bis [4- (4-aminophenoxy) phenoxy] diphenylsulfone.

G) 3,3'-diamino-4,4'-diphenoxybenzophenone having an aromatic substituent, 3,3 '
-Diamino-4,4'-dibiphenoxybenzophenone,
3,3′-diamino-4-phenoxybenzophenone,
3,3'-diamino-4-biphenoxybenzophenone.

H) 6, having a spirobiindane ring
6'-bis (3-aminophenoxy) -3,3,3 ', 3'-
Tetramethyl-1,1′-spirobiindane, 6,6′-bis (4-aminophenoxy) -3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindane.

I) The siloxane diamines, 1,
3-bis (3-aminopropyl) tetramethyldisiloxane, 1,3-bis (4-aminobutyl) tetramethyldisiloxane, α, ω-bis (3-aminopropyl) polydimethylsiloxane, α, ω-bis (3-Aminobutyl) polydimethylsiloxane.

J) Bis (aminomethyl) ether, bis (2-aminoethyl) ether, bis (3-aminopropyl) ether, bis (2-aminomethoxy) ethyl] ether and bis [ 2- (2-aminoethoxy) ethyl] ether, bis [2- (3-aminoprotoxy) ethyl] ether,
1,2-bis (aminomethoxy) ethane, 1,2-bis (2-aminoethoxy) ethane, 1,2-bis [2-
(Aminomethoxy) ethoxy] ethane, 1,2-bis [2- (2-aminoethoxy) ethoxy] ethane, ethylene glycol bis (3-aminopropyl) ether,
Diethylene glycol bis (3-aminopropyl) ether, triethylene glycol bis (3-aminopropyl) ether.

K) Methylenediamines, ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1, 8-Diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane.

L) 1,2-, which is an alicyclic diamine
Diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,2-di (2
-Aminoethyl) cyclohexane, 1,3-di (2-aminoethyl) cyclohexane, 1,4-di (2-aminoethyl) cyclohexane, bis (4-aminocyclohexyl) methane, 2,6-bis (amino Methyl) bicyclo [2,2,1] heptane, 2,5-bis (aminomethyl)
Bicyclo [2,2,1] heptane.

Further, diamines in which part or all of the hydrogen atoms on the aromatic ring of the above diamine are substituted with a fluoro group, a methyl group, a methoxy group, a trifluoromethyl group, or a trifluoromethoxy group can also be used. Further, depending on the purpose, an ethynyl group, a benzocyclobuten-4′-yl group, a vinyl group, an allyl group, a cyano group, an isocyanate group, a nitrile group, and an isopropenyl group serving as a crosslinking point are formed on the aromatic ring of the diamine. Even if a part or all of the hydrogen atoms are introduced as a substituent, they can be used. Furthermore, depending on the purpose, a vinylene group, a vinylidene group, and an ethynylidene group serving as a crosslinking point can be incorporated in the main chain skeleton instead of the substituent. For the purpose of introducing a branch, a part of the diamine may be replaced with a triamine or a tetraamine. These diamines can be used alone or in combination as needed.

As the tetracarboxylic dianhydride component used for the copolymerization, in addition to the above-mentioned aromatic tetracarboxylic dianhydrides, ethylene tetracarboxylic dianhydride, butanetetracarboxylic dianhydride, cyclopentane And aliphatic tetracarboxylic dianhydrides such as tetracarboxylic dianhydride.

In addition, an aromatic tetracarboxylic dianhydride in which part or all of the hydrogen atoms on the aromatic ring is substituted with a fluoro group, a methyl group, a methoxy group, a trifluoromethyl group, or a trifluoromethoxy group is used. Carboxylic dianhydrides can also be used. Further, depending on the purpose, an ethynyl group serving as a crosslinking point, benzocyclobutene-
A 4′-yl group, a vinyl group, an allyl group, a cyano group, an isocyanate group, a nitrilo group, and an isopropenyl group as a substituent on a part or all of the hydrogen atoms on the aromatic ring of the aromatic tetracarboxylic dianhydride; Can be used even if introduced. Furthermore, a vinylene group, a vinylidene group, and an ethynylidene group, which are crosslinking points, may be incorporated into the main chain skeleton instead of the substituent, preferably within a range that does not impair the moldability. Further, for the purpose of introducing a branch, a part of the tetracarboxylic dianhydride may be replaced with hexacarboxylic trianhydride or octacarboxylic tetraanhydride. These aromatic tetracarboxylic dianhydride components can be used alone or in combination as needed.

The method for producing a polyimide of the present invention can be carried out without using a solvent, but it is particularly preferable to carry out the reaction in an organic solvent. The solvent used in this reaction is not particularly limited, and examples thereof include the following solvents.

(A) Phenol solvents such as phenol, o-chlorophenol, m-chlorophenol,
p-chlorophenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5 -Xylenol.

(B) N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-, which are aprotic amide solvents 2-imidazolidinone, N-methylcaprolactam, hexamethylphosphorotriamide.

(C) 1,2-, which is an ether solvent,
Dimethoxyethane, bis (2-methoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane, tetrahydrofuran, bis [2- (2-methoxyethoxy) ethyl] ether, 1,4-dioxane.

(D) pyridine, which is an amine solvent,
Quinoline, isoquinoline, α-picoline, β-picoline, γ-picoline, isophorone, piperidine, 2,4-
Lutidine, 2,6-lutidine, trimethylamine, triethylamine, tripropylamine, tributylamine.

(E) Other solvents such as dimethyl sulfoxide, dimethyl sulfone, diphenyl ether,
Sulfolane, diphenyl sulfone, tetramethyl urea,
Anisole, water, benzene, toluene, o-xylene,
m-xylene, p-xylene, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, bromobenzene, o-dibromobenzene, m
-Dibromobenzene, p-dibromobenzene, o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, o-bromotoluene, m-bromotoluene, p-bromotoluene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone , Cyclohexanone, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentane, hexane, heptane, cyclohexane, dichloromethane,
Chloroform, carbon tetrachloride, fluorobenzene, methyl acetate, ethyl acetate, butyl acetate, methyl formate, ethyl formate.

These solvents may be used alone or in combination of two or more.

In the method for producing a polyimide according to the present invention, a terminal blocking agent can be used if necessary. This terminal blocking agent is not particularly limited. Representative examples include monoamines and dicarboxylic anhydrides.

