TW541324B - Polyimide and method of producing it, polyamic acid and method of producing it, and photoresist and insulation film composed thereof - Google Patents

Abstract

A polyimide having a repeating unit of the general formula (I) and a polyamic acid having a repeating unit of the formula (IV): (wherein, R1 and R2 represent H or a C1 to C20 alkyl group, and Z represents a condensed polycyclic aromatic group or an group of the following formulae: Herein, X represents -CO- or -C(=N2)-, Y represents a direct bond, -CH2-, -O-, -SO2-, -S-, -CO- or -C(=N2)-, and W represents a direct bond, -CH2-, -C(CH3)2-, -C(CF3)2-, -S-, -SO-, -SO2- or -O-. b, m and n are 0 or 1; r is a C1 to 4 alkyl group, halogen group or phenyl group; a is 0 or 1 to 3.).

Description

541324 V. Description of the invention 0) Technical Field The present invention relates to the solubility of heat-resistant solvents and novel polyimide compounds. It is a semi-integrated semi-membrane and interlayer insulation in the background. Flame retardant, electrical insulation, conveying machines are used to require heat-resistant electronic equipment to pass through its excellent semiconductor element insulation film, printing high-performance insulation layer and protection of mechanical properties, additive, or photosensitivity. Compared to the novel polyimide and polyamic acid. More specifically, it has excellent mechanical properties, adhesive properties, and photosensitivity and polyamic acid that exhibit high and low dielectric properties, or high sensitivity and high resolution. The polyimide and polyamic acid are very useful in light properties, and they are very useful as insulating films used in surface protective films for insulating films, special conductor devices, and highly integrated multilayer circuit boards. Tetraweilic acid dianhydride, coupled with mechanical feasibility, etc., is a neutral field. Awakening extends the financial and thermal properties, and the film material of the surface protection circuit. In the special layer, polyurethane has a flat pattern formation and diamine strength, and is used in electrical appliances. Recently, the electrical characteristic film and sealing substrate are based on the reaction scale of hemiamine. With the requirements of this year, mechanical equipment materials and solar conductor greases have excellent qualitative characteristics, and have been given characteristics, and the universe has also been used by computers and other multi-layer batteries. The inherent excellent processability and performance of the insurance industry also show arsonine, and it also has the financial and thermal properties of multi-body components such as interlayer coatings for high-concentration lines. And low dielectrics show its photosensitivity polyimide. The previous technology can

Burst 90110113.ptd Page 5 541324

5. Description of the invention (2) Japanese Patent No. 2 1 2 5 9 0 7 and Japanese Patent No. 1 7 6 7 8 1 are listed. It is a paper such as Pfeifer et al. (Pfeifer, J. and Rohde, 〇.,

Polyimides: Synthesis, Characterization, and Application, Proc. 2nd. Inti. Conf. Polyimides, p. 130 (1985)), etc., have a structure via a diphenyl structure in the framework and a photo-crosslinking reaction between alkyl groups. Negative-type photosensitive polyimide of a hardening mechanism (hereinafter referred to as a native, a structure). _ In this prior art, specifically 4,4, -diamino-3,3 ', 5,5'-tetrafluorenyldiphenylphosphonium and 2,3,5,6-tetramethyl are disclosed -1,4-Phenylamine is a kind of polyimide with two kinds of diamines and benzophenone tetraweiric acid. These photosensitive polyimides show a tendency to become more sensitive as the content of sulphuric groups in the molecule increases (POLYMER ENGINEERING AND SCIENCE, MID-NOVEMBER 1992, Vol. 32, No. 21, 1 6 twenty three -). Although this prior art also shows that the photosensitive small imine with high alkyl group content and high sensitivity, but if you want to increase the sensitivity to the south, you must design a diamine unit with a large number of carbon groups, so the status quo is not allowed. Does not increase manufacturing costs. Also, in the scope of the patent application of Japanese Patent No. 2 1 2 5 907, it is described that polyamines containing polyamines as the diamine units are used. It has a structure similar to the polyimide of the present invention (polyimide using a 1,1-dimethyldiamine group as a monoamine unit). However, this diamino group has not been documented for a specific production method. The manufacturing method is to first manufacture the raw materials, and then introduce the amino group into the nitro group and reduce it, and then reduce the aromatic ring according to the technology shown in US Patent No. 3 8 7 5 2 2 8 and so on.

Ring m ί 1

Mb 90110113.ptd Page 6 541324 V. Description of the invention (3) 9-5 0 4 7 9 4 As shown in the manufacturing example, in order to introduce a second amine group, the amine group is protected, trisylized, and deprotected. , Restore operations, etc. As such, the manufacture of diamino group must be combined with various technologies and undergoes many processes, and it can be speculated that it is not easy. In addition, Yamashita et al. Proposed that in the photo-crosslinking reaction of this institution, controlling the stereo coordination within the molecule has the possibility of improving the sensitivity of the obtained polyimide (after Yamashita, " Progress ", 192 years, 292 pages, 193 years). It is proposed that in addition to the method of increasing the content of fluorene groups in the molecule, there is a possibility of improving sensitivity, that is, a possibility of suppressing the cost of introducing an alkyl group and producing a highly sensitive photosensitive polyimide, In the photosensitive polyimide of this mechanism shown, it is not possible to increase the sensitivity of stereo coordination to the maximum and manufacture it at a low cost. All in all, according to this institution's high-sensitivity, high-resolution photosensitive polyimide, it is not satisfactory in terms of cheap supply, and it is in pursuit of developing a low-cost, high-sensitivity and high-resolution negative-type photosensitive polyimide. On the other hand, according to Japanese Patent Publication No. 7-11 6112, a diamine radical derivative and a method for producing the same have been reported. This diamine-based derivative is reported to be used as a raw material for isocyanate, epoxy resin, bismaleimide, etc., as an isocyanate hardener, and as a modifier for various resins and rubbers. However, this diamino radical derivative can be used as a monomer for polyimide, and the various polyimides obtained have excellent photosensitivity and show significantly high solvent solubility. It is completely unknown so far. _ Discovery of invention

90110113.ptd Page 7 V. Description of the invention (4) The purpose of the present invention is excellent, and a high-resolution resistive substance and an insulating film are added. Show cost invention. That is, the sulfonamide of the present invention. 541324 is a novel polyimide and polyamic acid that provides high heat resistance, mechanical properties, and adhesive properties that exhibit high solvent solubility and low dielectric properties, or high sensitivity and light properties. For example, it is useful in light and other applications. Imidic acid and polyamic acid. People carried out a dedication review, and the results were synthesized from a novel polyimide and a novel polyimide with a full skeleton. The polyimide and polyamic acid have excellent photosensitivity, low dielectric properties, and significantly high Solvent solubility, and the polymer having the repeating unit represented by the following general formula (I) is reached οπμα ^ ΥΠΟ ζ ΟΛ γο Ν

(In the formula, heart and heart each independently represent a hydrogen atom or a carbon number of 1 to 20 ethane groups, and Z is a condensed polycyclic aromatic group or the following formula

90110113.ptd Page 8 541324 V. Description of the invention (5)

At least one basis is selected from the group. However, X is -C 0-or -C (= N2)-, and Y is a direct bond, -CH2-, -〇-, -S02, -s-, -CO-, or -C (= N2)- W is a direct bond, -CH2-, -C (CH3) 2-, -C (CF3) 2-, -S-, -S0-, -S02-, or -0. 13 is an integer of 0 or 1, m and η each independently represent an integer of 0 or 1, r is independently an alkyl group of 1 to 4 carbon atoms, or a halo group or a phenyl group, and a is 0 or bu 3 Integer) Furthermore, in the present invention, a diamine ffman derivative represented by the following general formula (Π) and an aromatic tetracarboxylic dianhydride represented by the following general formula (II I) are used as the monomer. The method for producing polyimide having the above-mentioned repeating unit represented by the general formula (I) is its feature. D NH〇

(Ν) ο ο (III)

Y r ο ο Furthermore, the present invention is a polyamic acid having a repeating unit represented by the following general formula (IV)

90110113.ptd Page 9 541324 V. Description of the invention (6) UO Η Η

Ri ΗΟ-γ γ-ΟΗ R2 ο ο

, ch3 CH, (iv) (wherein the heart and the heart independently represent a hydrogen atom or an alkyl group of 20 carbon atoms, and Z is a condensed polycyclic aromatic group or the following formula

4 »At least one basis is selected from the group. However, X is -C0- or -C (= N2)-, Y is a direct bond, -CH2-, -0-, -so2, -s-, -C0-, or-'W is a direct bond , -CH2-, -C (CH3) 2-, -C (CF3) 2-, -S-, -S0-, -S02-, or -0 are integers representing 0 or 1, m and η are independently represented An integer of 0 or 1, r independently represents the carbon number

90110113.ptd Page 10 541324 V. Description of the invention (7) Four alkyl groups, or halo groups or phenyl groups, a is an integer of 0 or 1 to 3) Furthermore, the present invention uses the aforementioned general The diamine group derivative represented by the formula (II) and the aromatic tetracarboxylic dianhydride represented by the aforementioned general formula (III) as a monomer are characterized in that they have the above-mentioned overlap represented by the general formula (IV). Production method of unit polyamic acid. Furthermore, when the present invention calculates the optimal stable structure based on theoretical calculations, the absolute value of the dihedral angle α | α | in the repeated unit structure contained in the molecule is in the range of 8 2 ° or more and 9 8 ° or less. (However, the above-mentioned α is defined as four adjacent atoms C (carbonyl carbon of imidate) -N (nitrogen of imidate) -CC forming a dihedral angle, and is between -18 0 ° and 180 ° Range) is a characteristic polyimide. BEST MODE FOR CARRYING OUT THE INVENTION The ratio and ^ in the general formulae (I) and (IV) are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. Among them, an alkyl group having 20 carbon atoms is preferred, an alkyl group having 1 to 10 carbon atoms is more preferred, and an alkyl group having 5 carbon atoms is particularly preferred. Specifically, fluorenyl and isopropyl are preferred. There is no particular limitation on the position on the skeleton that is equal to or greater than 1,1-difluorenyl. However, particularly in general formula (I), both ratio and R2 are polyimersenes bonded at any of the 4, 5, or 6 positions on the 1,1-dimethyl Xuman skeleton. Amines are preferred because of their high solvent solubility. Furthermore, in the general formula (I), both the heart and the dagger are combined at any of the 4, 5, or 6 positions on the 1,1-diamidyl f full skeleton, and Z is The benzophenone-structured polyimide has a high solvent solubility and a high sensitivity photosensitivity.

