CN118221527A

CN118221527A - Polyimide precursor, polyimide film, and substrate

Info

Publication number: CN118221527A
Application number: CN202410327300.4A
Authority: CN
Inventors: 冈卓也; 小滨幸德; 中川美晴; 久野信治; 岩本圭司; 弘津健二; 桂良辅; 安田真治
Original assignee: Ube Corp
Current assignee: Ube Corp
Priority date: 2016-05-31
Filing date: 2017-05-31
Publication date: 2024-06-21
Also published as: TWI791277B; CN109415379A; JPWO2017209199A1; KR102347037B1; CN109312071B; JP7173204B2; TW202146531A; JP7052723B2; JP2021138952A; TWI742087B; JP2022116052A; WO2017209199A1; CN114854010B; JP6939779B2; WO2017209197A1; TW201802144A; CN114854010A; JP7327573B2; JPWO2017209197A1; KR20190014518A

Abstract

The present invention relates to a polyimide precursor, polyimide film, and substrate. The present invention also relates to a tetraester compound represented by the following chemical formula (M-2), wherein R ₅'、R₆' are each independently-CH ₂ -, or-CH ₂CH₂-,R₁₁、R₁₂、R₁₃、R₁₄ are each independently an alkyl group having 1 to 10 carbon atoms.

Description

Polyimide precursor, polyimide film, and substrate

The application is a divisional application, the application number of the original application is 202210579415.3, the application date is 2017, 5 and 31, and the application is named as polyimide precursor, polyimide film and substrate.

Technical Field

The present invention relates to a polyimide having excellent characteristics such as transparency, bending resistance, high heat resistance, and low linear thermal expansion coefficient, a precursor thereof, and a tetracarboxylic dianhydride used for producing the same.

Background

In recent years, with the advent of a highly informative society, development of optical materials such as optical fibers and optical waveguides in the field of optical communication, and liquid crystal alignment films and protective films for color filters in the field of display devices has been advanced. In particular, in the field of display devices, research on plastic substrates, which are lightweight and excellent in flexibility, and development of display panels capable of being bent or rounded, are actively conducted as substitutes for glass substrates. Therefore, a higher performance optical material that can be used for such applications is required.

Aromatic polyimides are colored to a tan color in nature due to intramolecular conjugation, formation of charge transfer complexes. Therefore, as a method of suppressing coloring, for example, the following method is proposed: the transparency is exhibited by introducing fluorine atoms into the molecule, imparting flexibility to the main chain, introducing bulky groups as side chains, and the like to hinder the formation of intramolecular conjugation, charge transfer complexes, and the like.

In addition, a method of imparting transparency by using a semi-alicyclic or full-alicyclic polyimide which does not theoretically form a charge transfer complex has been proposed. In particular, a number of semi-alicyclic polyimides having high transparency using an aromatic tetracarboxylic dianhydride as a tetracarboxylic acid component and an alicyclic diamine as a diamine component have been proposed; a highly transparent semi-alicyclic polyimide using an alicyclic tetracarboxylic dianhydride as the tetracarboxylic acid component and an aromatic diamine as the diamine component.

For example, patent document 1 discloses a semi-alicyclic polyimide precursor and polyimide obtained from an alicyclic tetracarboxylic acid component having at least one aliphatic 6-membered ring in the chemical structure and no aromatic ring, and an aromatic diamine component having at least one amide bond and an aromatic ring in the chemical structure. Specifically, in the example of patent document 1, bicyclo [2.2.2] octane-2, 3,5, 6-tetracarboxylic dianhydride, decahydro-1, 4:5, 8-dimethylnaphthalene-2, 3,6, 7-tetracarboxylic dianhydride, and the like are used as alicyclic tetracarboxylic acid components, and 4,4' -diaminobenzanilide and the like are used as aromatic diamine components having an amide bond and an aromatic ring. In the example of patent document 1, p-phenylenediamine, 2 '-bis (trifluoromethyl) benzidine, 4' -oxydiphenylamine, and the like are used as other diamine components.

Patent document 2 discloses a process for producing a polyamic acid, which comprises reacting a specific alicyclic tetracarboxylic dianhydride with a diamine in the presence of an inorganic salt as a catalyst. In example 8 of patent document 2, hexacyclo [6.6.1.1 ^3, ⁶.1^10,13.0^2,7.0^9,14 ] heptadeca-4,5,11,13-tetracarboxylic dianhydride as an alicyclic tetracarboxylic dianhydride was reacted with 4,4' -diaminodiphenyl ether in the presence of calcium chloride as a catalyst to synthesize polyamic acid, and imidized to obtain polyimide. However, in comparative example 5 of patent document 2, a polyamide acid was synthesized by reacting hexacyclo [6.6.1.1 ^3,6.1^10,13.0^2,7.0^9,14 ] heptadeca-4,5,11,13-tetracarboxylic dianhydride with 4,4' -diaminodiphenyl ether without adding calcium chloride as a catalyst, and imidization was performed, and it was shown that η _inh of the polyimide obtained by the imidization was low, and the film formation was impossible.

Regarding the semi-alicyclic polyimide, non-patent document 1 discloses a correlation between a moderate transition and strength characteristics in a soluble alicyclic polyimide obtained from tricyclodecenyl tetracarboxylic dianhydride (an addition product of benzene and maleic anhydride) and diaminodiphenyl ether.

Prior art literature

Patent literature

Patent document 1: international publication No. 2012/124664

Patent document 2: japanese patent laid-open No. 5-271409

Non-patent literature

Non-patent document 1: izvestiya Akademii Nauk Kazakhskoi SSR, seriya Khimicheskaya,1987, no.5, page 40

Disclosure of Invention

Problems to be solved by the invention

The present invention aims to provide a novel polyimide and a precursor thereof, which have excellent characteristics such as transparency, bending resistance, high heat resistance, low linear thermal expansion coefficient and the like. The present invention also provides a novel tetracarboxylic dianhydride for producing polyimide and a method for producing the same.

Means for solving the problems

The present invention relates to the following.

1. A polyimide precursor characterized by comprising at least one repeating unit represented by the following chemical formula (1-1),

The total content of the repeating units represented by the chemical formula (1-1) is 50 mol% or more based on the total repeating units.

[ Chemical 1]

(Wherein A ₁₁ is a 4-valent group represented by the following chemical formula (A-1) or a 4-valent group represented by the following chemical formula (A-2), B ₁₁ is a 2-valent group represented by the following chemical formula (B-1) or a 2-valent group represented by the following chemical formula (B-2), and X ₁、X₂ is each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkylsilyl group having 3 to 9 carbon atoms.)

[ Chemical 2]

(Wherein, R ₁、R₂、R₃ are each independently-CH ₂-、-CH₂CH₂ -, or-CH=CH-)

[ Chemical 3]

(Wherein R ₄ is-CH ₂-、-CH₂CH₂ -, or-CH=CH-)

[ Chemical 4]

( Wherein n ₁ represents an integer of 0 to 3, and n ₂ represents an integer of 0 to 3. Y ₁、Y₂、Y₃ each independently represents one selected from the group consisting of a hydrogen atom, a methyl group, a trifluoromethyl group, Q ₁、Q₂ each independently represents a direct bond, or is selected from the group consisting of formula: -NHCO-, -CONH-, -COO-, -OCO-, and a member of the group shown. )

[ Chemical 5]

(Wherein Y ₄ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

2. A polyimide precursor, characterized in that it comprises at least one repeating unit represented by the following chemical formula (1-2).

[ Chemical 6]

(Wherein A ₁₂ is a 4-valent group represented by the following chemical formula (A-3) or a 4-valent group represented by the following chemical formula (A-4), B ₁₂ is a 2-valent group having an aromatic ring or alicyclic structure, and X ₃、X₄ are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkylsilyl group having 3 to 9 carbon atoms.)

[ Chemical 7]

(Wherein, R ₅、R₆ are each independently-CH ₂-、-CH₂CH₂ -, or-CH=CH-)

[ Chemical 8]

(Wherein R ₇ is-CH ₂CH₂ -, or-CH=CH-)

3. The polyimide precursor according to the above item 2, wherein the total content of the repeating units represented by the above chemical formula (1-2) is 50 mol% or more based on the total repeating units.

4. A polyimide comprising at least one repeating unit represented by the following formula (2-1),

The total content of the repeating units represented by the chemical formula (2-1) is 50 mol% or more based on the total repeating units.

[ Chemical 9]

(Wherein A ₂₁ is a 4-valent group represented by the following chemical formula (A-1) or a 4-valent group represented by the following chemical formula (A-2), and B ₂₁ is a 2-valent group represented by the following chemical formula (B-1) or a 2-valent group represented by the following chemical formula (B-2))

[ Chemical 10]

[ Chemical 11]

(Wherein R ₄ is-CH ₂-、-CH₂CH₂ -, or-CH=CH-)

[ Chemical 12]

( Wherein n ₁ represents an integer of 0 to 3, and n ₂ represents an integer of 0 to 3. Y ₁、Y₂、Y₃ each independently represents one selected from the group consisting of a hydrogen atom, a methyl group, a trifluoromethyl group, Q ₁、Q₂ each independently is a direct bond, or is selected from the group consisting of formula: -NHCO-, -CONH-, -COO-, -OCO-, and a member of the group shown. )

[ Chemical 13]

5. A polyimide comprising at least one repeating unit represented by the following chemical formula (2-2).

[ Chemical 14]

(Wherein A ₂₂ is a 4-valent group represented by the following chemical formula (A-3) or a 4-valent group represented by the following chemical formula (A-4), and B ₂₂ is a 2-valent group having an aromatic ring or alicyclic structure.)

[ 15]

[ 16]

(Wherein R ₇ is-CH ₂CH₂ -, or-CH=CH-)

6. The polyimide according to the above item 5, wherein the total content of the repeating units represented by the above chemical formula (2-2) is 50 mol% or more based on the total repeating units.

7. A polyimide obtained from the polyimide precursor according to any one of the above items 1 to 3.

8. A film mainly comprising the polyimide obtained from the polyimide precursor according to any one of the above items 1 to 3, or the polyimide according to any one of the above items 4 to 6.

9. A varnish comprising the polyimide precursor according to any one of the above items 1 to 3, or the polyimide according to any one of the above items 4 to 6.

10. A polyimide film obtained using a varnish comprising the polyimide precursor according to any one of the above items 1 to 3 or the polyimide according to any one of the above items 4 to 6.

11. A substrate for a display, a touch panel, or a solar cell, comprising the polyimide obtained from the polyimide precursor according to any one of the above items 1 to 3, or the polyimide according to any one of the above items 4 to 6.

12. A tetracarboxylic dianhydride represented by the following chemical formula (M-1).

[ Chemical 17]

(Wherein R ₅'、R₆' are each independently-CH ₂ -, or-CH ₂CH₂ -)

13. A tetraester compound represented by the following chemical formula (M-2).

[ Chemical 18]

(Wherein R ₅'、R₆' is each independently-CH ₂ -, or-CH ₂CH₂-,R₁₁、R₁₂、R₁₃、R₁₄ is each independently an alkyl group having 1 to 10 carbon atoms.)

14. A tetraester compound represented by the following chemical formula (M-3).

[ Chemical 19]

15. A method for producing a tetracarboxylic dianhydride, comprising the steps of:

(A) astepofreactinganolefincompoundrepresentedbythefollowingchemicalformula(M-A-1)withanaliphaticsulfonylchlorideoranaromaticsulfonylchlorideinthepresenceofabasetoobtainanolefincompoundrepresentedbythefollowingchemicalformula(M-A-2);

[ chemical 20]

(Wherein R ₅'、R₆' are each independently-CH ₂ -, or-CH ₂CH₂ -)

[ Chemical 21]

(Wherein R ₅'、R₆' has the same meaning as above and R is an alkyl group or an aryl group with or without a substituent.)

(B) astepofreactinganolefincompoundrepresentedbytheaboveformula(M-A-2)withanalcoholcompoundandcarbonmonoxideinthepresenceofapalladiumcatalystandacoppercompoundtoobtainatetraestercompoundrepresentedbythefollowingformula(M-A-3);

[ chemical 22]

(Wherein R ₅'、R₆' and R are the same as defined above, and R ₁₁、R₁₂、R₁₃、R₁₄ are each independently an alkyl group having 1 to 10 carbon atoms.)

(C) astepofobtainingatetraestercompoundrepresentedbythefollowingchemicalformula(M-3)fromatetraestercompoundrepresentedbytheabovechemicalformula(M-A-3);

[ chemical 23]

(Wherein R ₅'、R₆'、R₁₁、R₁₂、R₁₃、R₁₄ has the same meaning as above.)

(D) A step of obtaining a tetraester compound represented by the following chemical formula (M-2) by an oxidation reaction of the tetraester compound represented by the above chemical formula (M-3);

[ chemical 24]

(E) And (2) reacting the tetraester compound represented by the above formula (M-2) in an organic solvent in the presence of an acid catalyst to obtain a tetracarboxylic dianhydride represented by the following formula (M-1).

[ Chemical 25]

(Wherein R ₅'、R₆' has the same meaning as above.)

16. A tetracarboxylic dianhydride represented by the following chemical formula (M-4).

[ Chemical 26]

(Wherein R ₇ is-CH ₂CH₂ -, or-CH=CH-)

17. A tetraester compound represented by the following chemical formula (M-5).

[ Chemical 27]

(Wherein R ₇ is-CH ₂CH₂ -, or-CH=CH-, and R ₂₁、R₂₂、R₂₃、R₂₄ are each independently an alkyl group having 1 to 10 carbon atoms.)

18. A dihalodicarboxylic anhydride represented by the following formula (M-6).

[ Chemical 28]

(Wherein X ₁₁、X₁₂ each independently represents any one of-F, -Cl, -Br, or-I.)

19. A dicarboxylic anhydride represented by the following chemical formula (M-7).

[ Chemical 29]

20. A method for producing a tetracarboxylic dianhydride, comprising the steps of:

(A) A step of reacting a dicarboxylic anhydride represented by the following chemical formula (M-B) with 1, 3-butadiene to obtain a dicarboxylic anhydride represented by the following chemical formula (M-7);

[ chemical 30]

[ 31]

(B) A step of reacting a dicarboxylic anhydride represented by the above formula (M-7) with a dihalogenating agent to obtain a dihalogenated dicarboxylic anhydride represented by the following formula (M-6);

[ chemical 32]

(C) A step of reacting a dihalodicarboxylic anhydride represented by the above formula (M-6) with maleic anhydride to obtain a tetracarboxylic dianhydride represented by the following formula (M-4-1);

[ 33]

(D) A step of reacting a tetracarboxylic dianhydride represented by the above formula (M-4-1) with an alcohol compound in the presence of an acid to obtain a tetraester compound represented by the following formula (M-5-1);

[ chemical 34]

(Wherein R ₂₁、R₂₂、R₂₃、R₂₄ is each independently an alkyl group having 1 to 10 carbon atoms.)

(E) A step of reacting a tetraester compound represented by the following chemical formula (M-5-2) with hydrogen in the presence of a metal catalyst to obtain a tetraester compound represented by the following chemical formula (M-5-1);

[ 35]

(Wherein R ₂₁、R₂₂、R₂₃、R₂₄ has the same meaning as above.)

(F) And (3) a step of reacting the tetraester compound represented by the above chemical formula (M-5-2) in an organic solvent in the presence of an acid catalyst to obtain a tetracarboxylic dianhydride represented by the following chemical formula (M-4-2).

[ 36]

21. A method for producing a tetracarboxylic dianhydride, comprising the steps of:

(A) A step of reacting a diene compound represented by the following chemical formula (M-C-1) with an acetylene compound represented by the following chemical formula (M-C-2) to obtain a diester compound represented by the following chemical formula (M-C-3);

[ 37]

(Wherein R ₄ is-CH ₂-、-CH₂CH₂ -, or-CH=CH-)

[ 38]

(Wherein R ₃₁、R₃₂ is independently an alkyl group having 1 to 10 carbon atoms or a phenyl group.)

[ 39]

(Wherein R ₄、R₃₁、R₃₂ has the same meaning as above.)

(B) A step of obtaining a diester compound represented by the following chemical formula (M-C-4) by an oxidation reaction of the diester compound represented by the chemical formula (M-C-3);

[ 40]

(Wherein R ₄、R₃₁、R₃₂ has the same meaning as above.)

(C) A step of reacting a diester compound represented by the above formula (M-C-4) with an alcohol compound and carbon monoxide in the presence of a palladium catalyst and a copper compound to obtain a tetraester compound represented by the following formula (M-C-5);

[ chemical 41]

(Wherein R ₄、R₃₁、R₃₂ has the same meaning as above and R ₃₃、R₃₄ are each independently an alkyl group having 1 to 10 carbon atoms.)

(D) And (3) a step of reacting the tetraester compound represented by the above chemical formula (M-C-5) in an organic solvent in the presence of an acid catalyst to obtain a tetracarboxylic dianhydride represented by the following chemical formula (M-9).

[ Chemical 42]

(Wherein R ₄ has the same meaning as above.)

ADVANTAGEOUS EFFECTS OF INVENTION

The present invention can provide a novel polyimide and a precursor thereof, which have excellent characteristics such as transparency, bending resistance, high heat resistance, and low linear thermal expansion coefficient, and a novel tetracarboxylic dianhydride used for the production thereof, and a method for producing the same.

The polyimide obtained from the polyimide precursor of the present invention and the polyimide of the present invention can be easily formed into fine circuits, and can be suitably used for forming substrates for display applications and the like. The polyimide obtained from the polyimide precursor of the present invention and the polyimide of the present invention can be suitably used for forming substrates for touch panels and solar cells.

Detailed Description

The polyimide precursor according to embodiment 1 of the present invention (hereinafter, also referred to as "polyimide precursor (1-1)") is a polyimide precursor comprising at least one repeating unit represented by the above-mentioned chemical formula (1-1), and the total content of the repeating units represented by the chemical formula (1-1) is 50 mol% or more with respect to the total of the repeating units. Wherein the above chemical formula (1-1) is represented by: of the 4 bonds from the 4-valent group A ₁₁ of the tetracarboxylic acid component, 1 is bound to-CONH-and 1 is bound to-CONH-B ₁₁ -, 1 binds to-COOX ₁ and 1 binds to-COOX ₂, and the above formula (1-1) includes all structural isomers thereof.

The polyimide precursor (1-1) of the present invention preferably contains, in total, 50 mol% or more, more preferably 60 mol% or more, still more preferably 70 mol% or more, and particularly preferably 80 mol% or more of one or more repeating units represented by the above chemical formula (1-1).

The polyimide precursor (1-1) of the present invention may contain two or more kinds of repeating units of the above chemical formula (1-1) having different types of A ₁₁ and/or B ₁₁. The polyimide precursor (1-1) of the present invention may contain one or more types of repeating units represented by the above formula (1-1) wherein A ₁₁ is a 4-valent group represented by the above formula (A-1), and one or more types of repeating units represented by the above formula (1-1) wherein A ₁₁ is a 4-valent group represented by the above formula (A-2).

In other words, the polyimide precursor (1-1) of the present invention is a polyimide precursor obtained from a tetracarboxylic acid component comprising a tetracarboxylic acid component providing the structure of the above-mentioned chemical formula (A-1) and/or a tetracarboxylic acid component providing the structure of the above-mentioned chemical formula (A-2), and a diamine component comprising a diamine component providing the structure of the above-mentioned chemical formula (B-1) and/or a diamine component providing the structure of the above-mentioned chemical formula (B-2).

The tetracarboxylic acid component providing the repeating unit of the above-mentioned chemical formula (1-1) is a tetracarboxylic acid component providing the structure of the above-mentioned chemical formula (A-1) and a tetracarboxylic acid component providing the structure of the above-mentioned chemical formula (A-2). Examples of the tetracarboxylic acid component providing the structure of the above formula (A-1) include tetradecahydro-1H, 3H-4,12:5,11:6, 10-trimethylbridged anthraceno [2,3-c:6,7-c '] difuran-1, 3,7, 9-tetraone, tetradecahydro-1H, 3H-4, 12-ethanol-5, 11:6, 10-dimethylbridged anthra [2,3-c:6,7-c' ] difuran-1, 3,7, 9-tetraone, tetradecahydro-1H, 3H-4,12:5, 11-diethanol-6, 10-methano-anthra [2,3-c:6,7-c '] difuran-1, 3,7, 9-tetraone, tetradecahydro-1H, 3H-4,12:5,11:6, 10-triethanol anthra [2,3-c:6,7-c' ] difuran-1, 3,7, 9-tetraone, tetradecahydro-1H, 3H-5, 11-ethanol-4, 12:6, 10-dimethyl anthra [2,3-c:6,7-c '] difuran-1, 3,7, 9-tetraone, tetradecahydro-1H, 3H-4, 12-ethylene bridge-5, 11:6, 10-dimethyl anthra [2,3-c:6,7-c' ] difuran-1, 3,7, 9-tetraone, tetradecahydro-1H, 3H-4,12:5, 11-dimethyl anthra [2, 3-c:5, 10-methyl anthra [2,3-c ] difuran-1, 3,7, 9-tetraone, tetradecahydro-1H, 3-c:3-c '] difuran-1, 3, 7-c-tetraone, 9-tetraone, tetradecahydro-1, 3-c:3, 3-c' ] difuran-1, 3,7, 6-c-tetraone, 10-methyl anthra [2,3-c ] tetraone, 7, 10-methyl anthra-1, 3, 7-c ] tetraone, 6, 3, 6-c-tetraone, 6-methyl anthra, 3, 6-tetraone, 6 tetramethyl-tetraone, 6,7, 6, methanol-four-one, a four-one, a four, the tetracarboxylic acid derivative other than tetracarboxylic dianhydride and the like may be exemplified as the tetracarboxylic acid component providing the structure of the above chemical formula (A-2), and examples thereof include 3a,4,10 a-tetrahydro-1H, 3H-4, 10-methanonaphtho [2,3-c:6,7-c ' ] difuran-1, 3,6, 8-tetralone, 3a,4,10 a-tetrahydro-1H, 3H-4, 10-ethanonaphtho [2,3-c:6,7-c ' ] difuran-1, 3,6, 8-tetralone, 3a,4,10 a-tetrahydro-1H, 3H-4, 10-methanonaphtho [2,3-c:6,7-c ' ] difuran-1, 3,6, 8-tetralone, and the corresponding tetracarboxylic acid, tetracarboxylic acid derivative other than tetracarboxylic dianhydride and the like. These tetracarboxylic acid components (tetracarboxylic acids, etc.) may be used singly or in combination of two or more. Here, the tetracarboxylic acid and the like mean tetracarboxylic acid derivatives such as tetracarboxylic acid and tetracarboxylic dianhydride, tetracarboxylic silyl ester, tetracarboxylic acid chloride and the like.