As the monoamine, for example, aniline,
o-toluidine, m-toluidine, p-toluidine,
2,3-xylidine, 2,4-xylidine, 2,5-xylidine, 2,6-xylidine, 3,4-xylidine, 3,
5-xylidine, o-chloroaniline, m-chloroaniline, p-chloroaniline, o-bromoaniline, m-
Bromoaniline, p-bromoaniline, o-nitroaniline, m-nitroaniline, p-nitroaniline, o-
Anisidine, m-anisidine, p-anisidine, o-phenetidine, m-phenetidine, p-phenetidine, o
-Aminophenol, m-aminophenol, p-aminophenol, 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-aminophenylphenyl ether,
2-aminobenzophenone, 3-aminobenzophenone, 4-aminobenzophenone, 2-aminophenylphenyl sulfide, 3-aminophenylphenyl sulfide, 4-aminophenylphenyl sulfide, 2-aminophenylphenyl sulfone, 3-aminophenylphenyl sulfone, 4-aminophenylphenylsulfone, 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, methylamine, dimethylamine, ethylamine, diethylamine,
Examples include propylamine, dipropylamine, isopropylamine, diisopropylamine, butylamine, dibutylamine, isobutylamine, diisobutylamine, pentylamine, dipentylamine, benzylamine, cyclopropylamine, cyclobutylamine, cyclopentylamine, and cyclohexylamine.

As the dicarboxylic anhydride, for example, phthalic anhydride, 2,3-benzophenone dicarboxylic anhydride, 3,4-benzophenone dicarboxylic anhydride, 2,3
-Dicarboxyphenyl ether anhydride, 3,4-dicarboxyphenyl phenyl ether anhydride, 2,3-biphenyl dicarboxylic anhydride, 3,4-biphenyl dicarboxylic anhydride, 2,3-dicarboxyphenyl phenyl sulfone anhydride 3,4-dicarboxyphenylphenylsulfone anhydride, 2,3-dicarboxyphenylphenylsulfide anhydride, 3,4-dicarboxyphenylphenylsulfide anhydride, 1,2-naphthalenedicarboxylic anhydride, 3-naphthalenedicarboxylic anhydride, 1,8-naphthalenedicarboxylic anhydride, 1,2-anthracenedicarboxylic anhydride, 2,3-anthracenedicarboxylic anhydride, 1,9-anthracenedicarboxylic anhydride, and the like. Can be

These monoamines and dicarboxylic anhydrides may have a part of their structure substituted with a group having no reactivity with amine or dicarboxylic anhydride.

In the method for producing a polyimide of the present invention, a catalyst can be used in combination. For example, the reaction can be performed in the presence of a base catalyst. Specifically, the above (d)
Various amine solvents, imidazole, N, N-
Organic bases such as dimethylaniline and N, N-diethylaniline, and inorganic bases represented by potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium bicarbonate, and sodium bicarbonate are exemplified.

In the method for producing a polyimide of the present invention,
The polymerization temperature and polymerization time vary depending on the presence and type of the solvent and catalyst used, but are generally 25 ° C to 250 ° C,
1 hour to 24 hours is sufficient.

Further, when the polyimide of the present invention is to be produced as a polyimide film, a varnish of a polyamic acid to be described later is applied on a glass plate.
A method of imidizing by heating or a method of directly heating and pressing polyimide powder to form a film is possible. Further, since the polyimide of the present invention has extremely high solubility in general-purpose organic solvents, it is also possible to form a film by dissolving the polyimide powder in an organic solvent, applying the powder on a glass plate, and removing the solvent. The general-purpose organic solvent used here is not particularly limited, and examples thereof include the solvents (a) to (e) described above as usable in the method for producing a polyimide.

The polyamic acid of the present invention has the general formula (I)
It has a repeating unit represented by V). In particular, the general formula (I
In V), a polyamic acid in which both R ¹ and R ² are bonded to any of the 4-, 5-, and 6-positions on the 1,1-dimethylindane skeleton is preferable because of having high solvent solubility.

Further, in the general formula (IV), R ₁ and R ₂ are both methyl groups, and these methyl groups are 1,1-
Polyamic acid bonded to the 4- and 6-positions on the dimethylindane skeleton and having Z as a benzophenone structure, that is, a polyamic acid having a repeating unit structure represented by the following formula (VIII) has high solvent solubility, It is preferable because high sensitivity can be obtained.

[0070]

Embedded image Further, in the general formula (IV), both R ₁ and R ₂ bind to any of the 4-, 5- or 6-positions on the 1,1-dimethylindane skeleton, and at the same time, X in the general formula (IV) But-
Polyamic acid which is CO- or C (= N ₂ )-is preferable because it has high solvent solubility and high photosensitivity can be obtained.

Further, in the general formula (IV), both R ₁ and R ₂ are the 4-position, 5-position on the 1,1-dimethylindane skeleton.
At the 6th or 6th position, and simultaneously with the general formula (IV)
The polyimide in which X is —CO— or C (＝ N ₂ ) — and Y is —CO— or C (＝ N ₂ ) — or S— has high solvent solubility and high sensitivity. Photosensitivity is obtained, which is preferable.

The logarithmic viscosity of the polyamic acid of the present invention is not particularly limited, but is generally from 0.1 to 2.0, preferably from 0.2 to 1.9, more preferably from 0.3 to 1.9. 0.8 is more preferable, 0.4 to 1.7 is particularly preferable, and 0.5 to 1.6 is most preferable. If the logarithmic viscosity of the polyamic acid is too low, the strength and toughness of the processed product generally decrease, which is not preferable. If the logarithmic viscosity of the polyamic acid is too high, the processability in commercialization generally deteriorates, which is not preferable. The method for evaluating the logarithmic viscosity of the polyamic acid is not particularly limited. For example, 2.50 g of a polyamic acid varnish (a polyamic acid solution using N-methyl-2-pyrrolidone as a solvent, having a concentration of 20% by weight) is used. N-methyl-2-pyrrolidone 10
After dissolving in 0 ml, it can be measured at 35 ° C.

The polyamic acid of the present invention can be prepared by adding various diamines and tetracarboxylic dianhydrides in addition to the repeating unit component having the structure represented by the general formula (IV) to various physical properties such as heat resistance, hygroscopicity and thermal expansion. For the purpose of controlling the coefficient, the dielectric constant, the refractive index, the birefringence, and the like, it may be obtained by copolymerization as necessary.

The polyamic acid of the present invention may be produced by any method. However, the method for producing a polyamic acid of the present invention uses a diaminoindane derivative represented by the general formula (II) and an aromatic tetracarboxylic dianhydride represented by the general formula (III) as monomers. It is characterized by doing. Specific examples of the diaminoindan derivative represented by the general formula (II) are as described above.