90110113.ptd Page 11 541324 V. Description of the invention (8) It is generally a polyamine. Yu Jiao's is good, dioxin is 1-convergence, so the ketone is 1. In the benzene photochemical formula (I), both & and dagger are methyl groups, and these methyl groups are on the full skeleton. The 4th and 6th positions are combined, and 2 is diamidine, that is, it has a repeating unit structure represented by the following formula (V), has high solvent solubility, and can obtain a high-sensitivity feeling

〇, Z in the general formulae (I) and (IV) defines X in the formula as -C0- or-(^ (two%)-, and Y is a direct bond, -CH2s〇2-, _s-, _co ~~ Or-C (1: 1 N2) _, if it is this group, the others are not particularly limited. Furthermore, in the general formula (I), both the heart and R2 are in a 1,1-difluorene radical full framework Polyimide bonded at any of the 4th, 5th, or 6th position, and at the same time X is -C0- or C (= N2)-has high solvent solubility and can obtain high sensitivity Therefore, in general formula (I), both R! And R2 are in the 4th, 5th or 6th position on the 1,1-difluorene-based Schman skeleton. Polyimide bonded in one position and X in the general formula (I) is -C0- or C (= N2)-, Y is -C0- or C (= N2)-or S- Solvent solubility and high sensitivity can be achieved. Also, in the general formula (I), the heart and the heart are fluorenyl groups, and these fluorenyl groups are in the 1,1-difluorenyl group. The 4th and 6th positions on the backbone are combined, and Z is 2, 2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydrite Raw

90110113.ptd Page 12 541324 V. Description of the invention (9) Polyimide formed into a structure, that is, a poly S & amine having a repeating unit structure shown by the following formula (VI), shows high solvent solubility , And low dielectricity is better

(VI) As shown in the previous literature by Yamashita et al. (Since Yamashita, "Polyimide's Recent Progress", 1992, p.29 (1993)), the benzophenone structure in the framework and The photocrosslinking reaction showed that in the photosensitive polydonkeyamine of the hardening mechanism, the intramolecular charge movement was inactivated with the photocrosslinking reaction. Therefore, in order to increase the sensitivity of the photosensitive polyimide, it is extremely important to suppress the intra-molecular charge movement. Therefore, in order to suppress the above-mentioned intramolecular charge transfer, the inventors discovered that the angle formed by the plane of the imidene ring and the plane of the aromatic ring of the nitrogen atom bonded to the imidene ring was designed in a specific range [right angle (Near 90 °)] polyimide to achieve very good results. That is, when the polyimide of the present invention calculates the most stable structure based on theoretical calculations, the angle formed by the plane of the imidoamine ring and the plane of the aromatic ring of the nitrogen atom bonded to the imido ring (hereinafter, abbreviated as Is the dihedral angle). The absolute value of α | α | is characterized by a range of 8 2 ° or more and 9 8 ° or less. As one of the methods for inhibiting the movement of the charge in the molecule of polyimide, a method of introducing a high accumulation of substituents into the diamine and controlling the stereo-coordination of the C-N bond of the imine is described. Polyimide having the repeating unit shown by the aforementioned general formula (I) satisfies the absolute value of such a dihedral angle

90110113.ptd Page 13 541324 V. Description of the invention (10) 丨 α I is a very suitable human-based generation group, controlling a large dihedral angle = introducing a high accumulation of diamine in diamine to achieve high photosensitivity Sensitization. What is the theoretical calculation method of the internal electric power of ρ system? Quantum Λ g π 1 Example 1 Molecular mechanics method and molecular mechanics method. Examples of the daughter force method include AM1 and PM3, extended bands Hljckel, MINDO / 3, MNDO, MNDO-fi A, and sieve WUo method. … The two-and-a-half-empirical calculation method and ab efficiency ... in terms of LI; use = to list MM1. In addition, 'by calculation' Specifically, for example, it is also possible to use the method of δ from δ = δ to δ. Construct, and then use the quantum force to optimize the molecular model of molecular mechanics Α system you: ί: It is not necessary to optimize the learning method. For example, it is effective to make a molecular model for the following examples. Zhi: The dihedral angle means that four atoms are formed side by side to form two planes; the angle is twenty-four: the second and third atoms are arranged on the Z axis in the atom, and the second one is arranged by the younger When it is on the ζ_χ plane, the first, second, and fourth atoms are projected on the χ-Υ plane, and the angle is measured. The sign of two = angle is not limited in the present invention. The absolute value of the dihedral angle U of the invention 1 of the invention described above is in the range of ί and 98 u, and the chemical structure is completely unlimited. The absolute value I α i of the dihedral angle α is 84. Above and 96. It is preferably at least 85 ° and 95 °. The following is more preferred, and 89 is particularly preferred. W The logarithmic viscosity of the polyimide of the present invention is not particularly limited, but m0, preferably 0.2 ~~ .9, preferably 1.8 ~ *, and 0.4 ~ j is 4 inches. 6 is the most suitable. The logarithmic viscosity of polyimide is too high.

90110113.ptd Page 14 541324 V. Description of the invention (11) If it is low, the logarithmic degree of ^ ~ poly after processing is generally too low, so it is not bad. "It is not good. The logarithmic viscosity of polyimide is limited to Yin's processability. For example, 0.50 g of polyimide is dissolved in dioxin and there is no special milliliter, and it is measured at 35 ° C. .Pyrrolidone 100: hair: In addition to the structure shown in the general formula 乂, polyimide is used to control various physical properties, such as heat resistance, early crystal repetition number, permittivity, refractive index, or complex refractive index. For the purpose of 'waiting', various diamines and tetracarboxylic dianhydrides are copolymerized by thermal and thermal expansion systems. 醯 The polyimide of the present invention can be produced by any method if required. Production of polyimide; leather Female i & 丨, 丨, Shi 丄, the base derivative of the present invention Γ: ΐ j The diamine anhydride represented by the general formula (11) described above is characterized as a monomer. 胥 面 四 carboxylic acid di 7 : The diamine radical full derivative shown in the gas (II) does not contain any t 1-di; 2 | 5, 7 ~ diamino-1 I 1-difluorenyl odd full, 4, 7-face only i and the amine group = kimono group, Λ-dimethyl group ", 5,7-diamino group], I, dimethyl_4dib'7 ~ diamino-1, p-dimethyl- 6-Ethyl Xuman ^ 丞 Isopropyl Sulfur , 7-diamino group ", 1, dimethylamino, R 7 Γ, 5,7-diamino-1, dimethyl ~ 4 ~ n-two * ^ i ~ diamine-1, bu Difluorenyl-6-n-propyl Xuman, 5 soil hydrazone, 1-dihydrazyl ~ 4 ~ 1 ° °, 7-diamino-6-second butyl A 7-diamino group ~ 1,1, -methylbutyl group, 5,7-diamino group dimethyl group: ^ ,, ~~ diamino group-1, budifluorenyl-6-n-butyl group Full butyl f diamine pvm Page 15 541324 V. Description of the invention (12) -1,1 ~~ Difluorenyl_4_ third butyl red, 5,7-diamino-1,1 _Difluorenyl-6-tert-butyl-Fuman, 5, 7-diamino-1,1,4,6-tetrafluorenylxman, 6,7-diamino-1,1,4 , 5 -tetrafluorenyl, 4, 7 -diamino-1,1,5,6-tetrafluorenylchiman, 5, 7 -diamino-1,1-difluorenyl-4, 6- Diethyl Xuman, 5, 7 -diamino-1,1_diamidino_4,6-diisopropyl, Manganese, 5,7 ~~ diamino-1,1,4-triamidine -6-second butyl scarman, etc. These diamine imprint derivatives can be used alone or in combination as needed. The method for producing the diamine imprint derivative represented by general formula (II) is described. Yukai Sho 6 4-5 0 8 4 8 etc .. That is, the reaction of benzene derivatives with isoprene to synthesize Fuman derivatives, and nitration of them, also in principle can be cheaply produced diamine group_ A full derivative. The aromatic tetracarboxylic dianhydride represented by the general formula (III) is not particularly limited, and examples thereof include trimellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic acid. Dianhydride, 3, 3 ', 4,4'-benzophenonetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfuric acid Anhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) pinene dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propanedi Anhydride, 2, 2-bis (3, 4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 1,3-bis (3,4-dicarboxyphenoxy Group) phthalic anhydride, 1,4-bis (3,4-dicarboxyphenoxy) phthalic anhydride, 4, 4-bis (3,4-dicarboxyphenoxy) biphthalic anhydride, 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'-benzophenone tetracarboxylic dianhydride, 2, 2' 3,3'-biphenyltetracarboxylic dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) -1, 1,1,3,3,3-hexafluoropropane dianhydride, bis (2,3-dicarboxyphenyl) ether di

90110113.ptd Page 16 541324 V. Explanation of the invention (13) Anhydride, bis (2, 3-dicarboxyphenyl) ¾ dianhydride, 1,3-bis (2, 3-dicarboxyphenoxy) phthalic anhydride , 1,4-bis (2,3-dicarboxyphenoxy) phthalic anhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,3-bis (3,4-dicarboxybenzoic acid Fluorenyl) phthalic anhydride, 1,4-bis (3,4-dicarboxybenzylfluorenyl) phthalic anhydride, 1,3-bis (2,3-dicarboxyphenylfluorenyl) phthalic anhydride, 1 4,4-bis (2,3-dicarboxyphenylfluorenyl) phthalic anhydride, 4, 4'-isophthalocyanine diphthalic anhydride, diazodiphenylmethane-3, 3 ', 4, 4'- Tetracarboxylic dianhydride, diazodiphenylphosphorane-2, 2 ', 3, 3'-tetracarboxylic dianhydride, 2, 3, 6, 7-thioxanthone tetraene dianhydride, 2, 3 , 6,7-onioquinone tetrahydroacid dianhydride, 2,3,6,7-gutanone tetracarboxylic dianhydride and the like. These aromatic tetracarboxylic dianhydrides can be used alone or as needed.