The diamine component providing the repeating unit of the above formula (1-1) is a diamine component providing the structure of the above formula (B-1) and a diamine component providing the structure of the above formula (B-2).

The diamine component having the structure represented by the above formula (B-1) has an aromatic ring, and when the diamine component has a plurality of aromatic rings, the aromatic rings are directly bonded independently of each other, and are bonded by an amide bond or an ester bond. The connection position between the aromatic rings is not particularly limited, and it is preferable that the amino group or the connection group between the aromatic rings is bonded at the 4-position. That is, the position of the connection between the aromatic rings in the group represented by the above formula (B-1) is not particularly limited, but it is preferable that the amide group (-CONH-) bonded to A ₁₁ or the connection group between the aromatic rings is bonded at the 4-position. By such bonding, the polyimide obtained may have a linear structure and may have low linear thermal expansion. When the diamine component having the structure represented by the above formula (B-1) has one aromatic ring, it is preferable to have a p-phenylene structure. That is, in the case where the group represented by the above formula (B-1) has one aromatic ring (in the case where n ₁ and n ₂ are 0), the group represented by the above formula (B-1) is preferably p-phenylene group with or without substituent (Y ₁), preferably unsubstituted p-phenylene group. In addition, the aromatic ring may be substituted with methyl or trifluoromethyl. The substitution position is not particularly limited.

The diamine component having the structure represented by the above formula (B-2) has an aliphatic 6-membered ring, and the aliphatic 6-membered ring may be substituted with an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and the like, and is preferably an unsubstituted aliphatic 6-membered ring in view of heat resistance and linear thermal expansion coefficient of the polyimide obtained. That is, in the group represented by the above formula (B-2), Y ₄ is preferably a hydrogen atom. The substitution position is not particularly limited. In addition, the diamine component providing the structure of the above chemical formula (B-2) preferably has a1, 4-cyclohexane structure as an aliphatic 6-membered ring. That is, the group represented by the above formula (B-2) is preferably a1, 4-cyclohexyl group with or without a substituent (Y ₄), preferably an unsubstituted 1, 4-cyclohexyl group.

The diamine component providing the structure of the above chemical formula (B-1) is not particularly limited, and examples thereof include p-phenylenediamine, m-phenylenediamine, benzidine, 3 '-diamino-biphenyl, 2' -bis (trifluoromethyl) benzidine, 3 '-bis (trifluoromethyl) benzidine, m-benzidine, 4' -diaminobenzanilide, 3,4 '-diaminobenzanilide, N' -bis (4-aminophenyl) terephthalamide, N, N '-p-phenylene bis (p-aminobenzamide), 4-aminophenoxy-4-diaminobenzoate, bis (4-aminophenyl) terephthalate, biphenyl-4, 4' -dicarboxylic acid bis (4-aminophenyl) ester, p-phenylene bis (p-aminobenzoate), bis (4-aminophenyl) - [1,1 '-biphenyl ] -4,4' -dicarboxylic acid ester, [1,1 '-biphenyl ] -4,4' -diylbis (4-aminobenzoate), and the like. Examples of the diamine component providing the structure of the above formula (B-2) include 1, 4-diaminocyclohexane, 1, 4-diamino-2-methylcyclohexane, 1, 4-diamino-2-ethylcyclohexane, 1, 4-diamino-2-n-propylcyclohexane, 1, 4-diamino-2-isopropylcyclohexane, 1, 4-diamino-2-n-butylcyclohexane, 1, 4-diamino-2-isobutylcyclohexane, 1, 4-diamino-2-sec-butylcyclohexane, 1, 4-diamino-2-tert-butylcyclohexane, 1, 2-diaminocyclohexane and the like. As the diamine component providing the structure of the above chemical formula (B-2), 1, 4-diaminocyclohexane is more preferable because the polyimide obtained has a low coefficient of thermal expansion. The steric structure at the 1,4 position of the diamine having a 1, 4-cyclohexane structure is not particularly limited, but is preferably a trans structure. In the case of the trans structure, coloring of the obtained polyimide may be further suppressed than in the case of the cis structure. One of these diamine components may be used alone, or two or more of these diamine components may be used in combination.

As B ₁₁ in the above chemical formula (1-1), that is, the 2-valent group represented by the above chemical formula (B-1) and the 2-valent group represented by the above chemical formula (B-2), a group represented by any one of the following chemical formulas (B-1-1) to (B-1-6) and (B-2-1) is preferable.

[ Chemical 43]

The diamine component of the repeating unit of the formula (1-1) in which B ₁₁ is the group of the formula (B-1-1) or (B-1-2) is 4,4 '-diaminobenzanilide, the diamine component of the repeating unit of the formula (1-1) in which B ₁₁ is the group of the formula (B-1-3) is bis (4-aminophenyl) terephthalate, the diamine component of the repeating unit of the formula (1-1) in which B ₁₁ is the group of the formula (B-1-4) is p-phenylenediamine, the diamine component of the repeating unit of the formula (1-1) in which B ₁₁ is the group of the formula (B-1-5) is 2,2' -bis (trifluoromethyl) benzidine, the diamine component of the repeating unit of the formula (1-1) in which B ₁₁ is the group of the formula (B-1-6) is p-phenylenediamine, and the diamine component of the repeating unit of the formula (1-1) in which B ₁₁ is the group of the formula (B-1-5) is p-phenylenediamine, and the diamine component of the repeating unit of the formula (B-1-1) is the repeating unit of the formula (B-1-2) is the methylene diamine component of the group of the formula (B-1-1).

In B ₁₁ in the above chemical formula (1-1), the total ratio of the groups represented by any one of the above chemical formulas (B-1-1) to (B-1-6) and (B-2-1) is preferably 30 mol% or more, more preferably 50 mol% or more, particularly preferably 70 mol% or more.

The polyimide precursor (1-1) of the present invention may contain a repeating unit other than the repeating unit represented by the above chemical formula (1-1). In one embodiment, the repeating units other than the repeating unit represented by the above chemical formula (1-1) (for example, the 4-valent group derived from the tetracarboxylic acid component is the 4-valent group represented by the above chemical formula (A-1), or the 4-valent group represented by the above chemical formula (A-2), and the repeating unit derived from the diamine component in which the 2-valent group has 2 or more aromatic rings and the aromatic rings are linked to each other by an ether bond (-O-) are preferably contained in the total repeating units, for example, at 30 mol% or less, or at 25 mol% or less, or at 20 mol% or at 10 mol% or less. In one embodiment, the 4-valent group derived from the tetracarboxylic acid component is a 4-valent group represented by the above-mentioned chemical formula (A-1) or a 4-valent group represented by the above-mentioned chemical formula (A-2), and the repeating unit derived from the diamine component has 2 or more aromatic rings and the aromatic rings are linked to each other by an ether bond (-O-) is contained in the total repeating units, for example, preferably at most 40 mol%, preferably at most 35 mol%, depending on the desired characteristics and use.

As the tetracarboxylic acid component providing other repeating units, other aromatic or aliphatic tetracarboxylic acids may be used. Examples thereof include, but are not particularly limited to, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane, 4- (2, 5-dioxotetrahydrofuran-3-yl) -1,2,3, 4-tetrahydronaphthalene-1, 2-dicarboxylic acid, pyromellitic acid, 3',4' -benzophenone tetracarboxylic acid, 3',4,4' -biphenyltetracarboxylic acid, 2, 3',4' -biphenyltetracarboxylic acid, 4' -oxybisphthalic acid, bis (3, 4-dicarboxyphenyl) sulfone dianhydride, m-terphenyl-3, 4,3',4' -tetracarboxylic dianhydride, p-terphenyl-3, 4,3',4' -tetracarboxylic dianhydride, dicarboxyphenyl dimethylsilane, dicarboxyphenoxydiphenyl sulfide, sulfonyl diphthalic acid, 1,2,3, 4-cyclobutanetetracarboxylic acid, isopropylidenediphenoxydiphthalic acid, cyclohexane-1, 2,4, 5-tetracarboxylic acid, [1,1' -bis (cyclohexane) ] -3,3', 4' -tetracarboxylic acid, [1,1' -bis (cyclohexane) ] -2, 3',4' -tetracarboxylic acid, [1,1' -bis (cyclohexane) ] -2,2', 3' -tetracarboxylic acid, 4' -methylenebis (cyclohexane-1, 2-dicarboxylic acid), 4' - (propane-2, 2-diyl) bis (cyclohexane-1, 2-dicarboxylic acid), 4,4' -Oxobis (cyclohexane-1, 2-dicarboxylic acid), 4' -thiobis (cyclohexane-1, 2-dicarboxylic acid), 4' -sulfonylbis (cyclohexane-1, 2-dicarboxylic acid), 4' - (dimethylsilanediyl) bis (cyclohexane-1, 2-dicarboxylic acid), 4' - (tetrafluoropropane-2, 2-diyl) bis (cyclohexane-1, 2-dicarboxylic acid), octahydrocyclopentadiene-1, 3,4, 6-tetracarboxylic acid, bicyclo [2.2.1] heptane-2, 3,5, 6-tetracarboxylic acid, 6- (carboxymethyl) bicyclo [2.2.1] heptane-2, 3, 5-tricarboxylic acid, Derivatives of bicyclo [2.2.2] octane-2, 3,5, 6-tetracarboxylic acid, bicyclo [2.2.2] oct-5-ene-2, 3,7, 8-tetracarboxylic acid, tricyclo [4.2.2.02,5] decane-3, 4,7, 8-tetracarboxylic acid, tricyclo [4.2.2.02,5] dec-7-ene-3, 4,9, 10-tetracarboxylic acid, 9-oxatricyclo [4.2.1.02,5] nonane-3, 4,7, 8-tetracarboxylic acid, decahydro-1, 4:5, 8-dimethylnaphthalene-2, 3,6, 7-tetracarboxylic acid, norcamphene-2-spiro-alpha-cyclopentanone-alpha '-spiro-2' -norcamphene-5, 5 ', 6' -tetracarboxylic acid, etc, Their acid dianhydrides. These tetracarboxylic acid components (tetracarboxylic acids, etc.) may be used singly or in combination of two or more. Among these, preferred are derivatives such as bicyclo [2.2.1] heptane-2, 3,5, 6-tetracarboxylic acid, bicyclo [2.2.2] octane-2, 3,5, 6-tetracarboxylic acid, decahydro-1, 4:5, 8-dimethylnaphthalene-2, 3,6, 7-tetracarboxylic acid, norbornane-2-spiro- α -cyclopentanone- α' -spiro-2 "-norbornane-5, 5",6 "-tetracarboxylic acid, and their acid dianhydrides.

In the case where the diamine component to be combined is a diamine component providing the structure of the above-mentioned chemical formula (B-1) and a diamine component other than the diamine component providing the structure of the above-mentioned chemical formula (B-2), one or two or more of a tetracarboxylic acid component providing the structure of the above-mentioned chemical formula (a-1) and a tetracarboxylic acid component providing the structure of the above-mentioned chemical formula (a-2) may be used as the tetracarboxylic acid component providing the other repeating unit.

As the diamine component providing other repeating units, other aromatic or aliphatic diamines may be used. There is no particular limitation on the type of the material, examples thereof include 4,4 '-oxydiphenylamine, 3' -oxydiphenylamine, bis (4-aminophenyl) sulfide, p-methylenebis (phenylenediamine), 1, 3-bis (4-aminophenoxy) benzene, 1, 3-bis (3-aminophenoxy) benzene, 1, 4-bis (4-aminophenoxy) benzene, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 2-bis (4-aminophenyl) hexafluoropropane, bis (4-aminophenyl) sulfone, 3-bis ((aminophenoxy) phenyl) propane 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (4- (4-aminophenoxy) diphenyl) sulfone, bis (4- (3-aminophenoxy) diphenyl) sulfone, octafluorobiphenyl amine, 3 '-dimethoxy-4, 4' -diaminobiphenyl 3,3 '-dichloro-4, 4' -diaminobiphenyl, 3 '-difluoro-4, 4' -diaminobiphenyl, 9-bis (4-aminophenyl) fluorene, 4 '-bis (4-aminophenoxy) biphenyl, 4' -bis (3-aminophenoxy) biphenyl, and the like, and derivatives thereof. One of these diamine components may be used alone, or two or more of these diamine components may be used in combination.

In the case where the tetracarboxylic acid component to be combined is a tetracarboxylic acid component providing the structure of the above-mentioned chemical formula (a-1) and another tetracarboxylic acid component other than the tetracarboxylic acid component providing the structure of the above-mentioned chemical formula (a-2), one or two or more of a diamine component providing the structure of the above-mentioned chemical formula (B-1) and a diamine component providing the structure of the above-mentioned chemical formula (B-2) may be used as the diamine component providing another repeating unit.

In one embodiment, for example, a diamine component having a plurality of aromatic rings, such as 4,4 '-oxydiphenylamine or 4,4' -bis (4-aminophenoxy) biphenyl, in which the aromatic rings are linked to each other by an ether bond (-O-) is preferably used in an amount of 30 mol% or less, or 25 mol% or less, or 20 mol% or less, or 10 mol% or less, based on 100 mol% of the diamine component. In one embodiment, the diamine component having a plurality of aromatic rings and having the aromatic rings bonded to each other via an ether bond (-O-) is used in an amount of, for example, preferably 40 mol% or less, and preferably 35 mol% or less, based on 100 mol% of the diamine component, depending on the desired properties and applications.

The polyimide precursor according to embodiment 2 of the present invention (hereinafter sometimes referred to as "polyimide precursor (1-2)") is a polyimide precursor comprising at least one repeating unit represented by the above-mentioned chemical formula (1-2). Wherein the above chemical formula (1-2) is represented by: of the 4 bonds from the 4-valent group A ₁₂ of the tetracarboxylic acid component, 1 is bound to-CONH-and 1 is bound to-CONH-B ₁₂ -, 1 binds to-COOX ₃ and 1 binds to-COOX ₄, and the above formula (1-2) includes all structural isomers thereof.

The total content of the repeating units represented by the chemical formula (1-2) is not particularly limited, but is preferably 50 mol% or more based on the total repeating units. That is, the polyimide precursor (1-2) of the present invention preferably contains 50 mol% or more of one or more of the repeating units represented by the above chemical formula (1-2) in total, more preferably 60 mol% or more, still more preferably 70 mol% or more, still more preferably 80 mol% or more, and particularly preferably 90 mol% or more.

The polyimide precursor (1-2) of the present invention may contain two or more kinds of repeating units of the above chemical formula (1-2) which differ in a ₁₂ and/or B ₁₂. The polyimide precursor (1-2) of the present invention may contain one or more of a ₁₂ which is a 4-valent group represented by the above chemical formula (a-3) and a repeating unit of the above chemical formula (1-2) in which a ₁₂ is a 4-valent group represented by the above chemical formula (a-4).

In other words, the polyimide precursor (1-2) of the present invention is a polyimide precursor obtained from a tetracarboxylic acid component containing a tetracarboxylic acid component providing the structure of the above chemical formula (a-3) and/or a tetracarboxylic acid component providing the structure of the above chemical formula (a-4), and a diamine component containing a diamine component having an aromatic ring or alicyclic structure (i.e., an aromatic diamine or alicyclic diamine).

The tetracarboxylic acid component providing the repeating unit of the above-mentioned chemical formula (1-2) is a tetracarboxylic acid component providing the structure of the above-mentioned chemical formula (A-3) and a tetracarboxylic acid component providing the structure of the above-mentioned chemical formula (A-4). Examples of the tetracarboxylic acid component providing the structure of the above formula (A-3) include 3a,4, 6a,9a,10,12 a-octahydro-1H, 3H-4,12:6, 10-dimethylanthra [2,3-c:6,7-c '] difuran-1, 3,7, 9-tetraone, 3a,4, 6a,9a,10,12 a-octahydro-1H, 3H-4, 12-ethanol-6, 10-methano-anthra [2,3-c:6,7-c' ] difuran-1, 3,7, 9-tetraone, 3a,4, 6a,9a,10,12 a-octahydro-1H, 3H-4,12:6, 10-diethanolanthanoid [2,3-c: examples of the tetracarboxylic acid component other than 6,7-c '] difuran-1, 3,7, 9-tetraone, 3a,4, 6a,9a,10,12 a-octahydro-1H, 3H-4, 12-ethylene bridge-6, 10-methano-anthra [2,3-c:6,7-c' ] difuran-1, 3,7, 9-tetraone, 3a,4, 6a,9a,10,12 a-octahydro-1H, 3H-4,12:6, 10-diethyle-methano [2,3-c:6,7-c '] difuran-1, 3,7, 9-tetraone, and the corresponding tetracarboxylic acid, tetracarboxylic acid derivatives other than tetracarboxylic acid dianhydride, and the tetracarboxylic acid component providing the structure of the above formula (A-4) include decahydro-1H, 3H-4, 10-ethanol-5, 9-methano [2,3-c:6,7-c' ] difuran 1H,3, 6, 12 a-octahydro-1H, 3H, 6, 10-c '] difuran 1, 3-6, 3-c-8-c' ] tetracarboxylic acid derivative other than tetracarboxylic acid derivative and the tetracarboxylic acid derivative. These tetracarboxylic acid components (tetracarboxylic acids, etc.) may be used singly or in combination of two or more. Here, the tetracarboxylic acid and the like mean tetracarboxylic acid derivatives such as tetracarboxylic acid and tetracarboxylic dianhydride, tetracarboxylic silyl ester, tetracarboxylic acid chloride and the like.

B ₁₂ in the above chemical formula (1-2) is a 2-valent group having an aromatic ring or alicyclic structure, and is preferably a 2-valent group having an aromatic ring in view of heat resistance of the obtained polyimide. The diamine component B ₁₂ in the chemical formula (1-2) is not particularly limited, and may be appropriately selected depending on the desired properties and use.

Examples of the diamine component providing the repeating unit of the above formula (1-2) include the same materials as those listed as the diamine component providing the structure of the above formula (B-1) of the above polyimide precursor (1-1) and the diamine component providing the structure of the above formula (B-2), and further those listed as the diamine component providing the other repeating unit other than the diamine component providing the structure of the above formula (B-1) and the diamine component providing the structure of the above formula (B-2), and the same materials may be suitably used. In the polyimide precursor (1-2), one of these diamine components may be used alone, or two or more of these diamine components may be used in combination.

B ₁₂ in the above chemical formula (1-2) is preferably a 2-valent group having an aromatic ring having 6 to 40 carbon atoms, and more preferably a group represented by the above chemical formula (B-1) exemplified in the above polyimide precursor (1-1). The group represented by the above formula (B-2) is also preferable as exemplified in the above polyimide precursor (1-1). Among these, the group represented by any one of the above-mentioned chemical formulas (B-1-1) to (B-1-6) and (B-2-1) is particularly preferable as B ₁₂ in the above-mentioned chemical formula (1-2).

As B ₁₂ in the above-mentioned chemical formula (1-2), a 2-valent group having 2 or more aromatic rings and part or all of the aromatic rings being linked to each other through an ether bond (-O-) is also preferable, and a group represented by any one of the following chemical formulas (B-3-1) to (B-3-4) is particularly preferable.

[ 44]

The diamine component of the repeating unit of the formula (1-2) in which B ₁₂ is the group of the formula (B-3-1) was 4,4 '-oxydiphenylamine, the diamine component of the repeating unit of the formula (1-2) in which B ₁₂ is the group of the formula (B-3-2) was 1, 4-bis (4-aminophenoxy) benzene, the diamine component of the repeating unit of the formula (1-2) in which B ₁₂ is the group of the formula (B-3-3) was 1, 3-bis (4-aminophenoxy) benzene, and the diamine component of the repeating unit of the formula (1-2) in which B ₁₂ is the group of the formula (B-3-4) was 4,4' -bis (4-aminophenoxy) biphenyl.

As described above, B ₁₂ in the chemical formula (1-2), that is, the diamine component can be appropriately selected according to the desired characteristics and use. In one embodiment, in B ₁₂ in the above chemical formula (1-2), the ratio of the group represented by the above chemical formula (B-1) and/or the group represented by the above chemical formula (B-2), more preferably the ratio of the groups represented by any of the above chemical formulas (B-1-1) to (B-1-6) and (B-2-1) is preferably 50 mol% or more, more preferably 60 mol% or more, more preferably 65 mol% or more, more preferably 70 mol% or more, or 75 mol% or more in total, for example. In one embodiment, in B ₁₂ in the above chemical formula (1-2), the ratio of the 2-valent groups having 2 or more aromatic rings and part or all of the aromatic rings being linked by an ether bond (-O-) is preferably 30 mol% or more, more preferably 50 mol% or more, in total, of the groups represented by any one of the above chemical formulas (B-3-1) to (B-3-4). In one embodiment, in B ₁₂ in the above chemical formula (1-2), the ratio of the group represented by the above chemical formula (B-1) and/or the group represented by the above chemical formula (B-2) is preferably 60 mol% or more, preferably 65 mol% or more, or 70 mol% or more, or 75 mol% or more, and the ratio of the group represented by any one of the above chemical formulas (B-3-1) to (B-3-4) is preferably 40 mol% or less, preferably 35 mol% or less, or 30 mol% or less, or 25 mol% or less.

The polyimide precursor (1-2) of the present invention may contain a repeating unit other than the repeating unit represented by the above chemical formula (1-2).