Further, R ₁ and R _{2 in} the general formula (II) are both methyl groups, and these methyl groups are bonded to the 4- and 6-positions on the 1,1-dimethylindane skeleton, ie, diaminoindane, 5,7-diamino-1,1,4,6-tetramethylindane represented by the formula (VII) and an aromatic tetracarboxylic dianhydride represented by the general formula (III) are used as monomers. The method used is preferred.

In producing the polyamic acid of the present invention, in addition to the diaminoindane derivative represented by the general formula (II) and the aromatic tetracarboxylic dianhydride represented by the general formula (III), various other A diamine and a tetracarboxylic dianhydride can be used together as a monomer and copolymerized.

The diamine component and the tetracarboxylic dianhydride component used for the copolymerization are not particularly limited. For example, the diamine and the tetracarboxylic dianhydride used for the copolymerization of the above-mentioned polyimide can be similarly mentioned. be able to. Further, for the purpose of introducing a branch, a part of the diamine is replaced with a triamine or a tetraamine, or a part of the tetracarboxylic dianhydride is replaced with a hexacarboxylic trianhydride or an octacarboxylic tetraanhydride. You may.

In the method for producing a polyamic acid according to the present invention, the solvent, terminal blocking agent and catalyst are the same as those used for the copolymerization of polyimide described above.

In the method for producing a polyamic acid according to the present invention, the polymerization temperature and the polymerization time vary depending on the solvent used and the presence or absence of the catalyst and the type thereof.
C., 1 to 24 hours is sufficient.

The novel photosensitive polyimide and polyamic acid of the present invention have excellent heat resistance, mechanical properties and adhesive properties, and also have high solvent solubility, low dielectric properties, or high sensitivity and high resolution photosensitivity. From semiconductor devices, thin film devices, interlayer insulating films and surface protective films, as photoresists, electronics, paints, printing inks, printing plates,
It can be widely used in areas such as adhesives.

The photoresist of the present invention has the general formula (I)
And / or a polyamic acid having a repeating unit represented by the following general formula (IV). Here, the photoresist means a substance that forms a chemical resistant, particularly an insoluble hardened film upon exposure.

The photoresist of the present invention may comprise, as its constituent components, any other components other than the polyimide and polyamic acid of the present invention, depending on the purpose, such as a sensitizer, a photopolymerization initiator, a monomer, and an oligomer. , A stabilizer, a wetting agent, a flow agent, a pigment, a dye, an adhesion promoter, and the like. The photoresist of the present invention is extremely useful in the fields of electronics, paints, printing inks, printing plates, adhesives, etc., as well as interlayer insulating films and surface protective films of semiconductor elements and thin film devices.

In the insulating film of the present invention, Z in the general formula (I) of the polyimide of the present invention is preferably

[0084]

Embedded image Is an insulating film made of polyimide. This insulating film can be applied to any conventionally known film forming method. For example, after applying a varnish of polyamic acid which is a precursor of the polyimide of the present invention on a desired substrate,
A method of imidizing by heating or a method of directly heating and pressing polyimide powder to form a film is possible. Further, it is also possible to form a film by dissolving the polyimide of the present invention in a general-purpose organic solvent, applying the solution on a substrate, and removing the solvent.

The multilayer wiring board of the present invention is a wiring board having the insulating film of the present invention as an interlayer insulating film. A conventionally known method can be applied to manufacture the multilayer wiring board. Specifically, for example, it can be manufactured by the following method. First, a varnish of the polyimide of the present invention or a precursor thereof is applied on a substrate on which a conductor layer having a predetermined pattern is formed, and baked to obtain a polyimide resin layer to be an interlayer insulating film. Thereafter, a patterning process using a photoresist, which is a known technique, is performed to form a through-hole in the polyimide resin layer, and a conductor layer is further formed thereon, thereby electrically connecting the through-hole. A layer wiring board is manufactured. By repeating this operation many times, a multilayer wiring board can be manufactured.

[0086]

EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto. Various tests in the examples were performed according to the following methods. (1) Logarithmic viscosity of polyimide powder and polyamic acid varnish: 0.50 g of polyimide powder or 2.50 g of polyamic acid varnish (20% by weight) was dissolved in 100 ml of N-methyl-2-pyrrolidone and measured at 35 ° C. (2) 5% weight loss temperature: DTA-TG in air
(TG-DTA2000, manufactured by Mac Science) at a heating rate of 10 ° C./min. (3) Glass transition temperature / crystal melting temperature: Differential scanning calorimetry (DSC, DSC310 manufactured by Mac Science)
Measured at 0 ° C / min according to 0). (4) Solvent solubility test: polyimide powder was added to each solvent for 20
% By weight and stirred at room temperature, and the dissolved state was visually checked. (5) Dielectric constant: Evaluation of dielectric constant is based on JIS-K6911.
Compliant with the law. (6) Mechanical properties of the film: Evaluation of the mechanical properties (tensile strength, tensile elongation and tensile modulus) of the film is based on ASTM.
-Complied with D882.

<Synthesis Example> 300 g (2.8 g) of m-xylene was placed in a reaction flask equipped with a stirrer, thermometer and cooling tube.
2 mol), cooled at -15 ° C, and 165 g (1.56 mol) of 93% sulfuric acid were dropped. to this,
68 g (1.00 mol) of isoprene and m-xylene 1
50 g (1.41 mol) of the mixture was added at a reaction temperature of -1.
It was kept at about 0 ° C., charged dropwise over 7 hours, and further stirred at the same temperature for 1 hour. After the completion of the reaction, the sulfuric acid layer is allowed to stand and separated,
300 g of 20% saline was added to the organic layer and neutralized with aqueous ammonia. This was heated to 70 to 80 ° C., and the aqueous layer was separated, and then excess m-xylene was distilled off under reduced pressure. The obtained residue was distilled off under reduced pressure to obtain colorless liquid 1,1,4,6-tetramethylindane. Yield 120 g (69% yield), b
p. 105-106 [deg.] C (2128 Pa).

¹ H-NMR (CDCl 3, TMS) ppm δ 1.25 (6H, s, 1-Me × 2) 1.90 (2H, t, 2-CH ₂ ) 2.21 (3H, s, 4 -Me or 6-Me) 2.31 ( 3H, s, 4-Me or 6-Me) 2.72 (2H, t, 3-CH 2) 6.77 (2H, s, 5-H and 7- H).