90110113.ptd Page 17 541324 V. Description of the invention (14) The diamine component used in the copolymerization is not particularly limited, and examples thereof include the following compounds. a) p-phenylenediamine and m-phenylenediamine with one benzene ring. b) has 2 phenyl rings, 3, 3'-diamino diphenyl ether, 3, 4'-diamino diphenyl ether, 4, 4'-diamino diphenyl ether, 3, 3'- Diaminodiphenylsulfide, 3, 4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenylsulfone, 3, 4 ' -Diaminodiphenylsulfone, 4, 4'-diaminodiphenylsulfone, 3, 3'-diaminobenzophenone, 4, 4'-diaminobenzophenone, 3, 4'-di Aminobenzophenone, 3, 3'-diaminodiphenylmethane, 4, 4'-diaminodiphenylmethane, 3, 4'-diaminodiphenylmethane, 2, 2-bis (3-aminophenyl) propane, 2,2-bis (4-aminophenyl) propane, 2- (3-aminephenyl) -2 · ~ (4-aminophenyl) propane, 2,2-bis (3-aminephenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-aminephenyl) -1,1,1,3, 3, 3-hexafluoropropane, 2- (3-aminophenyl) -2- (4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 1,1-di ( 3-Aminephenyl)-; 1-phenylethane, 1,1-bis (4-aminephenyl) -1-phenylethane, 1- (3-aminophenyl) -1- (4-amine Phenyl) -1-phenylethane. c) 1,3-bis (3-aminephenoxy) benzene, 1,3-bis (4-aminephenoxy) benzene, 1,4-bis (3-aminephenoxy) with 3 benzene rings ) Benzene, 1,4-bis (4-aminephenoxy) benzene, 1,3-bis (3-aminephenylfluorenyl) benzene, 1,3-bis (4-aminephenylfluorenyl) benzene, 1,3-bis (4-aminobenzylidene) benzene, 1,4-bis (3-aminebenzylidene) benzene, 1,4-bis (4-aminebenzylidene) benzene, 1, 3-bis (3-amino-α, α-diamidinoyl) benzene, 1,3-bis (4-amino-o:, α-diamidinoyl) benzene, 1,4-bis (3-Amino-α, α-dimethylfluorenyl) benzene, 1,4-bis (4-amino-α, α-dimethyloctyl) benzene, 1,3-bis (3-amine _ Α, α -bis (trifluorofluorenyl

90110113.ptd Page 18 541324 V. Description of the invention (15) Rodyl) benzene, 1,3-bis (4-amino-α, α-bis (trifluoromethylrodyl)) benzene, 1,4- Bis (3-amino-α, α_bis (trifluorofluorenylfluorenyl)) benzene, 1,4-bis (4-amino-bis (trifluoromethylbenzyl)) benzene, 2,6- Bis (3-aminophenoxy) benzonitrile, 2,6-bis (3-aminophenoxy) pyridine. d) 4, 4 '-bis (3-aminephenoxy) biphenyl, 4, 4' -bis (4-aminephenoxy) biphenyl, bis [4- (3- -amine) with 4 benzene rings Phenoxy) phenyl] ketone, bis [4- (4-aminephenoxy) phenyl] one, bis [4- (3-aminephenoxy) phenyl] sulfur, bis [4- (4- Aminephenoxy) phenyl] sulfur, bis [4- (3-aminephenoxy) phenyl] «, bis [4- (4-aminephenoxy) phenyl] hard, bis [4- (3 -Aminophenoxy) phenyl] ether, bis [4- (4-aminephenoxy) phenyl] ether, 2, 2-bis [4- (3-aminephenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3- (3-aminephenoxy) phenyl] -1,1,1,3, 3, 3-hexafluoropropane, 2, 2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane. e) 1,3-bis [4- (3-aminophenoxy) phenylfluorenyl] benzene, 1,3-bis [4- (4-aminophenoxy) phenylfluorene with five benzene rings Group] benzene, 1,4-bis [4- (3-aminephenoxy) phenylfluorenyl] benzene, 1,4-bis [4- (4-aminephenoxy) phenylfluorenyl] benzene, 1,3-bis [4- (3-aminephenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-aminephenoxy α, α-difluorene) Benzyl] benzene, 1,4-bis [4- (3-aminephenoxy) -〇:, 〇: -diamidinofluorenyl] benzene, 1,4-bis [4- (4-aminebenzene Oxy) -〇:, α-diamidinoyl] benzene. F) 4,4'-bis [4- (4-aminophenoxy) phenylamidino] diphenyl ether with 6 benzene rings , 4, 4'-bis [4- (4-amino-α, α-diamidinobenzyl) phenoxy] benzophenone, 4, 4'-bis [4- (4-amino-α , Α-Difluorenylbenzyl) phenoxy] diphenyl stone, 4,4'-bis [4- (4-aminephenoxy) phenoxy] diphenyl block.

90110113.ptd Page 19 541324 V. Description of the invention (16) g) 3,3'-diamino-4,4'-diphenoxybenzophenone, 3, 3'-di Amino-4, 4'-diphenoxybenzophenone, 3, 3'-diamino-4-phenoxybenzophenone, 3, 3'-diamino-4-benphenoxy Benzophenone. h) 6,6'-Bis (3-aminophenoxy) -3, 3, 3 ', 3'-tetrafluorenyl-1,1, -spirobiman, 6 ,, 6, -bis (4-aminephenoxy) -3,3,3,, 3, -tetrafluorenyl-l, Γ-spirobis.Γf is full. i) 1,3-bis (3-aminopropyl) tetramethyldisilanes, 1,3-bis (4-aminobutyl) tetramethyldisilanes, a , W-bis (3-aminopropyl) polydimethylsulfonium oxide, ck, w-bis (3-aminobutyl) polydifluorenyllithium oxide. j) Ethylene glycol diamine bis (aminofluorenyl) ether, bis (2-aminoethyl) ether, bis (3-aminopropyl) ether, bis (2-aminofluorenyloxy) ethyl] ether , Bis [2- (2-amineethoxy) ethyl] ether, bis [2- (3-aminepropoxy) ethyl] ether, 1,2-bis (aminemethoxy) ethane, 1 , 2-bis (2-amineethoxy) ethane, 1,2-bis [2- (aminefluorenyloxy) ethoxy] ethoxy, 1,2-bis [2- (2-amineethoxy) Group) ethoxy] ethane, ethylene glycol bis (3-aminopropyl) ether, diethylene glycol bis (3-aminopropyl) ether, and triethylene glycol bis (3-aminopropyl) ether. k) Ethylenediamines of fluorene diamines, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopyrene, and 1,6-diaminohexane , 1,7-diaminoheptamin, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminodeca Monoalkane, 1,12-diaminododecane. l) 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,2-di (2- Aminoethyl) cyclohexane, 1,3-bis (2-aminoethyl) cyclohexane, 1,4-bis (2-aminoethyl) cyclohexane, bis (4-aminecyclohexyl) methane, 2, 6-bis (aminemethyl) bicyclo [2, 2, 1] heptane, 2, 5-