As the tetracarboxylic acid component providing another repeating unit, other aromatic or aliphatic tetracarboxylic acids can be used, and examples thereof include the same materials as those listed as the tetracarboxylic acid component providing another repeating unit in the polyimide precursor (1-1). In addition, the tetracarboxylic acid component providing the repeating unit of the above-mentioned chemical formula (1-1) (i.e., the tetracarboxylic acid component providing the structure of the above-mentioned chemical formula (A-1) and the tetracarboxylic acid component providing the structure of the above-mentioned chemical formula (A-2)) may also be used. In the polyimide precursor (1-2), one of these tetracarboxylic acid components providing other repeating units may be used alone, or two or more of them may be used in combination.

In the case where the diamine component to be combined is a diamine having no aromatic ring and alicyclic structure, one or more of a tetracarboxylic acid component providing the structure of the above-mentioned chemical formula (a-3) and a tetracarboxylic acid component providing the structure of the above-mentioned chemical formula (a-4) may be used as the tetracarboxylic acid component providing other repeating units.

Other aromatic or aliphatic diamines may be used as the diamine component for providing other repeating units, and examples thereof include the same materials as those listed as the diamine component for providing other repeating units in the polyimide precursor (1-1). Further, as the diamine component providing the repeating unit of the above chemical formula (1-1) (i.e., the diamine component providing the structure of the above chemical formula (B-1) and the diamine component providing the structure of the above chemical formula (B-2)), those listed above may also be used. In the polyimide precursor (1-2), one of these diamine components providing other repeating units may be used alone, or two or more of them may be used in combination.

In the polyimide precursor [ polyimide precursor (1-1) and polyimide precursor (1-2) ] of the present invention, X ₁、X₂ in the above chemical formula (1-1) and X ₃、X₄ in the above chemical formula (1-2) are each independently any one of hydrogen, an alkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, or an alkylsilyl group having 3 to 9 carbon atoms. X ₁、X₂、X₃、X₄ can be changed in the kind of functional group and the rate of introduction of functional group by the production method described later.

When X ₁, X ₂、X₃, and X ₄ are hydrogen, the polyimide tends to be easily produced.

When X ₁, X ₂、X₃, and X ₄ are alkyl groups having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, the polyimide precursor tends to have excellent storage stability. In this case, X ₁ and X ₂、X₃ and X ₄ are more preferably methyl or ethyl.

When X ₁, X ₂、X₃, and X ₄ are alkylsilyl groups having 3 to 9 carbon atoms, the polyimide precursor tends to have excellent solubility. In this case, X ₁ and X ₂、X₃ and X ₄ are more preferably trimethylsilyl or t-butyldimethylsilyl.

The introduction rate of the functional group is not particularly limited, and in the case of introducing an alkyl group or an alkylsilyl group, X ₁ and X ₂、X₃ and X ₄ may be an alkyl group or an alkylsilyl group in an amount of 25% or more, preferably 50% or more, more preferably 75% or more, respectively.

Polyimide precursors of the present invention can be classified into: 1) Polyamic acid (X ₁ and X ₂、X₃ and X ₄ are hydrogen); 2) Polyamic acid esters (at least a portion of X ₁ and X ₂ are alkyl groups, at least a portion of X ₃ and X ₄ are alkyl groups); 3) 4) Polyamic acid silyl esters (at least a portion of X ₁ and X ₂ is alkylsilyl, at least a portion of X ₃ and X ₄ is alkylsilyl). The polyimide precursor of the present invention can be easily produced by the following production method for each of the classifications. However, the method for producing the polyimide precursor of the present invention is not limited to the following production method.

1) Polyamic acid

In the polyimide precursor of the present invention, the polyimide precursor can be suitably obtained as a polyimide precursor solution by reacting in a solvent a tetracarboxylic dianhydride as a tetracarboxylic acid component and a diamine component in a ratio of about equimolar, preferably a molar ratio of the diamine component to the tetracarboxylic acid component [ the number of moles of the diamine component/the number of moles of the tetracarboxylic acid component ] of preferably 0.90 to 1.10, more preferably 0.95 to 1.05, while suppressing imidization at a relatively low temperature of, for example, 120 ℃.

The method for synthesizing the polyimide precursor of the present invention is not limited, and more specifically, the polyimide precursor is obtained by dissolving a diamine in an organic solvent, adding a tetracarboxylic dianhydride to the solution slowly while stirring, and stirring for 1 to 72 hours at a temperature ranging from 0 to 120 ℃, preferably from 5 to 80 ℃. When the reaction is carried out at 80 ℃ or higher, the molecular weight may vary depending on the temperature history during polymerization, and imidization may be carried out by heat, so that a polyimide precursor may not be stably produced. The order of addition of the diamine and the tetracarboxylic dianhydride in the above production method is preferable because it is easy to increase the molecular weight of the polyimide precursor. In addition, the order of addition of the diamine and the tetracarboxylic dianhydride in the above production method may be reversed, and the precipitate may be reduced, which is preferable.

When the molar ratio of the tetracarboxylic acid component to the diamine component is excessive, the molar ratio of the tetracarboxylic acid component to the diamine component can be made approximately equivalent by adding a carboxylic acid derivative in an amount approximately equivalent to the excessive molar number of the diamine component, if necessary. The carboxylic acid derivative is preferably a tetracarboxylic acid which does not substantially increase the viscosity of the polyimide precursor solution, that is, does not substantially participate in molecular chain extension, or a tricarboxylic acid and its anhydride, a dicarboxylic acid and its anhydride, or the like which function as a capping agent.

2) Polyamic acid esters

The dicarboxylic acid diester is obtained by reacting tetracarboxylic dianhydride with an optional alcohol, and then reacting it with a chlorinating agent (thionyl chloride, oxalyl chloride, etc.), thereby obtaining the dicarboxylic acid diester. The diester dicarboxylic acid chloride and diamine are stirred at a temperature of-20 to 120 ℃, preferably-5 to 80 ℃ for 1 to 72 hours, thereby obtaining a polyimide precursor. When the reaction is carried out at 80 ℃ or higher, the molecular weight may vary depending on the temperature history during polymerization, and imidization may be carried out by heat, so that a polyimide precursor may not be stably produced. Further, a polyimide precursor can be simply obtained by dehydrating and condensing a diester dicarboxylic acid and a diamine using a phosphorus-based condensing agent, a carbodiimide condensing agent, or the like.

Since the polyimide precursor obtained by this method is stable, purification such as reprecipitation can be performed by adding a solvent such as water or alcohol.

3) Polyamic acid silyl ester (indirect method)

The diamine and the silylating agent are reacted in advance to obtain a silylated diamine. Purification of the silylated diamine is carried out by distillation or the like as needed. Then, the silylated diamine is dissolved in the dehydrated solvent in advance, and the tetracarboxylic dianhydride is added slowly while stirring, and stirred at a temperature ranging from 0 to 120 ℃, preferably from 5 to 80 ℃ for 1 to 72 hours, thereby obtaining a polyimide precursor. When the reaction is carried out at 80 ℃ or higher, the molecular weight may vary depending on the temperature history during polymerization, and imidization may be carried out by heat, so that a polyimide precursor may not be stably produced.

As the silylating agent used herein, a silylating agent containing no chlorine is used, and therefore, it is not necessary to purify the silylated diamine. Examples of the silylating agent containing no chlorine atom include N, O-bis (trimethylsilyl) trifluoroacetamide, N, O-bis (trimethylsilyl) acetamide, and hexamethyldisilazane. N, O-bis (trimethylsilyl) acetamide and hexamethyldisilazane are particularly preferable because they contain no fluorine atom and are low in cost.

In order to promote the reaction, an amine catalyst such as pyridine, piperidine, or triethylamine may be used in the silylation reaction of diamine. The catalyst can be used as a polymerization catalyst of polyimide precursor.

4) Polyamic acid silyl ester (direct method)

The polyamic acid solution obtained by the method of 1) and the silylating agent are mixed and stirred at a temperature ranging from 0 to 120 ℃, preferably from 5 to 80 ℃ for 1 to 72 hours, thereby obtaining a polyimide precursor. When the reaction is carried out at 80 ℃ or higher, the molecular weight may vary depending on the temperature history during polymerization, and imidization may be carried out by heat, so that a polyimide precursor may not be stably produced.

As the silylating agent used herein, a silylating agent containing no chlorine is used, and therefore, it is not necessary to purify the silylated polyamic acid or the obtained polyimide, and is therefore suitable. Examples of the silylating agent containing no chlorine atom include N, O-bis (trimethylsilyl) trifluoroacetamide, N, O-bis (trimethylsilyl) acetamide, and hexamethyldisilazane. N, O-bis (trimethylsilyl) acetamide and hexamethyldisilazane are particularly preferable because they contain no fluorine atom and are low in cost.

Since the above production methods can be carried out in an organic solvent, the varnish of the polyimide precursor of the present invention can be obtained easily as a result.

As the solvent used in the preparation of the polyimide precursor, for example, aprotic solvents such as N, N-dimethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1, 3-dimethyl-2-imidazolidinone, and dimethylsulfoxide are preferable, and N, N-dimethylacetamide and N-methyl-2-pyrrolidone are particularly preferable, and any kind of solvent can be used without any problem if the raw material monomer components and the polyimide precursor to be produced are dissolved, and therefore the structure thereof is not particularly limited. As the solvent, an amide solvent such as N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, etc. is preferably used; cyclic ester solvents such as gamma-butyrolactone, gamma-valerolactone, delta-valerolactone, gamma-caprolactone, epsilon-caprolactone, alpha-methyl-gamma-butyrolactone, and the like; carbonate solvents such as ethylene carbonate and propylene carbonate; glycol solvents such as triethylene glycol; phenol solvents such as m-cresol, p-cresol, 3-chlorophenol, and 4-chlorophenol; acetophenone, 1, 3-dimethyl-2-imidazolidinone, sulfolane, dimethyl sulfoxide, and the like. Further, other conventional organic solvents, namely phenol, o-cresol, butyl acetate, ethyl acetate, isobutyl acetate, propylene glycol methyl acetate, ethyl cellosolve, butyl cellosolve, 2-methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, tetrahydrofuran, dimethoxyethane, diethoxyethane, dibutyl ether, diethylene glycol dimethyl ether, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methyl ethyl ketone, acetone, butanol, ethanol, xylene, toluene, chlorobenzene, terpene, mineral essential oil, petroleum naphtha-based solvents, and the like can also be used. It should be noted that two or more solvents may be used in combination.

In the present invention, the logarithmic viscosity of the polyimide precursor is not particularly limited, but it is preferable that the logarithmic viscosity in an N, N-dimethylacetamide solution having a concentration of 0.5g/dL at 30℃is 0.2dL/g or more, more preferably 0.3dL/g or more. When the logarithmic viscosity is 0.2dL/g or more, the molecular weight of the polyimide precursor is high, and the obtained polyimide is excellent in mechanical strength and heat resistance.

In the present invention, the varnish of the polyimide precursor contains at least the polyimide precursor [ polyimide precursor (1-1) and/or polyimide precursor (1-2) ] of the present invention and a solvent. The ratio of the total amount of the tetracarboxylic acid component and the diamine component to the total amount of the solvent, the tetracarboxylic acid component and the diamine component is preferably 5 mass% or more, more preferably 10 mass% or more, and still more preferably 15 mass% or more. In general, the total amount of the tetracarboxylic acid component and the diamine component is preferably 60 mass% or less, more preferably 50 mass% or less, based on the total amount of the solvent, the tetracarboxylic acid component and the diamine component. This concentration is a concentration approximately due to the concentration of the solid content of the polyimide precursor, and when this concentration is too low, it is difficult to control the film thickness of the polyimide film obtained when the polyimide film is produced, for example.

The solvent used in the varnish of the polyimide precursor of the present invention is not particularly limited as long as the polyimide precursor is dissolved. As the solvent, an amide solvent such as N, N-dimethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone, or the like is preferably used; cyclic ester solvents such as gamma-butyrolactone, gamma-valerolactone, delta-valerolactone, gamma-caprolactone, epsilon-caprolactone, alpha-methyl-gamma-butyrolactone, and the like; carbonate solvents such as ethylene carbonate and propylene carbonate; glycol solvents such as triethylene glycol; phenol solvents such as m-cresol, p-cresol, 3-chlorophenol, and 4-chlorophenol; acetophenone, 1, 3-dimethyl-2-imidazolidinone, sulfolane, dimethyl sulfoxide, and the like. Further, other conventional organic solvents, namely phenol, o-cresol, butyl acetate, ethyl acetate, isobutyl acetate, propylene glycol methyl acetate, ethyl cellosolve, butyl cellosolve, 2-methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, tetrahydrofuran, dimethoxyethane, diethoxyethane, dibutyl ether, diethylene glycol dimethyl ether, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methyl ethyl ketone, acetone, butanol, ethanol, xylene, toluene, chlorobenzene, terpene, mineral essential oil, petroleum naphtha-based solvents, and the like can also be used. In addition, two or more of these may be used in combination. The solvent of the varnish of the polyimide precursor may be used as it is in the preparation of the polyimide precursor.

In the present invention, the viscosity (rotational viscosity) of the varnish of the polyimide precursor is not particularly limited, and the rotational viscosity measured at a shearing speed of 20 seconds ^-1 at a temperature of 25 ℃ using an E-type rotational viscometer is preferably 0.01 to 1000pa·seconds, more preferably 0.1 to 100pa·seconds. In addition, thixotropic properties may be imparted as needed. In the case of the viscosity in the above range, the coating or film forming is easy to handle, the rejection can be suppressed, and the leveling property is excellent, so that a good film can be obtained.

The varnish of the polyimide precursor of the present invention may optionally contain a chemical imidizing agent (an acid anhydride such as acetic anhydride, an amine compound such as pyridine or isoquinoline), an antioxidant, a filler (inorganic particles such as silica), a coupling agent such as a dye, a pigment or a silane coupling agent, a primer, a flame retardant, an antifoaming agent, a leveling agent, a rheology control agent (flow aid), a release agent, etc.

The polyimide according to embodiment 1 of the present invention (hereinafter, sometimes referred to as "polyimide (2-1)") is the following polyimide: comprises at least one repeating unit represented by the above formula (2-1), wherein the total content of repeating units represented by the formula (2-1) is 50 mol% or more based on the total repeating units. That is, the polyimide (2-1) of the present invention can be obtained by using the above-mentioned tetracarboxylic acid component and diamine component used for obtaining the polyimide precursor (1-1) of the present invention, and the tetracarboxylic acid component and diamine component are preferably the same as those of the polyimide precursor (1-1) of the present invention.

The chemical formula (2-1) corresponds to the chemical formula (1-1) of the polyimide precursor (1-1), and a ₂₁、B₂₁ in the chemical formula (2-1) corresponds to a ₁₁、B₁₁ in the chemical formula (1-1), respectively.

The polyimide according to embodiment 2 of the present invention (hereinafter sometimes referred to as "polyimide (2-2)") is a polyimide comprising at least one repeating unit represented by the above chemical formula (2-2). The total content of the repeating units represented by the chemical formula (2-2) is not particularly limited, but is preferably 50 mol% or more based on the total repeating units. That is, the polyimide (2-2) of the present invention can be obtained by using the above-mentioned tetracarboxylic acid component and diamine component used for obtaining the polyimide precursor (1-2) of the present invention, and the tetracarboxylic acid component and diamine component are preferably the same as those of the polyimide precursor (1-2) of the present invention.

The chemical formula (2-2) corresponds to the chemical formula (1-2) of the polyimide precursor (1-2), and a ₂₂、B₂₂ in the chemical formula (2-2) corresponds to a ₁₂、B₁₂ in the chemical formula (1-2), respectively.

The polyimide (2-1) of the present invention can be suitably produced by subjecting the polyimide precursor (1-1) of the present invention as described above to a dehydration ring-closure reaction (imidization reaction). The polyimide (2-2) of the present invention can be suitably produced by subjecting the polyimide precursor (1-2) of the present invention as described above to a dehydration ring-closure reaction (imidization reaction). The method of imidization is not particularly limited, and a known method of thermal imidization or chemical imidization may be suitably applied.

The polyimide thus obtained may be in the form of a film, a laminate of a polyimide film and another substrate, a coating film, a powder, beads, a molded article, a foam, a varnish, or the like, as appropriate.

In the present invention, the logarithmic viscosity of the polyimide is not particularly limited, but the logarithmic viscosity in an N, N-dimethylacetamide solution having a concentration of 0.5g/dL at 30℃is preferably 0.2dL/g or more, more preferably 0.4dL/g or more, particularly preferably 0.5dL/g or more. When the logarithmic viscosity is 0.2dL/g or more, the polyimide obtained is excellent in mechanical strength and heat resistance.

In the present invention, the varnish of polyimide contains at least the polyimide of the present invention and the solvent, and the polyimide is preferably 5 mass% or more, more preferably 10 mass% or more, still more preferably 15 mass% or more, and particularly preferably 20 mass% or more, based on the total amount of the solvent and the polyimide. When the concentration is too low, it is difficult to control the film thickness of the polyimide film obtained when the polyimide film is produced, for example.

The solvent used in the varnish of polyimide of the present invention is not particularly limited as long as polyimide is dissolved. As the solvent, the solvent used in the varnish of the polyimide precursor of the present invention can be used in the same manner.

In the present invention, the viscosity (rotational viscosity) of the varnish of the polyimide is not particularly limited, and the rotational viscosity measured at a shearing speed of 20 seconds ^-1 at a temperature of 25 ℃ using an E-type rotational viscometer is preferably 0.01 to 1000pa·seconds, more preferably 0.1 to 100pa·seconds. In addition, thixotropic properties may be imparted as needed. In the case of the viscosity in the above range, the coating or film forming is easy to handle, the rejection can be suppressed, and the leveling property is excellent, so that a good film can be obtained.

The varnish of the polyimide of the present invention may be optionally added with an antioxidant, a filler (inorganic particles such as silica), a dye, a pigment, a coupling agent such as a silane coupling agent, a primer, a flame retardant, a defoaming agent, a leveling agent, a rheology control agent (flow aid), a release agent, and the like.

The polyimide obtained from the polyimide precursor of the present invention and the polyimide of the present invention are not particularly limited, and the linear thermal expansion coefficient at the time of film formation from 100℃to 250℃may be preferably 45ppm/K or less, more preferably 40ppm/K or less. When the linear thermal expansion coefficient is large, a difference between the linear thermal expansion coefficient and the linear thermal expansion coefficient of a conductor such as a metal is large, and defects such as warpage increase may occur in forming a circuit board.

The polyimide obtained from the polyimide precursor of the present invention and the polyimide of the present invention are not particularly limited, and the total light transmittance (average light transmittance at a wavelength of 380nm to 780 nm) in the case of a film having a thickness of 10 μm may be preferably 70% or more, more preferably 75% or more, and still more preferably 80% or more. When the light source is used for display applications or the like, if the total light transmittance is low, the light source needs to be enhanced, and there is a problem that energy is consumed.

The thickness of the film made of the polyimide of the present invention is preferably 1 to 250. Mu.m, more preferably 1 to 150. Mu.m, still more preferably 1 to 50. Mu.m, particularly preferably 1 to 30. Mu.m, depending on the application. When the polyimide film is used in applications such as display applications where light is transmitted through the polyimide film, if the polyimide film is too thick, the light transmittance may be lowered.

The polyimide obtained from the polyimide precursor of the present invention and the polyimide of the present invention are not particularly limited, and the 5% weight reduction temperature as an index of heat resistance of the polyimide may be preferably 420 ℃ or higher, more preferably 450 ℃ or higher. When a gas barrier film or the like is formed on polyimide such as a transistor formed on polyimide, if the heat resistance is low, there is a case where expansion occurs between polyimide and the barrier film due to degassing accompanied by decomposition of polyimide or the like.

The polyimide obtained from the polyimide precursor of the present invention and the polyimide of the present invention can be suitably used for applications such as a transparent substrate for a display, a transparent substrate for a touch panel, or a substrate for a solar cell.

Next, an example of a polyimide film/substrate laminate or a method for producing a polyimide film using the polyimide precursor of the present invention will be described. However, the method is not limited to the following method.

The varnish of the polyimide precursor of the present invention is cast onto a substrate such as ceramics (glass, silicon, alumina, etc.), metals (copper, aluminum, stainless steel, etc.), heat-resistant plastic films (polyimide films, etc.), and dried in vacuum, in an inert gas such as nitrogen, or in air, using hot air or infrared rays, at a temperature in the range of 20 to 180 ℃, preferably 20 to 150 ℃. Next, the polyimide precursor film thus obtained is peeled off from the substrate, and the ends of the film are fixed, and in this state, the polyimide film/substrate laminate or polyimide film is produced by thermal imidization using hot air or infrared rays at a temperature of, for example, 200 to 500 ℃, more preferably about 250 to 460 ℃ in a vacuum, in an inert gas such as nitrogen, or in air. In order to prevent the obtained polyimide film from being oxidized and deteriorated, the imidization by heating is preferably performed in vacuum or in an inert gas. If the temperature for heating imidization is not excessively high, the reaction may be carried out in air.

In addition, the imidization reaction of the polyimide precursor may be performed by the following chemical treatment instead of the thermal imidization by the heat treatment as described above: specifically, the polyimide precursor is immersed in a solution containing a dehydrative ring-closure reagent such as acetic anhydride in the presence of a tertiary amine such as pyridine or triethylamine. Further, by preliminarily pouring these dehydrative ring-closure reagents into a varnish of a polyimide precursor, stirring, casting the varnish onto a substrate, and drying the varnish, a partially imidized polyimide precursor can be produced, and the obtained partially imidized polyimide precursor film can be peeled off from the substrate, and the end of the film can be fixed, and in this state, the above-described heat treatment can be further performed, whereby a polyimide film/substrate laminate, or a polyimide film can be obtained.

The polyimide film/base material laminate thus obtained, or the polyimide film can be provided with a flexible conductive substrate by forming a conductive layer on one or both surfaces thereof.