120 g (0.688 mol) of 1,1,4,6-tetramethylindane thus obtained was
Nitric acid 101 having a specific gravity of 1.52, previously cooled to -5 ° C.
g (1.5 mol), 417 g of 98% sulfuric acid (4.17 mol)
l) and 300 g of 1,2-dichloroethane were added dropwise over 2 hours while maintaining the reaction temperature at -5 to 0 ° C. After charging, the mixture was further stirred at the same temperature for 1 hour. After the completion of the reaction, 400 g of water was added to the reaction solution while cooling, and the sulfuric acid layer was diluted. 500 g of water was added to the separated organic layer, and 1,2-dichloroethane was azeotropically distilled off. The precipitated crystals were filtered, washed with water, and dried to obtain 5,7-dinitro-1,1,4 as pale yellow crystals. , 6-Tetramethylindane was obtained. Yield 175g (96% yield) mp.
93 ° C.

¹ H-NMR (CDCl 3, TMS) ppm δ 1.38 (6H, s, 1-Me × 2) 2.08 (2H, t, 2-CH ₂ ) 2.20 (3H, s, 4 -Me or 6-Me) 2.28 ( 3H, s, 4-Me or 6-Me) 3.87 (2H, t, 3-CH 2) elemental analysis (%) C H N calculated 59.09 6 .10 10.60 Analytical value 59.03 5.86 10.52.

The obtained 5,7-dinitro-1,1,4,6-
175 g (0.662 mol) of tetramethylindane is dissolved in 500 g of methanol, and 5% -Pd / C 17.
After adding 5 g (50% water-containing product), 50 to 6
Stirred at 0 ° C. for 84 hours. After completion of the reaction, the mixture was filtered and the filtrate was concentrated under reduced pressure. The resulting residue was distilled under reduced pressure to obtain 5,7-diamino-1,1,4,6-tetramethylindane as pale yellow crystals. 124 g (92.1% yield), mp. 77-
78.5 ° C, bp. 148 to 150 ° C (399 Pa).

¹ H-NMR (CDCl 3, TMS) ppm δ 1.38 (6H, s, 1-Me × 2) 1.86 (2H, t, 2-CH ₂ ) 1.99 (3H, s, 4 -Me or 6-Me) 2.03 ( 3H, s, 4-Me or 6-Me) 2.73 (2H, t, 3-CH 2) 3.3~3.5 (4H, br s, NH ₂ x 2) Elemental analysis (%) Calculated for CHN 76.42 9.87 13.71 Analytical value 75.61 10.25 13.95.

Example 1 A five-necked reactor equipped with a nitrogen inlet tube, a thermometer, a reflux condenser, and a stirrer was charged with 5,7-
4.1 g of diamino-1,1,4,6-tetramethylindane
(0.02 mol), 6.4 g (0.02 mol) of benzophenonetetracarboxylic dianhydride, and γ as a catalyst
0.3 g (0.003 mol) of picoline was weighed out. 42 g of m-cresol was added thereto, and the mixture was stirred under a nitrogen atmosphere, heated to 150 ° C. over 2 hours, and reacted at 150 ° C. for 7 hours. Water generated during the reaction was removed out of the system. The solution was cooled to 30 ° C., and the obtained viscous polymer solution was discharged into 2 liters of vigorously stirred methanol. A precipitate in the form of a yellow powder was obtained.
The precipitate was further washed with 30 ml of methanol and filtered. This yellow powder was pre-dried at 50 ° C. for 4 hours and then dried at 220 ° C. for 4 hours under a nitrogen stream.

The logarithmic viscosity, glass transition temperature, and 5% weight loss temperature of the obtained polyimide powder are as follows. Logarithmic viscosity: 0.53 dl / g Glass transition temperature: not observed 5% weight loss temperature: 429 ° C.

The structure of this yellow powder was identified by the following analysis. ¹ H-NMR (CDCl ₃ ): δ 8.3 (2H, s), 8.
3 (2H, s), 8.1 (2H, d, J = 7.3 Hz), 2.9
(2H, br), 2.1 (3H, s), 2.0 (2H, br),
1.9 (3H, s), 1.2 (6H, s) Infrared absorption spectrum: 2956 cm ^-1 (methylene C-
H stretching), 1730cm ^-1 (imide C = O stretching), 168
2 cm ^-1 (conjugated C = O stretch), 1459 cm ^-1 and 142
5 cm ^-1 (aromatic ring CC stretching).

When the solvent solubility (20% by weight) of the obtained polyimide powder was examined, chloroform, N, N
-Dimethylacetamide, N-methyl-2-pyrrolidone, m-cresol, THF (tetrahydrofuran),
It was confirmed that it was soluble in cyclopentanone and the like.

FIG. 1 shows ¹ H of the novel polyimide of this example.
-Shows an NMR spectrum. Where the horizontal axis is the chemical shift,
The vertical axis indicates intensity. FIG. 2 shows an infrared absorption spectrum of the novel polyimide of this example. Here, the horizontal axis represents the wave number (the number of waves per unit length), and the vertical axis represents the transmittance.

Example 2 The polyimide powder obtained in Example 1 was dissolved in cyclopentanone to form a 20% by weight solution, which was applied on a copper plate. This is heated at 50 ° C under nitrogen stream, 18
Dry at 0 ° C. for 4 hours each. The coating thickness at this time is 10 μm
Met. The polyimide film was subjected to photomasking and irradiated with 365 nm (i-line) at 40 mJ / cm ² . This was processed using N, N-dimethylformamide as a developing solution, and dried at 50 ° C. for 30 minutes. As a result, image formation was confirmed. The sensitivity (exposure amount at which the film thickness becomes 50%) was determined to be 22 mJ / cm ² .

Example 3 A 5-necked reactor equipped with a nitrogen inlet tube, a thermometer, a reflux condenser, and a stirrer was charged with 5,7-
Diamino-1,1,4,6-tetramethylindane 4.08
6 g (0.02 mol), 6.316 g (0.0196 mol) of benzophenonetetracarboxylic dianhydride, and 0.118 g (0.0008 m) of phthalic anhydride as a terminal blocking agent
ol), 3.8 g (0.02 mol) of p-toluenesulfonic acid monohydrate and 1.6 g of pyridine (0.0 g) as catalysts.
2 mol) was weighed. 50 g of N-methyl-2-pyrrolidone and 50 g of toluene were added thereto, and the mixture was stirred under a nitrogen atmosphere, heated to 150 ° C. over 2 hours, and reacted at 150 ° C. for 10 hours. Water generated during the reaction was removed outside the system by azeotropic distillation with toluene. The mixture was cooled to 30 ° C., and the obtained viscous polymer solution was discharged into 2 liters of vigorously stirred methanol. As a result, a yellow powdery precipitate was obtained. This precipitate is further treated with methanol 1
It was washed with 00 ml and filtered. 50 pieces of this yellow powder
After preliminary drying at 4 ° C. for 4 hours, drying was performed at 220 ° C. for 4 hours under a nitrogen stream. The logarithmic viscosity, glass transition temperature, and 5% weight loss temperature of the obtained polyimide powder are as follows. Logarithmic viscosity: 0.53 dl / g Glass transition temperature: not observed 5% weight loss temperature: 431 ° C.