90110113.ptd Page 20 541324 V. Description of the invention (17) Bis (amine methyl) bis, the above diyl, fluorenyl, methylamine, etc. can also use a group, benzocyclobutanyl, domain, All of the hydrogen can also be made instead of the substituent, and the oxygen and triamine of the aromatic ring of [2,2,1] heptaneamine can be copolymerized with carboxylic acid dianhydride. After substitution, it will be used as a propyl and tetracarboxylic acid group. If the group is not the same, the anhydrides used in the group, cyclopentyl aromatic fluoro group, aromatic crosslinking point cyano group, and dianhydride are introduced. It is also possible to use a triamine in combination with a fluoromethyl group or, depending on the purpose, a vinyl group, an amine in the vinyl chain skeleton of the above substituent type. Examples of the dianhydride component include aromatic oxy groups and trianhydrides of anhydrides such as ethylene dianhydride. Phenylcycloolefin-4'- group and isopropene atoms are considered as crosslinking points. In addition to mixed quaternary acid, it can also be used on the aromatic ring of alkanetetracarboxylic acid tetracarboxylic acid difluorenyl group and fluorene tetracarboxylic acid diethyl isocyanate. Furthermore, as a cross-linking, it is preferable that two or all of the hydrogen atoms of the tetracarboxylic acid which are part of the main bond skeleton and which are part of the main bond skeleton are replaced by fluorine or trifluorofluorenyl. One part of the aromatic ring of acetylene, allyl, cyano, and diamine isocyanate which is the crosslinking point is introduced and used. Moreover, depending on the target group, vinylidene group, and alkynylene group. In addition, it is substituted for the purpose of introducing branches, tetraamines. These two groups are the same as the above tetracarboxylic dianhydride, a part of the aliphatic tetracarboxylic acid bicyclic fluorofluorenyl group, or trivalent. In addition, some or all of the hydrogen atoms of the butene-4'- group, the phenyl group, the nitro group, and the isopropyl group are in the alkenyl group and the vinylidene group without damage. In addition, the anhydrides include aromatic tetracarboxylic acid hexacarboxylic acid, butane tetracarboxylic anhydride, and the like. Or all of the hydrofluorofluorenyl groups, but also vinyl, olefins, aromatic groups to replace the processability of the group, and acetylene branched into the anhydride, octacarboxylic acid

90110113.ptd Page 21 541324 V. Description of the invention (18) Acid tetraanhydride substitution. These aromatic tetracarboxylic dianhydride components may be used singly or in combination as necessary. The method for producing polyimide of the present invention can be carried out without using a solvent, but it is particularly preferable to perform 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 in phenolic solvents, ortho-phenol, m-chlorophenol, p-chlorophenol, o-pyrophenol, m-pyrophenol, p-pyrophenol, 2,3-xylenol, 2,4- Xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol. (b) N, N-difluorenylamine, N, N-difluorenylacetamide, N, N-diethylacetamide, N-fluorenyl-2 in aprotic solvents -Pyrrolidone, 1,3-diamidino-2-imidazolidinone, N-methylcaprolactone, hexamethyltriammonium phosphate. (c) 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane, tetrahydrofuran, bis [2- (2-fluorenoxyethoxy) ethyl] ether, 1,4-dioxane. (d) Amine-based solvents, phosphine, heterophilin, alpha-methyl squeak bite, /?-methyl σ specific bite, 7 " -methyl stilt bite, isophorone, etc. Base sigma, 2,4-difluorenyl orbipyridine, 2,6-difluorenylpyridine, trimethylamine, triethylamine, tripropylamine, tributylamine. (e) Dimethylsulfoxide, dimethylsulfone, diphenyl ether, sulfolane, diphenylsulfone, tetramethylurea, anisole, water, benzene, toluene, o-diphenylbenzene, m- Diphenylbenzene, p-diphenylbenzene, benzene, p-dichlorobenzene, m-diphenylbenzene, p-dichlorobenzene, bromobenzene, o-dibromobenzene, m-dibromobenzene, p-diphenyl

90110113.ptd Page 22 541324 V. Description of the invention (19) Bromobenzene, ortho-antimonene, meta-antimonyl, p-chlorobenzylbenzene, ortho-bromophenyl, m-bromophenyl, p-bromo Toluene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methyl alcohol, ethanol, propanol, isopropanol, butanol, isobutanol, pentane, hexane , Heptane, cyclohexane, dichloromethane, aerosol, carbon tetrafluoride, fluorobenzene, ethyl acetate, ethyl acetate, butyl acetate, ethyl acetate, ethyl acetate. These solvents can be used alone or in combination of two or more. In the method for producing polyimide of the present invention, an end-capping agent may be used if necessary. This capping agent is not particularly limited. Typical blocking agents include monoamines and dicarboxylic anhydrides. Examples of the monoamine include aniline, o-anisidine, m-anisidine, p-anisidine, 2, 3-dianiline, 2, 4-diphenylaniline, 2, 5-xylidine, 2, 6- Diphenylaniline, 3, 4-diphenylaniline, 3, 5-diphenylaniline, ortho-anisidine, meta-anisidine, para-anisidine, ortho-bromoaniline, meta-bromoaniline, para-bromoaniline, O-nitroaniline, m-nitroaniline, p-nitroaniline, o-anisidine, m-anisidine, p-anisidine, o-phenylethylamine, m-phenylethylamine, p-phenylethylamine , 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-aminophenyldiphenyl sulfide, 3-aminophenyldiphenyl Sulfide, 4-aminophenyldiphenylsulfide, 2-aminophenyldiphenylsulfone, 3-aminophenyldiphenylsulfone, 4-aminophenyldiphenylsulfone, naphthylamine, naphthylamine, 1-amino group Unitary minutes, 2-

90110113.ptd Page 23 541324 V. Description of the invention (20) Amine group 1_Cai S points, 4-amino group 1-Cai acid, 5-amino group 1-Cai Zifen, 7-amino group 2- Tsai S points, 8-Amino-1-naphthoic acid, 8-Amino-2-Cai S points, 1-Amino groups, 2-Amino groups, 9-Amino groups, Methylamine, Diamine, Ethylamine, diethylamine, propylamine, dipropylamine, isopropylamine, diisopropylamine, butylamine, dibutylamine, isobutyl'amine, diisobutylamine, pentylamine, dipentylamine, elderamine, cyclopropylamine, cyclic Butylamine, cyclopentylamine, cyclohexylamine, etc. Examples of the dicarboxylic anhydride include phthalic anhydride, 2,3-benzophenonedicarboxylic anhydride, 3,4-benzophenonedicarboxylic anhydride, 2,3-dicarboxyphenyl ether anhydride, and 3,4-dicarboxyphenylbenzene. Ether anhydride, 2,3-diphenyldicarboxylic anhydride, 3,4-diphenyldicarboxylic anhydride, 2,3-dicarboxyphenyldiphenylsulfone anhydride, 3,4-dicarboxyphenyldiphenylsulfone anhydride, 2 , 3-dicarboxyphenyldiphenylsulfide anhydride, 3,4-dicarboxyphenyldiphenylsulfide anhydride, 1,2-naphthalenedicarboxylic acid anhydride, 2,3-naphthalenedicarboxylic acid anhydride, 1,8-naphthalene Dicarboxylic anhydride, 1,2-anthracene dicarboxylic anhydride, 2,3-scallion dicarboxylic anhydride, 1,9_scallion dicarboxylic anhydride, and the like. These monoamines and dicarboxylic anhydrides may also be partially structured, and it may not be substituted by a group which is not reactive with the amine or dicarboxylic anhydride. In the method for producing polyimide of the present invention, a catalyst may be used in combination. For example, it may be performed in the presence of an alkali catalyst. Specific examples include the various amine solvents described in the above item (d), and organic bases such as imidazole, N, N-difluorenylaniline, N, N-diethylaniline, potassium hydroxide, and sodium hydroxide. , Potassium carbonate, sodium carbonate, potassium bicarbonate, sodium bicarbonate and other inorganic bases. In the method for producing 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 generally range from 2 5 ° C to 250 ° C for 1 hour to 24 hours is sufficient. Furthermore, when it is intended to manufacture the polyimide film of the present invention into a polyimide film,

90110113.ptd Page 24 541324 V. Description of the invention (21) After the solubility of the arsenicized hand-film-like manipulator can be used, the polymer of the present invention can be polymerized in a common manufacturing method for flat glass. Bit. In particular, the base acid is filled with skeleton acid, and because of its photosensitivity, it is coated on a glass plate because of its photosensitivity to a poly structure bonded to a 1,1-benzophenone structure. After the cloth is applied, it is heated and blended, or the polyimide powder is directly heated and pressurized. In addition, the polyimide of the present invention is highly soluble in commonly used organic materials, so the polyimide powder can be dissolved in an organic solvent, and the film can be formed by coating and desolvating the solvent on the board. The organic solvent herein is not particularly limited, and examples thereof include the solvents (a) to (e) previously listed for use with polys & amines. Amidine is a repeating formula represented by the aforementioned general formula (IV). In general formula (IV), both R1 and R2 are the 4th, 5th, or 6th position bonded to 1,1--2. Polyamines at either position are preferred because of their high solvent solubility. In the general formula (IV), the heart and the dagger are fluorenyl groups. These fluorenyl groups are the 4th and 6th positions on the skeleton of the fluorenyl leaf, and Z is a diamino acid, which has the following formula (VIII The repeating unit acid shown in) is preferable because it has high solvent solubility and high sensitivity.

(VIII) Furthermore, in general formula (IV), both the heart and the heart are any of the 4th, 5th, or 6th positions bound to the 1,1-difluorenyl fman skeleton, and At the same time, X in the general formula (IV) is -C0- or Cb%)-PolyS &

90110113.ptd Page 25 541324 V. Description of the invention (22) A> The solubility of each agent and high sensitivity can be achieved. And, in the general formula (IV), the mind and the mind are combined with any of the 4, 5, or 6 positions on the 1,1-base reward fman skeleton, and at the same time, the general formula (IV) X is -C0- or C (42)-, Y is ~ C0- or c (42) —or ^: I imine 'because it has solubility in solvents and can obtain high sensitivity photosensitivity Sex is better. The logarithmic viscosity of the polyamic acid of the present invention is not particularly limited, but it is generally ~ 2.0, preferably 0.2 ~ 1.9, more preferably 0.3 ~ 1.8, and 0.4 ~ 17 ^, , '〇.5 ~ 1.6 is the most suitable. If the logarithmic viscosity of polyguilinic acid is too low, the second is to reduce the strength and workability of the product after processing, so it is not good. If the logarithmic viscosity of polyfluorene :: is too high, it generally results in sub-processability of the product, so it is not good. The evaluation of the logarithmic viscosity of polyamic acid can be determined by, for example, polyamic acid varnish (a polyacetic acid solution of N-methyl i ^ skin 2 inch, a concentration of 2 ◦ wt%) 2.5. ： After dissolving in 100 ml of pyrrolidone, and in addition to the general formula (IV)-ingredients of polymethylamino acid of 3, methyl-2-benzamine, the various diamines and tetracarboxylic acids are repeated. Units such as heat resistance, endothermicity, and thermal expansion coefficient = various physical properties, e.g. emissivity, etc., may be copolymerized as required. Inclusion, refractive index, or refolding The polyamic acid of the present invention can be produced by any method. The method for producing the polyamic acid is that the above two j may be used. However, the present invention is characterized in that the acryl derivative and the diamine anhydride represented by the aforementioned general formula (11 I) and formula (I I) are used in the monomer. The specific example of the aromatic tetracarboxylic acid bi-organism of the general formula (1) is as described above. The diamine group Xu Manyan shown in 1).