The flexible conductive substrate can be obtained by, for example, the following method. That is, as a first method, a conductive layer of a conductive substance (metal or metal oxide, conductive organic substance, conductive carbon, or the like) is formed on the surface of a polyimide film by sputtering, vapor deposition, printing, or the like without peeling the polyimide film from the substrate, to produce a conductive laminate of a conductive layer/polyimide film/substrate. Thereafter, the conductive layer/polyimide film laminate is peeled off from the base material as necessary, whereby a transparent and flexible conductive substrate composed of the conductive layer/polyimide film laminate can be obtained.

As a second method, a polyimide film is peeled off from a substrate of a polyimide film/substrate laminate to obtain a polyimide film, and a conductive layer of a conductive substance (metal or metal oxide, conductive organic substance, conductive carbon, or the like) is formed on the surface of the polyimide film in the same manner as in the first method, whereby a transparent and flexible conductive substrate composed of the conductive layer/polyimide film laminate or the conductive layer/polyimide film/conductive layer laminate can be obtained.

In the first and second methods, before the conductive layer is formed on the surface of the polyimide film, an inorganic layer such as a gas barrier layer of water vapor, oxygen, or the like, or a light adjustment layer may be formed by sputtering, vapor deposition, gel-sol method, or the like, as necessary.

The conductive layer is appropriately formed with a circuit by photolithography, various printing methods, an inkjet method, or the like.

The substrate of the present invention thus obtained has a circuit having a conductive layer on the surface of a polyimide film made of the polyimide of the present invention via a gas barrier layer or an inorganic layer as required. The substrate is flexible and can easily form a fine circuit. Therefore, the substrate can be suitably used as a substrate for a display, a touch panel, or a solar cell.

That is, the flexible thin film transistor is manufactured by further forming a transistor (an inorganic transistor, an organic transistor) on the substrate by vapor deposition, various printing methods, an inkjet method, or the like, and is suitably used as a liquid crystal element, an EL element, or a photoelectric element for a display device.

The tetracarboxylic dianhydride represented by the above chemical formula (M-1) and the tetracarboxylic dianhydride represented by the above chemical formula (M-4) used for producing the polyimide precursor (1-2) of the present invention and the polyimide (2-2) of the present invention are novel compounds.

The method for producing the tetracarboxylic dianhydride represented by the above chemical formula (M-1) will be described below.

The tetracarboxylic dianhydride represented by the above chemical formula (M-1) can be synthesized by referring to Japanese unexamined patent publication No. 2010-184898, 、J.Chin.Chem.Soc.1998,45,799、Tetrahedron 1998,54,7013、Helvetica.Chim.Acta.2003,86,439、Angew.Chem.Int.Ed.Engl.1989,28,1037, for example, according to the reaction scheme shown below. Here, a tetracarboxylic dianhydride represented by the formula (M-1) wherein R ₅'、R₆ 'is-CH ₂ -is described as an example, namely 3a,4, 6a,9a,10,12 a-octahydro-1H, 3H-4,12:6, 10-dimethylanthra [2,3-c:6,7-c' ] difuran-1, 3,7, 9-tetraketone (DMADA), but other tetracarboxylic dianhydrides can be produced in the same manner.

[ 45]

(Wherein R is an alkyl group or an aryl group with or without a substituent, and R ₁₁、R₁₂、R₁₃、R₁₄ is each independently an alkyl group having 1 to 10 carbon atoms.)

(Step 1)

In step 1, in the case of synthesizing tetracarboxylic dianhydride (DMADA) of the formula (M-1) wherein R ₅'、R₆' is-CH ₂ -, p-Benzoquinone (BQ) and Cyclopentadiene (CP) are reacted to synthesize 1, 4a,5, 8a,9a,10 a-octahydro-1, 4:5, 8-dimethanoanthracene-9, 10-Dione (DNBQ). In the case of synthesizing tetracarboxylic dianhydride of the formula (M-1) wherein R ₅'、R₆' is-CH ₂CH₂ -, 1, 3-cyclohexadiene may be reacted with BQ instead of Cyclopentadiene (CP).

The amount of the cyclopentadiene (or 1, 3-cyclohexadiene or the like) to be used is preferably 1.0 to 20 moles, more preferably 1.5 to 10.0 moles, based on 1 mole of p-Benzoquinone (BQ).

The reaction is usually carried out in an organic solvent. The organic solvent to be used is not particularly limited as long as it does not inhibit the reaction, and examples thereof include amides such as N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone; urea such as N, N-dimethylimidazolidinone; sulfoxides such as dimethyl sulfoxide and sulfolane; nitriles such as acetonitrile and propionitrile; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, and t-butanol; ethers such as diisopropyl ether, dioxane, tetrahydrofuran, and cyclopropylmethyl ether; aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as hexane, cyclohexane, heptane, octane, etc.; halogenated hydrocarbons such as methylene chloride, chloroform, 1, 2-dichloroethane, chlorobenzene, etc.; esters such as ethyl acetate and butyl acetate; alcohols and aromatic hydrocarbons are preferably used, such as acetone, methyl ethyl ketone and methyl isobutyl ketone. These organic solvents may be used alone or in combination of two or more.

The amount of the organic solvent to be used is appropriately adjusted in accordance with the uniformity and stirring property of the reaction solution, and is preferably 1 to 50g, more preferably 2 to 30g, relative to 1g of BQ.

The reaction is carried out, for example, by mixing BQ and CP in an organic solvent and stirring. The reaction temperature in this case is preferably 0 to 150℃and more preferably 15 to 60℃and the reaction pressure is not particularly limited.

(Step 2)

In step 2, DNBQ obtained in step 1 is reacted with sodium borohydride to synthesize 1, 4a,5, 8a, 9a,10 a-decahydro-1, 4:5, 8-dimethylanthracene-9, 10-Diol (DNHQ).

The amount of sodium borohydride is preferably 0.5 to 10 moles, more preferably 1.5 to 5.0 moles, per DNBQ moles of sodium borohydride.

The reaction is usually carried out in an organic solvent. The organic solvent to be used is not particularly limited as long as it does not inhibit the reaction, and examples thereof include amides such as N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone; urea such as N, N-dimethylimidazolidinone; sulfoxides such as dimethyl sulfoxide and sulfolane; nitriles such as acetonitrile and propionitrile; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, and t-butanol; ethers such as diisopropyl ether, dioxane, tetrahydrofuran, and cyclopropylmethyl ether; aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as hexane, cyclohexane, heptane, octane, etc.; esters such as ethyl acetate and butyl acetate; alcohols, ethers, and aromatic hydrocarbons are preferably used, such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. These organic solvents may be used alone or in combination of two or more.

The amount of the organic solvent is appropriately adjusted in accordance with the uniformity and stirring property of the reaction solution, and is preferably 1 to 100g, more preferably 5 to 50g, relative to DNBQ g.

The reaction is carried out, for example, by mixing DNBQ with sodium borohydride in an organic solvent and stirring. The reaction temperature in this case is preferably-20 to 150 ℃, more preferably 0 to 50 ℃, and the reaction pressure is not particularly limited.

(Step 3)

In step 3, DNHQ obtained in step 2 is reacted with methanesulfonyl chloride in the presence of a base to synthesize 1, 4a,5, 8a, 9a,10 a-decahydro-1, 4:5, 8-dimethanoanthracene-9, 10-diyl-dimesylate (DNCMS; in this case, R is-CH ₃[-SO₂ R is methanesulfonyl (-SO ₂CH₃) ]. Instead of methanesulfonyl chloride, other aliphatic sulfonyl chloride or aromatic sulfonyl chloride may be used.

A base is used in this reaction. Examples of the base used in the reaction include secondary amines such as dibutylamine, piperidine and 2-methylpiperidine; tertiary amines such as triethylamine and tributylamine; pyridines such as pyridine, picoline, dimethylaminopyridine, etc.; quinolines such as quinoline, isoquinoline, and methylquinoline; alkali metal hydrides such as sodium hydride and potassium hydride; alkali metal alkoxides such as sodium methoxide, sodium ethoxide, sodium isopropoxide, potassium tert-butoxide, and the like; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal hydrogencarbonates such as sodium hydrogencarbonate and potassium hydrogencarbonate; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide are preferably tertiary amines, pyridines, quinolines, and alkali metal carbonates. These bases may be used alone or in combination of two or more.

The amount of the base to be used is preferably 0.01 to 200 moles, more preferably 0.1 to 100 moles, per DNHQ moles.

Sulfonyl chloride was used in this reaction. Examples of the sulfonyl chloride used in the reaction include aliphatic sulfonyl chlorides such as methanesulfonyl chloride, ethanesulfonyl chloride and trifluoromethanesulfonyl chloride; aromatic sulfonyl chlorides such as benzenesulfonyl chloride, toluenesulfonyl chloride and nitrobenzenesulfonyl chloride are preferably used as the aliphatic sulfonyl chloride. These sulfonyl chlorides may be used alone or in combination of two or more.

The amount of the sulfonyl chloride to be used is preferably 1.5 to 10 moles, more preferably 1.8 to 5 moles, relative to DNHQ moles.

The reaction is usually carried out in an organic solvent. The organic solvent to be used is not particularly limited as long as it does not inhibit the reaction, and examples thereof include amides such as N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone; urea such as N, N-dimethylimidazolidinone; pyridines such as pyridine, picoline, dimethylaminopyridine, etc.; quinolines such as quinoline, isoquinoline, and methylquinoline; sulfoxides such as dimethyl sulfoxide and sulfolane; nitriles such as acetonitrile and propionitrile; ethers such as diisopropyl ether, dioxane, tetrahydrofuran, and cyclopropylmethyl ether; aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as hexane, cyclohexane, heptane, octane, etc.; esters such as ethyl acetate and butyl acetate; acetone, methyl ethyl ketone, methyl isobutyl ketone, etc., and preferably pyridine is used. These organic solvents may be used alone or in combination of two or more.

The amount of the organic solvent is appropriately adjusted in accordance with the uniformity and stirring property of the reaction solution, and is preferably 1 to 200g, more preferably 10 to 100g, relative to DNHQ g.

The reaction is carried out, for example, by mixing DNHQ, a base, and sulfonyl chloride in an organic solvent and stirring the mixture. The reaction temperature in this case is preferably-20 to 150 ℃, more preferably 0 to 50 ℃, and the reaction pressure is not particularly limited.

(Step 4)

In step 4, methanol and carbon monoxide are reacted with DNCMS obtained in step 3 in the presence of a palladium catalyst and a copper compound to synthesize tetramethyl-9, 10-bis ((methylsulfonyl) oxy) tetradecahydro-1, 4:5, 8-dimethylanthracene-2, 3,6, 7-tetracarboxylic acid ester (DNMTE; in this case, R ₁₁～R₁₄ is methyl). Instead of methanol, another alcohol compound corresponding to the desired ester compound may be used.

Examples of the alcohol compound used in the reaction include methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, t-butanol, pentanol, methoxyethanol, ethoxyethanol, ethylene glycol, triethylene glycol, and the like, and methanol, ethanol, n-propanol, and isopropanol are preferably used, and methanol, ethanol, and isopropanol are more preferably used. These alcohol compounds may be used alone or in combination of two or more.

The amount of the alcohol compound to be used is preferably 1 to 100g, more preferably 5 to 50g, relative to DNCMS g.

Palladium catalysts are used in this reaction. The palladium catalyst used in the reaction is not particularly limited as long as it contains palladium, and examples thereof include palladium halides such as palladium chloride and palladium bromide; palladium organic acid salts such as palladium acetate and palladium oxalate; palladium inorganic acid salts such as palladium nitrate and palladium sulfate; palladium carbon or palladium alumina, etc. having palladium supported on a carrier such as carbon or alumina, palladium chloride or palladium carbon is preferably used.

The amount of the palladium catalyst to be used is preferably 0.001 to 1 mol, more preferably 0.01 to 0.5 mol, based on DNCMS mol of the catalyst.

Copper compounds are used in this reaction. Examples of the copper compound used in the reaction include monovalent copper compounds such as copper (I) oxide, copper (I) chloride, and copper (I) bromide; a divalent copper compound such as copper (II) oxide, copper (II) chloride, and copper (II) bromide is preferably used, and copper (II) chloride is more preferably used. These copper compounds may be used alone or in combination of two or more.

The amount of the copper compound is preferably 1.0 to 50 moles, more preferably 4.0 to 20 moles, per DNCMS moles.

In the present reaction, an organic solvent other than the above alcohol compound may be used. The organic solvent used is not particularly limited as long as it does not inhibit the reaction, and examples thereof include aliphatic carboxylic acids (e.g., formic acid, acetic acid, propionic acid, trifluoroacetic acid, etc.), organic sulfonic acids (e.g., methanesulfonic acid, trifluoromethanesulfonic acid, etc.), ketones (e.g., acetone, butanone, cyclohexanone, etc.), aliphatic hydrocarbons (e.g., N-pentane, N-hexane, N-heptane, cyclohexane, etc.), amides (e.g., N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, etc.), ureas (N, N' -dimethylimidazolidinone, etc.), ethers (e.g., diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, 1, 2-methylenedioxybenzene, etc.), aromatic hydrocarbons (e.g., benzene, toluene, xylene, etc.), halogenated aromatic hydrocarbons (e.g., chlorobenzene, 1, 2-dichlorobenzene, 1, 3-dichlorobenzene, 1, 4-dichlorobenzene, etc.), nitroaromatic hydrocarbons (e.g., nitrobenzene, etc.), halogenated hydrocarbons (e.g., nitrobenzene, etc.), carbon tetrachloride, dichloromethane, dichloroethane, 1, 2-dichlorobenzene, ethyl acetate, etc.), sulfoxides (e.g., sulfolane, etc.), nitrites (e.g., methyl sulfone, etc.), sulfolane, etc.), and esters (e.g., ethyl acetate, etc.), sulfolane, etc. Aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons and halogenated aromatic hydrocarbons are preferably used. These organic solvents may be used alone or in combination of two or more.

The amount of the organic solvent is appropriately adjusted in accordance with the uniformity and stirring property of the reaction solution, and is preferably 1 to 100g, more preferably 5 to 50g, relative to DNCMS g.

The reaction is carried out, for example, by mixing DNCMS with an alcohol compound, a palladium catalyst and a copper compound in an organic solvent, and stirring them under a carbon monoxide atmosphere. The reaction temperature in this case is preferably-20 to 100 ℃, more preferably 0 to 50 ℃, and the reaction pressure is not particularly limited.

(Step 5)

In step 5, tetramethyl-1, 2,3, 4a,5,6,7,8,9 a-decahydro-1, 4:5, 8-dimethylbridged anthracene-2, 3,6, 7-tetracarboxylic acid ester (DMHAE) is synthesized by the demethylation reaction of DNMTE obtained in step 4. The compound obtained in the step 5 is a tetraester compound represented by the above chemical formula (M-3), and is a novel compound.

The reaction is carried out, for example, by heating DNMTE in an organic solvent, stirring, or the like, as necessary. The reaction temperature in this case is preferably-20 to 200℃and more preferably 25 to 180℃and the reaction pressure is not particularly limited.

The reaction may be carried out by heating and stirring the reaction mixture without adding a base thereto, but in order to capture strongly acidic methanesulfonic acid produced as a by-product, a base is preferably used. The base to be used is not particularly limited as long as it does not inhibit the reaction, and examples thereof include secondary amines such as dibutylamine, piperidine and 2-methylpiperidine; tertiary amines such as triethylamine and tributylamine; pyridines such as pyridine, picoline, dimethylaminopyridine, etc.; quinolines such as quinoline, isoquinoline, and methylquinoline; alkali metal hydrides such as sodium hydride and potassium hydride; alkali metal alkoxides such as sodium methoxide, sodium ethoxide, sodium isopropoxide, potassium tert-butoxide, and the like; alkali metal carbonates such as sodium carbonate, potassium carbonate, and lithium carbonate; alkali metal hydrogencarbonates such as sodium hydrogencarbonate and potassium hydrogencarbonate; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide are preferably tertiary amines, pyridines, quinolines, and alkali metal carbonates. These bases may be used alone or in combination of two or more.

The amount of the base to be used is preferably 1.5 to 5 moles, more preferably 1.8 to 3 moles, relative to DNMTE moles.

The reaction is usually carried out in an organic solvent. The organic solvent to be used is not particularly limited as long as it does not inhibit the reaction, and examples thereof include amides such as N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, and N, N-dimethylisobutylamide; urea such as N, N-dimethylimidazolidinone; sulfoxides such as dimethyl sulfoxide and sulfolane; nitriles such as acetonitrile and propionitrile; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, and t-butanol; ethers such as diisopropyl ether, dioxane, tetrahydrofuran, and cyclopropylmethyl ether; aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as hexane, cyclohexane, heptane, octane, etc.; halogenated hydrocarbons such as methylene chloride, chloroform, 1, 2-dichloroethane, chlorobenzene, etc.; esters such as ethyl acetate and butyl acetate; for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc., amides, ureas, nitriles are preferably used. These organic solvents may be used alone or in combination of two or more.

The amount of the organic solvent is appropriately adjusted in accordance with the uniformity and stirring property of the reaction solution, and is preferably 1 to 100g, more preferably 2 to 50g, relative to DNMTE g.

(Step 6)

In step 6, tetramethyl-1, 2,3,4,5,6,7, 8-octahydro-1, 4:5, 8-dimethylanthracene-2, 3,6, 7-tetracarboxylic acid ester (DMAME) is synthesized by the aromatization reaction (oxidation reaction) of DMHAE obtained in step 5. The compound obtained in the 6 th step is a tetraester compound represented by the above chemical formula (M-2), and is a novel compound.

The reaction is carried out, for example, by heating DMHAE and an oxidizing agent for aromatization in a solvent, stirring, and the like as needed. The reaction temperature in this case is preferably 25 to 150 ℃, more preferably 40 to 120 ℃, and the reaction pressure is not particularly limited.

In this reaction, an oxidizing agent is used for the purpose of aromatization. The oxidizing agent to be used is not particularly limited as long as it does not inhibit the reaction, and for example, benzoquinones such as 2, 3-dichloro-5, 6-dicyano-p-benzoquinone and chloranil are used.

The amount of the oxidizing agent is preferably 0.5 to 5 moles, more preferably 0.8 to 3 moles, relative to DMHAE moles.

The reaction is usually carried out in a solvent. The solvent to be used is not particularly limited as long as it does not inhibit the reaction, and examples thereof include water; amides such as N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, and N, N-dimethylisobutyl amide; urea such as N, N-dimethylimidazolidinone; nitriles such as acetonitrile and propionitrile; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, and t-butanol; ethers such as diisopropyl ether, dioxane, tetrahydrofuran, and cyclopropylmethyl ether; aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as hexane, cyclohexane, heptane, octane, etc.; halogenated hydrocarbons such as methylene chloride, chloroform, 1, 2-dichloroethane, chlorobenzene, etc.; esters such as ethyl acetate and butyl acetate; for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc., aromatic hydrocarbons, halogenated hydrocarbons, ethers, alcohols, and water are preferably used. It should be noted that these solvents may be used alone or in combination of two or more kinds

The amount of the solvent to be used is appropriately adjusted in accordance with the uniformity and stirring property of the reaction solution, and is preferably 1 to 100g, more preferably 2 to 50g, relative to DMHAE g.

(Step 7)

In step 7, 3a,4, 6a,9a,10,12 a-octahydro-1H, 3H-4,12:6, 10-dimethylanthra [2,3-c:6,7-c' ] difuran-1, 3,7, 9-tetraone (DMADA) is synthesized by the dehydration reaction of DMAME obtained in step 6. The compound obtained in the 7 th step is a tetracarboxylic dianhydride represented by the above chemical formula (M-1).

The reaction is carried out, for example, by heating DMAME in an organic solvent in the presence of an acid catalyst while stirring. The reaction temperature in this case is preferably 50 to 130℃and more preferably 80 to 120℃and the reaction pressure is not particularly limited.

An acid catalyst is used in this reaction. The acid catalyst used in the reaction is not particularly limited as long as it is an acid, and examples thereof include inorganic acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, chlorosulfuric acid, and nitric acid; organic sulfonic acids such as methanesulfonic acid, benzenesulfonic acid, and p-toluenesulfonic acid; halogenated carboxylic acids such as chloroacetic acid and trifluoroacetic acid, ion exchange resins, silica gel sulfate, zeolite, and acidic alumina, and the like are preferably used as the inorganic acids and organic sulfonic acids, and more preferably as the organic sulfonic acids. These acids may be used alone or in combination of two or more.

The amount of the acid catalyst to be used is preferably 0.0001 to 0.1 mol, more preferably 0.001 to 0.05 mol, based on DMAME mol.

The reaction is preferably carried out in a solvent. As the solvent used, organic acid solvents such as formic acid, acetic acid, and propionic acid are preferable. These solvents may be used alone or in combination of two or more.

The amount of the solvent is appropriately adjusted in accordance with the uniformity and stirring property of the reaction solution, and is preferably 0.1 to 100g, more preferably 1 to 10g, relative to DMAME g.

The details of each reaction are described by way of examples, and those skilled in the art can vary the solvent, the amount of the solvent to be fed, the reaction conditions, etc., and can separate and purify the reaction product after completion of each reaction by, for example, a usual method such as filtration, extraction, distillation, sublimation, recrystallization, column chromatography, etc.

Next, a method for producing the tetracarboxylic dianhydride represented by the above chemical formula (M-4) will be described.

The tetracarboxylic dianhydride represented by the above chemical formula (M-4) can be synthesized by referring to Helv.Chim.acta.1975,58,160, macromolecules 1993,26,3490, etc., for example, according to the reaction scheme shown below.

[ Chemical 46]

(Wherein X ₁₁、X₁₂ is each independently-F, -Cl, -Br, or-I, and R ₂₁、R₂₂、R₂₃、R₂₄ is each independently an alkyl group having 1 to 10 carbon atoms.)

(Step 1)

In step 1, 5-norbornene-2, 3-dicarboxylic anhydride (NA) is reacted with 1, 3-butadiene to synthesize 3a, 4a,5, 8a,9 a-octahydro-4, 9-methanonaphtho [2,3-c ] furan-1, 3-dione (OMNA). The compound obtained in the step 1 is a dicarboxylic anhydride represented by the above chemical formula (M-7), and is a novel compound.