The structure of this yellow powder was identified by the following analysis. ¹ H-NMR (CDCl ₃ ): δ 8.3 (2H, s), 8.
3 (2H, s), 8.1 (2H, d, J = 7.3 Hz), 2.9
(2H, br), 2.1 (3H, s), 2.0 (2H, br),
1.9 (3H, s), 1.2 (6H, s) Infrared absorption spectrum: 2956 cm -1 (methylene C-
H stretching), 1730cm ^-1 (imide C = O stretching), 168
2 cm ^-1 (conjugated C = O stretch), 1459 cm ^-1 and 142
5 cm ^-1 (aromatic ring CC stretching).

When the solvent solubility (20% by weight) of the obtained polyimide powder was examined, chloroform, N, N
It was confirmed that the compound was soluble in dimethylacetamide, N-methyl-2-pyrrolidone, m-cresol, THF, cyclopentanone and the like.

Example 4 Using the polyimide powder obtained in Example 3, a polyimide film was prepared in the same manner as in Example 2, and was exposed and developed. Its sensitivity was 31 mJ / cm ² .

<Comparative Example 1> 2,3,5,6-Te
3.29 g of tramethyl-1,4-phenylenediamine
(0.02 mol), benzophenonetetracarboxylic acid
Using 6.32 g (0.0196 mol) of dianhydride,
0.12 g (0.0008 mol) of phthalic anhydride as a sealing material
Example 1 except that l) was added before and after the reaction.
8.12 g of a polyimide powder was obtained in the same manner as described above.
The logarithmic viscosity of this polyimide powder was 0.88 dl / g.
Was. The same one as in Example 2 using the obtained polyimide powder
A polyimide film is prepared by the
went. Its sensitivity is 62mJ / cm ^TwoMet.

Example 5 A five-necked reactor equipped with a nitrogen inlet tube, a thermometer, a reflux condenser, and a stirrer was provided with 5,7-
4.1 g of diamino-1,1,4,6-tetramethylindane
(0.02 mol) and N-methyl-2-pyrrolidone 1
5 g was added, and the mixture was stirred under a nitrogen atmosphere at room temperature and dissolved over 30 minutes. 6.3 g (0.0195 mol) of benzophenonetetracarboxylic dianhydride was quantitatively added to the reaction system with 9 g of N-methyl-2-pyrrolidone. After stirring was continued for 5 hours at room temperature under a nitrogen atmosphere, 0.15 g (0.0010 mol) of phthalic anhydride was added as a terminal blocking agent to N
-Methyl-2-pyrrolidone was added quantitatively by 7 g.
After stirring for 2.5 hours under a nitrogen atmosphere at room temperature, the reaction was completed. The logarithmic viscosity of the obtained polyamic acid varnish is 0.26.
dl / g.

Example 6 The polyamic acid varnish obtained in Example 5 was applied on a glass plate. This was dried at 30 ° C. for 1 hour under a nitrogen stream to obtain a polyamic acid film. When four pieces of this film were immersed in an aqueous solution of N, N-dimethylacetamide, N-methyl-2-pyrrolidone, m-cresol and 2% tetramethylammonium hydroxide for 60 seconds, all the films were completely dissolved. The temperature of the polyamic acid film was raised from 30 ° C. to 250 ° C. over 2 hours in a nitrogen stream,
The mixture was heated at 0 ° C. for 2 hours to obtain a polyimide film having a coating thickness of 10 μm.

Example 7 A 5-necked reactor equipped with a nitrogen inlet tube, a thermometer, a reflux condenser, and a stirrer was provided with 5,7-
Diamino-1,1,4,6-tetramethylindane 4.08
6 g (0.02 mol), 8.36 g of 4,4′-isophthaloyl diphthalic anhydride (0.0196 mol)
l), 0.118 g (0.1%) of phthalic anhydride as a terminal blocking agent.
0004 mol), 3.8 g (0.02 mol) of p-toluenesulfonic acid monohydrate and 1.6 parts of pyridine as catalysts.
g (0.02 mol) was weighed. N-methyl-
50 g of 2-pyrrolidone and 50 g of toluene were added, and the mixture was stirred under a nitrogen atmosphere and heated to 150 ° C. over 2 hours.
The reaction was performed at 150 ° C. for 10 hours. Water generated during the reaction was removed outside the system by azeotropic distillation with toluene. Cool to 30 ° C,
The resulting viscous polymer solution was discharged into 2 liters of vigorously stirred methanol to obtain a yellow powdery precipitate, which was separated by filtration. The precipitate was further washed with 100 ml of methanol and filtered. This yellow powder was pre-dried at 50 ° C. for 4 hours, and then dried under a nitrogen stream at 220 ° C.
Dry at 4 ° C. for 4 hours. The logarithmic viscosity, glass transition temperature, and 5% weight loss temperature of the obtained polyimide powder are as follows. Logarithmic viscosity: 0.65 dl / g Glass transition temperature: Not observed 5% weight loss temperature: 428 ° C.

Further, when the solvent solubility (20% by weight) of the obtained polyimide powder was examined, chloroform, N, N-
Dimethylacetamide, N-methyl-2-pyrrolidone,
It was confirmed that it was soluble in m-cresol, THF, cyclopentanone and the like.

Example 8 A polyimide film was prepared in the same manner as in Example 2 except that the polyimide powder obtained in Example 7 was used and cyclopentanone was used as a developer. Development was performed. Its sensitivity is 2
It was 3 mJ / cm ² .