541324 V. Description of the invention (23) Furthermore, the heart of the general formula (II) and 1 ^ 2 are fluorenyl groups, and these fluorenyl groups are the fourth position bound to the 1,1-difluorenyl 'Xuman skeleton. And the diamine group at position 6, which is the 5,7-diamino group-1,1,4,6-tetramethylpyranyl group represented by the aforementioned formula (VII), and the general formula (III) The method of using the aromatic tetracarboxylic dianhydride shown in the monomer is preferred. In the production of the polyamino acid of the present invention, in addition to the diamine group & man derivative represented by general formula (II) and the aromatic tetracarboxylic dianhydride represented by general formula (III), various other Diamine and tetracarboxylic dianhydride are used in the monomer and copolymerized. The diamine component and the tetracarboxylic dianhydride component used for the copolymerization are not particularly limited, and examples thereof include the diamine and the tetracarboxylic dianhydride used in the polyimide copolymerization described above. In addition, for the purpose of introducing branches, a part of the diamine may be replaced by triamines and tetraamines, and a part of the tetracarboxylic dianhydride may be replaced by hexacarboxylic acid, trianhydride, and octacarboxylic acid tetraanhydride. . In the method for producing a polyamic acid according to the present invention, the solvents, capping agents, and catalysts may be the same as those used in 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 presence and type of the solvent and catalyst used, but are generally from 0 ° C to 100 ° C and from 1 hour to 24 hours is sufficient. The novel photosensitive polyimide and polyamic acid of the present invention are excellent in heat resistance, mechanical properties, and adhesive properties, coupled with high solvent solubility, low dielectric properties, and high sensitivity and high resolution photosensitivity. Therefore, it can be used in the fields of electronic photoresistors, coatings, printing inks, printing plates, adhesives, etc., including interlayer insulation films and surface protective films such as semiconductor devices and thin film devices.

90110113.ptd Page 27 5. Description of the Invention (24) Widely used. The photoresist of the present invention is a polyamine containing polyimide and a polyamine having the repeating unit represented by the general formula (I), either or both of which are the repeating units shown by 'di). Acid means having by exposure. Here, the photoresist means a substance. The photoresist of the present invention, especially for the formation of an insoluble hard film, may contain, in addition to the present invention, arsonite and polyamic acid, a photopolymerization initiator, and a monolith / Any other ingredients, for example, sensitizers, pigments, dyes, adhesives, stabilizers, wetting agents, flow: Photoresist in semiconductor devices? And so on as its constituents. The surface protection film of this hair is the first of the "Electric Film" special film device and other interlayer insulation films and adhesives in the field of coatings, printing oils, inks, printing plates, insulation of the invention. Z is 4 " imine, especially any thin M ,, bar, taste film made of polyimide of general p3C cf3. This insulating film is applicable; ^ \ 鲶 amino acid ㈣, in the desired method of polyimide precursors of polyamines, after the g π soil is coated, it is heated to make it ^ r ># law. X, ίί thionite is directly heated and pressurized to form a thin film: After that, it is coated on the substrate, and there is a stack, and the butrolol agent is dissolved in the mixture to make it thin. Noon

90110113.ptd Page 28 541324

V. Description of the invention (25) The multilayer wiring board of the present invention is a wiring board having the <0 edge film of the present invention. In this multilayer wiring substrate, the ::: film is used as an interlayer ^ method that was previously known. Specifically, for example, it can be manufactured as follows, and can be applied: First, it is manufactured on a substrate on which a specified patterned conductor layer is formed. Diamine or its precursor varnish is applied and baked as Poly I of the invention to obtain a polyimide resin layer. Thereafter, a polyimide resin layer that is patterned by using a public interlayer insulating film ^ is made, two = 2, and a conductor layer is formed thereon by light a, and a through-hole portion ^ ^ is perforated, and On-layer wiring substrate. Thereafter, this operation is repeated many times, and the second substrate can be used to make the substrate. The following is a detailed description of the present invention according to the examples. This test is limited. The various tests in the examples are carried out in accordance with the methods shown below. / Shellfish (1) Logarithmic viscosity of melamine powder and polyamic acid varnish: Polyurethane powder 0 · 50 g or polyamine varnish (20% by weight) 2 · 500 g is dissolved in 100 ml of N-methyl-2-pyrrolidone, and then measured at 35. (2) 5 % Weight reduction temperature: DTA-TG (TG-DTA 2 0 0 0 manufactured by Mark Science) was used in the air, and the temperature was measured at a temperature increase rate of 1 (pC / min. (3) Glass transition temperature, crystal melting temperature: According to the difference Scanning calorimetry (DSC, DSC31 by Marc Science Co., Ltd.) was measured at a temperature rise rate of 〇 ° C / min. (4) Solvent solubility test: 20% by weight of imidic acid powder was charged. In each solvent, teach at room temperature

541324 V. Description of the invention (26) Mixing ‘ya’ to visually confirm the dissolved state. (5) Dielectric rate: The rate was evaluated according to JIS-K691 1 method. (6) Mechanical properties of the film: Mechanical properties of the film (tensile strength, tensile evaluation according to ASTM-D 882 .. Elongation) &lt; Synthesis Example &gt; In a device equipped with a stirrer, thermometer and cooling pipe The reaction flask was charged with 300 g of mono-benzene (2.82 moles) and -5. Cool and add 165 g (1.56 mol) of sulfuric acid dropwise. In it, 68 grams of isoprene (10093 mol) and m-II. A mixture of 150 g (1.41 mol) of toluene was charged dropwise at a reaction temperature maintained at about -10 C for 7 hours, and then stirred at room temperature for J hours. After the reaction was completed, the sulfuric acid layer was allowed to stand and separate, and 300 g of 20% saline was added to the organic layer, and neutralized with ammonia water. After warming it at 70-800 ° C and separating the aqueous layer, the excess m-xylene was distilled off under reduced pressure. The obtained residue was distilled off under reduced pressure to obtain a colorless liquid of 1,4-, 4-tetramethyl Qiman. Yield: 120 g (69% yield), bp. 105 to 106 ° C (2128Pa) ^ -NMR (CDC13, TMS) ppm 5 1. 25 (6H? S, 1-Me x 2) 1. 90 (2H , t, 2-CH2) 2.21 (3H, s, 4-Me or 6-Me) 2, 31 (3H, s, 4-Me or 6-Me) 2.72 (2H, t, 3-CH2) 6 77 (2H, s, 5-H and 7-H)

90110113.ptd Page 30 541324 V. Description of the invention (27) The 1,1,4,6-tetramethylene group obtained in this way will be filled with 120 grams (0.68 mol) before cooling to -5 ° C specific gravity 1.52 nitric acid (101 g d · 5 mol), 98% sulfuric acid 41.7 g (4.17 mol) and 1,2-dichloroethane 3,000 g mixed / In the cereal, the reaction temperature was kept at -5 to 0, and the solution was added dropwise over 2 hours. After loading, stir at the same temperature for another hour. After the reaction was completed, 400 g of the reaction solution was charged while cooling, and the sulfuric acid layer was diluted, and then the organic layer was allowed to stand and separate. 500 grams of water was added to the separated organic layer, and the precipitated crystals were distilled off with 1,2,1 gas, and the precipitated crystals were filtered, washed with water, and dried to obtain 5,7 -2 of pale yellow crystals. Nitro-1,1,4,6 -tetrafluorenyl is fully charged. Yield 175 g (96% yield) mp 9 bu 93 ° C. NMR (CDC13, TMS) ppm δ 1.38 (6H, s, 1-Me x 2) 2. 08 (2H, t, 2-CH2) 2 · 20 (3Η, s, 4-Me or 6-Me) 2 · 28 (3Η, s, 4-Me or 6-Me) 3.87 (2Η, t, 3-CH2) Elemental analysis (%) CH Calculated value 5 9. 0 9 6.1 0 Analyzed value 5 9.0 3 5.8 6 No. 5, 7-Dinitrate Φ 10.60 10 · 52 Shi Xiaoji -1,1,4,6-tetramethylpyridine 175 g (0.662 mol) dissolved in 500 g of methanol, add 5% -Pd / C After 17.5 grams (50% water), stir at 50 ~ 60 ° C for 8 4 hours under a hydrogen atmosphere. After the reaction was completed, the mixture was filtered and the filtrate was concentrated under reduced pressure. The resulting residue was distilled off under reduced pressure to obtain amine-1,1,4,6-tetramethylammonium, a color crystal. Capacity I? 4