The reaction is carried out, for example, by adding NA to a pressure-resistant vessel such as an autoclave, introducing 1, 3-butadiene, and heating and stirring the mixture. The reaction temperature in this case is preferably 80 to 220℃and more preferably 100 to 180℃and the reaction pressure is not particularly limited.

The amount of the 1, 3-butadiene is preferably 0.5 to 5 mol, more preferably 0.8 to 3 mol, based on 1mol of NA.

In this reaction, an organic solvent may or may not be used. The solvent to be used is not particularly limited as long as it does not inhibit the reaction, and examples thereof include ketones (e.g., acetone, butanone, cyclohexanone, etc.), aliphatic hydrocarbons (e.g., N-pentane, N-hexane, N-heptane, cyclohexane, etc.), amides (e.g., N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, N-dimethylisobutylamide, etc.), ureas (N, N' -dimethylimidazolidinone, etc.), ethers (e.g., diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, 1, 2-methylenedioxybenzene, etc.), aromatic hydrocarbons (e.g., benzene, toluene, xylene, etc.), halogenated aromatic hydrocarbons (e.g., chlorobenzene, 1, 2-dichlorobenzene, 1, 3-dichlorobenzene, 1, 4-dichlorobenzene, etc.), nitroaromatic hydrocarbons (e.g., nitrobenzene, etc.), halogenated hydrocarbons (e.g., methylene chloride, chloroform, carbon tetrachloride, 1, 2-dichloroethane, etc.), carboxylic acids (e.g., ethyl acetate, propyl acetate, etc.), nitriles (e.g., toluene, 2-methylenedioxybenzene, etc.), sulfoxides (e.g., phenol, etc.), sulfoxides (e.g., toluene, sulfoxides, etc.), phenols (e.g., phenol, etc.). Aliphatic hydrocarbons and aromatic hydrocarbons are preferably used. These organic solvents may be used alone or in combination of two or more.

When an organic solvent is used, the amount of the organic solvent to be used is appropriately adjusted in accordance with the uniformity and stirring property of the reaction solution, and is preferably 0.1 to 100g, more preferably 1 to 50g, relative to NA1 g.

(Step 2)

In step 2, the OMNA obtained in step 1 is reacted with bromine as a dihalating agent to synthesize 6, 7-dibromodecahydro-4, 9-carbazo [2,3-c ] furan-1, 3-dione (DBDNA; in this case, X ₁₁、X₁₂ is-Br). Instead of bromine, other dihalogenating agents described later may be used. The compound obtained in the step 2 is a dihalodicarboxylic anhydride represented by the above formula (M-6), and is a novel compound.

The reaction is carried out, for example, by mixing and stirring the OMNA and the dihalogenating agent in an organic solvent. The reaction temperature in this case is preferably-100 to 50℃and more preferably-80 to 30℃and the reaction pressure is not particularly limited.

In this reaction, a dihalogenating agent such as bromine is used. The dihalogenating agent used in the reaction is not particularly limited as long as it can dihalide an olefin, and examples thereof include halogens such as fluorine, chlorine, bromine and iodine, and their pyridinium salts and ammonium salts, tribromide salts such as pyridinium tribromide and benzyl trimethyl ammonium tribromide, and halides such as chlorine fluoride, bromine chloride, iodine bromide and iodine tribromide, and their pyridinium salts and ammonium salts, and the halogen is preferably used, and bromine is particularly preferably used.

The amount of the dihalide is preferably 0.5 to 5 moles, more preferably 0.8 to 2 moles, based on 1 mole of OMNA.

The reaction is usually carried out in an organic solvent. The solvent to be used is not particularly limited as long as it does not inhibit the reaction, and examples thereof include ketones (e.g., acetone, butanone, cyclohexanone, etc.), aliphatic hydrocarbons (e.g., N-pentane, N-hexane, N-heptane, cyclohexane, etc.), amides (e.g., N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, N-dimethylisobutylamide, etc.), ureas (N, N' -dimethylimidazolidinone, etc.), ethers (e.g., diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, 1, 2-methylenedioxybenzene, etc.), aromatic hydrocarbons (e.g., benzene, toluene, xylene, etc.), halogenated aromatic hydrocarbons (e.g., chlorobenzene, 1, 2-dichlorobenzene, 1, 3-dichlorobenzene, 1, 4-dichlorobenzene, etc.), nitroaromatic hydrocarbons (e.g., nitrobenzene, etc.), halogenated hydrocarbons (e.g., methylene chloride, chloroform, carbon tetrachloride, 1, 2-dichloroethane, etc.), carboxylic acids (e.g., ethyl acetate, propyl acetate, butyl acetate, etc.), nitriles (e.g., toluene, 2-methylenedioxybenzene, etc.), sulfoxides (e.g., phenol, sulfoxides, etc.), phenols (e.g., toluene, sulfoxides, etc.), phenols (e.g., phenol, etc.), sulfoxides, etc. Aliphatic hydrocarbons and halogenated hydrocarbons are preferably used. These organic solvents may be used alone or in combination of two or more.

The amount of the organic solvent is appropriately adjusted in accordance with the uniformity and stirring property of the reaction solution, and is preferably 0.1 to 100g, more preferably 1 to 50g, relative to 1g of OMNA.

(Step 3)

In step 3, DBDNA obtained in step 2 is reacted with maleic anhydride to synthesize 3a, 4a, 5a,8a, 9a,10 a-decahydro-1H, 3H-4, 10-ethanol-5, 9-methanonaphtho [2,3-c:6,7-c' ] difuran-1, 3,6, 8-tetralone (EEMDA). The compound obtained in the 3 rd step is a novel compound which is a tetracarboxylic dianhydride represented by the above chemical formula (M-4) wherein R ₇ is-ch=ch-.

The reaction is carried out, for example, by mixing DBDNA with maleic anhydride, heating and stirring. The reaction temperature in this case is preferably 100 to 250℃and more preferably 120 to 230℃and the reaction pressure is not particularly limited.

The amount of the maleic anhydride is usually 1 mol or more, preferably 2 mol or more, and more preferably 4 mol or more, based on DBDNA mol.

In this reaction, DBDNA as a solid was mixed with maleic anhydride to carry out the reaction. The theoretically required amount of maleic anhydride is 1 mole relative to DBDNA, but when about 1 mole is used, the reactant after the completion of the reaction may be solidified in the reaction vessel and difficult to take out. On the other hand, when maleic anhydride (melting point 52 to 56 ℃) is used in an amount exceeding the equimolar amount, the reaction temperature is higher than the melting point of maleic anhydride, so that the excessive maleic anhydride is liquid and acts as a solvent, and the reaction system becomes a suspension. After the completion of the reaction, the reaction temperature is cooled to a temperature suitable for the operation (for example, about 100 ℃), and then an organic solvent is added to the system and filtered, whereby EEMDA having a high purity can be obtained.

Examples of the organic solvent to be added after the reaction include ketones (for example, acetone, butanone, cyclohexanone, etc.), aliphatic hydrocarbons (for example, N-pentane, N-hexane, N-heptane, cyclohexane, etc.), amides (for example, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, N-dimethylisobutylamide, etc.), ureas (N, N' -dimethylimidazolidinone, etc.), ethers (for example, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, 1, 2-methylenedioxybenzene, etc.), aromatic hydrocarbons (for example, benzene, toluene, xylene, etc.), halogenated aromatic hydrocarbons (e.g., chlorobenzene, 1, 2-dichlorobenzene, 1, 3-dichlorobenzene, 1, 4-dichlorobenzene, etc.), nitroaromatic hydrocarbons (e.g., nitrobenzene, etc.), halogenated hydrocarbons (e.g., methylene chloride, chloroform, carbon tetrachloride, 1, 2-dichloroethane, etc.), carboxylic acid esters (e.g., ethyl acetate, propyl acetate, butyl acetate, etc.), nitriles (e.g., acetonitrile, propionitrile, benzonitrile, etc.), sulfoxides (e.g., dimethyl sulfoxide, etc.), sulfones (e.g., sulfolane, etc.), and the like. Aliphatic hydrocarbons and aromatic hydrocarbons are preferably used. These organic solvents may be used alone or in combination of two or more.

The amount of the organic solvent is appropriately adjusted in accordance with the uniformity and stirring property of the solution to be prepared, and is preferably 0.1 to 30mL, more preferably 0.5 to 20mL, relative to DBDNA g.

(Step 4)

In step 4, EEMDA obtained in step 3 is reacted with methanol to synthesize tetramethyl-1, 4a,5,6,7,8 a-octahydro-1, 4-ethanol-5, 8-methanonaphthalene-6, 7,10, 11-tetracarboxylic acid ester (EEMDE; in this case, R ₂₁～R₂₄ is methyl). Instead of methanol, another alcohol compound corresponding to the desired ester compound may be used. The compound obtained in the 4 th step is a tetraester compound represented by the above chemical formula (M-5) wherein R ₇ is-ch=ch-, and is a novel compound.

The reaction is carried out, for example, by mixing EEMDA, orthoesters, alcohols in the presence of an acid and stirring the mixture. The reaction temperature in this case is preferably 20 to 150 ℃, more preferably 50 to 100 ℃, and the reaction pressure is not particularly limited.

Acids are used in this reaction. The acid used in the reaction is not particularly limited, and examples thereof include inorganic acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, chlorosulfuric acid, and nitric acid; organic sulfonic acids such as methanesulfonic acid, benzenesulfonic acid, and p-toluenesulfonic acid; halogenated carboxylic acids such as chloroacetic acid and trifluoroacetic acid, ion exchange resins, silica gel sulfate, zeolite, and acidic alumina, and the like are preferably used, and inorganic acids are more preferably used. These acids may be used alone or in combination of two or more.

The amount of the acid to be used is preferably 0.01 to 10 moles, more preferably 0.05 to 3 moles, per EEMDA moles.

In this reaction, an alcohol compound is used. Examples of the alcohol compound used in the reaction include methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, t-butanol, pentanol, methoxyethanol, ethoxyethanol, ethylene glycol, triethylene glycol, and the like, and methanol, ethanol, n-propanol, and isopropanol are preferably used, and methanol and ethanol are more preferably used. These alcohol compounds may be used alone or in combination of two or more.

The amount of the alcohol compound is preferably 0.1 to 200g, more preferably 1 to 100g, relative to EEMDA g.

In this reaction, an organic solvent other than the above alcohols may be used. The organic solvent used is not particularly limited as long as it does not inhibit the reaction, and examples thereof include aliphatic carboxylic acids (e.g., formic acid, acetic acid, propionic acid, trifluoroacetic acid, etc.), organic sulfonic acids (e.g., methanesulfonic acid, trifluoromethanesulfonic acid, etc.), ketones (e.g., acetone, butanone, cyclohexanone, etc.), aliphatic hydrocarbons (e.g., N-pentane, N-hexane, N-heptane, cyclohexane, etc.), amides (e.g., N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, etc.), ureas (N, N' -dimethylimidazolidinone, etc.), ethers (e.g., diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, 1, 2-methylenedioxybenzene, etc.), aromatic hydrocarbons (e.g., benzene, toluene, xylene, etc.), halogenated aromatic hydrocarbons (e.g., chlorobenzene, 1, 2-dichlorobenzene, 1, 3-dichlorobenzene, 1, 4-dichlorobenzene, etc.), nitroaromatic hydrocarbons (e.g., nitrobenzene, etc.), halogenated hydrocarbons (e.g., nitrobenzene, etc.), carbon tetrachloride, dichloromethane, dichloroethane, 1, 2-dichlorobenzene, ethyl acetate, etc.), sulfoxides (e.g., sulfolane, etc.), nitrites (e.g., methyl sulfone, etc.), sulfolane, etc.), and esters (e.g., ethyl acetate, etc.), sulfolane, etc. Aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons and halogenated aromatic hydrocarbons are preferably used. These organic solvents may be used alone or in combination of two or more.

The amount of the organic solvent other than the above alcohols is preferably 0.1 to 200g, more preferably 1 to 100g, relative to EEMDA g.

In this reaction, orthoesters are used. Examples of orthoesters include compounds represented by the following formula, for example, trimethyl orthoformate and triethyl orthoformate, and trimethyl orthoformate is preferably used.

[ 47]

Wherein R ^f represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom. R ^e represents an alkyl group having 1 to 5 carbon atoms, preferably a methyl group or an ethyl group, and more preferably a methyl group. The 3R ^e groups may be the same or different, and are preferably the same.

The orthoesters are used in an amount of preferably 0.5g or more, more preferably 1 to 5g, based on EEMDA g.

(Step 5)

In step 5, EEMDE obtained in step 4 is reacted with hydrogen to synthesize tetramethyl-decahydro-1, 4-ethanol-5, 8-methanonaphthalene-2, 3,6, 7-tetracarboxylic acid ester (EMDE). The compound obtained in the step 5 is a tetraester compound represented by the above chemical formula (M-5) wherein R ₇ is-CH ₂CH₂ -and is a novel compound.

The reaction is carried out, for example, by mixing EEMDE and the metal catalyst in a solvent, and stirring while heating as necessary under a hydrogen atmosphere. The reaction temperature in this case is preferably 0 to 150℃and more preferably 10 to 120 ℃. The reaction pressure is preferably 0.1 to 20MPa, more preferably 0.1 to 5MPa.

Hydrogen was used in this reaction. The amount of hydrogen used is preferably 0.8 to 100 moles, more preferably 1 to 50 moles, relative to EEMDE moles.

A metal catalyst is used in this reaction. The metal catalyst used is not particularly limited as long as the olefin moiety in the structure EEMDE can be hydrogenated, and examples thereof include rhodium-based catalysts (rhodium carbon, wilkinson complex, etc.), palladium-based catalysts (palladium carbon, palladium alumina, palladium silica gel, etc.), platinum-based catalysts (platinum carbon, platinum alumina, etc.), nickel-based catalysts (raney nickel catalyst, sponge nickel catalyst, etc.), and the like. The catalyst is preferably a rhodium-based catalyst or a palladium-based catalyst, and more preferably a rhodium-based catalyst.

The amount of the metal catalyst used is preferably 0.0001 to 1 mol, more preferably 0.001 to 0.8 mol, based on EEMDE mol of the metal atom transition.

Solvents are preferably used in the present reaction. The solvent used is not particularly limited as long as it does not inhibit the reaction, and examples thereof include water, alcohols (e.g., methanol, ethanol, N-propanol, isopropanol, N-butanol, sec-butanol, tert-butanol, etc.), ketones (e.g., acetone, butanone, cyclohexanone, etc.), aliphatic hydrocarbons (e.g., N-pentane, N-hexane, N-heptane, cyclohexane, etc.), amides (e.g., N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, N-dimethylisobutylamide, etc.), ureas (N, N' -dimethylimidazolidinone, etc.), ethers (e.g., diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, 1, 2-methylenedioxybenzene, etc.), aromatic hydrocarbons (e.g., benzene, toluene, xylene, etc.), halogenated aromatic hydrocarbons (e.g., chlorobenzene, 1, 2-dichlorobenzene, 1, 4-dichlorobenzene, etc.), nitroaromatic hydrocarbons (e.g., nitrobenzene, etc.), halogenated hydrocarbons (e.g., dichloromethane, 1, 2-dichloroethane, carboxylic acid, sulfolane, etc.), phenols (e.g., phenol, sulfolane, etc.), sulfolane, etc., methyl sulfone, etc. Alcohols, amides, aliphatic hydrocarbons and aromatic hydrocarbons are preferably used. These solvents may be used alone or in combination of two or more.

The amount of the solvent is appropriately adjusted in accordance with the uniformity and stirring property of the reaction solution, and is preferably 0.1 to 100g, more preferably 1 to 50g, relative to EEMDE g.

(Step 6)

In step 6, decahydro-1H, 3H-4, 10-ethanol-5, 9-methanonaphtho [2,3-c:6,7-c' ] difuran-1, 3,6, 8-tetralone (EMDA) is synthesized by dehydration of the EMDE obtained in step 5. The compound obtained in the 6 th step is tetracarboxylic dianhydride represented by the above chemical formula (M-4) wherein R ₇ is-CH ₂CH₂ -.

The reaction is carried out, for example, by heating and stirring EMDE in an organic solvent in the presence of an acid catalyst. The reaction temperature in this case is preferably 50 to 130℃and more preferably 80 to 120℃and the reaction pressure is not particularly limited.

The amount of the acid catalyst to be used is preferably 0.001 to 0.5 mol, more preferably 0.001 to 0.2 mol, based on 1 mol of EMDE.

The amount of the solvent to be used is appropriately adjusted in accordance with the uniformity and stirring property of the reaction solution, and is preferably 0.1 to 100g, more preferably 1 to 10g, relative to 1g of EMDE.

According to the present invention, there can be provided a novel method for producing a tetracarboxylic dianhydride represented by the above chemical formula (M-9) which can provide the structure of the above chemical formula (A-2) as a tetracarboxylic acid component. Next, a method for manufacturing the same will be described.

The tetracarboxylic dianhydride represented by the above chemical formula (M-9) can be synthesized by referring to can.J.chem.1975,53,256, tetrahedron Lett.2003,44,561, etc., for example, according to the reaction scheme shown below. Here, a tetracarboxylic dianhydride represented by the formula (M-9) wherein R ₄ is-CH ₂ -, namely 3a,4,10 a-tetrahydro-1 h,3h-4, 10-methanonaphtho [2,3-c:6,7-c' ] difuran-1, 3,6, 8-tetralone (BNDA) is described as an example, but other tetracarboxylic dianhydrides can be produced in the same manner.

[ 48]

(Wherein R ₃₁、R₃₂ is independently an alkyl group having 1 to 10 carbon atoms or a phenyl group, and R ₃₃、R₃₄ is independently an alkyl group having 1 to 10 carbon atoms.)

(Step 1)

In step 1, when tetracarboxylic dianhydride (BNDA) having the chemical formula (M-9) wherein R ₄ is-CH ₂ -is synthesized, cis-1, 4-dichloro-2-butene (DCB) is reacted with Cyclopentadiene (CP) to synthesize 5, 6-bis (chloromethyl) bicyclo [2.2.1] hept-2-ene (BCMN). In the case of synthesizing tetracarboxylic dianhydride of the formula (M-9) wherein R ₄ is-CH ₂CH₂ -, 1, 3-cyclohexadiene may be reacted with DCB instead of Cyclopentadiene (CP).

The reaction is carried out, for example, by mixing and stirring DCB and CP. The reaction temperature in this case is preferably 50 to 250 ℃, more preferably 150 to 220 ℃, and the reaction pressure is not particularly limited.

CP is a monomer of Dicyclopentadiene (DCP), and can be quantitatively obtained by heating DCP at 160 to 200 ℃. The CP used in step 1 may be produced in the system by thermal decomposition of DCP. DCP is the compound shown in the scheme.

The amount of the CP to be used is preferably 0.2 to 10 moles, more preferably 0.5 to 5 moles, based on 1 mole of DCB.

In this reaction, an organic solvent may or may not be used. The organic solvent to be used is not particularly limited as long as it does not inhibit the reaction, and examples thereof include aliphatic carboxylic acids (e.g., formic acid, acetic acid, propionic acid, trifluoroacetic acid, etc.), organic sulfonic acids (e.g., methanesulfonic acid, trifluoromethanesulfonic acid, etc.), alcohols (e.g., methanol, ethanol, isopropanol, t-butanol, ethylene glycol, triethylene glycol, etc.), ketones (e.g., acetone, butanone, cyclohexanone, etc.), aliphatic hydrocarbons (e.g., N-pentane, N-hexane, N-heptane, cyclohexane, etc.), amides (e.g., N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, etc.), ureas (N, N' -dimethylpyrrolidone, etc.), ethers (e.g., diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, 1, 2-methylenedioxybenzene, etc.), aromatic hydrocarbons (e.g., benzene, toluene, xylene, etc.), halogenated aromatic hydrocarbons (e.g., chlorobenzene, 1, 2-dichlorobenzene, 1, 3-dichlorobenzene, 1, 4-dichlorobenzene, etc.), nitroaromatic hydrocarbons (e.g., nitrobenzene, etc.), halogenated hydrocarbons (e.g., dichloromethane, chloroform, carbon tetrachloride, 1, 2-dichloroethane, etc.), carboxylic acid esters (e.g., ethyl acetate, propyl acetate, butyl acetate, etc.), nitriles (e.g., acetonitrile, propionitrile, benzonitrile, etc.), sulfoxides (e.g., dimethyl sulfoxide, etc.), sulfones (e.g., sulfolane, etc.), phenols (e.g., phenol, methylphenol, etc.), carboxylic acid esters (e.g., ethyl acetate, propyl acetate, etc.), P-chlorophenol, etc.), and the like. Aliphatic hydrocarbons and aromatic hydrocarbons are preferably used. These organic solvents may be used alone or in combination of two or more.

When an organic solvent is used, the amount of the organic solvent to be used is appropriately adjusted in accordance with the uniformity and stirring property of the reaction solution, and is preferably 0.2 to 10g, more preferably 0.3 to 5g, relative to 1g of DCB.

(Step 2)

In step 2, the reaction of BCMN obtained in step 1 with a base is performed to effect dechlorination and hydrogenation, thereby synthesizing 5, 6-dimethylenebicyclo [2.2.1] hept-2-ene (CYDE).

The reaction is carried out, for example, by mixing BCMN with a base in a solvent and stirring. The reaction temperature in this case is preferably 0 to 150℃and more preferably 20 to 120℃and the reaction pressure is not particularly limited.

A base is used in this reaction. Examples of the base used in the reaction include secondary amines such as dibutylamine, piperidine and 2-methylpiperidine; tertiary amines such as triethylamine and tributylamine; pyridines such as pyridine, picoline, dimethylaminopyridine, etc.; quinolines such as quinoline, isoquinoline, and methylquinoline; alkali metal hydrides such as sodium hydride and potassium hydride; alkali metal alkoxides such as sodium methoxide, sodium ethoxide, sodium isopropoxide, potassium tert-butoxide, and the like; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal hydrogencarbonates such as sodium hydrogencarbonate and potassium hydrogencarbonate; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide are preferably tertiary amines, alkali metal alkoxides, alkali metal carbonates and alkali metal hydroxides. These bases may be used alone or in combination of two or more.