Example 9 A five-necked reactor equipped with a nitrogen inlet tube, a thermometer, a reflux condenser, and a stirrer was provided with 5,7-
4.1 g of diamino-1,1,4,6-tetramethylindane
(0.02 mol) and N-methyl-2-pyrrolidone 1
5 g was added, and the mixture was stirred under a nitrogen atmosphere at room temperature and dissolved over 30 minutes. In this reaction system, 8.36 g of 4,4'-isophthaloyldiphthalic anhydride (0.0196 mol
l) was added quantitatively with 9 g of N-methyl-2-pyrrolidone. After stirring for 5 hours under a nitrogen atmosphere at room temperature,
0.118 g of phthalic anhydride (0.000 g) was used as a terminal blocking agent.
4 mol) was added quantitatively with 7 g of N-methyl-2-pyrrolidone. After stirring for 2.5 hours under a nitrogen atmosphere at room temperature, the reaction was completed. The logarithmic viscosity of the obtained polyamic acid varnish was 0.37 dl / g.

<Example 10> A polyamic acid film was prepared in the same manner as in Example 6 except that the polyamic acid varnish obtained in Example 9 was used, and immersed in each solvent. Also completely dissolved. The polyamide acid film was heated in the same manner as in Example 6 to obtain a polyimide film having a coating thickness of 10 μm.

<Example 11> A five-necked reactor equipped with a nitrogen inlet tube, a thermometer, a reflux condenser, and a stirrer was charged with 5,7.
-Diamino-1,1,4,6-tetramethylindane 4.0
86 g (0.02 mol) of 0.691 g (0.0019) of 2,3,6,7-thioxanthone tetracarboxylic dianhydride
6mol), 5.684 g (0.017464 mol) of benzophenonetetracarboxylic dianhydride, 0.118 g (0.0004 mol) of phthalic anhydride as a terminal blocking agent, and 3.8 g of p-toluenesulfonic acid monohydrate as a catalyst (0.0
2 mol) and 1.6 g (0.02 mol) of pyridine were weighed. 50 g of N-methyl-2-pyrrolidone and 50 g of toluene were added thereto, stirred under a nitrogen atmosphere, heated to 150 ° C. over 2 hours, and reacted at 150 ° C. for 10 hours. Water generated during the reaction was removed outside the system by azeotropic distillation with toluene. The mixture was cooled to 30 ° C., and the obtained viscous polymer solution was discharged into 2 liters of vigorously stirred methanol. As a result, a yellow powdery precipitate was obtained. The precipitate was further washed with 100 ml of methanol and filtered. This yellow powder was pre-dried at 50 ° C. for 4 hours and then dried at 220 ° C. for 4 hours under a nitrogen stream. The logarithmic viscosity, glass transition temperature, and 5% weight loss temperature of the obtained polyimide powder are as follows. Logarithmic viscosity: 0.62 dl / g Glass transition temperature: Not observed 5% weight loss temperature: 420 ° C.

When the solvent solubility (20% by weight) of the obtained polyimide powder was examined, chloroform, N, N-
Dimethylacetamide, N-methyl-2-pyrrolidone,
It was confirmed that it was soluble in m-cresol, THF, cyclopentanone and the like.

<Example 12> A polyimide film was prepared in the same manner as in Example 2 except that the polyimide powder obtained in Example 11 was used and cyclopentanone was used as a developing solution. Development was performed. Its sensitivity was 20 mJ / cm ² .

Example 13 A 5-necked reactor equipped with a nitrogen inlet tube, a thermometer, a reflux condenser, and a stirrer was charged with 5,7.
-Diamino-1,1,4,6-tetramethylindane 4.1
g (0.02 mol) and 15 g of N-methyl-2-pyrrolidone were added, and the mixture was stirred at room temperature under a nitrogen atmosphere and dissolved over 30 minutes. In this reaction system, 0.691 g of 2,3,6,7-thioxanthonetetracarboxylic dianhydride (0.001 g) was added.
96 mol) and 5.684 g (0.017464 mol) of benzophenonetetracarboxylic dianhydride were added quantitatively with 9 g of N-methyl-2-pyrrolidone. After continuing stirring at room temperature under a nitrogen atmosphere for 5 hours, 0.118 g (0.0004 mol) of phthalic anhydride was added as a terminal blocking agent to N-
It was added quantitatively with 7 g of methyl-2-pyrrolidone.
After stirring for 2.5 hours under a nitrogen atmosphere at room temperature, the reaction was completed. The logarithmic viscosity of the obtained polyamic acid varnish is 0.36.
dl / g.

Example 14 A polyamic acid film was prepared in the same manner as in Example 6 except that the polyamic acid varnish obtained in Example 13 was used, and immersed in each solvent. Also completely dissolved.
The polyamide acid film was heated in the same manner as in Example 6 to obtain a polyimide film having a coating thickness of 10 μm.

Example 15 [Theoretical Calculation: Calculation Examples 1 to 7]
> Molecular modeling software (CS Chem3D Pr)
Using o), a molecular model of A, B or C represented by the following formula (IX) was prepared. This molecular model was optimized using semi-empirical molecular orbital calculation (AM1) to obtain an optimally stabilized structure. Table 1 summarizes the results of examining the absolute value | α | of the dihedral angle α in this structure.

[0117]

Embedded image

[0118]

[Table 1] In Table 1, the model corresponding to the polyimide of the present invention is Calculation Example 6, and this model has the largest dihedral angle. That is, it was proved by calculation that the polyimide of the present invention was controlled to a three-dimensional structure having a large dihedral angle. This result theoretically explains that the characteristic structure of the polyimide of the present invention suppresses intramolecular charge transfer and achieves high sensitivity of photosensitive performance.

Example 16 In a five-necked reactor equipped with a nitrogen inlet tube, a thermometer, a Dean-Stark tube equipped with a reflux condenser, and a stirrer, 5,7-diamino-1,1,4,6- 10.2 g (0.05 mol) of tetramethylindane, 10.8 g (0.0495 mol) of pyromellitic dianhydride, 0.148 g (0.001 mol) of phthalic anhydride, 4.0 g (0.05 mol) of pyridine, 9.5 g (0.05 mol) of p-toluenesulfonic acid monohydrate was weighed. 70 g of N-methyl-2-pyrrolidone and 70 g of toluene
g, and the mixture was stirred under a nitrogen atmosphere, heated to a reflux temperature of 135 ° C. over 2 hours, and reacted for 8 hours. Water generated during the reaction was removed out of the system. Thereafter, the mixture was cooled to 30 ° C., and the resulting viscous polymer solution was discharged into 2 liters of vigorously stirred methanol. A precipitate in the form of a brown powder was obtained. The precipitate was further washed with 100 ml of methanol and filtered. This brown powder was pre-dried at 50 ° C. for 4 hours, and then dried under a nitrogen stream for 22 hours.
Dry at 0 ° C. for 4 hours. The logarithmic viscosity, glass transition temperature, and 5% weight loss temperature of the obtained polyimide powder are as follows. Logarithmic viscosity: 0.46 dl / g Glass transition temperature: Not observed 5% weight loss temperature: 442 ° C.