Μ 90110113.ptd Page 31 541324 V. Description of the invention (28) grams (yield 92.1%) mp. 77 ~ 78.5 ° C, bp · 148 ~ 150 ° C (3 9 9 Pa) 'H-NMR (CDC13, TMS) ppm 5 1. 38 (6H, s, 1-Me x 2) 1. 86 (2H, t, 2-CH2) 1 · 99 (3H, s, 4-Me or 6-Me) 2 · 03 ( 3H, s, 4-Me or 6-Me) 2.73C2H, t, 3-CH2) 3.3 to 3.5 (4Η, br s, ΝΗ2χ2) Elemental analysis (%) CH n 13.71 13.95 Calculated value 76.42 9. 87 Analysis Value 75.61 10. 25 &lt; Example 1 &gt; In a 5-port reactor provided with a nitrogen introduction pipe, a thermometer, a reflux cooler, and a stirring device, weigh 5,7-diamino group-II 4,6-four Fluorenyl. Xu Man 4.1 g (0.02 mol), benzophenone tetracarboxylic dianhydride 6.4 g (0.02 mol), and γ-fluorenylpyridine as a catalyst 0.3 grams (0.03 moles). 42 g of m-pyrophenol was added thereto, and the mixture was stirred under a nitrogen atmosphere. The temperature was raised to 150 ° C. over 2 hours, and then reacted at 150 ° C. for 7 hours. The water produced in the reaction was discharged out of the system. After cooling to 30 ° C and discharging the obtained viscous polymer solution in 2 liters of vigorously stirred methanol, a yellow powdery precipitate was obtained and filtered off. This precipitate was washed with 30 ml of methanol and filtered off. This general color powder was pre-dried at 50 ° C for 4 hours, and then under a nitrogen flow at 22 ° C. 〇Dry for 4 hours. Log viscosity of obtained polyimide powder, dehydration temperature, 5% weight loss

541324 V. Description of the invention (29) The lower temperature is as follows. Log viscosity · 0.53 dl / g Glass transition temperature: No 5% weight reduction temperature was observed: 4 2 9. 0 This yellow powder is based on the following analysis, according to H-NMRCCDC13): 8.3 (2Η, δ ), 8.3 (2H, S), .l (2H, d, J ^ 7.3Hz), 2.9 (2H, br), 2.1 (3H) S), (2H_'b1 *) 'l9 (3H, S), 1.2 (6H, S) Infrared absorption light details: / "Base: shrinkage", i73〇cm-i (Imidamine c = 0 stretch), cm /, Ehr ~ 〇 stretch), 1459cm-i and i425cm- i (Aromatic ring cC expansion and contraction) In addition, the solvent solubility (20% by weight) of the iminoamine powder obtained from the weekly investigation was confirmed in chloroform, ΜΜ ~ _ 7 Ν, Ν ～ Dimethylacetamide, N-fluorenyl-2-pyrrolidone, m-cresol diTHF (tetrahydrofuran), cyclopentanone, etc. are soluble. Not shown, the novel polyimide of this embodiment The spectrum of amidine. Here the horizontal axis is the chemical shift, and the vertical axis is the intensity. Also, the new axeman of this example is shown in FIG. 2 And the light and dark are absorbed by the lines. The horizontal axis is the wave number (the wave number of the mother's early bit length), and the vertical axis is the transmittance. &Lt; Example 2 &gt; Tongue Ϊ :, J: Water imidic acid powder held in Example 1 was dissolved in cyclohexanone and coated on a 20 V ri i St copper plate. It was placed under a stream of nitrogen under 50 and # &gt;: Dry for 4 hours. At this time, the coating film thickness is 10 / m. The polyurethane film is tamped with a cover of 7 mm. π T / 2 mm and 3 6 5 mm. (i-rays) irradiate 40 m J / c mz. Treat the silly solution with μ μ ^ D, and use N, M ~ dimethylformamide for treatment, and treat with 50

541324

V. Description of the invention (30) When dried at 30 ° C for 30 minutes, confirm the formation of the image. When the sensitivity (50% film thickness exposure) was obtained, it was 22 mJ / cm2. '&lt; Example 3 &gt;Fang; in a 5-port reactor equipped with a rat gas introduction, temperature, reflux cooler, and stirring device, weigh 5,7-diamino-1,1,4,6 -Tetramethyl group, boasting 4.086 g (0.0 2 mol), benzophenone tetracarboxylic dianhydride 6.316 g (0.0196 mol), and phthalic anhydride as a capping agent 0.118 g (〇. 〇 〇〇mole), as the catalyst of p-xanthoxyflavonic acid-hydrate 3.8 grams (0. 002 mole) and pyridine 1.6 grams (0.02 mol). Add 50 g of N-fluorenyl-2 -gallidone and 50 g of toluene, and stir in a nitrogen atmosphere. The temperature is raised to 150 ° C over 2 hours, and then at 150 ° C. The reaction took 10 hours. The water produced in the reaction was azeotropically discharged from the system. After cooling to 30 ° C and discharging the obtained viscous polymer solution in 2 liters of vigorously stirred methanol, a yellow powdery precipitate was obtained and filtered. This precipitate was washed with 100 ml of methanol and filtered off. This yellow powder was pre-dried at 50 ° C for 4 hours, and then dried under nitrogen at 4 ° C for 2 hours. The logarithmic viscosity, glass transition temperature, and 5% weight reduction temperature of the obtained polyurethane powder were as follows. Logarithmic viscosity: 0.53 dl / g Glass transition temperature: No 5% weight reduction temperature was observed: 431 This vapor-colored powder was structured according to the following analysis. NMR (CDC13) ·· 58.3 (2H, S), 8.3 (2H, S), 8.1 (2H, d, J = 7. 3Hz), 2.9 (2H, br), 2.1 (3H, S)

541324

2.0 (2H, br), 1.9 (3H, S), 1.2 (6H, S) infrared absorption spectrum: 2 9 5 6 ^ 4 (methylene CH stretching) ^ 7 3 0 ^ 1 ^ (amidoamine 〇0 Expansion), 1 6 82CHT1 (Conjugate 00 Expansion), 1 45 9CHT1 and 1 425CIT1 (Aromatic ring, and solvent solubility (200% by weight) of the obtained polyimide powder obtained from the investigation) , N-dimethylacetamidamine, n-fluorenyl-21-pyrrolidone, m-cresol, butyl HF, cyclopentanone, etc. are soluble. Example &lt; Example 4 &gt; Use 3 Example 3 The polyimide powder was prepared, and a polyimide film was produced in the same manner as in Example 2, and exposed and developed. The sensitivity was 3 1 m J / c m2 〇 &lt; Comparative Example 1 &gt; Except The raw materials are 3.29 g (0.02 mol) of 2,3,5,6-tetrafluorenyl-1,4-phenylenediamine and 6,32 g (0.0196 mol) of benzophenone tetracarboxylic dianhydride. In addition, 0.12 g of ugly anhydride (0. () () () 8 mol) of the capping material was added before reaction and addition of reaction, according to the same method as in Example 丨 to obtain 8 · i 2 g of polyimide powder. The polyimide powder has a logarithmic viscosity of 0.88 dl / g. The same method of Example 2, produced polyalkylene amines thin donkey / ethylene into play and exposure, developing its sensitivity was 62mJ / cm2.

&lt; Example 5 &gt; In a 5-port reaction equipped with a gas introduction pipe, an itching device, a light meter, a reflux cooler, and a stirrer, ^ 4,, I was added. Samarium, diamino-1,1,4, tetramethylene radical, 4.1 g (0.02 mole) and ν-formal A 0, which is similar to fluorene, 15 g of 2-Tyrrolidone and room temperature Stir under nitrogen for 30 minutes, and get jealous-/ Ling Jie. Benzophenone tetra

90110113.ptd Page 35 541324 I. Description of the invention (32) Pompano ~ S dried 6.3 g (0.0195 mol) each with N-methyl-2-role;): 9 g of ketone was added to it. After stirring at room temperature under a nitrogen atmosphere for 5 hours, phthalic anhydride (0.15 g (0.0010 mol)) as a terminal agent was added at an amount of N-methyl-2. Add quantitatively. Stir at room temperature under a nitrogen atmosphere for 2.5 hours. The reaction is complete. The logarithmic viscosity of the obtained polyamic acid varnish was 0.26 dl / g. &lt; Example 6 &gt;

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 stream of air to obtain a polyamic acid film. Four tablets of this pancreas were immersed in N, N-dimethylformamide, N-fluorenyl-2-pyrrolidine, m-toluene, and 2% tetramethylammonium hydroxide aqueous solution. In seconds, any film was completely dissolved. In addition, the polyamic acid film was heated from 30 C to 250 ° C for 2 hours under a nitrogen stream, and then heated at 25Q ° C for 2 hours to obtain a polyimide film having a thickness of 10 #m. &lt; Example 7 &gt; In a 5-port reactor equipped with a nitrogen inlet pipe, a thermometer, a reflux cooler, and a stirring device, 5,7-diamine-il 4, 6-tetramethyl Xuman 4.086 was weighed out. G (〇.〇02 mol), 4, 4'-isophthalocyanine diphthalic anhydride 8. 36 g

(0 · 0 1 96 mol), phthalic anhydride 0.18 g (0.004 mol) as a capping agent, p-toluenesulfonic acid-hydrate as a catalyst 3.8 grams (0. 02 moles) and mouth-to-mouth bite 1.6 gram (0. 02 moles). To this were added 50 g of v-fluorenyl-2-pyrrolidone and toluene 50. It was stirred under a nitrogen atmosphere, heated to 150 ° C over 2 hours, and then reacted at 150 ° C for 10 hours. The water produced in the reaction was azeotropically removed from the system with toluene. Cool to 30 and place the resulting viscous polymer solution in