The amount of the base to be used is preferably 1 to 20 moles, more preferably 1.5 to 10 moles, relative to BCMN moles.

The reaction is generally preferably carried out in a solvent. The solvent to be used is not particularly limited as long as it does not inhibit the reaction, and examples thereof include water, alcohols (e.g., methanol, ethanol, isopropanol, t-butanol, ethylene glycol, triethylene glycol, etc.), aliphatic hydrocarbons (e.g., N-pentane, N-hexane, N-heptane, cyclohexane, etc.), amides (e.g., N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, etc.), ureas (N, N' -dimethylimidazolidinone, etc.), ethers (e.g., diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, 1, 2-methylenedioxybenzene, etc.), aromatic hydrocarbons (e.g., benzene, toluene, xylene, etc.), sulfoxides (e.g., dimethyl sulfoxide, etc.), sulfones (e.g., sulfolane, etc.), and the like. Preferably, water, alcohols, ethers are used. These solvents may be used alone or in combination of two or more.

The amount of the solvent is appropriately adjusted in accordance with the uniformity and stirring property of the reaction solution, and is preferably 0.1 to 100g, more preferably 0.2 to 50g, relative to BCMN g.

(Step 3)

In step 3, CYDE obtained in step 2 is reacted with dimethyl acetylenedicarboxylate (DMAD) to synthesize dimethyl 1,4,5, 8-tetrahydro-1, 4-methanonaphthalene-6, 7-dicarboxylate (CYME; in this case, R ₃₁、R₃₂ is methyl). Other acetylene dicarboxylic acid diesters described later may be used as the dimethyl acetylene dicarboxylic acid.

The reaction is carried out, for example, by mixing CYDE with DMAD in a solvent and stirring. The reaction temperature in this case is preferably 0 to 150℃and more preferably 20 to 120℃and the reaction pressure is not particularly limited.

In this reaction, an acetylene dicarboxylic acid diester such as DMAD is used. The acetylenedicarboxylic acid diester used is selected to correspond to the desired ester compound. Examples of the dicarboxylic acid diester of acetylene used in the reaction include dimethyl acetylene dicarboxylate, diethyl acetylene dicarboxylate, and dipropyl acetylene dicarboxylate, and dimethyl acetylene dicarboxylate and diethyl acetylene dicarboxylate are preferably used. In addition, diphenyl acetylenedicarboxylate may also be used. The 2 substituents bound to acetylene may be the same or different.

The amount of the acetylene dicarboxylic acid diester such as DMAD is preferably 0.8 to 20 mol, more preferably 1 to 10 mol, based on CYDE mol.

The reaction is generally preferably carried out in a solvent. The solvent to be used is not particularly limited as long as it does not inhibit the reaction, and examples thereof include water, alcohols (e.g., methanol, ethanol, isopropanol, t-butanol, ethylene glycol, triethylene glycol, etc.), ketones (e.g., acetone, butanone, cyclohexanone, etc.), aliphatic hydrocarbons (e.g., N-pentane, N-hexane, N-heptane, cyclohexane, etc.), amides (e.g., N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, etc.), ureas (N, N' -dimethylimidazolidinone, etc.), ethers (e.g., diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, 1, 2-methylenedioxybenzene, etc.), aromatic hydrocarbons (e.g., benzene, toluene, xylene, etc.), halogenated aromatic hydrocarbons (e.g., chlorobenzene, 1, 2-dichlorobenzene, 1, 3-dichlorobenzene, 1, 4-dichlorobenzene, etc.), nitroaromatic hydrocarbons (e.g., nitrobenzene, etc.), halogenated hydrocarbons (e.g., methylene chloride, chloroform, carbon tetrachloride, 1, 2-dichloroethane, etc.), carboxylic acid esters (e.g., ethyl acetate, propyl acetate, butyl acetate, etc.), nitriles (e.g., acetonitrile, propionitrile, benzonitrile, etc.), sulfoxides (e.g., dimethyl sulfoxide, etc.), sulfones (e.g., sulfolane, etc.), phenols (e.g., phenol, methylphenol, p-chlorophenol, etc.), and the like. Preferably, water, alcohols, ethers, aliphatic hydrocarbons, and aromatic hydrocarbons are used. These solvents may be used alone or in combination of two or more.

The amount of the solvent is appropriately adjusted in accordance with the uniformity and stirring property of the reaction solution, and is preferably 0.2 to 200g, more preferably 0.3 to 100g, relative to CYME g.

(Step 4)

In step 4, dimethyl 1, 4-dihydro-1, 4-carbaryl-6, 7-dicarboxylate (CYPDM) is synthesized by the aromatisation reaction (oxidation reaction) of CYME obtained in step 3.

The reaction is carried out, for example, by stirring CYME and an oxidizing agent for aromatization in a solvent. The reaction temperature in this case is preferably-20 to 150 ℃, more preferably 0 to 120 ℃, and the reaction pressure is not particularly limited.

The amount of the oxidizing agent is preferably 0.5 to 10 moles, more preferably 0.8 to 5 moles, per CYME moles of the oxidizing agent.

The reaction is usually carried out in a solvent. The solvent to be used is not particularly limited as long as it does not inhibit the reaction, and examples thereof include water; amides such as N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, and N, N-dimethylisobutyl amide; urea such as N, N-dimethylimidazolidinone; nitriles such as acetonitrile and propionitrile; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, and t-butanol; ethers such as diisopropyl ether, dioxane, tetrahydrofuran, and cyclopropylmethyl ether; aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as hexane, cyclohexane, heptane, octane, etc.; halogenated hydrocarbons such as methylene chloride, chloroform, 1, 2-dichloroethane, chlorobenzene, etc.; esters such as ethyl acetate and butyl acetate; for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc., aromatic hydrocarbons, halogenated hydrocarbons, ethers, alcohols, and water are preferably used. These solvents may be used alone or in combination of two or more.

The amount of the solvent to be used is appropriately adjusted in accordance with the uniformity and stirring property of the reaction solution, and is preferably 1 to 100g, more preferably 2 to 50g, relative to CYME g.

(Step 5)

In step 5, CYPDM obtained in step 4 is reacted with methanol and carbon monoxide in the presence of a palladium catalyst and a copper compound to synthesize tetramethyl-1, 2,3, 4-tetrahydro-1, 4-methanonaphthalene-2, 3,6, 7-tetracarboxylic acid ester (BNME; in this case, R ₃₁～R₃₄ is methyl). Instead of methanol, another alcohol compound corresponding to the desired ester compound may be used.

The reaction is carried out, for example, by mixing CYPDM with an alcohol corresponding to a desired ester compound, a palladium catalyst and a copper compound in an organic solvent, and stirring the mixture under a carbon monoxide atmosphere. The reaction temperature in this case is preferably-10 to 100℃and more preferably-10 to 70℃and the reaction pressure is not particularly limited.

In this reaction, an alcohol compound is used. Examples of the alcohol compound used in the reaction include methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, t-butanol, pentanol, methoxyethanol, ethoxyethanol, ethylene glycol, triethylene glycol, and the like, and methanol, ethanol, n-propanol, and isopropanol are preferably used, and methanol, ethanol, and isopropanol are more preferably used. These alcohol compounds may be used alone or in combination of two or more.

The amount of the alcohol compound is preferably 0.1 to 200g, more preferably 1 to 100g, relative to CYPDM g.

In this reaction, an organic solvent other than the above alcohols may be used. The organic solvent to be used is not particularly limited as long as it does not inhibit the reaction, and examples thereof include formic acid, aliphatic carboxylic acids (e.g., acetic acid, propionic acid, trifluoroacetic acid, etc.), organic sulfonic acids (e.g., methanesulfonic acid, trifluoromethanesulfonic acid, etc.), aliphatic hydrocarbons (e.g., N-pentane, N-hexane, N-heptane, cyclohexane, etc.), amides (e.g., N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, etc.), ureas (N, N' -dimethylimidazolidinone, etc.), ethers (e.g., diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, 1, 2-methylenedioxybenzene, etc.), aromatic hydrocarbons (e.g., benzene, toluene, xylene, etc.), halogenated aromatic hydrocarbons (e.g., chlorobenzene, 1, 2-dichlorobenzene, 1, 3-dichlorobenzene, 1, 4-dichlorobenzene, etc.), nitroaromatic hydrocarbons (e.g., nitrobenzene, etc.), halogenated hydrocarbons (e.g., dichloromethane, carbon tetrachloride, 1, 2-propanediol, etc.), carboxylic acids (e.g., ethyl acetate, butyl acetate, etc.), sulfoxides (e.g., methyl sulfone, etc.), sulfoxides (e.g., methyl sulfones, etc.), and the like. Aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons and halogenated aromatic hydrocarbons are preferably used. These organic solvents may be used alone or in combination of two or more.

The amount of the organic solvent other than the above alcohols is preferably 0.1 to 200g, more preferably 1 to 100g, relative to CYPDM g.

The palladium catalyst used in the reaction is not particularly limited as long as it contains palladium, and examples thereof include palladium halides such as palladium chloride and palladium bromide; palladium organic acid salts such as palladium acetate and palladium oxalate; palladium inorganic acid salts such as palladium nitrate and palladium sulfate; palladium complexes such as bis (acetylacetonate) palladium, bis (1, 1-5, 5-hexafluoroacetylacetonate) palladium, and the like; palladium carbon or palladium alumina, etc. in which palladium is supported on a carrier such as carbon or alumina, palladium chloride or palladium carbon is preferably used.

The amount of the palladium catalyst to be used is preferably 0.0001 to 0.2 mol, more preferably 0.001 to 0.1 mol, based on CYPDM mol.

The copper compound used in the reaction is not particularly limited as long as Pd (0) can be oxidized to Pd (II) in the case where Pd (II) in the palladium catalyst is reduced to Pd (0), and examples thereof include copper compounds, iron compounds, and the like, and copper compounds are preferable. Specific examples of the copper compound used in the reaction include copper, copper acetate, copper propionate, copper n-butyrate, copper 2-methylpropionate, copper pivalate, copper lactate, copper butyrate, copper benzoate, copper trifluoroacetate, copper bis (acetylacetonate), copper bis (1, 1-5, 5-hexafluoroacetylacetonate), copper chloride, copper bromide, copper iodide, copper nitrate, copper nitrite, copper sulfate, copper phosphate, copper oxide, copper hydroxide, copper trifluoromethanesulfonate, copper p-toluenesulfonate, and copper cyanide. Specific examples of the iron compound include iron (III) chloride, iron (III) nitrate, iron (III) sulfate, and iron (III) acetate. Preferably, a divalent copper compound is used, and more preferably, copper (II) chloride is used. Here, "copper compound" is used in the sense of including elemental copper in addition to the so-called compound. These copper compounds may be used alone or in combination of two or more.

The amount of the copper compound is preferably 4 to 50 moles, more preferably 5 to 20 moles, per CYPDM moles.

(Step 6)

In step 6, 3a,4,10 a-tetrahydro-1H, 3H-4, 10-methanonaphtho [2,3-c:6,7-c' ] difuran-1, 3,6, 8-tetralone (BNDA) is synthesized by dehydration reaction of BNME obtained in step 5. The compound obtained in the step 6 is a tetracarboxylic dianhydride represented by the above chemical formula (M-9).

The reaction is carried out, for example, by heating BNME in an organic solvent in the presence of an acid catalyst while stirring. The reaction temperature in this case is preferably 50 to 130℃and more preferably 80 to 120℃and the reaction pressure is not particularly limited.

The amount of the acid catalyst to be used is preferably 0.001 to 0.5 mol, more preferably 0.001 to 0.2 mol, based on BNME mol.

The amount of the solvent is appropriately adjusted in accordance with the uniformity and stirring property of the reaction solution, and is preferably 0.1 to 100g, more preferably 1 to 10g, relative to BNME g.

Examples

The present invention will be further described below with reference to examples and comparative examples. The present invention is not limited to the following examples.

In the following examples, the evaluation was performed by the following methods.

< Evaluation of polyimide film >

[ Total light transmittance ]

The total light transmittance (average transmittance at 380nm to 780 nm) of a polyimide film having a film thickness of 10 μm was measured using an ultraviolet-visible spectrophotometer/V-650 DS (manufactured by Japan spectroscopy).

[ Tensile elastic modulus, elongation at break, breaking Strength ]

The polyimide film was punched into a dumbbell shape of IEC-540 (S) standard, and test pieces (width: 4 mm) were produced, and the initial tensile elastic modulus, breaking point elongation, and breaking strength were measured at a length between chucks of 30mm and a tensile speed of 2 mm/min using TENSILON manufactured by ORIENTEC Co.

[ Coefficient of Linear thermal expansion (CTE), tg ]

A polyimide film having a film thickness of 10 μm was cut into a long shape having a width of 4mm, and a test piece was produced, and the temperature was raised to 500℃at a rate of 20℃per minute under a load of 2g and a load of 15mm between chucks using TMA/SS6100 (manufactured by SII Nanotechnology Co., ltd.). The linear thermal expansion coefficient of 100℃to 250℃was determined from the TMA curve obtained. The inflection point of the TMA curve was defined as Tg (glass transition temperature).

[5% Weight reduction temperature ]

A polyimide film having a film thickness of 10 μm was used as a test piece, and the temperature was raised from 25℃to 600℃in a nitrogen gas stream at a heating rate of 10℃per minute by using a thermogravimetry apparatus (Q5000 IR) manufactured by TA INSTRUMENTS Co. From the weight curve obtained, a 5% weight reduction temperature was obtained.

The following materials used in each example are abbreviated as follows.

[ Diamine component ]

DABAN:4,4' -diaminobenzanilides

PPD: para-phenylenediamine

TFMB:2,2' -bis (trifluoromethyl) benzidine

4,4' -ODA:4,4' -oxydiphenylamine

TPE-R:1, 3-bis (4-aminophenoxy) benzene

BAPB:4,4' -bis (4-aminophenoxy) biphenyl

Tra-DACH: trans-1, 4-diaminocyclohexane

[ Tetracarboxylic acid component ]

TNDA: decatetrahydro-1H, 3H-4,12:5,11:6, 10-trimethyl anthra [2,3-c:6,7-c' ] difuran-1, 3,7, 9-tetraketone

BNDA:3a,4,10 a-tetrahydro-1 h,3h-4, 10-methanonaphtho [2,3-c:6,7-c' ] difuran-1, 3,6, 8-tetralone DMADA:3a,4, 6a,9a,10,12 a-octahydro-1H, 3H-4,12:6, 10-dimethylanthra [2,3-c:6,7-c' ] difuran-1, 3,7, 9-tetralone

EMDAdx: (3 aR,4R,5S,5aR,8aS,9R,10S,10 aS) -decahydro-1H, 3H-4, 10-ethanol-5, 9-methanonaphtho [2,3-c:6,7-c' ] difuran-1, 3,6, 8-tetralone

EMDAxx: (3 aR,4R,5S,5aS,8aR,9R,10S,10 aS) -decahydro-1H, 3H-4, 10-ethanol-5, 9-methanonaphtho [2,3-c:6,7-c' ] difuran-1, 3,6, 8-tetralone

[ Solvent ]

NMP: n-methyl-2-pyrrolidone

DMAc: n, N-dimethylacetamide

The structural formulas of the tetracarboxylic acid component and the diamine component used in examples and comparative examples are shown in table 1.

TABLE 1

[ Synthesis of example S-1 (DMADA) ]

[ 49]

Into a 2L-capacity reaction vessel were charged 1500mL of toluene and 153.3g (1.39 mol) of p-Benzoquinone (BQ). Then, 183.5g (2.78 mmol) of cyclopentadiene was added dropwise over 2 hours while maintaining the temperature at 25 to 30℃and then reacted at 25℃for 20 hours. The reaction mixture was concentrated to dryness, 1490g of ethanol was added to the concentrate, and the mixture was stirred overnight. After that, the solid was filtered, washed with ethanol and dried in vacuo at 60℃to give 227g of a pale red solid. To 227g of the pale red solid thus obtained, 1350g of ethanol was added, and the mixture was stirred at 80℃for 1 hour, followed by filtration of the solid. The filtrate was dissolved in 1080g of chloroform, 10g of activated carbon was added thereto, and the mixture was stirred for 1 hour. After that, filtration was performed, the filtrate was concentrated to dryness, and the obtained solid was dried in vacuo at 60 ℃ to obtain 1, 4a,5, 8a,9a,10 a-octahydro-1, 4: 184g of 5, 8-dimethanoanthracene-9, 10-Dione (DNBQ) (purity 100% based on ¹ H-NMR analysis, yield 55.3%).

Physical properties of DNBQ are as follows.

¹H-NM R(CDCl₃,σ(ppm));1.29(d,J＝8.5Hz,2H),1.46(d,J＝8.5Hz,2H),2.87(s,2H),3.36(s,2H),6.19(t,J＝1.8Hz,2H)Cl-MS(m/z);241(M+1)

To a reaction vessel having a capacity of 5L, DNBQ100.5g (31.7 mmol), methanol 1.5L and tetrahydrofuran 1.5L were charged. Then, 30.0g (60.3 mmol) of sodium borohydride was added at a temperature of 5℃for 1 hour, followed by a reaction at a temperature of 5 to 10℃for 7 hours. Then, 1L of a saturated aqueous ammonium chloride solution was added dropwise at a temperature of 5℃and then the temperature was raised to 25 ℃. The white solid precipitated in the reaction solution was filtered, and the solvent was distilled off under reduced pressure. The precipitated white solid was filtered, 1.5L of ion-exchanged water was added to the obtained white solid, and the mixture was stirred at 40℃for 1 hour. After that, the white solid was filtered, washed twice with 200mL of ion-exchanged water, washed twice with 100mL of ethyl acetate, and vacuum-dried to obtain 1, 4a,5, 8a, 9a,10 a-decahydro-1, 4 as a white solid: 84.2g of 5, 8-dimethylbridged anthracene-9, 10-Diol (DNHQ) (purity 100% based on ¹ H-NMR analysis, yield 82%).

Physical properties of DNHQ are as follows.

¹H-NMR(DMSO-d₆,σ(ppm));0.99(d,J＝7.8Hz,1H),1.16(d,J＝7.8Hz,1H),1.26-1.34(m,2H),1.52-1.62(m,2H),2.34-2.42(m,2H),2.77(s,2H),2.85(s,2H),2.91(brs,2H),4.26(s,1H),4.28(s,1H),6.04(t,J＝1.8Hz,2H),6.09(t,J＝1.8Hz,2H)Cl-MS(m/z);245(M+1)

To a 5L-capacity reaction vessel were added 87.0g (356 mmol) of DNHQS, 4.3g (35.2 mmol) of N, N-dimethylaminopyridine and 1740g of pyridine, and the mixture was cooled to a temperature of 5 ℃. Then, 87.0g (760 mmol) of methanesulfonyl chloride was added dropwise over 20 minutes, followed by heating to a temperature of 25℃and reacting at that temperature for 9 hours. 2500g of ion-exchanged water was then added dropwise thereto, and the precipitated white solid was filtered. The white solid obtained was washed 5 times with 200mL of 10% hydrochloric acid, 200mL of 10% aqueous sodium hydrogencarbonate solution, and further 200mL of ion-exchanged water, and dried in vacuo. 128.9g of the obtained white solid was dissolved in 2800g of ethyl acetate, and dried (dehydrated) with 35g of anhydrous magnesium sulfate. Subsequently, the ethyl acetate solution was passed through a silica gel column, and the solvent was distilled off by an evaporator to obtain 1, 4a,5, 8a, 9a,10 a-decahydro-1, 4: 124.5g of 5, 8-dimethylbridged anthracene-9, 10-diyl-Dimesylate (DNCMS) (purity 99% based on ¹ H-NMR analysis, yield 87.4%).

Physical properties of DNCMS are as follows.

¹H-NMR(DMSO-d₆,σ(ppm));1.18(d,J＝8.3Hz,1H),1.32(d,J＝8.2Hz,1H),1.39-1.42(m,2H),2.00-2.15(m,2H),2.81(s,2H),2.85-2.90(m,2H),2.97(s,2H),3.22(s,6H),4.10-4.20(m,2H),6.23(s,2H),6.27(s,2H)Cl-MS(m/z);401(M+1)

To a reaction vessel having a capacity of 1L, 364g of methanol, 62g of chloroform, 136g (1011 mmol) of copper (II) chloride and 6g (33.7 mmol) of palladium chloride were added and stirred. After the atmosphere gas in the system was replaced with carbon monoxide, DNCMS g (67.3 mmol) of a solution dissolved in 178g of chloroform was added dropwise over 3 hours, and the mixture was reacted at 20 to 25℃for 4 hours. Then, the atmosphere in the system was changed from carbon monoxide to argon, and then the solvent was distilled off from the reaction mixture, and 621g of chloroform was added. The same operation was repeated twice. Insoluble material was then removed from the resulting dark green suspension by filtration. The resulting solution was washed 3 times with 324g of saturated aqueous sodium hydrogencarbonate solution and 3 times with 324g of purified water, and then 2.7g of anhydrous magnesium sulfate and 2.7g of activated carbon were added to the organic layer and stirred. Then, the solution was filtered and concentrated under reduced pressure to obtain 51g of a white solid. Next, purification by silica gel chromatography (developing solvent; hexane: ethyl acetate=10:1 (volume ratio)) gave 9, 10-bis ((methylsulfonyl) oxy) tetradecahydro-1, 4 as a white solid: 27g of 5, 8-dimethylbridged anthracene-2, 3,6, 7-tetracarboxylic acid ester (DNMTE) (purity 97.1pa, yield 64.4% based on HPLC analysis).

Physical properties of DNMTE are as follows.