Further, when the solvent solubility (20% by weight) of the obtained polyimide powder was examined, it was found that it was soluble in chloroform, N-methyl-2-pyrrolidone, m-cresol, THF, cyclopentanone and the like. It was confirmed.

Example 17 Example 17 was repeated except that pyromellitic anhydride in Example 16 was changed to 14.6 g (0.0495 mol) of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride. The processing was performed as in Example 1. The logarithmic viscosity, glass transition temperature, and 5% weight loss temperature of the obtained pale yellow polyimide powder are as follows. Logarithmic viscosity: 0.96 dl / g Glass transition temperature: Not observed 5% weight loss temperature: 431 ° C.

When the solvent solubility (20% by weight) of the obtained polyimide powder was examined, it was found that the polyimide powder was soluble in chloroform, N-methyl-2-pyrrolidone, m-cresol, THF, cyclopentanone and the like. It was confirmed.

Example 18 The pyromellitic anhydride in Example 16 was replaced with 15.4 g (0.0495 mol) of bis (3,4-dicarboxyphenyl) ether dianhydride.
The processing was performed in the same manner as in Example 1 except for changing to. Logarithmic viscosity, glass transition temperature, 5% of the obtained pale yellow polyimide powder
The weight loss temperatures are as follows: Logarithmic viscosity: 0.66 dl / g Glass transition temperature: Not observed 5% weight loss temperature: 429 ° C.

Further, when the solvent solubility (20% by weight) of the obtained polyimide powder was examined, it was found that the polyimide powder was soluble in chloroform, N-methyl-2-pyrrolidone, m-cresol, THF, cyclopentanone and the like. It was confirmed.

Example 19 The pyromellitic anhydride in Example 16 was replaced with 17.7 g (0.0495 mol) of bis (3,4-dicarboxyphenyl) sulfone dianhydride.
The processing was performed in the same manner as in Example 1 except for changing to. Logarithmic viscosity, glass transition temperature, 5% of the obtained pale yellow polyimide powder
The weight loss temperatures are as follows: Logarithmic viscosity: 0.38 dl / g Glass transition temperature: Not observed 5% weight loss temperature: 422 ° C.

When the solvent solubility (20% by weight) of the obtained polyimide powder was examined, it was found that the polyimide powder was soluble in chloroform, N-methyl-2-pyrrolidone, m-cresol, THF, cyclopentanone and the like. It was confirmed.

Example 20 In a five-necked reactor equipped with a nitrogen inlet tube, a thermometer, a Dean-Stark tube equipped with a reflux condenser, and a stirring device, 5,7-diamino-1,1,4,6- Tetramethylindane 10.2 g (0.05 mol), 2,2
-Bis (3,4-dicarboxyphenyl) -1,1,1,
2,2,0 g of 3,3,3-hexafluoropropane dianhydride
(0.0495 mol), 0.148 g of phthalic anhydride
(0.001 mol), pyridine 4.0 g (0.05 mol)
l), 9.5 g of p-toluenesulfonic acid monohydrate (0.0
5 mol) was weighed. To this, 70 g of N-methyl-2-pyrrolidone and 70 g of toluene were added, stirred under a nitrogen atmosphere, heated to a reflux temperature of 135 ° C. over 2 hours, and reacted for 8 hours. Water generated during the reaction was removed out of the system. Thereafter, the mixture was cooled to 30 ° C., and the obtained viscous polymer solution was discharged into 2 liters of vigorously stirred methanol to obtain a pale yellow powdery precipitate, which was separated by filtration. The precipitate was further washed with 100 ml of methanol and filtered. This pale yellow powder was pre-dried at 50 ° C. for 4 hours and then dried at 220 ° C. for 4 hours under a nitrogen stream.
The logarithmic viscosity, glass transition temperature and 5% weight loss temperature of the obtained pale yellow polyimide powder are as follows. Logarithmic viscosity: 0.56 dl / g Glass transition temperature: not observed 5% weight loss temperature: 436 ° C.

When the solvent solubility (20% by weight) of the obtained polyimide powder was examined, the polyimide powder was dissolved in chloroform, N-methyl-2-pyrrolidone, m-cresol, THF, cyclopentanone, ethyl acetate, acetone and the like. It was confirmed that it was soluble.

This polyimide powder was dissolved in dimethylacetamide to prepare a 20% by weight varnish, which was applied on a glass plate, and then was applied at 180 ° C. for 4 hours under a nitrogen stream, and then at 100 ° C. under reduced pressure. 8 hours, further under reduced pressure 180
Drying was performed at 16 ° C. for 16 hours to obtain a polyimide film having a thickness of 16 μm. When the dielectric constant (ε) of this film was measured, it was ε = 2.68. Further, in the same manner as above, a polyimide film having a thickness of 60 μm was prepared, and the mechanical properties of the film were measured.
It was 0 MPa, the tensile modulus was 2.3 GPa, and the tensile elongation was 5%.

[0130]

As described above, according to the present invention, excellent heat resistance, mechanical properties, and adhesive properties, as well as high solvent solubility, low dielectric properties, or high sensitivity and high resolution photosensitivity are exhibited. New polyimide and polyamic acid can be provided at low cost. These are very useful especially in the use of a photoresist that is exposed at 365 nm (i-line), and are highly integrated semiconductor devices and highly integrated multi-layer wiring boards including an insulating film, particularly an insulating film as a surface protective film or an interlayer insulating film. It is very useful in applications.

[Brief description of the drawings]

FIG. 1 is a diagram showing a ¹ H-NMR spectrum of a novel polyimide of Example 1.