541324 V. Description of the invention (33) Strongly stir the alcohol 2 and release it. When discharged in / 4 ', a yellow powdery precipitate was obtained. The precipitate of the yellow powder H was washed with 100 ml of methanol, filtered, and dried at 221C for 4 hours. After C was pre-dried for 4 hours, the temperature at "lower temperature" was as follows. Logarithmic viscosity, glass transition temperature, 5% by weight minus logarithmic viscosity: 0.65 d 丨 / breaking state temperature: go to §, 0 / ^ He measured 5 / 〇 weight reduction temperature: 428 ^ again In the investigation, the solvent solubility (20% by weight) of cyclopentanone, etc. was confirmed to be soluble in aerosol, Γ sulfenimide powder, m-p-phenol, Thfn, ~ dimethylacetamidine. Amine, N-methyl-2-D-pyrrolidine &lt; Example 8 &gt; In addition to using Example 7 叱 π A li ^ '7-P; Jin Fu Zhi Bin imidamine powder' and using cyclopentanone Except for the developing solution, M—j was evaluated as a film, and polyurethane thin film, sub-order *, &gt; were developed in the same manner as in Example 2. Its sensitivity is 2 3 m J / c m2. &lt; Example 9 &gt; In a 5-port reactor equipped with a nitrogen introduction pipe, a thermometer, a reflux cooler, and a stirring device, 5, 7-diamino group 1, 4, 6-tetramethylsulfonium was added. 1 g (0.02 moles) and 15 g of N-fluorenyl-2-pyrrolidone and dissolved under a nitrogen atmosphere at room temperature for 30 minutes to dissolve. In this reaction system, 8.36 g of 4,4, -isophthalic acid dianhydride anhydride (0.0196 mol) was quantitatively added as 9 g of N-fluorenyl-2-orbitalone. After stirring at room temperature under a nitrogen atmosphere for 5 hours, 0.118 g (0.0 0 0 4 mol) of phthalic anhydride as a blocking agent was used, and N-methyl-2-

9〇ll〇113. Ptd

Page 37 M1324 V. Description of the invention (34) After 7 g of oral pyrrolidone was given, the reaction was completed. // m Stir for 2.5 hours at room temperature under a nitrogen atmosphere. 0.37 d 1 / g. * The logarithmic viscosity of the amine varnish is &lt; Example 10 &gt; Except that the same method as in Example 9 and Example 6 was used to make the polyamine, according to the implementation, any film was completely dissolved. In addition, the solvents were immersed in the respective solvents, and the polyacrylic acid film was heated to obtain a film in the same manner as the coating method. Polyimide Φ of soil extension 〇 &lt; Example 1 1 &gt; In a five-port reaction state equipped with a nitrogen introduction pipe, a thermometer, an ancient σσ ^, τ reversion cold state, and a stirring device, Weigh 5, 7-diamino M, κ 6-tetramethyl &gt; 0.86 g (0 mol), 2, 3, 6, 7-thioxanthone tetracarboxylic dianhydride. 691 g of C0.0 0 196 mol), benzophenone tetracarboxylic dianhydride 5 684 g (0.01764 mol), phthalic anhydride as end-capping agent 0.18 g (0.000 g) 4 mole), p-toluenesulfonic acid-hydrate 3.8 g (0. 002 mole) and pyridine 6 g (0. 02 mole) as a catalyst. To this was added NG-methyl-2- caloric scorch_50 g, 50 g of toluene, and stirred under a nitrogen atmosphere. The temperature was raised to 50 ° C. over 2 hours, and then reacted at 150 ° C. for 10 hours. . When the water produced in the reaction was azeotropically exhausted from toluene, it was cooled to 30 ° C. and the resulting viscous polymer solution was discharged in 2 liters of strong / mixed methanol to obtain a yellow powder. The precipitate is filtered out. This precipitate was washed with methanol and filtered off. This yellow powder was pre-dried at 50 ° C for 4 hours and then under a nitrogen flow at 22 ° C. (: Dry for 4 hours.

90) 10113.ptd Page 38 541324

5 ° / 〇 Weight reduction The logarithmic viscosity and glass transition temperature of the obtained polyurethane powder are as follows. Log viscosity: 0.6 2 d 1 / g Glass transition temperature: No 5% weight loss temperature was observed: 4 2 0 t: Also, the solvent solubility of the obtained polyimide powder (in the case of 20 weight%) It was confirmed to be soluble in chloroform, N, N-difluorenylacetamide, N-fluorenyl-2m-rrolidone, m-fluorenol, butyl HF, cyclopentanone, etc. &lt; Example 1 2 &gt; A polyimide film was prepared according to the same method as in Example 2 except that the polyimide powder obtained in Example 11 was used, and cyclopentyl g was also used as a developing solution, and exposed and developed. The sensitivity is 20 mJ / cm2. 彳 &lt; Example 1 3 &gt; In a 5-port reactor equipped with a nitrogen introduction tube, a thermometer, a reflux cooler, and a stirring device, 5, 7, diamino-1 was added. 1,4,6 -tetramethylhexyl ^ set 4 · 1 g (0 · 02 mole) and 15 g of N-methyl-2 ~ pyrrolidone and stir in the chamber ^ ^ &gt; Dissolve in 30 minutes. In this reaction system, 2,3, f broad atmosphere ton_tetra-acid dianhydride 691 g (0.0 0 196 mol) and diphenyl_tetraacous acid acetic anhydride 5. 684 g (0.0 1 764 moles) -fluorenyl-2-, pyrrolidone 9 grams ^ man = added in quantity. After stirring for 5 hours at room temperature under nitrogen atmosphere, 0.118 grams of phthalic anhydride (0 · 0 0 04 mol) will be used as the end-fixing agent, with N-fluorenyl- as the seal. 7 g of ketone was added quantitatively. The reaction was completed after stirring at room temperature under a nitrogen atmosphere for 2 · 5 hours. The logarithmic viscosity of the obtained polyamic acid varnish was 0 3 6 d '<Example 14 &gt; Q1 / g .

541324 V. Description of the invention (36) Except using the polyamic acid varnish obtained in Example 13 except that the polyamino acid film was prepared according to the same method as in Example 6, and any film was completely immersed in each solvent Dissolve. Further, the polyimide film was heated in the same manner as in Example 6 to obtain a polyimide film having a coating film thickness of 10 // m. &lt; Example 15 [Theoretical calculation ·· Calculation examples 1 to 7] &gt; Using Molecular Modeling Soft (CS Chem 3D Pro), a molecular model of A, B, or C represented by the following formula (IX) was prepared. For this molecular model, semi-empirical molecular calculation (AM1) was used to optimize and obtain the most stable structure. In this structure, the results of investigating the absolute value of the dihedral angle α | α | are summarized in Table 1.

H3c

Β

C (IX) Table 1 Model compound Ri r2 Dihedral angle a Calculation example 1 C ch3 — 65 Calculation example 2 A ch3 ch3 71 Calculation example 3 A ch3 Et 81 Ο

__ 隐 Ｍ 90110113.ptd Page 40 541324

In Table 1, the dihedral angle of the 彳 -L type corresponding to the present amine is the largest. That is to say, the three-dimensional structure with a large module angle can be proved by calculations. The characteristic structure of the polyimide according to the present invention is to reduce the cost and achieve a high sensitivity of the photosensitivity. Door ^ and moving, Asia &lt; Example 1 6 &gt;

In a 5-port reactor with a nitrogen introduction tube, a thermometer, a Dean and Stark tube with a reflux cooler, and a stirring device, weigh 5,7-diamino group-1, 1,4,6-tetramethyl Xuman 1.02 g Γ〇2 5 mol), trimellitic dianhydride 10.8 g (0.049 5 mol), phthalic anhydride 0.148 g (0.001 Moore), sulfolidine (0.05 mol), p-toluenesulfonic acid-hydrate 9.5 g (0.05 mol). To this was added 70 g of N-methyl-2-pyrrolidone and 70 g of toluene, and the mixture was stirred under a nitrogen atmosphere for 2 hours to react. "Time. The water produced in the reaction was discharged from the system: == 0. After C, and discharging the obtained viscous polymer solution in 2 liters of methanol which was strongly stirred off, a brown powder-like precipitate was obtained and filtered. The precipitate was washed with 100 ml of methanol and filtered. This yellow powder was pre-dried at 500 ° C for 4 hours, and then dried at 220 t for 4 hours under a nitrogen flow. The logarithmic viscosity, hydration temperature, and 5% weight loss temperature of the obtained iminium powder were as follows Logarithmic viscosity: 0.46 6 d 1 / g 90110113.ptd Page 41 541324 V. Description of the invention (38) Glass breaking temperature: 5% weight loss temperature was not observed. 442 In addition, paid for the investigation Solvent solubility of polyimide powder (2 days, confirmed in aerobic, N-methyl-2-pyridine), THp strict + mT 丞 Z pyrrolidone, m-cresol, 丄 H t, mounting Soluble in pentanone, etc. &lt; Example 1 7 &gt; In Example 16, except that trimellitic acid was changed to 3, 3 = acid diamidine. 6 Other than (0.04 95 mole), in Example) is present at a% Φ ",: Ϊ &quot; Γί alkylene amine acid logarithmic viscosity of powder, broken Ma transition temperature, 5 / a weight loss temperature as follows. Logarithmic viscosity: 0.96 d 1 / g Glass transition temperature: No 5% weight loss temperature observed: 4 3 1 t: The solvent solubility of the imine powder (20% by weight) ) Said π, indeed δ is tolerated by chloroform, N-fluorenyl-2 · ~ mouth slightly;): Endone, m ~~ phenylbenzene, THF, cyclopentanone, etc. are soluble. <Example 1 8 &gt; In Example 16 except that trimellitic anhydride was changed to bis (3,4-dicarboxyphenyl) ether dianhydride 15.4 g (0.0 49 5 moles), the same procedure as in Example i was performed. 3.:! Light yellow = logarithmic viscosity, submarine transformation temperature, and 5% reset reduction temperature of sub-fermented amine powder are as follows.