¹H-NMR(CDCl₃,σ(ppm));1.49(d,J＝10Hz,2H),2.31(d,J＝10Hz,2H),2.62-2.67(m,2H),2.69(s,2H),2.87(s,4H),3.06(s,6H),3.19(s,2H),3.32(s,2H),3.64(s,6H),3.66(s,6H),4.98-5.12(m,2H)Cl-MS(m/z);637(M+1)

6.4G (86.8 mmol) of lithium carbonate and 130g of N, N' -dimethylformamide were charged into a 500 mL-capacity reaction vessel, and the temperature was raised to 150 ℃. Subsequently, a mixture of 27.6g (42.1 mol) of DNMTE and 130g of N, N' -dimethylformamide was added dropwise thereto over 1 hour, and the mixture was reacted at this temperature for 15 hours. After completion of the reaction, the reaction solution was concentrated under reduced pressure to obtain 22.4g of a white solid. Next, purification by silica gel chromatography (developing solvent; hexane: ethyl acetate=10:1 (volume ratio)), followed by recrystallization (solvent ratio; toluene/heptane=2:3) gave tetramethyl 1,2,3, 4a,5,6,7,8,9 a-decahydro-1, 4 as a white solid: 13.9g of 5, 8-dimethylbridged anthracene-2, 3,6, 7-tetracarboxylic acid ester (DMHAE) (purity 95.1pa, yield 72.2% based on HPLC analysis).

Physical properties of DMHAE are as follows.

¹H-NMR(CDCl₃,σ(ppm));1.36(d,J＝10Hz,1H),1.56(d,J＝10Hz,1H),2.05(d,J＝10Hz,1H),2.29(d,J＝10Hz,1H),2.56(s,2H),2.83(s,2H),2.90(d,J＝1.6Hz,2H),3.05(s,2H),3.07(d,J＝1.6Hz,2H),3.61(s,6H),3.65(s,6H),5.10(s,2H)Cl-MS(m/z);445(M+1)

To a 300mL reaction vessel were charged 68mL of toluene and 7.3g (31.9 mmol) of 2, 3-dichloro-5, 6-dicyano-p-benzoquinone, and the temperature was raised to 80 ℃. A solution of DMHAE13.5g (30.4 mmol) dissolved in 200mL of toluene was added dropwise and allowed to react for 8 hours. After completion of the reaction, the reaction mixture was concentrated, and 130mL of chloroform was added to the concentrate to obtain a black tea suspension. Then, filtration was performed to separate a dark red-black filtrate and a filtrate. After the filtrate was washed 3 times with 100mL of a saturated aqueous sodium hydrogencarbonate solution, 12g of anhydrous magnesium sulfate was added to the obtained organic layer to dehydrate the organic layer. Subsequently, filtration was performed, and the filtrate was concentrated to dryness to obtain 5.6g of a reddish brown solid. Further, 100mL of chloroform was added to the above-mentioned dark red-black filtrate, and the same operation was performed to obtain 4.0g of a reddish brown solid. For 9.6g of the resulting reddish brown solid, purification by recrystallization (solvent ratio; toluene: heptane=1:7) gave tetramethyl-1, 2,3,4,5,6,7, 8-octahydro-1, 4 as milky white solid: 7.4g of 5, 8-dimethylbridged anthracene-2, 3,6, 7-tetracarboxylic acid ester (DMAME) (purity 99.9pa, yield 56.6% based on HPLC analysis).

Physical properties of DMAME are as follows.

¹H-NMR(CDCl₃,σ(ppm));1.80(d,J＝9.6Hz,2H),2.43(d,J＝9.6Hz,2H),2.68(d,J＝1.6Hz,4H),3.53(s,4H),3.67(s,12H),7.06(s,2H)Cl-MS(m/z);442(M+1)

A100 mL-capacity reaction vessel was charged with 5.27g (11.9 mmol) of DMAG, 26.3g of formic acid, and 47mg (0.24 mmool) of p-toluenesulfonic acid monohydrate, and reacted at 98℃for 30 hours. After completion of the reaction, the reaction mixture was concentrated under reduced pressure, and 30g of toluene was added to the concentrate. This operation was repeated 6 times, and the formic acid was distilled off almost completely. The resulting suspension was filtered, and the resulting solid was washed with 30g of toluene and dried under vacuum at 80℃to give 4.0g of milky solid. Thereafter, recrystallization was performed using acetic anhydride, and further, recrystallization was performed using N, N' -dimethylacetamide, to obtain 3a,4, 6a,9a,10, 12, 12 a-octahydro-1 h,3h-4, 12:6, 10-dimethylanthra [2,3-c: 3.28g of 6,7-c' ] difuran-1, 3,7, 9-tetraone (DMADA) (purity 98.3% based on ¹ H-NMR analysis, yield 77.3%).

Physical properties of DMADA are as follows.

¹H-NMR(DMSO-d₆,σ(ppm));1.61(d,J＝10.8Hz,2H),1.81(d,J＝10.8Hz,2H),3.04(s,2H),3.04(s,2H),3.76(s,4H),7.39(s,2H)Cl-MS(m/z);351(M+1)

[ Example S-2-1 (EMDAdx Synthesis)

[ 50]

600G (3.66 mol) of cis-5-norbornene-bridge-2, 3-dicarboxylic anhydride (endo-NA) was charged into a 3L-capacity autoclave, followed by 1.20g of 2, 6-dibutylhydroxytoluene. After the nitrogen substitution in the system, 221g (4.09 mol) of 1, 3-butadiene was added at a temperature of-25℃and reacted overnight at a temperature of 150-160℃to give 760g of a white solid. The above operation was repeated twice to obtain 2258g of a white solid (yield: 36%). Then, 9.7L of toluene was added to 2258g of the obtained white solid, and the mixture was heated and stirred at a temperature of 102℃to dissolve the solid. After stirring at this temperature for 10 minutes, 2.6L of heptane was added, cooled to room temperature and stirred overnight, and the precipitated solid was filtered. After washing the obtained solid with 2.6L of heptane, vacuum drying was performed at 40℃for 5 hours to obtain 691g of a white solid.

To a reaction vessel having a capacity of 5L, 691g of the resulting white solid and 2.1L of toluene were charged. After heating and stirring at 98 ℃, 1.1L of heptane was added and cooled to room temperature, followed by stirring overnight. The precipitated solid was filtered, washed with 1.1L of heptane and dried under vacuum at 40℃for 3 hours to give 634g of (3 aR,4S,9R,9 aS) -3a, 4a,5, 8a,9 a-octahydro-4, 9-methanonaphtho [2,3-c ] furan-1, 3-dione (OMNAdx) as a white solid (purity 99.1% based on ¹ H-NMR analysis, yield 26%).

Physical properties of OMNAdx are as follows.

¹H-NMR(CDCl₃,σ(ppm));1.50(d,J＝11Hz,1H),1.52-1.63(m,3H),1.78-1.87(m,2H),2.12(d,J＝11Hz,1H),2.24-2.35(m,2H),2.54-2.59(m,2H),3.42(dd,J＝2.1Hz,J＝3.5Hz,2H),5.83-5.91(m,2H)Cl-MS(m/z);219(M+1)

To a 20L-capacity reaction vessel were added OMNAdx g (2.54 mol) of methylene chloride and 9.5L of methylene chloride. A solution of 496g (3.1 mol) of bromine dissolved in 4.9L of methylene chloride was added dropwise thereto while cooling to a temperature of-55 to-43℃and reacted for 1 hour. After the completion of the reaction, the solvent was removed by an evaporator, and 600mL of heptane was added to the obtained solid, followed by stirring. Then, the white solid was filtered, washed with 4.5L of heptane and dried under reduced pressure at 40℃to obtain 805g of (3 aR,4S,9R,9 aS) -6, 7-dibromodecahydro-4, 9-methanonaphtho [2,3-c ] furan-1, 3-dione (DBDNAdx) as a white solid (purity 100% based on ¹ H-NMR analysis, yield 78%).

Physical properties of DBDNAdx are as follows.

¹H-NMR(CDCl₃,σ(ppm));1.52-1.76(m,2H),1.88-2.05(m,4H),2.05-2.24(m,2H),2.57(brs,2H),3.48(t,J＝2.5Hz,2H),4.30(ddd,J＝3.6Hz,J＝5.4Hz,J＝12.5Hz,1H),4.68(dt,J＝3.3Hz,J＝3.5Hz,1H)Cl-MS(m/z);379(M+1)

130G (1.33 mol) of maleic anhydride and DBDNAdx g (264.5 mmol) of maleic anhydride were charged into a 2L-capacity reaction vessel, and reacted at a temperature of 187℃for 2 hours. After the completion of the reaction, the reaction mixture was cooled to 100℃and 400mL of toluene was added. Cooling to around room temperature, filtering the precipitated solid, washing with toluene, and vacuum drying at 60 ℃ to obtain (3 ar,4r,5s,5ar,8as,9r,10s,10 as) -3a, 4a, 5a,8a, 9a,10 a-decahydro-1 h,3h-4, 10-ethanol-5, 9-methanonaphtho [2, 3-c) as a gray solid: 75g of 6,7-c' ] difuran-1, 3,6, 8-tetraone (EEMDAdx) (purity 98.4% based on ¹ H-NMR analysis, yield 89%).

Physical properties of EEMDAdx are as follows.

¹H-NMR(CDCl₃,σ(ppm));1.04(d,J＝10.8Hz,1H),1.82(s,2H),2.30(d,J＝10.8Hz,1H),2.62(s,2H),3.20(s,2H),3.39(m,2H),3.42(d,J＝2.1Hz,J＝3.4Hz,2H),6.20(dd,J＝3.2Hz,J＝4.5Hz,2H)Cl-MS(m/z);314(M+1)

To a reaction vessel having a capacity of 2L, EEMDAdx g (239 mmol), trimethyl orthoformate 152g, methanol 1500g and concentrated sulfuric acid 22.5g were charged and reacted at 63℃for 23 hours. After completion of the reaction, the reaction mixture was concentrated under reduced pressure, 600g of a saturated aqueous sodium hydrogencarbonate solution was added to the concentrated residue, and the mixture was extracted with 500g of chloroform. The organic layer was washed twice with 200g of water, dried (dehydrated) over anhydrous magnesium sulfate (MgSO ₄), filtered, and the filtrate was concentrated under reduced pressure to obtain 80.7g of a solid. Then, crystallization was performed using 150g of toluene and 450g of heptane, to obtain 75g of tetramethyl (1R, 4S,5R,6S,7R,8S,10S, 11R) -1, 4a,5,6,7,8 a-octahydro-1, 4-ethanol-5, 8-methanonaphthalene-6, 7, 10, 11-tetracarboxylic acid ester (EEMDEdx) as a white solid (purity 100% based on ¹ H-NMR analysis, yield 77%).

Physical properties of EEMDEdx are as follows.

¹H-NMR(CDCl₃,σ(ppm));0.81(d,J＝11Hz,1H),2.29(s,2H),2.43(s,2H),2.58(d,J＝11Hz,1H),2.86(t,J＝2.0Hz,2H),3.00(brs,2H),3.05(s,2H),3.57(s,6H),3.65(s,6H),6.28(dd,J＝3.3Hz,J＝4.6Hz,2H)Cl-MS(m/z);407(M+1)

To a reaction vessel having a capacity of 200mL was added EEMDEdx g (14.8 mmol), 120g of methanol, and 3g of a 10% rhodium-carbon catalyst (manufactured by N.E. CHEMCAT, 50% by weight of aqueous material). After hydrogen substitution in the system, hydrogen was pressurized to 0.9MPa and reacted at 80 ℃ for 4 hours at an internal temperature. After the reaction, the reaction mixture was washed with 100mL of N, N' -dimethylformamide and taken out. The resulting reaction suspension was filtered through celite, and concentrated under reduced pressure to give a white solid. This operation was repeated 7 times to obtain 41.2g (purity 99.9% based on GC analysis, yield 97%) of a white solid. Then, purification was performed with a silica gel column (developing solvent; hexane/ethyl acetate=3/1 (v/v)), to obtain 35g of tetramethyl (1 r,2r,3s,4s,5r,6s,7r,8 s) -decahydro-1, 4-ethanol-5, 8-carbaryl-2, 3,6, 7-tetracarboxylic acid ester (EMDEdx) as a white solid (purity 100% based on GC analysis, yield 83%).

Physical properties of EMDEdx are as follows.

¹H-NMR(CDCl₃,σ(ppm));1.25(d,J＝11Hz,1H),1.49(d,J＝9.0Hz,2H),1.79(d,J＝9.OHz,2H),2.00(s,2H),2.14(s,2H),2.24(d,J＝11Hz,1H),2.51(s,2H),2.90(s,2H),3.02(t,J＝2.0Hz,2H),3.63(s,6H),3.64(s,6H)Cl-MS(m/z);409(M+1)

To a 300 mL-capacity reaction vessel were added EMDEdx g (73.4 mmol), 150g of formic acid, 280mg (1.47 mmol) of p-toluenesulfonic acid monohydrate, and the mixture was reacted at a temperature of 95℃to 99℃for 16 hours. After completion of the reaction, the reaction mixture was concentrated under reduced pressure, and 72mL of toluene was added to the concentrate. This operation was repeated 6 times, and the formic acid was distilled off almost completely. The resulting suspension was filtered, and the resulting solid was washed with 35mL of toluene and dried in vacuo at 80℃to give 23.4g of a gray solid. Thereafter, recrystallization was repeated using acetic anhydride, N' -dimethylacetamide to give (3 ar,4r,5s,5ar,8as,9r,10s,10 as) -decahydro-1 h,3h-4, 10-ethanol-5, 9-methanonaphtho [2, 3-c) as a white solid: 18.9g of 6,7-c' ] difuran-1, 3,6, 8-tetraone (EMDAdx) (purity 98.5% based on ¹ H-NMR analysis, yield 80%).

Physical properties of EMDAdx are as follows.

¹H-NMR(DMSO-d₆,σ(ppm));1.17(d,J＝9.9Hz,2H),1.48(d,J＝12Hz,1H),1.45-1.68(m,4H),2.04-2.14(m,3H),2.69(s,2H),3.29(s,2H),3.55(dd,J＝1.2Hz,J＝2.1Hz,2H)Cl-MS(m/z);317(M+1)

[ Example S-2-2 (EMDAxx Synthesis)

[ 51]

To a 3L autoclave was charged 600g (3.66 mol) of cis-5-norbornene-exo-2, 3-dicarboxylic anhydride (exo-NA) and 300mg of 2, 6-dibutylhydroxytoluene. After the nitrogen substitution in the system, 319g (5.91 mol) of 1, 3-butadiene was added at an internal temperature of-25℃and stirred at a reaction temperature of 140 to 166℃for 35 hours to obtain 866.2g of a white solid (yield 58%). Then, 866.2g of the obtained white solid was recrystallized from toluene to obtain 359g of (3 aR,4R,9S,9 aS) -3a, 4a,5, 8a,9 a-octahydro-4, 9-methanonaphtho [2,3-c ] furan-1, 3-dione (OMNAxx) as white crystals (purity 100% based on ¹ H-NMR analysis, yield 45%).

Physical properties of OMNAxx are as follows.

¹H-NMR(CDCl₃,σ(ppm));1.19(d,J＝12Hz,1H),1.52-1.63(m,2H),1.73-1.82(m,2H),1.89(d,J＝12Hz,1H),2.27-2.40(m,2H),2.56(t,J＝1.2Hz,2H),2.98(d,J＝1.2Hz,2H),5.80-5.92(m,2H)Cl-MS(m/z);219(M+1)

To a 3L-capacity reaction vessel was added OMNAxx g (550 mmol) of methylene chloride 2.2L. Cooled to a temperature of-65 to-60 ℃, and 105.4g (660 mmol) of bromine dissolved in 200mL of methylene chloride was added dropwise over 2 hours to react for 1 hour. This operation was performed twice. Then, the reaction solution was collected twice and concentrated by an evaporator to obtain a pale brown solid. To the resulting pale brown solid was added 1.5L of heptane and filtered. Then, the filtered solid was washed with 500mL of heptane and vacuum-dried to obtain 313g of (3 aR,4R,9S,9 aS) -6, 7-dibromodecahydro-4, 9-methanonaphtho [2,3-c ] furan-1, 3-dione (DBDNAxx) as a white solid (purity 100% based on ¹ H-NMR analysis, yield 75%). The filtrate was concentrated under reduced pressure, washed with 500mL of heptane, and then dried in vacuo to obtain DBDNAx78.1 g (purity 100% based on ¹ H-NMR analysis, yield 19%) as a white solid.

Physical properties of DBDNAxx are as follows.

¹H-NMR(CDCl₃,σ(ppm));1.28(d,J＝12Hz,1H),1.62(q,J＝12Hz,1H),1.84-2.24(m,5H),2.59(s,2H),3.03(dd,J＝7.3Hz,J＝23Hz,2H),4.32(ddd,J＝3.3Hz,J＝5.5Hz,J＝12Hz,1H),4.73(dd,J＝3.0Hz,J＝7.0Hz,1H)Cl-MS(m/z);379(M+1)

To a reaction vessel having a capacity of 2L, 259g (2.64 mol) of maleic anhydride and DBDNAxx g (529 mmol) were charged, and the mixture was reacted at a reaction temperature of 190℃for 2 hours. After the completion of the reaction, the reaction mixture was cooled to 100℃and 900mL of toluene was added. Cooled to around room temperature and the precipitated solid was filtered off. After the obtained solid was washed with 900mL of toluene, it was dried under reduced pressure at 60℃for 3 hours to obtain (3 aR,4R,5S,5aS,8aR,9R,10S,10 aS) -3a, 4a, 5a,8a, 9a,10 a-decahydro-1H, 3H-4, 10-ethanol-5, 9-methano [2, 3-c) as a pale brown solid: 140.2g of 6,7-c' ] difuran-1, 3,6, 8-tetraone (EEMDAxx) (purity 97.2% based on ¹ H-NMR analysis, yield 82%).

The same procedure was performed for DBDNAxx g (476 mmol) to obtain EEMDAxx139.2g (¹ H-NMR purity 98.9% yield 92%) as a pale brown solid.

Physical properties of EEMDAxx are as follows.

¹H-NMR(CDCl₃,σ(ppm));0.59(d,J＝12Hz,1H),2.01(s,2H),2.12(d,J＝12Hz,1H),2.55(s,2H),2.98(d,J＝1.4Hz,2H),3.20-3.30(m,4H),6.20(dd,J＝3.1Hz,J＝4.4Hz,2H)Cl-MS(m/z);314(M+1)

To a 20L-capacity reaction vessel, EEMDAxx254.9g (794.8 mmol), methanol 10L, trimethyl orthoformate 533g, and concentrated sulfuric acid 63g were added, and the mixture was stirred at 61 to 67℃for 79 hours. After completion of the reaction, the reaction solution was concentrated under reduced pressure to obtain 513g of a gray solid. The obtained solid was dissolved in 3256g of chloroform and added dropwise to 1700g of 7 wt% sodium hydrogencarbonate aqueous solution. To the separated organic layer, 31.6g of anhydrous magnesium sulfate and 26.8g of activated carbon were added, and after stirring at room temperature for 1 hour, the mixture was filtered, and the filtrate was washed with 322g of chloroform and concentrated under reduced pressure to obtain 325.3g of a gray solid. Then, the obtained gray solid was recrystallized from methanol to obtain 294.9g of tetramethyl (1 r,4s,5r,6r,7s,8s,10s,11 r) -1, 4a,5,6,7,8 a-octahydro-1, 4-ethanol-5, 8-methanonaphthalene-6, 7, 10, 11-tetracarboxylic acid ester (EEMDExx) as a white solid (purity 100% based on GC analysis, yield 91%).

Physical properties of EEMDExx are as follows.

¹H-NMR(CDCl₃,σ(ppm));1.55(d,J＝11Hz,1H),1.61(s,2H),2.29(d,J＝11Hz,1H),2.43(s,2H),2.62(d,J＝1.9Hz,2H),2.97(s,2H),3.03(s,2H),3.58(s,6H),3.60(s,6H),6.23(dd,J＝3.2Hz,J＝4.6Hz,2H)Cl-MS(m/z);407(M+1)

To a 3L autoclave, 98.2g (242 mmol) of EEMDExx and 1720g of methanol were charged, and 49.1g of a 10% rhodium-carbon catalyst (manufactured by N.E. CHEMCAT, 50% aqueous material) was added. After hydrogen substitution in the system, hydrogen was pressurized to 0.9MPa and reacted at 80 ℃ for 4 hours at an internal temperature. After the completion of the reaction, the precipitated solid was dissolved in 3235g of N, N' -dimethylformamide, and the reaction product was taken out, followed by filtration through celite to remove the catalyst. For EEMDExx97.3g (239 mmol), this operation was performed twice. Then, all the filtrates were combined and concentrated under reduced pressure to give 289.1g of a gray solid. The obtained gray solid was recrystallized from 700g of chloroform and 4373g of heptane to obtain 283.0g of tetramethyl (1R, 2R,3S,4S,5R,6R,7S, 8S) -decahydro-1, 4-ethanol-5, 8-carbaryl-2, 3,6, 7-tetracarboxylic acid ester (EMDExx) as a light gray solid (purity 99.9pa based on GC analysis, yield 96%).

Physical properties of EMDExx are as follows.

¹H-NMR(CDCl₃,σ(ppm));1.52(d,J＝9.0Hz,2H),1.58(s,2H),1.76(d,J＝9.0Hz,2H),1.95-2.10(m,4H),2.52(s,2H),2.71(d,J＝1.6Hz,2H),2.84(s,2H),3.63(s,6H),3.64(s,6H)Cl-MS(m/z);409(M+1)

A reaction vessel having a capacity of 3L was charged with EMDExx282.0g (689.7 mmol), formic acid 1410g, and p-toluenesulfonic acid monohydrate 3.28g (17 mmol), and reacted at a temperature of 95℃to 97℃for 19 hours. After completion of the reaction, the reaction mixture was concentrated under reduced pressure, and 700mL of toluene was added to the concentrate. This operation was repeated 6 times, and the formic acid was distilled off almost completely. The resulting suspension was filtered, and the resulting solid was washed with 490mL of toluene and dried in vacuo at 80℃to give 219.6g of a gray solid. Thereafter, recrystallization was performed using acetic anhydride, and further, recrystallization was performed using N, N' -dimethylformamide, to obtain (3 ar,4r,5s,5as,8ar,9r,10s,10 as) -decahydro-1 h,3h-4, 10-ethanol-5, 9-methanonaphtho [2, 3-c) as a white solid: 175.9g of 6,7-c' ] difuran-1, 3,6, 8-tetraone (EMDAxx) (purity 99.4% based on ¹ H-NMR analysis, yield 96%).