FIG. 2 is a view showing an infrared absorption spectrum of a novel polyimide of Example 1.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H05K 3/46 C08L 79:08 Z // C08L 79:08 H01L 21/30 502R (31) Priority claim number Japanese Patent Application 2001-100886 (P2001-100886) (32) Priority Date March 30, 2001 (3.3.30 2001) (33) Country of Priority Claim Japan (JP) (31) Priority Claim Number Japanese Patent Application 2001 (32) Priority date March 30, 2001 (March 30, 2001) (33) Priority claiming country Japan (JP) (31) Priority claim number Japanese Patent Application 2001-100888 ( (32) Priority Date March 30, 2001 (March 30, 2001) (33) Priority Country Japan (JP) (72) Inventor Takashi Kuroki 580-32 Nagaura, Sodegaura City, Chiba Prefecture Mitsui (72) Inventor Shoji Tamai 580-32 Nagaura, Sodegaura-shi, Chiba Mitsui Chemicals, Inc. F term (reference) 2H025 AA01 AA02 AA10 AA20 AB16 AB17 CB25 CB41 4F071 AA60 AF02 AF13 AF39 AF58 AH02 AH15 BA02 BB02 BC01 BC02 4J043 PA02 PA19 QB15 QB26 QB33 RA35 SA06 SA43 SA44 SA03 UB21 UA21 UA21 UA23 UB28 UB30 VA02 VA03 VA06 VA07 ZA02 ZA06 ZA12 ZA31 ZA46 ZB22 ZB47 ZB50 5E346 CC10 EE20 5G305 AA07 AA11 AB10 AB36 AB40 BA18 CA25 CA38

Claims (12)

[Claims] 1. A polyimide having a repeating unit represented by the following general formula (I). Embedded image (Wherein, R ₁ and R ₂ each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and Z represents a condensed polycyclic aromatic group or a compound represented by the following formula: At least one group selected from the group consisting of However, X is -CO- or -C (= N ₂₎ - indicates, Y is a direct _{bond, -CH 2 -, - O -} , - SO 2 -, - S -, - CO- or -C
(= N ₂ )-, W is a direct bond, -CH _2- , -C (CH
₃ ) _2- , -C (CF ₃ ) _2- , -S-, -SO-, -SO ₂ -or-
Indicates O-. b represents an integer of 0 or 1, m and n each independently represent an integer of 0 or 1, r represents each independently an alkyl group having 1 to 4 carbon atoms, a halogen group or a phenyl group. And a represents 0 or an integer of 1 to 3. ) 2. A compound according to claim 1, wherein both R ₁ and R ₂ in formula (I) are methyl groups, and these methyl groups are bonded to the 4- and 6-positions on the 1,1-dimethylindane skeleton. Item 1
The polyimide as described. 3. Use of a diaminoindane derivative represented by the following general formula (II) and an aromatic tetracarboxylic dianhydride represented by the following general formula (III) as monomers: And a method for producing a polyimide having a repeating unit represented by the following general formula (I). Embedded image Embedded image (Wherein, R ₁ and R ₂ each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and Z represents a condensed polycyclic aromatic group or a compound represented by the following formula: At least one group selected from the group consisting of However, X is -CO- or -C (= N ₂₎ - indicates, Y is a direct _{bond, -CH 2 -, - O -} , - SO 2 -, - S -, - CO- or -C
(= N ₂ )-, W is a direct bond, -CH _2- , -C (CH
₃ ) _2- , -C (CF ₃ ) _2- , -S-, -SO-, -SO ₂ -or-
Indicates O-. b represents an integer of 0 or 1, m and n each independently represent an integer of 0 or 1, r represents each independently an alkyl group having 1 to 4 carbon atoms, a halogen group or a phenyl group. And a represents 0 or an integer of 1 to 3. ) 4. R ₁ and R _{2 in} the general formulas (I) and (II) are both methyl groups, and these methyl groups are bonded to the 4- and 6-positions on the 1,1-dimethylindane skeleton. The method for producing a polyimide according to claim 3, wherein 5. A polyamic acid having a repeating unit represented by the following general formula (IV). Embedded image (Wherein, R ₁ and R ₂ each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and Z is a condensed polycyclic aromatic group or a compound represented by the following formula: At least one group selected from the group consisting of However, X is -CO- or -C (= N ₂₎ - indicates, Y is a direct _{bond, -CH 2 -, - O -} , - SO 2 -, - S -, - CO- or -C
(= N ₂ )-, W is a direct bond, -CH _2- , -C (CH
₃ ) _2- , -C (CF ₃ ) _2- , -S-, -SO-, -SO ₂ -or-
Indicates O-. b represents an integer of 0 or 1, m and n each independently represent an integer of 0 or 1, r represents each independently an alkyl group having 1 to 4 carbon atoms, a halogen group or a phenyl group. And a represents 0 or an integer of 1 to 3. ) 6. The compound according to claim 1, wherein both R ₁ and R _{2 in} the general formula (IV) are methyl groups, and these methyl groups are bonded to the 4- and 6-positions on the 1,1-dimethylindane skeleton. Item 5
Polyamic acid as described. 7. A diaminoindane derivative represented by the following general formula (II) and an aromatic tetracarboxylic dianhydride represented by the following general formula (III) are used as monomers. And a method for producing a polyamic acid having a repeating unit represented by the following general formula (IV). Embedded image Embedded image (Wherein, R ₁ and R ₂ each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and Z is a condensed polycyclic aromatic group or a compound represented by the following formula: At least one group selected from the group consisting of However, X is -CO- or -C (= N ₂₎ - indicates, Y is a direct _{bond, -CH 2 -, - O -} , - SO 2 -, - S -, - CO- or -C
(= N ₂ )-, W is a direct bond, -CH _2- , -C (CH
₃ ) _2- , -C (CF ₃ ) _2- , -S-, -SO-, -SO ₂ -or-
Indicates O-. b represents an integer of 0 or 1, m and n each independently represent an integer of 0 or 1, r represents each independently an alkyl group having 1 to 4 carbon atoms, a halogen group or a phenyl group. And a represents 0 or an integer of 1 to 3. ) 8. R ₁ and R _{2 in} the general formulas (IV) and (II) are both methyl groups, and these methyl groups are bonded to the 4- and 6-positions on the 1,1-dimethylindane skeleton. The method for producing a polyamic acid according to claim 7, wherein 9. The polyimide according to claim 1 and a polyimide according to claim 5.
A photoresist containing one or both of the above-mentioned polyamic acids. 10. Z in the general formula (I) is: An insulating film comprising the polyimide according to claim 1. 11. A multilayer wiring board having the insulating film according to claim 10 as an interlayer insulating film. 12. When the optimum stabilized structure is calculated based on theoretical calculation, the absolute value | α | of the dihedral angle α is in the range of 82 ° to 98 ° in the repeating unit structure contained in the molecule (however, The above α is a dihedral angle formed by four adjacent atoms C (carbonyl carbon of imide) —N (nitrogen of imide) —CC, and is defined in the range of −180 ° or more and 180 ° or less.)
A polyimide.