Logarithmic viscosity: 0.6 6 d 1 / g Glass transition temperature: No 5% weight loss observed: 4 2 9 ° C

Page 42 90110113.ptd 541324

Solvent solubility of polyimide powder paid by Nishimura (20 weight: 'Confirmed to be soluble in chloroform, N-methyl_2-doubled ... THF, cyclopentanone, etc. &Lt; Example 1 9 &gt; The temperature at which the weight reduction of 5% of the two cores of V2 and Γ was performed in the same manner as in Example 16 except that the trimellitene 3;) code 2 and 7 grams (G._mol) was used. 4 logarithmic 4 degree breaking temperature

Logarithmic viscosity: 0.38 dl / g Glass breaking temperature · No 5% weight loss temperature was observed: 422 t: In addition, the solvent solubility of the polyurethane powder obtained by the investigation was% by weight) ¥, confirmed at Soluble in aerosol, N-methyl-2-pyrrolidone, m-cresol, butanone, cyclopentanone, etc. Knife &lt; Example 2 0 &gt; In a 5-port reactor equipped with a nitrogen introduction tube, a thermometer, a Dean I with a reflux cooler, a Dean and Stark tube, and a stirring device, a scale was weighed. Take 5, 7-diamino-1,1,4,6-tetramethyl-saturated · 02 g (0.05 mole), 2,2-bis (3,4-dicarboxyphenyl) ) -1,1,1,3,3,3-hexafluoropropane dianhydride 22.0 g (0.0495 mol), phthalic anhydride 0.48 g (0.0 (π mol)), specific bite 4.0 g (0.05 mol), p-pyrhotolite flavonic acid-hydrate g. 5 g (0.05 mol). To this was added N-fluorenyl-2 -roleol :): Endone 7 0 g and 70 g of toluene were stirred under a nitrogen atmosphere, and the temperature was raised to 1 35 ° C over 2 hours, followed by a reaction for 8 hours. 2. Drain the water produced in the reaction outside the system. Cool it to 30%, and get the resulting

541324 V. Description of the invention (40) =: When the polymer solution is discharged in 2 liters of vigorously stirred methanol, _ / n n color ^ known precipitates are obtained and filtered. This precipitate was washed and filtered using Party A's liters. The yellow powder was pre-dried at 50 ° C for 4 hours, and the lice = shed, and dried at 220 t for 4 hours. _ The lower temperature is as follows: 4, the normalized temperature, the 5% weight reduction logarithmic viscosity ... 0.5 dl / g glass breaking temperature ... no 5% weight reduction temperature was observed ... 436 it again 'investigation At the time of the obtained polyimide powder, it was confirmed that it was soluble in chloroform, N_methyl_2_pyrrole / solubility (20% by weight) butan HF, cyclopentanone, and the like. Vanone, m-cresol 1. Put this polyimide powder in a varnish with dimethylacetic acid concentration, and apply it on a glass plate: dissolve to 20% by weight 18. Can be dried for 4 hours, continue to decompress, and then Under nitrogen flow, it is dried at 180 ° t for 16 hours under pressure, and dried at 0 ° C. for 8 hours, and then at M. When this film is used to determine the dielectric properties (£) of 16 and the mechanical properties are determined, Tensile strength 68: 丨: ,, 3 Gpa, tensile strength 5%. Pa, tensile modulus of elasticity: 兄 'Brother, if according to the present invention, the% two adhesion characteristics are excellent &amp; I? Jia provides heat resistance, high sensitivity, high resolution (sensitivity: Γ-cleaving solubility, and low median avoidance of citric acid. It is based on the new Iρ of the raw material.), Which is different from 3 6 5nm (i-ray) In the application of photoresist of arsenite and polyimide, 541324 V. Description of the invention (41) is very useful, and it is a highly integrated semiconductor device for insulating films, especially including insulating films as surface protective films and interlayer insulating films. It is very useful in the application of highly integrated multilayer wiring boards.

90110113.ptd Page 45 541324

90110113.ptd Page 46

Claims (1)

541324 90110113.ptd Page 47 541324 t. Number of patent applications. M and η each independently represent an integer of 0 or 1. r respectively independently represents a alkynyl, or halo or phenyl group having 1 to 4 carbon atoms. A is (Indicating an integer of 0 or 1 to 3) 0 2. For example, the polyimide of the scope of patent application, wherein the heart of the general formula (I) and R2 are both methyl groups, these fluorenyl groups are bound to 1,1 -4th and 6th positions on the Nihon Kiman skeleton. 3. A method for producing a polyimide having a repeating unit represented by the following general formula (I), which is characterized by using a diamino group derivative represented by the following general formula (II), and The aromatic tetracarboxylic dianhydride represented by the general formula (III) is described as a monomer · 90110113.ptd Page 48 541324 6. Scope of patent application z is a condensed polycyclic aromatic group or the following formula 至少 ⑴a at least one kind of group is selected; however, X is -CO-, Y is a direct bond, -CH2--S〇2, -S-, -c (= n2)-, and w is a direct Bond, -ch2-, -c (ch3) 2- n2) CO- or -C (CF3 2-, -S-, -SO-, -802- or -〇-; b is an integer representing 0 or 1, m and η each independently represent an integer of 0 or 1; r each independently represents an alkyl group, or halo group or phenyl group having 1 to 4 carbon atoms; and a is an integer representing 0 or 1 to 3). 4. For example, the method for manufacturing polyimide of the scope of patent application, wherein the hearts of general formulae (I) and (II) and R2 are fluorenyl groups, and these fluorenyl groups are bonded to 1, 1-difluorene The fourth and sixth positions on the base full frame. 5. A polyamic acid having a repeating unit represented by the following general formula (V) 90110113.ptd Page 49 541324 Scope of patent application Ri ΗΟ-γ &quot; γ-ΟΗ R2 Ο Ο V ″ 0 p ——ν-Λ, / -ν-ζ ch3 CH, (IV) (wherein Xin and ^ each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; Z is a condensed polycyclic aromatic group or the following formula: (At least one type is selected from the group consisting of Oa ❿; however, X is -CO- or -C (= N2)-, and Y is a direct bond, -CH2_, -〇-, -S02, -S-,- CO- or -C (= N2)-, W is a direct bond, -CH2-, -C (CH3) 2-, -C (CF3) 2-, _S-, -S0-, -S02-, or -〇 -; b is an integer representing 0 or 1, hi and η each independently represent an integer of 0 or 1, and r each independently represents a carbon number Φ 90110113.ptd Page 50 541324 6. Apply for 1 to 4 alkyl, or, halo or phenyl groups in the patent application range, a is an integer representing 0 or 1 to 3) ° 6. Polyamino acid, in which the heart of general formula (IV) and R2 are fluorenyl groups, and these fluorenyl groups are the 4th and 6th positions bound to the 1,1-difluorenyl Schman skeleton. 〇07. A method for producing a polyamic acid having a repeating unit represented by the following general formula (IV), which is characterized by using a diaminoxanthine derivative represented by the following general formula (Π), As the monomer 二 (II) (III), an aromatic tetracarboxylic dianhydride represented by the following general formula (II I) is used. Everyone Yy ° 〇〇 (iv) (In the formula, Xin and Hua independently represent a hydrogen atom or an alkyl group of 20 carbon atoms, and Z is a condensed polycyclic aromatic group or the following formula: 90110113.ptd Page 51 541324 At least one kind of group is selected from the group; however, X is -CO- or =, Y is a direct bond, -CH2-, -〇-, _s〇2, -s-, -C0- or-, and W is Table is not a direct bond, -CH2_, -C (CH3) 2-, -C (CF3) 2-, -S-, -S0-, -S02-or -0; b is an integer representing 0 or 1, m And η each independently represent an integer of 0 or 1; r each independently represents an alkyl group, or halo group or phenyl group having 1 to 4 carbon atoms; a is an integer representing 0 or 1 to 3) 0 8. If applying for a patent The method for producing polyamic acid in the seventh item, wherein the hearts of the general formulae (IV) and (II) and R2 are both fluorenyl groups, and these fluorenyl groups are bonded to the 1,1-difluorenyl sulfanyl skeleton 4th and 6th. 9. A photoresist comprising any one or both of polyimide as described in the scope of patent application No. 1 and polyamic acid as described in the scope of patent application No. 5 90110113.ptd Page 52 541324 6. Scope of patent application. 1 0. — An insulating film, wherein Z in the general formula (I) is It is composed of polyimide as claimed in the first patent application. 1 1. A multi-layer wiring substrate, which is an interlayer insulating film having an insulating film as in item 10 of the scope of patent application. 1 2. A kind of polyimide, which is characterized in that when calculating the most stable structure based on theoretical calculations, the absolute value of the dihedral angle α | α | is 8 2 ° or more in the repeated unit structure contained in the molecule 9 8. The following range (however, the above-mentioned α is defined as a dihedral angle formed by 4 adjacent atoms C (carbonyl carbon of imidate) -N (nitrogen of imidate) -CC, and is -180 or more and 180 or less range). 90110113.ptd Page 53