Further, using EMDAxx g of the obtained solution, purification was performed under sublimation conditions of 250 to 290℃and 5Pa to obtain EMDAxx g (purity 100% by ¹ H-NMR analysis, recovery 97.6%) as a white solid.

Physical properties of EMDAxx are as follows.

¹H-NMR(DMSO-d₆,σ(ppm));0.98(d,J＝13Hz,1H),1.15(d,J＝9.4Hz,2H),1.57(d,J＝9.4Hz,2H),1.81(s,2H),1.91(d,J＝13Hz,1H),2.17(s,2H),2.63(s,2H),3.04(s,2H),3.19(s,2H)Cl-MS(m/z);317(M+1)

[ Example S-3 (BNDA Synthesis)

[ 52]

To a 1L-capacity autoclave were added 233g (1.76 mol) of cis-1, 4-dichloro-2-butene, 245g (1.96 mol) of dicyclopentadiene, and 176mL of toluene. After nitrogen substitution in the system, the reaction was carried out at 180℃for 5 hours. The autoclave was opened and the reaction was taken out and concentrated.

Next, 149g (1.13 mol) of cis-1, 4-dichloro-2-butene, 156g (1.25 mol) of dicyclopentadiene and 112mL of toluene were charged into a 1L-capacity autoclave. After nitrogen substitution in the system, the reaction was carried out at 180℃for 5 hours. The autoclave was opened and the reaction was taken out and concentrated.

The reaction products (concentrated residues) obtained in the total of two reactions were combined (total 942 g), and distilled under reduced pressure to obtain 396.8g of 5, 6-bis (chloromethyl) bicyclo [2.2.1] hept-2-ene (BCMN) as a pale brown liquid (purity 74.7% by GC analysis, yield 65%).

Physical properties of BCMN are as follows.

¹H-NMR(CDCl₃,σ(ppm));1.37(d,J＝8.4Hz,1H),1.56(d,J＝8.4Hz,1H),2.55-2.67(m,2H),3.06-3.17(m,4H),3.47(dd,J＝5.8Hz,J＝10Hz,2H),6.25(t,J＝2.0Hz,2H)Cl-MS(m/z);191(M+1)

To a reaction vessel having a capacity of 5L, 307g (4.65 mol) of 85wt% aqueous sodium hydroxide solution, 2.3L of ethanol, 396.8g (1.55 mol) of BCMN was added, and the mixture was heated and stirred at a reaction temperature of 78℃for 41 hours. After the reaction was completed, the resulting suspension was filtered. Then, the filtrate was cooled to a temperature of 10℃and 120g of concentrated sulfuric acid was added dropwise while cooling to a temperature of 10 to 20℃to obtain a suspension. The resulting suspension was filtered, and the filtrate was distilled under reduced pressure at 55-58 ℃ C./290-300 mmHg to give 2424g of an ethanol solution of 5, 6-dimethylene bicyclo [2.2.1] hept-2-ene (CYDE).

Physical properties of CYDE are as follows.

¹H-NMR(CDCl₃,σ(ppm));1.57(d,J＝8.2Hz,1H),1.77(d,J＝8.2Hz,1H),3.30(d,J＝1.8Hz,2H),4.95(s,2H),5.16(s,2H),6.19(s,2H)Cl-MS(m/z);119(M+1)

To a reaction vessel having a capacity of 10L, 2424g of the resulting CYDE ethanol solution and 264.3g (1.86 mol) of dimethyl acetylenedicarboxylate were added, and the mixture was reacted at a reaction temperature of 70 to 78℃for 17 hours. After the completion of the reaction, ethanol was distilled off under reduced pressure to obtain 369.3g of a brown liquid. Next, purification was performed by silica gel column chromatography (developing solvent; hexane: ethyl acetate=15:1 (volume ratio)), to obtain, as a brown liquid, 126g of a fraction (1) containing dimethyl 1,4,5, 8-tetrahydro-1, 4-carbaryl-6, 7-dicarboxylate (CYME) (purity 85.6pa based on GC analysis), and 177g of a fraction (2) (purity 50.9pa based on GC analysis) of 2 fractions [ total yield (yield based on BCMN) 49% ].

Physical properties of CYME are as follows.

¹H-NMR(CDCl₃,σ(ppm));1.98(d,J＝0.8Hz,2H),2.85-3.02(m,2H),3.21-3.40(m,4H),3.76(s,6H),6.76(t,J＝1.8Hz,2H)Cl-MS(m/z);261(M+1)

To a reaction vessel having a capacity of 3L, 126g (purity: 85.6pa%;414.4 mmol) of fraction (1) containing CYME, 138g (607.9 mmol) of methylene chloride 1.3L and 2, 3-dichloro-5, 6-dicyano-p-benzoquinone were charged under Ar atmosphere, and reacted at 20℃for 7 hours.

In addition, 177g (purity: 50.9pa%;346.1 mmol) of fraction (2) containing CYME, 890mL of methylene chloride, 97.7g (430.4 mmol) of 2, 3-dichloro-5, 6-dicyano-p-benzoquinone were charged into a reaction vessel having a capacity of 3L under an Ar atmosphere, and reacted at 20℃for 7 hours.

The reactants obtained in the two reactions were combined and concentrated under reduced pressure to give 457.4g of a brown liquid. Next, purification was performed by silica gel chromatography (developing solvent; hexane: ethyl acetate=15:1 (capacity ratio)) to obtain 248.9g of a red oily substance. This oily substance was dissolved in ethyl acetate 2L, washed 3 times with 500mL of saturated aqueous sodium hydrogencarbonate, further washed with 500mL of saturated brine, dehydrated and dried over sodium sulfate and filtered, and then the filtrate was concentrated under reduced pressure to obtain 146g of dimethyl 1, 4-dihydro-1, 4-carbazol-6, 7-dicarboxylic acid ester (CYPDM) as a red oily substance (purity 99.1pa, yield 74% based on GC analysis).

Physical properties of CYPDM are as follows.

¹H-NMR(CDCl₃,σ(ppm));2.26(d,J＝7.6Hz,1H),2.36(d,J＝7.6Hz,1H),3.85(s,6H),3.94(t,J＝1.8Hz,2H),6.77(t,J＝1.8Hz,2H),7.56(s,2H)Cl-MS(m/z);259(M+1)

To a reaction vessel having a capacity of 500mL, 135g of methanol, 41g of chloroform, 52g (387 mmol) of copper (II) chloride, and 14mg (0.08 mmol) of palladium chloride were added. After the atmosphere gas in the system was replaced with carbon monoxide, CYPDM g (76.7 mmol) of a solution dissolved in 66g of chloroform was added dropwise over 6 hours, and the mixture was reacted at room temperature for 3 hours. Then, the atmosphere in the system was changed from carbon monoxide to argon, and then the solvent was distilled off from the reaction mixture, followed by addition of 300g of chloroform. Further, the mixture was concentrated under reduced pressure, the solvent was distilled off, and 300g of chloroform was added thereto. Insoluble material was then removed from the resulting dark green suspension by filtration. The obtained solution was washed 3 times with 240g of a saturated aqueous sodium hydrogencarbonate solution and then with 240g of purified water, and after 3 times, 4g of anhydrous magnesium sulfate and 2g of activated carbon were added to the organic layer and stirred. Then, the solution was concentrated under reduced pressure after filtration to obtain 26.7g of a pale brown solid. Next, purification was performed by silica gel chromatography (developing solvent; hexane: ethyl acetate=15:1 (volume ratio)), followed by recrystallization (solvent ratio; toluene/heptane=2.5:1 (volume ratio)), to obtain 22.4g (purity 94.8pa, yield 67.5% based on HPLC analysis) of tetramethyl-1, 2,3, 4-tetrahydro-1, 4-methanonaphthalene-2, 3,6, 7-tetracarboxylic acid ester (BNME) as a white solid.

Physical properties of BNME are as follows.

¹H-NMR(CDCl₃,σ(ppm));1.89(d,J＝10Hz,1H),2.54(d,J＝10Hz,1H),2.74(d,J＝2.0Hz,2H),3.67(t,J＝2.0Hz,2H),3.70(s,6H),3.89(s,6H),7.57(s,2H)Cl-MS(m/z);377(M+1)

To a reaction vessel having a capacity of 200mL was added BNME g (50.4 mmol), 60g of formic acid and 194.2mg (1.02 mmol) of p-toluenesulfonic acid monohydrate, and the mixture was reacted at an internal temperature of 95℃to 99℃for 57 hours. After completion of the reaction, the reaction mixture was concentrated under reduced pressure, and 42g of toluene was added to the concentrate. This operation was repeated 7 times, and the formic acid was distilled off almost completely. The resulting suspension was filtered, and the resulting solid was washed with 21g of toluene and dried in vacuo at 80℃to give 16.1g of a milky solid. Then, recrystallization was performed using acetic anhydride, and further, recrystallization was performed using N, N' -dimethylacetamide, to obtain 3a,4, 10, 10 a-tetrahydro-1 h,3h-4, 10-methanonaphtho [2,3-c ] as a white solid: 8.39g of 6,7-c' ] difuran-1, 3,6, 8-tetraone (BNDA) (purity 98.8% based on ¹ H-NMR analysis, yield 57.9%).

Further, using BNDA g of the obtained solution, purification was carried out under sublimation conditions of 220 to 230℃and 5Pa, whereby 11.6g of BNDA (purity 100% based on ¹ H-NMR analysis, recovery rate: 76.4%) was obtained as a white solid.

Physical properties of BNDA are as follows.

¹H-NMR(DMSO-d₆,σ(ppm));1.79(d,J＝15Hz,1H),1.93(d,J＝15Hz,1H),3.21(s,2H),4.05(s,2H),8.07(s,2H)Cl-MS(m/z);285(M+1)

Example 1

DABA 0.60g (2.6 mmol) was charged into a reaction vessel replaced with nitrogen gas, and 6.29gNMP was added in an amount to reach 20 mass% of the total mass of the charged monomers (the sum of the diamine component and the carboxylic acid component), and stirred at room temperature for 1 hour. To this solution was slowly added TNDA1.12g (2.6 mmol). Stirring was carried out at room temperature for 48 hours to give a polyimide precursor solution which was uniform and viscous.

The polyimide precursor solution filtered by the PTFE membrane filter was applied to a glass substrate, and the polyimide precursor solution was directly heated to 440 ℃ from room temperature on the glass substrate under a nitrogen atmosphere (oxygen concentration: 200ppm or less) to carry out thermal imidization, thereby obtaining a colorless and transparent polyimide film/glass laminate. Then, the obtained polyimide film/glass laminate was immersed in water, and then peeled off and dried to obtain a polyimide film having a film thickness of 10. Mu.m.

The results obtained by measuring the properties of the polyimide film are shown in table 2.

Example 2

To a reaction vessel replaced with nitrogen gas were added 1.00g (4.4 mmol) of DABA, 0.07g (0.6 mmol) of PPD and 0.46g (1.3 mmol) of BAPB, and 11.54gNMP in an amount of 25% by mass of the total charged monomers (sum of diamine component and carboxylic acid component) was added, followed by stirring at room temperature for 1 hour. To this solution was slowly added TNDA2.32g (6.3 mmol). Stirring was carried out at room temperature for 48 hours to give a polyimide precursor solution which was uniform and viscous.

The polyimide precursor solution filtered by the PTFE membrane filter was applied to a glass substrate, and the polyimide precursor solution was directly heated to 460 ℃ from room temperature on the glass substrate under a nitrogen atmosphere (oxygen concentration: 200ppm or less) to carry out thermal imidization, thereby obtaining a colorless and transparent polyimide film/glass laminate. Then, the obtained polyimide film/glass laminate was immersed in water, and then peeled off and dried to obtain a polyimide film having a film thickness of 10. Mu.m.

Comparative example 1

BAPB 1.00g (2.7 mmol) was charged into the reaction vessel replaced with nitrogen, and 6.00g of NMP was added in an amount to 25% by mass of the total charged monomer (sum of diamine component and carboxylic acid component), followed by stirring at room temperature for 1 hour. To this solution was slowly added TNDA 1.00.00 g (2.7 mmol). Stirring was carried out at room temperature for 48 hours to give a polyimide precursor solution which was uniform and viscous.

The polyimide precursor solution filtered by the PTFE membrane filter was applied to a glass substrate, and the polyimide precursor solution was directly heated to 430 ℃ from room temperature on the glass substrate under a nitrogen atmosphere (oxygen concentration: 200ppm or less) to carry out thermal imidization, thereby obtaining a colorless and transparent polyimide film/glass laminate. Then, the obtained polyimide film/glass laminate was immersed in water, and then peeled off and dried to obtain a polyimide film having a film thickness of 10. Mu.m.

Comparative example 2

To a reaction vessel replaced with nitrogen gas, 0.70g (3.5 mmol) of 4,4' -ODA was charged, 7.95g of DMAc was added in an amount such that the total mass of the charged monomers (the sum of the diamine component and the carboxylic acid component) became 20 mass%, and the mixture was stirred at room temperature for 1 hour. To this solution was slowly added TNDA 1.29.29 g (3.5 mmol). Stirring was carried out at room temperature for 48 hours to give a polyimide precursor solution which was uniform and viscous.

Example 3

To a reaction vessel replaced with nitrogen gas, DABAN 0.23.23 g (1.0 mmol) of NMP (2.70 g) was added in an amount to give 16 mass% of the total mass of the charged monomers (the sum of the diamine component and the carboxylic acid component), and the mixture was stirred at room temperature for 1 hour. To this solution was slowly added BNDA0.29g (1.0 mmol) obtained in example S-3. Stirring was carried out at room temperature for 48 hours to give a polyimide precursor solution which was uniform and viscous.

The polyimide precursor solution filtered by the PTFE membrane filter was applied to a glass substrate, and the polyimide precursor solution was directly heated to 320 ℃ from room temperature on the glass substrate under a nitrogen atmosphere (oxygen concentration: 200ppm or less) to carry out thermal imidization, thereby obtaining a colorless and transparent polyimide film/glass laminate. Then, the obtained polyimide film/glass laminate was immersed in water, and then peeled off and dried to obtain a polyimide film having a film thickness of 10. Mu.m.

Example 4

To a reaction vessel replaced with nitrogen gas, 0.40g (3.7 mmol) of PPD was added, and 5.81g of NMP was added in an amount such that the total mass of the charged monomers (the sum of the diamine component and the carboxylic acid component) became 20 mass%, and the mixture was stirred at room temperature for 1 hour. To this solution was slowly added BNDA 1.05.05 g (3.7 mmol) obtained in example S-3. Stirring was carried out at room temperature for 48 hours to give a polyimide precursor solution which was uniform and viscous.

The polyimide precursor solution filtered by the PTFE membrane filter was applied to a glass substrate, and the polyimide precursor solution was directly heated to 350 ℃ from room temperature on the glass substrate under a nitrogen atmosphere (oxygen concentration: 200ppm or less) to carry out thermal imidization, thereby obtaining a colorless and transparent polyimide film/glass laminate. Then, the obtained polyimide film/glass laminate was immersed in water, and then peeled off and dried to obtain a polyimide film having a film thickness of 10. Mu.m.

Example 5

To a reaction vessel replaced with nitrogen gas, 1.52g (4.7 mmol) of TFMB was added, and 11.41g of NMP was added in an amount such that the total mass of the charged monomers (the sum of the diamine component and the carboxylic acid component) became 20% by mass, and the mixture was stirred at room temperature for 1 hour. To this solution was slowly added BNDA 1.35.35 g (4.7 mmol) obtained in example S-3. Stirring was carried out at room temperature for 48 hours to give a polyimide precursor solution which was uniform and viscous.

Example 6

To a reaction vessel replaced with nitrogen gas were added DABAN 0.40.40 g (1.8 mmol), 0.70g (2.2 mmol) of TFMB and 0.16g (0.4 mmol) of BAPB, 10.00g of NMP in an amount of 20% by mass based on the total mass of the charged monomers (sum of diamine component and carboxylic acid component) was added, and the mixture was stirred at room temperature for 1 hour. To this solution was slowly added 1.24g (4.4 mmol) of BNDA obtained in example S-3. Stirring was carried out at room temperature for 48 hours to give a polyimide precursor solution which was uniform and viscous.

Example 7

To a reaction vessel replaced with nitrogen gas, 0.39g (3.5 mmol) of tra-DACH was added, and 11.14g of NMP was added in an amount such that the total mass of the charged monomers (the sum of the diamine component and the carboxylic acid component) became 11 mass%, and the mixture was stirred at room temperature for 1 hour. To this solution was slowly added BNDA 0.98.98 g (3.5 mmol) obtained in example S-3. Stirring was carried out at room temperature for 48 hours to give a polyimide precursor solution which was uniform and viscous.

Comparative example 3

To a reaction vessel replaced with nitrogen gas, 0.60g (3.0 mmol) of 4,4' -ODA was added, 13.06g of NMP was added in an amount such that the total mass of the charged monomers (the sum of the diamine component and the carboxylic acid component) became 10 mass%, and the mixture was stirred at room temperature for 1 hour. To this solution was slowly added BNDA 0.85.85 g (3.0 mmol) obtained in example S-3. Stirring was carried out at room temperature for 48 hours to give a polyimide precursor solution which was uniform and viscous.

Example 8

To a reaction vessel replaced with nitrogen gas, 0.70g (3.5 mmol) of 4,4' -ODA was added, 25.57g of NMP was added in an amount such that the total mass of the charged monomers (the sum of the diamine component and the carboxylic acid component) became 7 mass%, and the mixture was stirred at room temperature for 1 hour. To this solution was slowly added 1.22g (3.5 mmol) of DMDA1 obtained in example S-1. Stirring was carried out at room temperature for 48 hours to give a polyimide precursor solution which was uniform and viscous.

Example 9

To a reaction vessel replaced with nitrogen gas, 1.20g (4.1 mmol) of TPE-R was charged, 11.39g of NMP was added in an amount such that the total mass of the charged monomers (the sum of the diamine component and the carboxylic acid component) became 25 mass%, and the mixture was stirred at room temperature for 1 hour. To this solution was slowly added EMDAxx 1.32.32 g (4.1 mmol) obtained in example S-2-2. Stirring was carried out at room temperature for 48 hours to give a polyimide precursor solution which was uniform and viscous.

The polyimide precursor solution filtered by the PTFE membrane filter was applied to a glass substrate, and the polyimide precursor solution was directly heated to 450 ℃ from room temperature on the glass substrate under a nitrogen atmosphere (oxygen concentration: 200ppm or less) to carry out thermal imidization, thereby obtaining a colorless and transparent polyimide film/glass laminate. Then, the obtained polyimide film/glass laminate was immersed in water, and then peeled off and dried to obtain a polyimide film having a film thickness of 10. Mu.m.

TABLE 2

From the results shown in Table 2-1, it can be seen that: in the case of using TNDA as the tetracarboxylic acid component, compared with the case of using only diamine (4, 4' -ODA, BAPB) having an ether bond (-O-) as the diamine component, in the case of using diamine (DABAN, PPD) having no ether bond (-O-) and providing the structure of the above chemical formula (B-1), the heat resistance of the obtained polyimide is increased while maintaining sufficient transparency and mechanical properties, and the linear thermal expansion coefficient is lowered (examples 1,2 and comparative examples 1, 2). In the case of using BNDA as the tetracarboxylic acid component, it is known that: when a diamine (DABAN, PPD, TFMB) having no ether bond (-O-) and a diamine (tra-DACH) having a structure of the above formula (B-2) are used, the linear thermal expansion coefficient of the obtained polyimide is extremely low and the heat resistance is equal to or higher than when only a diamine (4, 4' -ODA) having an ether bond (-O-) is used as the diamine component (examples 3 to 7 and comparative example 3).

It is also known that: when the diamine component to be combined is the same, the linear thermal expansion coefficient of the obtained polyimide is lower in the case of using DMADA as the tetracarboxylic acid component than in the case of using BNDA (example 8 and comparative example 3).

In addition, even when EMDA was used as the tetracarboxylic acid component, polyimide having a low linear thermal expansion coefficient, high heat resistance and sufficient properties was obtained (example 9).

Industrial applicability

The present invention can provide a polyimide having excellent characteristics such as transparency, bending resistance, high heat resistance, and low linear thermal expansion coefficient, a precursor thereof, and a novel tetracarboxylic dianhydride used for producing the same. The polyimide obtained from the polyimide precursor of the present invention and the polyimide of the present invention have high transparency and low linear thermal expansion coefficient, are easy to form a fine circuit, and have solvent resistance, and therefore can be particularly suitably used for forming a substrate for display applications and the like.

Claims

1. A tetraester compound represented by the following chemical formula (M-2),

[ Chemical 18]

Wherein R ₅'、R₆' is each independently-CH ₂ -, or-CH ₂CH₂-,R₁₁、R₁₂、R₁₃、R₁₄ is each independently an alkyl group having 1 to 10 carbon atoms.

2. A tetraester compound represented by the following formula (M-3),

[ Chemical 19]

3. A tetraester compound represented by the following formula (M-5),

[ Chemical 27]

Wherein R ₇ is-CH ₂CH₂ -, or-CH=CH-, and R ₂₁、R₂₂、R₂₃、R₂₄ is independently an alkyl group having 1 to 10 carbon atoms.

4. A dihalodicarboxylic anhydride represented by the following formula (M-6 a),

[ Chemical 28]

Wherein X ₁₁、X₁₂ each independently represents any one of-F, -Cl, -Br, or-I.

5. A dicarboxylic anhydride represented by the following formula (M-7 a),

[ Chemical 29]